TW453141B - Printed circuit board and its manufacture method - Google Patents

Printed circuit board and its manufacture method Download PDF

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Publication number
TW453141B
TW453141B TW88116213A TW88116213A TW453141B TW 453141 B TW453141 B TW 453141B TW 88116213 A TW88116213 A TW 88116213A TW 88116213 A TW88116213 A TW 88116213A TW 453141 B TW453141 B TW 453141B
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Taiwan
Prior art keywords
layer
resin
metal
circuit board
conductor
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TW88116213A
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Chinese (zh)
Inventor
Honchin En
Masayuki Hayashi
Dongdong Wang
Kenichi Shimada
Motoo Asai
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Ibiden Co Ltd
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Priority claimed from JP27601098A external-priority patent/JP2000114726A/en
Priority claimed from JP27601198A external-priority patent/JP2000114678A/en
Priority claimed from JP29045098A external-priority patent/JP2000124601A/en
Priority claimed from JP31044598A external-priority patent/JP2000138456A/en
Application filed by Ibiden Co Ltd filed Critical Ibiden Co Ltd
Application granted granted Critical
Publication of TW453141B publication Critical patent/TW453141B/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

This invention describes a multi-layer printed circuit board with excellent fracture toughness, dielectric constant, adhesion and processability. The invented multi-layer printed circuit board has an insulation resin layer on the substrate and a conductive circuit is formed on the insulation resin layer. It is characterized by using polyolefin resin as the insulation resin layer.

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A7 4 53 1 4 1 __B7______ 五、發明說明（I ) [技術範疇] 本發明係關於印刷電路板以及該印刷電路板之製造方 法。 [技術背景] 伴隨著訊號的高頻化，組件基板的材料也逐漸要求其 具有低介電常數、低介電耗損因數。因此組件基板的材料 的主流也從陶瓷逐漸演變爲樹脂° 再者，最近因電路之高密度化被要隶的緣故，電路多 層化之所謂的增厚多層電路基板之印刷電路板逐漸成爲主 流。 所謂多層增厚電路基板之多層印刷電路板係由半加成 法等所製造出，於稱爲核心的〇.6~l.5mm厚度之玻璃布等 所補強之樹脂基板上，將銅等構成之導體電路與層間樹脂 絕緣層交互地積層而製作之。此多層印刷電路板之夾有層 間樹脂絕緣層的導體電路間的連接，係以通孔來進行。 以往，增厚多層印刷電路板係由例如特開平9 -130050號公報、特公平4 —55555號公報、特開平7-235743號公報等揭示之方法所製造的。 具體而言，首先，於貼上銅箔之銅面積層板處形成貫 通孔，接著施以無電解鍍銅處理以形成通孔(through hole) 。接著，將基板的表面予以圖案狀蝕刻處理形成導體電路 ，於此導體電路的表面以無電解鍍敷或飩刻等來形成粗·化 面，而於具有該粗化面之導體電路上形成環·氧樹脂、丙嫌 酸系樹脂、氟樹脂或這些樹脂的混合物所成之層間樹脂絕 3 . n a— n I I r n ϋ ϋ n ϋ I I 一ajI n I I n n I I (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 本紙張尺度適用中國國家標準忙~5)八4規格（210«297公釐） 經濟部智慧財產局員工消費合作社印製 4 53 1 4 1 A7 _B7_ 五、發明說明（&gt;) 緣層後，進行曝光、顯像處理或是以雷射處理形成通孔用 開口，之後，經過UV硬化、正式硬化以形成層間樹脂絕 緣層。 進一步，於層間樹脂絕緣層上施以粗化形成處理後’ 於所形成之粗化面形成薄的無電解鍍敷膜’而於此無電解 鍍敷膜上形成防鍍膜之後，以電解電鏟進行增厚，在將防 鍍膜剝離後進行蝕刻，以形成和下層導體電路透過通孔來 連接之導體電路。 將此不斷重複之後，爲保護做爲最外層之導體電路乃 形成防焊層，而於防焊層形成開口’對開口部分之導體層 施以電鍍等以形成焊墊之後，藉由形成焊接凸塊來製造增 厚多層印刷電路板。 如此般習知的製造方法之中，爲確保與導體電路之密 接性，乃於層間樹脂絕緣層及導體電路的表面施以粗化形 成處理，因此當傳送高頻率訊號時，由於表面效應造成訊 號僅傳送到粗化之導體電路的表面部分’有時由於該表面 之凹凸而產生訊號傳送的雜訊。 又，通常於層間樹脂絕緣層所使用之環氧丙烯酸酯的 破斷韌性低，對使用該樹脂的電路板而言’會由於熱循環 使得導體電路及樹脂絕緣層的界面部有易於發生破斷的傾 向。 又，如此般製造出之多層印刷電路板’由於將環氧樹 脂、丙烯酸系樹脂等之混合物使用於層間樹脂絕緣層’故 介電常數在GHz區域會高達3.5以上，若搭載著使用GHz 4 本紙張尺度適用111國國家標準（CNS)A4規格（210 X 297公釐） —-装·---r---—訂--------- (請先閲讀背面之注意事項再填寫本頁) A7 4 53 1 4 1 ---------B7___. 五、發明說明（〇 ) 區域之高頻率訊號之LS；[晶片，則會由於層間樹脂絕緣層 爲高介電常數，而發生訊號延遲或訊號錯誤的情況。 又’對於在層間樹脂絕緣層使用氟樹脂的多層印刷電 路板而言’雖然該氟樹脂具有低介電常數、低吸濕性且破 裂韌性亦佳’但對在設置層間樹脂絕緣層時的壓合過程而 言’需要在接近350°C的溫度下加熱，因此對曝露於此種 加熱環境的電路板而言，其容易變質。 又’於特開平6 —283860號公報所揭示之多層印刷電 路板之製造方法當中，首先，於基板上形成之內層導體電 路表面藉由無電解鍍敷以設置Cu-Ni-P所構成之針狀合 金的粗化層，接著，於此粗化層上形成層間樹脂絕緣層後 ’再於此層間樹脂絕緣層設置通孔形成用的開孔。之後， 對此基板施以電鍍處理，使得開孔中塡充導體，同時於層 間樹脂絕緣層上彤成外層導體電路。又，將此種導體電路 的形成與層間樹脂絕緣層的形成不斷重複以進行多層化。 若依據此特開平6- 283860號公報所揭示之方法，對 多層增厚電路基板而言，則藉由於導體電路上形成之Cu-Ni- P所構成之針狀合金，將得以確保該導體電路與其上 形成之層間樹脂絕緣層間的密接性。 然而通常於電路板的製造中，或是以酸洗淨基板，或 是將設有通孔用開孔之層間樹脂絕緣層的表面先以鉻酸等 處理，此時，若於導體電路上形成Cu-Ni-P所構成之針 狀合金的粗化層，其將與構成導體電路的銅之間產生局部 電池反應，而有導體電路溶解的情形。 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝--------訂---------線 (諳先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局負工消费合作社印製 I------ I------ 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 五、發明說明（4 ) 爲防止此種導體電路溶解，於特開平9- 130050號公 報所揭示之方法則是闡明對由Cu_Ni —P所構成之針狀合 金的粗化層以Sn等金屬被覆來抑制局部電池反應的技術。 然而，對製成品層次的多層印刷電路板而言，由於導 體電路有粗有密，欲以Sn層對由Cu_Ni_p構成之針狀合 金的粗化層完全被覆有所困難，因此要將導體電路之溶解 完全阻止是困難的。又於導體電路施以由Cu — Ni — P所構 成之針狀合金的電鍍處理時，若鑛浴的使用次數變多而造 成鑛浴的惡化’將會發生於導體電路表面難以形成鍍膜的 問題。 另外，已於先前所述般，於導體電路上施以粗化形成 處理之時，僅於被粗化之導體電路的表面部分有訊號的傳 送’而起因於該表面之凹凸會有產生訊號傳送延遲的情形 。又此種問題，相較於陶瓷基板，在使用具有低介電常數 及低介電耗損因數之樹脂基板時更爲明顯。 再者，樹脂基板較金屬基板或陶瓷基板因其放熱性不 佳容易蓄熱，其結果’構成導體電路之銅離子之擴散速度 變快，會有引起遷移現象而破壞層間絕緣的問題。 因此，於特開平7 —45598號公報及特開平7- 94865 號公報中，所揭示之技術係於陶瓷或金屬基板的—面以旋 轉塗敷等方式塗佈形成樹脂層，於該樹脂層上以濺鍍方式 設置可提昇與導體電路之密接性的金屬(Cr、Ni、Ti等）， 而於其上面形成導體電路。 然而此種技術係主要於基板的一面增厚出導體電路及 6 !農--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） A7 453 1 4 1 ____B7____ 五、發明說明（&lt; ) -------------農·__ (請先閱讀背面之注意事項再填寫本頁) 層間樹脂絕緣層之技術，不同於使用陶瓷基板及金屬基板 的情況，樹脂基板並不能抑制層間樹脂絕緣層的收縮或膨 脹，有時會發生彎板情形，或是由於這些收縮、膨脹造成 層間樹脂絕緣層與導體電路的界面發生裂開的情形。 再者，若欲以此技術實際上形成導體電路之時，其問 題在於由Cr、Ni、Ti等金屬所構成之金屬層與導體電路間 容易發生剝離。 --線' 發生此種問題的原因，係於樹脂絕緣層的表面上，若 使用物理蒸鍍法來設置金屬層時，由於該金屬層曝露於高 溫中’該表面會被氧化’如果就這樣於表面處形成有氧化 層之金屬層上面來形成導體電路，因金屬層與導體電路間 隔著氧化層之故，其密接性會變低，所以導體電路變得容 易剝離。又’即使採化學蒸鍍或電鍍來形成金屬層的情形 ，藉由放置於空氣中也會產生該表面氧化，因此導體電路 變得容易剝離。 經濟部智慧財產局員工消費合作社印製 又，以金屬層而言’若使用Ni及A1等形成鈍態之金 屬，而欲採用鹽酸或硫酸等較容易管理的酸以行蝕刻時， 一旦蝕刻時產生氧化物由於其很難被上述之酸加以分解， 會有蝕刻不能順利進行的問題點。 而且’若於這些金屬的表面形成氧化物被膜時，欲以 蝕刻加以除去會更加困難。 再者’由於這些金屬會溶解於濃硝酸及王水等強酸中 ，即使可採用以濃硝酸爲基本成分之物或氰化物、氟化物 等進行蝕刻，但由於這些酸係爲劇毒物而難以處理，所以 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 297公釐） d53 1 4 1 A7 B7 經濟部智慧財產局員工消費合作杜印製 五、發明說明（) 有過程管理的困難以及對作業環境造成不良影響的問題。 又，以粗化形成處理而言’在進行電鍍銅等而形成厚 膜之後，進行無電解鍍鎳而於厚膜之上形成薄的鍍鎳膜’ 再於其上形成由Cu-Ni-P合金所構成之粗化膜’以防止 導體電路及通孔上面形成之層間樹脂絕緣層自導體電路或 通孔處剝離。 然而，於習知之多層印刷電路板的製造方法之中’在 電鍍膜上形成無電解鍍敷鎳膜之後，若於其上面形成Cu-Ni-P合金粗化層，通常，原本鍍鎳膜與Cu —Ni-P合金 粗化層之間應有大的密接性，但此處卻和預期的相反其密 接性小，因而Cu-Ni-P合金粗化層有容易自鍍鎳膜上剝 離的問題。 又，於導體電路上施以Cu-Ni-P合金的電鍍處理時 ，若鍍浴的使甩次數變多而造成鍍浴的惡化，將會發生於 導體電路表面難以形成鍍膜現象的問題。 又，如上述之多層印刷電路板的製造過程中，爲形成 Sn等金屬的被覆層，有必要於具有粗化面之導體電路上施 以無電解鍍敷處理，此會使製造過程複雜化而提高製造成 本。 又’若於此種具有Sn等金屬的被覆層之導體電路上形 成通孔，則於加熱時或熱循環時，通孔與通孔下之導體電 路的接觸部分會發生剝離造成通孔的連接可靠度下降。 [發明之實施型態] 有鑑於上述情況，本發明之目的係提供一種多層印刷 8 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公釐) I--11 — — — — — II» · I--I---— III — — — — · (請先閱讀背面之注意事項再填寫本頁) A7 ^53141 _____B7_ 五、發明說明（Ί ) 電路板，其具有優良之破斷韌性、介電常數、密接性、加 工性等。 又，本發明之目的係提供一種多層印刷電路板及其製 造方法，係具有小的介電常數及介電耗損因數’即使使用 GHz區域的高頻率訊號也不易發生訊號延遲及訊號錯誤’ 又，其剛性等之機械特性亦優，而具有導體電路彼此連接 的可靠度高之層間樹脂絕緣層。 又，本發明之目的係提供一種多層印刷電路板’其構 成係將基板以酸處理之時，能夠完全阻止因導體電路的局 部電池反應造成之導體電路的溶解，又’於導體電路施以 由Cu- Ni-P合金構成之針狀合金的電鍍處理時’能充分 地進行電鍍析出反應，而能確實形成粗化層° 又，本發明之目的係提供一種多層印刷電路板及其製 造方法，其不僅可防止訊號傳送的延遲’同時可製造設置 於樹脂絕緣層的表面上之與金屬層及導體電路有優異密接 性之多層印刷電路板。 又，本發明之目的係提供一種多層印刷電路板’係可 維持層間樹脂絕緣層與導體電路的密接性’防止訊號的雜 訊，同時可避免遷移現象、板彎及龜裂的發生s 又，本發明之目的係提供一種多層印刷電路板及其製 造方法，其與層間樹脂絕緣層及導體電路有優異的密接性 、容易形成精緻圖案、於高頻率區域有優異之訊號傳送性 、具有優異的焊接耐熱性，並且基板的板彎及龜裂特性亦 優良。 9 本紙張尺度適用中國囡家標準（CNS)A4規格（210 X 297公釐） — — — — — — — — — — — I* — — 一SJ1111111&lt; ! J1 (請先閱讀背面之注意^項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 ^53 1 4 1 A7 _ B7 五、發明說明（f ) 又，本發明之目的係提供一種導體電路的形成方法以 及使用該方法之多層印刷電路板之製造方法，係可使用管 理容易之酸性蝕刻液進行選擇性的蝕刻’其結果’可形成 與樹脂基板等之基板有優異密接性的平坦形狀之導體電路 又，本發明之目的係提供一種金屬膜的形成方法以及 使用該方法之多層印刷電路板之製造方法，其中於基板上 所形成之鎳膜與鎳膜上形成之其他金屬間的密接性大。 又，本發明之目的係提供一種多層印刷電路板，其構 成係將基板以酸處理之時，能夠完全阻止因導體電路的·局 部電池反應造成之導體電路的溶解，又，於導體電路施以 依電鍍之Cu-Ni-P合金的析出等粗化處理時，能充分地 進行電鍍析出反應，而能確實形成粗化層。 又，本發明之目的係提供一種多層印刷電路板之製·'造 方法及以該製造方法製造之多層印刷電路板，其中於導體 電路上形成之粗化面可受粗化液之充分的保護，不僅可充 分確保與於粗化面上形成之通孔的連接可靠度，且包含有 可將製造過程簡略化之上述粗化面的保護膜之形成方法。· 本發明之第一群係爲一種多層印刷電路板，係於基板 上設置樹脂絕緣層，而於該樹脂絕緣層形成導體電路之多 層印刷電路板之中，其特徵爲，上述樹脂絕緣層係由聚烯 烴述之所形成。 ’ 就上述之聚烯烴系樹脂而言，以熱硬化型聚烯烴樹脂 或是熱可塑型聚烯烴樹脂爲宜。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1--------訂---------線— (請先W讀背面之注意事項再填寫本頁) 4531 4 1 A7 經濟部智慧財產局員工消費合作杜印製 B7 五、發明說明（4 ) 就上述之熱可塑型聚烯烴樹脂而言’以熔點在2〇〇°c 以上之物爲宜。 就上述之聚烯烴系樹脂而言，較佳者係由以下構造式 (1)所示之一種重複單位所形成之樹脂’或者是上述重複單 位當中由兩種以上相異之單位共聚合所形成之樹脂。 1 &gt; 但是，η爲1〜10000 X爲氫、烷基、苯基、羥基、C2〜C3之不飽和碳氫化 合物、氧基或者是內酯基。 . 又，上述之聚烯烴系樹脂，較佳者爲其分子主鏈中具 有雙鍵、氧結構 '內酯結檎、單環戊二烯結構或多環戊二 烯結構之樹脂。 又，本發明之第一群所使用的聚烯烴樹脂，較佳者係 這些聚烯烴系樹脂之兩種以上相異樹脂混合所成之物，或 兩種以上相異的聚烯烴系樹脂經相互交聯所成之物、或是 這些聚烯烴系樹脂與熱硬化型樹脂之混合樹脂。 上述導體電路’較佳者係擇自長週期型之週期表的第 4Α族至第1Β族之第扣第7週期的金屬(但是Cu除外）、Α1 以及Sn之中一種以上的金屬構成之金屬層而設於樹脂絕緣 層上者^ 又，上述之金屬層，較佳者係設於平坦的樹脂絕緣層 11 ^紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） .I - - - n 1J ^1 ί - I · H ϋ I - .-_ I n 1 ϋ — ϋ I I I - I &lt;請先閱讀背面之注意i項再填寫本頁) A7 ^ 53 1 4 1 _____B7___ 五、發明說明（) 上所形成者。 又’上述之樹脂絕緣層，較佳者係表面經由電漿處择 或是輝光放電處理所形成者。 上述基板，較佳者係其內部或是表面形成有導體電路 〇 本發明之第二群的第一發明’係於基板上依序形成夢 體電路及樹脂絕緣層，又這些導體電路透過通孔連接而形 成多層印刷電路板，其特徵爲，上述之樹脂絕緣層係由環 烯烴系樹脂所彤成者。 ' 上述之樹脂絕緣層，較佳者係於1GHz之介電常數在 0.3以下，介電損耗因子在0.01以下》 上述環烯烴系樹脂，較佳者係2 —原菠烷、5 —亞乙基 - 2-原菠烷或是這些之衍生物所成之單體的單聚合物或共 聚合物。 上述環烯烴樹脂，較佳者係熱硬化性環烯烴樹脂》 本發明之第二群的第二發明’係於基板上導體電路及 樹脂絕緣層被依序形成，又這些導體電路透過通孔連接而 形成多層印刷電路板之製造方法中’其特徵爲，於基板上 形成之導體電路上面，將由環烯烴樹脂所形成之薄膜於真 空下或是減壓下行壓合積層以形成層間樹脂絕緣層。 上述多層印刷電路板之製造方法中’較佳者係於基板 上形成之導體電路上面，由環烯烴樹脂形成層間樹脂絕緣 層之後，對上述之層間樹脂絕緣層照射雷射光以形成通孔 用開口。 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----I--I----· I - II I I 訂·11 — ιιί· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局具工消費合作社印 經濟部智慧財產局員工消費合作社印製 4 53 1 4 1 A7 ____B7___ 五、發明說明（、l) 本發明之第三群的第一發明，係於設有下層導體電路 之基板上層間樹脂絕緣層及上層導體電路被依序形成有多 層化之多層印刷電路板，其特徵爲’上述之下層導體電路 表面處，形成有擇自Ni、Co、Sn以及貴金屬中至少1種的 金屬所成之金屬層，又於該金屬層上形成有由Cu - Ni_P 所成之粗化層。· 上述層間樹脂絕緣層，較佳者係設有通孔，而該通孔 係透過上述之擇自Ni ' Co、Sn以及貴金屬中至少1種的金 屬所成之金屬層以及上述粗化層，而與於基板上形成之上 述下層導體電路以電連接之。 上述粗化層，較佳者係由離子化傾向較Cu爲高且在 Ti以下之含有至少1種金屬的金屬層或是貴金屬層被覆所 形成者。 上述通孔，較佳者係以鍍膜積層所成者。 本發明之第四群，係於樹脂基板上形成樹脂絕緣層及 導體電路之製造方法，其特徵爲，上述樹脂絕緣層的表芦 係設有擇自屬於長週期型之週期表的第4A族〜第1B族範 圍之第4〜第7週期的金屬、A1以及Sn之中至少一種以上 的金屬以形成金屬層後，將上述金屬層表面以酸洗淨’接 著於上述金屬層上形成導體電路。 _ 上述之擇自屬於長週期型之週期表的第4A族〜第1B 族範圍之第4~第7週期的金屬' A1以及Sn之中至少一種 以上的金屬，較佳者係擇自Ni、Cr、Mo、Ti、W、Cu、A1 、Sn、Pt、Pd以及Au之中至少一種以上的金屬。 . 13 本紙張尺度通用中國國家標準（CNS)A4規格（210 χ 297公t) --------裝*!---—訂· -------線 (請先Μ讀背面之注帝華項再填寫本頁) 4531 4 1 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（p) 上述樹脂絕緣層，較佳者係爲平坦的表面。 上述之酸，較佳者係擇自鹽酸、硫酸、醋酸、磷酸之 中至少一種以上的酸或是混酸。 本發明之第五群，係於樹脂基扳之兩面設有樹脂絕緣 層，該樹脂絕緣層上形成有導體電路之具有此構造之多層 印刷電路板，其特徵爲，上述之導體電路係於上述樹脂絕 緣層的表面透過擇自長週期型之週期表的第4A族至第ίΒ 族之第4〜第7週期的金屬(但是Cu除外）、Α1以及Sn之中 一種以上的金屬構成之金屬層所形成者。 上述之金屬層，較佳者係擇自以、Fe、w、Mo、Sn、 Ni、Co、Cr、Ti以及貴金屬之中至少一種以上的金屬之包 含有該等金屬之層。 上述樹脂絕緣層，較佳者係爲平坦的表面。 上述樹脂絕緣層，較佳者係爲熱硬化型聚烯烴樹脂或 是熱可塑性聚烯烴樹脂。 上述樹脂絕緣層，較佳者係其表面被施以電漿處理或 是輝光放電處理。 上述導體電路之表面，較佳者係設有擇自長週期型之 週期表的第4A族至第1B族之第4〜第7週期的金屬(但是 Cvi除外）、A1以及Sn之中一種以上的金屬構成之金屬層’ 而於該金屬層上形成有層間樹脂絕緣層或是防焊層。 於上述樹脂絕緣層之表面形成之金屬層上’較佳者係 再形成Cu層，接著於該Cu層上形成導體電路。 上述金屬層之厚度，較佳者係爲0.01~0.2/zm。 14 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公爱） I I I -----裝--------訂 --------線 (請先閲讀背面之注意事項再填寫本頁) 4531 4 1 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明（J ) 本發明之第六群的第一發明’係於樹脂基板之兩面透 過通孔彼此連接以形成下層導體電路’又於這些下層導體 電路上分別設有層間樹脂絕緣層’接著於這些層間樹脂絕 緣層上分別形成上層導體電路’而具有此種構造之多層印 刷電路板之中，其特徵爲，上述下層導體電路其表面至少 一部份係透過擇自長週期型之週期表的第4A族至第1B族 之第4〜第7週期的金屬(但是Cu除外）' A1以及Sn之中一 種以上的金屬構成之金屬層所形成。 上述之金屬層，較佳者係擇自Al、Fe、W、Mo、SiT、 Ni、Co、Cr、Ti以及貴金屬之中至少一種以上的金屬所構 成者。 上述之樹脂絕緣層，較佳者係由熱硬化型聚烯烴樹脂 或是熱可塑性聚烯烴樹脂之其中一種所構成者。 ’ 上述之層間樹脂絕緣層，較佳者係表面爲平均粗度Ra 在1 μιη以下之平坦面。 本發明之第六群的第二發明，係於樹脂基板的兩面分 別形成有導體層，而於個別之導體層上，對應著欲配線之 圖案而設置防鍍膜後，於非防鍍膜部分形成鍍膜之後去除 上述之防鍍膜，並且將該防鍍膜下的導體層經由蝕刻處理 以形成下層導體電路，接著透過該下層導體電路上形成之 層間樹脂層而形成上層導體電路，而在此多層印刷電路板 製造方法之中，其特徵係在上述非防鍍膜部分形成鍍膜之 後，於該鍍膜表面之至少一部份形成有擇自長週期型之週 期表的第4Α族至第1Β族之第4〜第7週期的金屬(但是Cu * 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公笼) 袭----- ----訂---------線 〈請先Μ讀背面之注意事項再填寫本頁) A7 4531 4 1 __B7____^^--- 五、發明說明（#) 除外）、A1以及Sii之中一種以上的金屬構成之金麋層° % 本發明之第七群的第一發明，其特徵爲包含至少'下t 之過程，亦即： 緣 (a) 於表面形成鈍性膜之金屬所成之第1導體層 基板上的形成過程； (b) 於上述第1導體層上以比上述表面形成鈍彳生@ = @ 屬有較小離子化傾向的金屬所構成之第2導體層的形 程； (c) 使用酸性蝕刻液進行選擇性的蝕刻將導髖&gt; 成區域之第1導體層及第2導體層同時予以蝕刻過® ° 上述表面形成鈍性膜之金屬，較佳者係擇自Ni 'A7 4 53 1 4 1 __B7______ 5. Description of the Invention (I) [Technical Category] The present invention relates to a printed circuit board and a manufacturing method of the printed circuit board. [Technical Background] With the high frequency of signals, the materials of module substrates are gradually required to have a low dielectric constant and a low dielectric loss factor. Therefore, the mainstream of the material of the component substrates has gradually evolved from ceramics to resins. Furthermore, recently, due to the high density of circuits, the so-called thickened multilayer circuit substrates of printed circuits have gradually become the mainstream. The multilayer printed circuit board of the so-called multilayer thickened circuit board is manufactured by a semi-additive method or the like, and is made of copper or the like on a resin substrate reinforced with a glass cloth of 0.6 to 1.5 mm in thickness called a core. The conductor circuit and the interlayer resin insulation layer are alternately laminated and manufactured. In this multilayer printed circuit board, the connection between the conductor circuits with the interlayer resin insulation layer is made through holes. Conventionally, thickened multilayer printed circuit boards have been manufactured by methods disclosed in, for example, Japanese Patent Application Laid-Open No. 9-130050, Japanese Patent Application No. 4-55555, Japanese Patent Application Laid-Open No. 7-235743. Specifically, first, a through-hole is formed at a copper-area laminate with a copper foil attached thereto, and then an electroless copper plating process is performed to form a through-hole. Next, the surface of the substrate is subjected to a patterned etching process to form a conductor circuit, and a roughened surface is formed on the surface of the conductor circuit by electroless plating or engraving, and a loop is formed on the conductor circuit having the roughened surface. · Interlayer resin made of oxygen resin, acrylic acid resin, fluororesin or mixture of these resins. 3. na—n II rn ϋ ϋ n ϋ II—ajI n II nn II (please read the precautions on the back first) (Fill in this page) Duo printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed on paper This paper is applicable to Chinese national standards ~ 5) 8 4 size (210 «297 mm) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 4 53 1 4 1 A7 _B7_ 5. Description of the invention (&gt;) After the edge layer, exposure, development processing or laser processing is used to form openings for through holes, and then UV curing and formal curing are performed to form an interlayer resin insulation layer. Furthermore, after performing a roughening formation process on the interlayer resin insulating layer, 'a thin electroless plating film is formed on the formed roughened surface', and after forming an anti-plating film on the electroless plating film, an electrolytic electric shovel is used. Thickening is performed, and the resist is peeled off and then etched to form a conductor circuit that is connected to the lower-layer conductor circuit through a through hole. After repeating this continuously, in order to protect the conductor circuit as the outermost layer, a solder mask is formed. After the solder mask is formed with an opening, the conductive layer of the opening is subjected to electroplating or the like to form a solder pad. Block to make thickened multilayer printed circuit boards. In such a conventional manufacturing method, in order to ensure the tightness with the conductor circuit, the interlayer resin insulation layer and the surface of the conductor circuit are roughened to form a surface. Therefore, when transmitting a high-frequency signal, the signal is caused by the surface effect. Noise transmitted to only the surface portion of the roughened conductor circuit may cause signal transmission noise due to the unevenness of the surface. In addition, the epoxy acrylate generally used in an interlayer resin insulation layer has a low breaking toughness. For a circuit board using the resin, the interface between the conductor circuit and the resin insulation layer is liable to break due to thermal cycling. Propensity. In addition, the multilayer printed circuit board manufactured in this way has a dielectric constant as high as 3.5 or higher in the GHz region because a mixture of epoxy resin and acrylic resin is used for the interlayer resin insulation layer. Paper size is applicable to 111 national standards (CNS) A4 specifications (210 X 297 mm) —- installed · --- r ----ordered --------- (Please read the precautions on the back before (Fill in this page) A7 4 53 1 4 1 --------- B7___. V. Description of the invention (0) LS of high frequency signal in the area; [wafer, because the interlayer resin insulation layer is high dielectric Constant and signal delay or signal error occurs. Also, for a multilayer printed circuit board using a fluororesin as an interlayer resin insulation layer, the fluororesin has a low dielectric constant, low hygroscopicity, and good fracture toughness. In the process, it needs to be heated at a temperature close to 350 ° C. Therefore, it is easy for the circuit board exposed to such a heating environment to deteriorate. In the method of manufacturing a multilayer printed circuit board disclosed in Japanese Unexamined Patent Publication No. 6-283860, first, the surface of the inner-layer conductor circuit formed on the substrate is formed by electroless plating with Cu-Ni-P. After the roughened layer of the needle-shaped alloy is formed, an interlayer resin insulating layer is formed on the roughened layer, and then an opening for forming a through hole is provided in the interlayer resin insulating layer. After that, the substrate is subjected to electroplating treatment so that a conductor is filled in the opening, and an outer conductor circuit is formed on the interlayer resin insulation layer. In addition, the formation of such a conductor circuit and the formation of an interlayer resin insulating layer are repeated repeatedly for multilayering. According to the method disclosed in Japanese Patent Laid-Open No. 6-283860, for a multilayer thickened circuit substrate, the conductor circuit can be ensured by a needle-like alloy composed of Cu-Ni-P formed on the conductor circuit. Adhesion to the interlayer resin insulation layer formed on it. However, usually in the manufacture of circuit boards, either the substrate is cleaned by acid, or the surface of the interlayer resin insulation layer provided with through-hole openings is first treated with chromic acid or the like. At this time, if it is formed on a conductor circuit, The roughened layer of acicular alloy composed of Cu-Ni-P will cause a local battery reaction with the copper constituting the conductor circuit, and the conductor circuit may be dissolved. 5 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) Packing -------- Order --------- line (谙 Read the precautions on the back before filling (This page) Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economics I -------- I ------ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 A7 V. Description of the Invention (4) In order to prevent the dissolution of such a conductor circuit, a method disclosed in Japanese Patent Application Laid-Open No. 9-130050 is to clarify a technique for suppressing a local battery reaction by coating a roughened layer of a needle-shaped alloy composed of Cu_Ni-P with a metal such as Sn. . However, for multilayer printed circuit boards at the finished product level, because the conductor circuits are coarse and dense, it is difficult to completely cover the roughened layer of the needle-like alloy composed of Cu_Ni_p with the Sn layer. It is difficult to completely prevent dissolution. In addition, when conducting electroplating of a needle-shaped alloy composed of Cu—Ni—P on a conductor circuit, if the number of times the mineral bath is used increases and the mineral bath deteriorates, it will occur that it is difficult to form a coating on the surface of the conductor circuit. . In addition, as previously described, when a roughening process is performed on a conductor circuit, only the surface portion of the roughened conductor circuit has a signal transmission, and a signal transmission occurs due to the unevenness of the surface. Delayed situations. Such a problem is more obvious when a resin substrate having a lower dielectric constant and a lower dielectric loss factor is used than a ceramic substrate. Furthermore, resin substrates tend to store heat more easily than metal substrates or ceramic substrates due to their poor heat dissipation properties. As a result, the diffusion speed of copper ions constituting a conductor circuit becomes faster, which may cause migration and damage interlayer insulation. Therefore, in Japanese Unexamined Patent Publication No. 7-45598 and Japanese Unexamined Patent Publication No. 7-94865, the technique disclosed is applied to a ceramic or metal substrate by spin coating or the like to form a resin layer, and the resin layer is formed on the resin layer. A metal (Cr, Ni, Ti, etc.) capable of improving the adhesion with a conductor circuit is provided by sputtering, and a conductor circuit is formed thereon. However, this technology is mainly on the side of the substrate to thicken the conductor circuits and 6 wires. (Please read the precautions on the back before filling in this page ) This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love) A7 453 1 4 1 ____B7____ 5. Description of the invention (&lt;) ------------- Agricultural · __ (Please read the precautions on the back before filling in this page.) The technology of the interlayer resin insulation layer is different from the case of using ceramic substrates and metal substrates. The resin substrate cannot inhibit the shrinkage or expansion of the interlayer resin insulation layer, and it may bend. In the case of a board, or the interface between the interlayer resin insulation layer and the conductor circuit is cracked due to these shrinkage and expansion. Furthermore, when a conductor circuit is actually formed by this technique, a problem is that a metal layer composed of a metal such as Cr, Ni, Ti, and the like is easily peeled from the conductor circuit. --The cause of this problem is the surface of the resin insulation layer. If the metal layer is set by physical vapor deposition, the surface will be oxidized because the metal layer is exposed to high temperatures. The conductor circuit is formed on the metal layer on which an oxide layer is formed on the surface. Since the metal layer and the conductor circuit are separated from each other by the oxide layer, the adhesiveness thereof is lowered, so the conductor circuit is easily peeled. In addition, even when a metal layer is formed by chemical vapor deposition or electroplating, the surface oxidation is generated by being left in the air, so that the conductor circuit is easily peeled. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Since the oxide is difficult to be decomposed by the above-mentioned acid, there is a problem that etching cannot be performed smoothly. Furthermore, if an oxide film is formed on the surface of these metals, it will be more difficult to remove it by etching. Furthermore, since these metals are dissolved in strong acids such as concentrated nitric acid and aqua regia, even if they can be etched with a substance based on concentrated nitric acid or cyanide or fluoride, these acids are difficult to handle because they are highly toxic. Therefore, 7 paper standards are in accordance with Chinese National Standard (CNS) A4 specifications (210 297 mm) d53 1 4 1 A7 B7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperation Du V. Description of the Invention () Difficulties in process management and Problems that adversely affect the working environment. In the roughening formation process, "after forming a thick film by electroplating copper or the like, electroless nickel plating is performed to form a thin nickel-plated film on the thick film", and then Cu-Ni-P is formed thereon. The roughened film made of alloy 'prevents the interlayer resin insulation layer formed on the conductor circuit and the through hole from peeling off from the conductor circuit or the through hole. However, in the conventional method for manufacturing a multilayer printed circuit board, after forming an electroless nickel plating film on a plating film, if a roughened layer of Cu-Ni-P alloy is formed thereon, usually, the nickel plating film and the The Cu—Ni-P alloy roughened layers should have large adhesion, but here it is contrary to expectations, and its adhesion is small. Therefore, the Cu-Ni-P alloy roughened layers are easily peeled from the nickel plating film. problem. In addition, when a Cu-Ni-P alloy plating process is applied to a conductor circuit, if the number of spins of the plating bath is increased and the plating bath is deteriorated, a problem that it is difficult to form a plating film on the surface of the conductor circuit will occur. In addition, in the manufacturing process of the multilayer printed circuit board described above, in order to form a coating layer of metal such as Sn, it is necessary to apply an electroless plating treatment to a conductor circuit having a roughened surface, which complicates the manufacturing process and Increase manufacturing costs. Also, if a through-hole is formed in such a conductor circuit having a coating layer of a metal such as Sn, the contact portion of the through-hole and the conductor circuit under the through-hole will be peeled off during heating or thermal cycling, resulting in the connection of the through-hole. Reliability drops. [Implementation Modes of the Invention] In view of the above, the object of the present invention is to provide a multi-layer printing 8 paper size applicable to the Chinese National Standard (CNS) A4 specification (2) 0 X 297 mm) I--11 — — — — — II »· I--I ---— III — — — — (Please read the notes on the back before filling out this page) A7 ^ 53141 _____B7_ 5. Description of the invention (Ί) Circuit board, which has excellent Breaking toughness, dielectric constant, adhesion, processability, etc. In addition, the object of the present invention is to provide a multilayer printed circuit board and a method for manufacturing the same, which have a small dielectric constant and a dielectric loss factor 'even if high-frequency signals in the GHz region are used, signal delays and signal errors are unlikely to occur', Its mechanical properties such as rigidity are also excellent, and it has an interlayer resin insulation layer with high reliability in connecting conductor circuits to each other. In addition, the object of the present invention is to provide a multilayer printed circuit board whose structure is such that when the substrate is treated with an acid, the dissolution of the conductor circuit caused by the local battery reaction of the conductor circuit is completely prevented, and the conductor circuit is subjected to During the electroplating process of a needle-shaped alloy made of a Cu-Ni-P alloy, the plating precipitation reaction can be sufficiently performed, and a roughened layer can be surely formed. Furthermore, the object of the present invention is to provide a multilayer printed circuit board and a method for manufacturing the same, It can not only prevent the delay of signal transmission, but also manufacture a multilayer printed circuit board with excellent adhesion to metal layers and conductor circuits, which is provided on the surface of the resin insulation layer. In addition, the object of the present invention is to provide a multilayer printed circuit board that "maintains the adhesion between the interlayer resin insulation layer and the conductor circuit" to prevent signal noise, and at the same time to avoid the occurrence of migration, board bending and cracking. An object of the present invention is to provide a multilayer printed circuit board and a method for manufacturing the same, which have excellent adhesion with interlayer resin insulation layers and conductor circuits, are easy to form delicate patterns, have excellent signal transmission properties in high frequency regions, and have excellent Welding heat resistance, and board bending and cracking characteristics of the substrate are also excellent. 9 This paper size is in accordance with Chinese Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — — I * — — One SJ1111111 &lt;! J1 (Please read the note on the back first ^ (Fill in this page again.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy. A method for forming a circuit and a method for manufacturing a multilayer printed circuit board using the method can be selectively etched using an acidic etching solution that is easy to manage. As a result, a flat shape having excellent adhesion to a substrate such as a resin substrate can be formed. It is also a conductor circuit. It is an object of the present invention to provide a method for forming a metal film and a method for manufacturing a multilayer printed circuit board using the method, in which a nickel film formed on a substrate and other metals formed on the nickel film are in close contact with each other. Sex. Another object of the present invention is to provide a multilayer printed circuit board having a structure capable of completely preventing the dissolution of the conductor circuit caused by the local circuit reaction of the conductor circuit when the substrate is treated with an acid, and applying the conductor circuit to the conductor circuit. During the roughening treatment such as precipitation of a Cu-Ni-P alloy plated, a plating precipitation reaction can be sufficiently performed, and a roughened layer can be surely formed. Another object of the present invention is to provide a method for manufacturing a multilayer printed circuit board and a multilayer printed circuit board manufactured by the manufacturing method, wherein the roughened surface formed on the conductor circuit can be fully protected by the roughening solution. , Not only can fully ensure the connection reliability with the through hole formed on the roughened surface, but also includes a method for forming a protective film on the roughened surface that can simplify the manufacturing process. · The first group of the present invention is a multilayer printed circuit board, which is provided with a resin insulating layer on a substrate, and the resin insulating layer forms a conductive circuit in a multilayer printed circuit board, characterized in that the resin insulating layer is Formed from polyolefins. The polyolefin resin is preferably a thermosetting polyolefin resin or a thermoplastic polyolefin resin. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1 -------- Order --------- Line — (Please read the precautions on the back first (Fill in this page) 4531 4 1 A7 Consumer Cooperation of Intellectual Property Bureau, Ministry of Economic Affairs, Du printed B7 V. Description of the invention (4) For the above thermoplastic polyolefin resins, those with a melting point above 200 ° c Better. As for the above-mentioned polyolefin-based resin, it is preferred that the resin is formed of a repeating unit represented by the following structural formula (1), or is formed by copolymerizing two or more different units among the repeating units. The resin. 1 &gt; However, η is 1 to 10000, and X is hydrogen, alkyl, phenyl, hydroxyl, C2 to C3 unsaturated hydrocarbon, oxy or lactone group. The polyolefin resin is preferably a resin having a double bond, an oxygen structure, a lactone structure, a monocyclopentadiene structure, or a polycyclopentadiene structure in the molecular main chain. The polyolefin resin used in the first group of the present invention is preferably a mixture of two or more dissimilar resins of these polyolefin-based resins, or two or more dissimilar polyolefin-based resins are mutually Crosslinked products, or mixed resins of these polyolefin resins and thermosetting resins. The above-mentioned conductor circuit is preferably a metal composed of one or more metals from Group 4A to Group 7 of the long-period periodic table (except Cu), A1, and Sn. It is provided on the resin insulation layer ^ Also, the above-mentioned metal layer is preferably provided on a flat resin insulation layer 11 ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) .I ---n 1J ^ 1 ί-I · H ϋ I-.-_ I n 1 ϋ — ϋ III-I &lt; Please read the note on the back before filling in this page) A7 ^ 53 1 4 1 _____B7___ 5 , The invention description () formed by. The above-mentioned resin insulation layer is preferably formed by plasma treatment or glow discharge treatment on the surface. The above substrate is preferably a conductor circuit formed on the inside or the surface of the substrate. The first invention of the second group of the present invention is that a dream circuit and a resin insulation layer are sequentially formed on the substrate, and these conductor circuits pass through the holes. The multilayer printed wiring board is connected to form a multilayer printed circuit board, wherein the resin insulating layer is made of a cycloolefin resin. '' The above-mentioned resin insulation layer is preferably a dielectric constant of 0.3 or less and a dielectric loss factor of 0.01 or less at 1 GHz. "The above cycloolefin-based resin is preferably 2-ortho- spinane and 5-ethylene. -2-Orthospinane or monomers or copolymers of monomers derived from these derivatives. The above-mentioned cycloolefin resin is preferably a thermosetting cycloolefin resin. The second invention of the second group of the present invention is that the conductor circuit and the resin insulating layer on the substrate are sequentially formed, and these conductor circuits are connected through the through holes. The manufacturing method of forming a multilayer printed circuit board is characterized in that a thin film formed of a cycloolefin resin is laminated on a conductor circuit formed on a substrate under vacuum or under reduced pressure to form an interlayer resin insulating layer. In the above-mentioned manufacturing method of the multilayer printed circuit board, 'preferably, it is on the conductor circuit formed on the substrate, and after the interlayer resin insulation layer is formed of a cycloolefin resin, the interlayer resin insulation layer is irradiated with laser light to form openings for through holes. . 12 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----- I--I ---- · I-II II Order · 11 — ιιί · (Please read the Please fill in this page for further information.) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives of the Ministry of Economic Affairs. Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics. 4 53 1 4 1 A7 An invention relates to a multilayer printed circuit board in which an interlayer resin insulating layer on a substrate provided with a lower-layer conductor circuit and an upper-layer conductor circuit are sequentially formed into a multilayered printed circuit board, characterized in that 'the surface of the lower-layer conductor circuit described above is selectively formed. A metal layer made of at least one of Ni, Co, Sn, and a precious metal, and a roughened layer made of Cu-Ni_P is formed on the metal layer. · The above interlayer resin insulating layer is preferably provided with a through hole, and the through hole is a metal layer made of at least one kind selected from Ni 'Co, Sn, and a noble metal, and the roughened layer, It is electrically connected to the above-mentioned lower-layer conductor circuit formed on the substrate. The roughened layer is preferably formed by coating with a metal layer or a precious metal layer having a higher ionization tendency than Cu and containing at least one metal below Ti. The above-mentioned through holes are preferably formed by coating and laminating. The fourth group of the present invention is a method for manufacturing a resin insulating layer and a conductor circuit on a resin substrate, characterized in that the surface of the resin insulating layer is provided with Group 4A selected from the periodic table belonging to the long period type. After forming at least one or more of the metals in the 4th to 7th cycles of the Group 1B range, A1, and Sn to form a metal layer, the surface of the metal layer is acid-washed, and then a conductor circuit is formed on the metal layer. . _ The above-mentioned choice is at least one metal from the metals of A4 and Sn in the 4th to 7th periods of the group 4A to 1B in the long-period periodic table. The preferred one is Ni, At least one metal selected from Cr, Mo, Ti, W, Cu, A1, Sn, Pt, Pd, and Au. . 13 This paper is in accordance with the Chinese National Standard (CNS) A4 specification (210 χ 297 male t) -------- installation *! ----- order · ------- line (please first M Read the note on the back of Dihua and fill out this page again) 4531 4 1 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (p) The above resin insulation layer is preferably a flat surface. The aforementioned acid is preferably selected from at least one of hydrochloric acid, sulfuric acid, acetic acid, and phosphoric acid, or a mixed acid. The fifth group of the present invention is provided with a resin insulating layer on both sides of a resin-based board, and a multilayer printed circuit board having such a structure is formed with a conductor circuit on the resin insulating layer, characterized in that the above-mentioned conductor circuit is based on the above The surface of the resin insulating layer is a metal layer composed of one or more metals selected from metals (except Cu) of Group 4A to ίΒ of Group 4A to Group ί of the long-period periodic table. Formed by. The above-mentioned metal layer is preferably a layer containing at least one metal selected from the group consisting of Fe, w, Mo, Sn, Ni, Co, Cr, Ti, and noble metals. The resin insulating layer is preferably a flat surface. The resin insulating layer is preferably a thermosetting polyolefin resin or a thermoplastic polyolefin resin. It is preferable that the surface of the resin insulating layer is treated with a plasma treatment or a glow discharge treatment. The surface of the conductor circuit is preferably one or more of metals (except Cvi), A1, and Sn selected from Groups 4A to 1B Groups 4 to 7 of the long period periodic table. The metal layer is made of metal, and an interlayer resin insulating layer or a solder mask is formed on the metal layer. On the metal layer formed on the surface of the resin insulating layer, it is preferable to further form a Cu layer, and then form a conductor circuit on the Cu layer. The thickness of the metal layer is preferably 0.01 to 0.2 / zm. 14 This paper size applies to China National Standard (CNS) A4 specifications (2) 0 X 297 Public Love III ----- installation -------- order -------- line (please first Read the notes on the reverse side and fill in this page) 4531 4 1 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economics, B7. V. Invention Description (J) The first invention of the sixth group of the present invention is on both sides of the resin substrate. Holes are connected to each other to form lower-layer conductor circuits, and interlayer resin insulation layers are respectively provided on these lower-layer conductor circuits, and then upper-layer conductor circuits are respectively formed on these interlayer resin insulation layers. , Characterized in that at least a part of the surface of the above-mentioned lower-layer conductor circuit passes through metals selected from Groups 4A to 1B Groups 4 to 7 of the long-period periodic table (except Cu) 'A1 and A metal layer made of one or more metals among Sn. The above-mentioned metal layer is preferably composed of at least one metal selected from Al, Fe, W, Mo, SiT, Ni, Co, Cr, Ti, and a noble metal. The resin insulating layer is preferably composed of one of a thermosetting polyolefin resin or a thermoplastic polyolefin resin. The above-mentioned interlayer resin insulating layer is preferably a flat surface having an average roughness Ra of 1 μm or less. The second invention of the sixth group of the present invention is that a conductive layer is formed on both sides of the resin substrate, and a plating film is formed on each of the conductive layers corresponding to the pattern to be wired, and then a plating film is formed on the non-plating portion Thereafter, the above-mentioned anti-plating film is removed, and the conductor layer under the anti-plating film is subjected to an etching treatment to form a lower-layer conductor circuit, and then an upper-layer conductor circuit is formed through an interlayer resin layer formed on the lower-layer conductor circuit, and a multilayer printed circuit board is formed here. In the manufacturing method, after forming a coating film on the non-anti-plating film portion, at least a part of the surface of the coating film is formed with Groups 4A to 1B of the periodic table selected from the long period type. 7 cycles of metal (but Cu * 15 This paper size applies to China National Standard (CNS) A4 specification (210 X 297 male cage)) ------------ Order --------- line < Please read the precautions on the back before filling in this page) A7 4531 4 1 __B7 ____ ^^ --- 5. Except for the description of the invention (#)), A1 and Sii are composed of more than one type of metal. The first invention of the seventh group of inventions, which features Including the process of at least 'lower t', that is: (a) the formation process on the first conductor layer substrate made of a metal forming a passive film on the surface; (b) on the above first conductor layer, compared with the above The formation of a blunt surface on the surface @ = @ belongs to the shape of the second conductor layer made of a metal with a lower ionization tendency; (c) Selective etching using an acidic etching solution will lead the hip &gt; The conductor layer and the second conductor layer are etched at the same time. ° The metal forming a passive film on the above surface is preferably selected from Ni ′

Cr、Ti、Nb、Ta、Ai 之中至少一種。 於上述表面形成鈍性膜之金屬係Ni，又較Ni有/J、@ 離子化傾向的金屬所成之第2導體層，較佳者係擇自Cu ' Sn以及Pb之中至少一種的金屬所成者。 - 於上述表面形成鈍性膜之金屬係A1，又較六1有小離 子化傾向的金屬所成之第2導體層，較佳者係擇自Cu ' Sn 以及Pb之中至少一種的金屬所成者。 上述酸性蝕刻液，較佳者係爲硫酸水溶液、鹽酸水溶 液或是硫酸-過氧化氫混合水溶液。 本發明之第七群的第二發明，係於絕緣基板上，形成 樹脂絕緣層與導體電路之多層印刷電路板的製造方法中’ 其特徵爲，包含至少下述⑷~(e)之過程’亦即： , (a)於表面形成鈍性膜之金屬所成之第1導體層在樹脂 16 本紙張尺度適用中國國家標準(CNS&gt;A4規格（210X 297公釐〉 III — — ~ — — — — — — — 11 II I — — . — — — If — — — ί請先間讀背面之注意事瑣存填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 53 1 4 1 經濟部智慧財產局具工消費合作社印製 A7 B7 五、發明說明（3) 絕緣層上的形成過程； (b) 於上述第丨導體層上以比上述表面形成鈍性膜之-屬有較小離子化傾向的金屬所構成之第2導體層的形成過 程； (c) 於上述第2導體層上防鍍膜的形成過程； (d) 於形成有防鍍膜之上述第2導體層上、以電鍍之藥 3導體層的形成過程： (e) 將防鍍膜剝離之後，使用酸性蝕刻液對存在於防鍍 膜之下的第1導體層及第2導體層同時予以蝕刻的過程·。 於上述表面形成鈍性膜之金屬，較佳者係擇自Ni、Co 、Cr、Ti、Nb、Ta、A1之中至少一種。於上述表面形成鈍 性膜之金屬係Ni ’又比Ni有較小離子化傾向的金屬所成 之第2導體層，較佳者係擇自Cu、Sn、Pb以及Fe之中至 少一種的金屬所成者。 * 表面形成鈍性膜之金屬係A1，又比A1有較小離子化 傾向的金屬所成之第2導體層，較佳者係擇自Cu、Sn、Pb 以及Fe之中至少一種的金屬所成者^ 上述酸性蝕刻液，較佳者係爲硫酸水溶液、鹽酸水g 液或是硫酸-過氧化氫混合水溶液。 本發明之第八群的第一發明，其特徵係將Ni膜上存在 之氧化膜以具有濃度2.CM0.0莫爾/升之還原性酸的水溶液 去除之後，於上述之Ni膜的表面形成另外的金屬膜。 ‘ 上述還原性酸的水溶液，較佳者係爲鹽酸或氫氟酸。 上述還原性酸的水溶液濃度，較佳者係爲4.0〜8.0莫爾 17 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐) I I ί ---- I I ----J ^ *------I I --- (請先閲讀背面之注意事項再填窝本頁). 經濟部智慧財產局員工消費合作社印製 4 53 1 4 1 A7 ------B7_____ 五、發明說明（山） /升。 本發明之第八群的第二發明之多層印刷電路板的製造 方法係包含有： (a) 於形成有下層導體電路之基板上設置層間樹脂絕緣 層’而於該層間樹脂絕緣層設置通孔用開口之過程； (b) 於上述層間樹脂絕緣層上形成金屬膜之過程； (c) 於上述金屬膜上形成防鍍膜之過程； (d) 於施行電鍍之後，形成Ni膜而於上述防鍍膜之間 形成電鍍膜及Ni膜之過程； (e) 去除上述防鍍膜之後，將既存於上述防鍍膜下之上 述金屬膜以蝕刻去除之而形成上層導體電路及通孔的過程 :以及 · (f) 於上述上層導體電路上形成由Cu — Nl —p合金構成 之粗化層的過程。 其特徵爲，於上述(e)之過程終了之後，將存在於上述At least one of Cr, Ti, Nb, Ta, and Ai. The second conductive layer made of a metal based on Ni which has a passive film on the surface and has a tendency to ionize / J, @ than Ni, is preferably a metal selected from at least one of Cu 'Sn and Pb. The accomplished. -The second conductor layer made of metal A1 with a passive film formed on the above surface and a metal with a lower ionization tendency than Liu 1 is more preferably selected from at least one of Cu 'Sn and Pb. Successor. The acidic etching solution is preferably a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, or a sulfuric acid-hydrogen peroxide mixed aqueous solution. The second invention of the seventh group of the present invention relates to a method for manufacturing a multilayer printed circuit board on an insulating substrate, forming a resin insulating layer and a conductor circuit. 'It is characterized by including at least the following processes (e) to (e)' That is: (a) The first conductor layer made of a metal forming a blunt film on the surface is resin 16 This paper size applies the Chinese national standard (CNS &gt; A4 specification (210X 297 mm> III — — ~ — — —) — — — — 11 II I — —. — — — If — — — ί Please read the notes on the reverse side and fill in this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 4 53 1 4 1 Printed by the Bureau of Property, Industrial and Consumer Cooperatives A7 B7 V. Description of the invention (3) The formation process on the insulation layer; (b) On the above-mentioned conductor layer, a passive film is formed than on the surface-it has less ionization Forming process of the second conductor layer made of a preferred metal; (c) Formation process of the anti-plating film on the second conductor layer; (d) Electroplating medicine on the second conductor layer on which the anti-plating film is formed 3 Formation process of the conductor layer: (e) Peel off the anti-plating film Then, the process of simultaneously etching the first conductor layer and the second conductor layer existing under the anti-plating film using an acidic etchant. The metal forming the passive film on the surface is preferably selected from Ni, Co, At least one of Cr, Ti, Nb, Ta, and A1. The second conductive layer made of a metal based on a metal Ni 'that forms a passive film on the surface and has a smaller ionization tendency than Ni is preferably selected. Formed from at least one metal of Cu, Sn, Pb, and Fe. * The second conductor layer made of a metal system A1 with a passive film on the surface and a metal with a lower ionization tendency than A1 is preferable. The above is selected from the group consisting of metals of at least one of Cu, Sn, Pb, and Fe ^ The acidic etching solution is preferably a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, or a sulfuric acid-hydrogen peroxide mixed aqueous solution. The first invention of the eighth group is characterized in that the oxide film existing on the Ni film is removed by an aqueous solution having a reducing acid having a concentration of 2.CM0.0 Moore / liter, and an additional layer is formed on the surface of the Ni film. Metal film. 'The aqueous solution of the reducing acid is preferably hydrochloric acid Hydrofluoric acid. The concentration of the above-mentioned reducing acid in the aqueous solution is preferably 4.0 to 8.0 Moore. 17 The paper size is applicable to the Chinese National Standard (CNS) A4 (210x297 mm) II Ⅱ ---- -J ^ * ------ II --- (Please read the notes on the back before filling in this page). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 1 4 1 A7 ----- -B7 _____ 5. Description of the invention (mountain) / liter. The manufacturing method of the multilayer printed circuit board of the second invention of the eighth group of the present invention includes: (a) interlayer resin insulation is provided on the substrate on which the lower conductor circuit is formed; Layer 'and the process of providing openings for through holes in the interlayer resin insulating layer; (b) the process of forming a metal film on the interlayer resin insulating layer; (c) the process of forming a plating resist on the metal film; (d) After the electroplating is performed, a process of forming a Ni film and forming a plating film and a Ni film between the anti-plating films is performed; (e) after removing the anti-plating films, the metal film existing under the anti-plating films is formed by etching and removing Process of upper conductor circuits and vias: and (f) In the above upper conductor The process of forming a roughened layer of Cu—Nl—p alloy on a bulk circuit. It is characterized in that after the end of the process of (e) above, it will exist in the above

Ni膜之氧化膜以具有濃度2 0〜10 0莫爾/升的還原性酸的水 溶液予以去除^ 只要上述還原性酸的水溶液之濃度爲2 〇〜1〇 〇莫爾/升 ，就不會對基板造成影響而能將氧化物去除。 上述還原性酸的水溶液，較佳者係爲鹽酸或氫氟酸^ 上述還原性酸的水溶液之濃度，較佳者係爲4 〇〜8.〇莫 爾/升。 本發明之第九群，係於設有下層導體電路之基板上層 間樹脂絕緣層及上層導體電路被依序形成有多層化之多唐The oxide film of the Ni film is removed with an aqueous solution of a reducing acid having a concentration of 20 to 100 mol / liter ^ As long as the concentration of the aqueous solution of the reducing acid is 200 to 100 mol / liter, the It affects the substrate and can remove oxides. The aqueous solution of the reducing acid is preferably hydrochloric acid or hydrofluoric acid. The concentration of the aqueous solution of the reducing acid is preferably 40 to 8.0 mol / liter. The ninth group of the present invention is that the interlayer resin insulation layer on the substrate provided with the lower-layer conductor circuit and the upper-layer conductor circuit are sequentially formed with multiple layers.

本紙張尺度制中國國家標i|MCNS)A4規格⑵Qx 297公爱J 装---------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 453 1 4 1 經濟部智慧財產局貝工消費合作社印製 B7 五、發明說明（川） 印刷電路板，其特徵爲’於上述之下層導體電路表面處， 形成有擇自離子化傾向大於等於Sn且小於等於A1之金屬 及貴金屬所構成的群中至少1種的金屬所成之金屬層，又 於該金屬層上形成有粗化層。 擇自上述離子化傾向大於等於Sn且小於等於A1之金 屬及貴金屬所構成的群中至少1種的金屬，較佳者係擇自 Al、Cr、Fe、Zn、Ni、Co、Sn及貴金屬所構成的群中至少 1種的金屬。 上述粗化層，較佳者係爲Cu_Ni-P合金所成之物、 上述層間樹脂絕緣層’較佳者係設有通孔’而該通孔 係透過上述之自離子化傾向大於等於sn且小於等於A1之 金屬及貴金屬所構成的群中選出至少1種的金屬所成之金 屬層以及上述粗化層’而與於基板上形成之上述下層導體 電路以電連接之。 ‘ 上述粗化層，較佳者係由離子化傾向較Cu爲高且在 Ti以下之含有至少1種金屬的金屬層或是貴金屬層被覆所 形成者。 上述通孔，較佳者係以鍍膜塡充所成者。 本發明之第十群之第一發明之多層印刷電路板的製造 過程，係於導體電路形成之後施以粗化處理而於導體電路 上形成粗化面’具有上述粗化面之導體電路以層間樹脂絕 緣層被覆之後藉由不斷的重複通孔用開口之形成過程’而 於絕緣性基板上形成由夾有層間樹脂絕緣層之複數層構成 之導體電路，其特徵爲，於導體電路上形成粗化面後’藉 19 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） I -------- 1 f I! I I 訂·--I---- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明) 由施以氧化處理，以使得上述粗化面之表面整體形成氧化 膜，之後1再形成層間樹脂絕緣層。 上述導體電路形成粗化面之後，較佳者係在大氣周圍 氣氛下，以80~200°C加熱10分鐘〜3小時來施以氧化處理 ，而於上述粗化面之表面整體形成氧化膜^ 本發明之第十群之第二發明的多層印刷電路板’係於 該表面形成有以粗化面構成之導體電路之基板上’形成層 間樹脂絕緣層，而於上述層間樹脂絕緣層形成通孔用開口 ，接著，於上述通孔用開口形成導電體以構成通孔’其特 徵係於上述以粗化面構成之導體電路表面全體’形成由氧 化膜所構成之被覆層。 上述由氧化膜所構成之被覆層的厚度，較佳者係爲 0.01〜0.2 /z m。 [圖面之簡單說明] 圖1之⑷到⑴所示，係爲本發明之第一群的多層印刷 電路板製造過程之一部分的剖面圖。 ’ 圖2之⑻到(e)所示，係爲本發明之第一群的多層印刷 電路板製造過程之一部分的剖面圖。 圖3之⑻到(d)所示，係爲本發明之第一群的多層印刷 電路板製造過程之一部分的剖面圖。 ‘ 圖4之(a)到(d)所示，係爲本發明之第二群的多層印刷 電路板製造過程之一部分的剖面圖。 圖5之(a)到(d)所示，係爲本發明之第二群的多層印刷 電路板製造過程之一部分的剖面圖》 ^ 20 本紙張尺度適用中囡@家標準（CNS&gt;A4規格（210 X 297公釐） -----------裝———訂---------線 (請先閱讀背面之注意事項再填寫本頁) A7 453141 ___ B7__________—' 五、發明說明（A ) 圖6之(a)到(d)所示，係爲本發明之第二群的多層印刺 電路板製造過程之一部分的剖面圖。 · 圖7之⑻到(c)所示，係爲本發明之第二群的多層印刷 電路板製造過程之一部分的剖面圖。 圖8之⑷到(c)所示，係爲本發明之第二群的多層印刷 電路板製造過程之一部分的剖面圖。 · 圖9之⑻到⑷所示，係爲本發明之第三群的多層印刷 .電路板製造過程之一部分的剖面圖。 圖10之(a)到(d)，係爲本發明之第三群的多層印刷電 路板製造過程之一部分的剖面圖。 . 圖11之⑻到⑷所示，係爲本發明之第三群的多層印 刷電路板製造過程之一部分的剖面圖。 圖12之⑷到(c)所示，係爲本發明之第三群的多層印 刷電路板製造過程之一部分的剖面圖。 . 圖13之⑷到⑷所示，係爲本發明之第三群的多層印 刷電路板製造過程之一部分的剖面圖。 圖Η所示係爲本發明之第三群的另外之多層印刷電路 板的一製造過程之的剖面圖。 . 圖15之⑷到⑴所示，係爲本發明之第四群的多層印 刷電路板製造過程之一部分的剖面圖。 圖16之⑷到⑹所示，係爲本發明之第四群的多層印 刷電路板製造過程之一部分的剖面圖。 . 圖17之⑻到(d)所示，係爲本發明之第四群的多層印 刷電路板製造過程之一部分的剖面圖。 21 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — — — — — — I— I- i I I I {請先閱讀背面之注意事項再填寫本頁) 訂· 線 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局具工消費合作社印製 453141 A7 ___B7_____ 五、發明說明（/) 圖18之⑻到(c)所示，係爲本發明之第四群的多層印 刷電路板製造過程之一部分的剖面圖。 圖19之⑷到⑴所示’係爲本發明之第五群的多層印 刷電路板製造過程之一部分的剖面圖。 圖20之⑷到⑹所示，係爲本發明之第五群的多層印 刷電路板製造過程之一部分的剖面圖。 圖21之⑻到(d)所示，係爲本發明之第五群的多層印 刷電路板製造過程之一部分的剖面圖。 ， 圖22之(a)、（b)所示，係爲本發明之第五群的多層印 刷電路板製造過程之一部分的剖面圖。 圖23之⑷到(f)所示，係爲本發明之第六群的多層印 刷電路板製造過程之一部分的剖面圖。 . 圖24之(a)到⑹所示，係爲本發明之第六群的多層印 刷電路板製造過程之一部分的剖面圖° 圖25之⑻到(d)所示，係爲本發明之第六群的多層印 刷電路板製造過程之一部分的剖面圖。 . 圖26之(a)、（b)，係爲本發明之第六群的多層印刷電 路板製造過程之一部分的剖面圖。 圖27之(a) 、（b)，係爲本發明之第六群的多層印刷電 路板製造過程之一部分的剖面圖。 ， 圖28之⑷到⑹所示，係爲本發明之第七群的多層印 刷電路板製造過程之一部分的剖面圖。 圖29之⑷到(f)所示，係爲本發明之第七群的多層印 刷電路板製造過程之一部分的剖面圖。 ， 22 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------β 11!111 -^ I ί (請先Μ讀背面之注意事項再填寫本頁) 經濟部智慧財產局負工消費合作社印製 4 53 14 1 a? B7 五、發明說明（w) 圖30之⑷到(e)所示，係爲本發明之第七群的多層印 刷電路板製造過程之一部分的剖面圖》 圖31之⑷到(d)所示，係爲本發明之第七群的多層印 刷電路板製造過程之一部分的剖面圖。 圖32之⑷到(c)所示，係爲本發明之第七群的多層印 刷電路板製造過程之一部分的剖面圖。 圖33之(a)到(d)所示，係爲本發明之第八群的多層$ 刷電路板製造過程之一部分的剖面圖。 圖34之(a)到(d)所示，係爲本發明之第八群的多層印 刷電路板製造過程之一部分的剖面圖。 圖35之(a)到(d)所示，係爲本發明之第八群的多層91 刷電路板製造過程之一部分的剖面圖。 圖36之(a)到(d)所示，係爲本發明之第八群的多層印 刷電路板製造過程之一部分的剖面圖。 圖37之⑷到(c)所示，係爲本發明之第八群的多層EP 刷電路板製造過程之一部分的剖面圖。 圖38之(a)到⑷所示，係爲本發明之第九群的多層印 刷電路板製造過程之一部分的剖面圖。 圖39之(a)到(d)所示，係爲本發明之第九群的多層印 刷電路板製造過程之一部分的剖面圖。 圖40之(a)到⑷所示，係爲本發明之第九群的多層印 刷電路板製造過程之一部分的剖面圖。 圖41之⑷到⑻所示，係爲本發明之第九群的多層印 刷電路板製造過程之一部分的剖面圖。 23 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I - ------------------------I —-- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453141 A7 B7 五、發明說明（π ) 圖42之(a)到(d)所示，係爲本發明之第九群的多層印 刷電路板製造過程之一部分的剖面圖。 圖43之(a)、（b)所示，係爲本發明之第九群的多層印 刷電路板製造過程之一部分的剖面圖。 圖44之(a)到(d)所示，係爲本發明之第十群的多層印 刷電路板製造過程之一部分的剖面圖。 圖45之(a)到(d)所示，係爲本發明之第十群的多層印 刷電路板製造過程之一部分的剖面圖。 圖46之⑷到(d)所示，係爲本發明之第十群的多層印* 刷電路板製造過程之一部分的剖面圖。 圖47之(a)到(c)所示，係爲本發明之第十群的多層印 刷電路板製造過程之一部分的剖面圖。 圖48之⑻到(c)所示，係爲本發明之第十群的多層印’ 刷電路板製造過程之一部分的剖面圖。 圖49之⑷到(c)所示，係爲本發明之第十群的多層印 刷電路板製造方法之氧化膜的形成過程之剖面圖。 圖50之⑷到(c)所示，係爲先前的多層印刷電路板製' 造方法之氧化膜的形成過程之剖面圖。 [發明之詳細的揭示] 本發明之第一群的多層印刷電路板，其特徵係使用聚 烯烴系樹脂做爲樹脂絕緣層。* 就此聚烯烴系樹脂而言，有熱硬化型聚烯烴樹脂及熱 可塑型聚烯烴樹脂，特別是以使用熱硬化型聚烯烴樹脂爲 佳。其理由，係就於層間樹脂絕緣層上再設置層間樹脂絕 24 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公茇） ----------I--裝----II 訂.！ 線 {請先閱讀背面之注意事項再填寫本頁) ¢53 1 4 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（A) ’ 緣層之多層印刷電路板之製造過程而言，若對下層側之層 間樹脂絕緣層使用熱硬化型之聚烯烴系樹脂，則加熱壓擠 時不會有變形的產生，且通孔之位置的偏移小。 · 另一方面，就熱可塑型聚烯烴樹脂而言，其破斷韌性 ί直高在熱循環時可抑制由於導體電路與樹脂的熱膨脹係數 不同所發生之龜裂。 就此熱可塑型聚烯烴樹脂而言，較佳者係其熔點在 2〇〇°C以上。其理由，係若熔點在200°C以上，因加熱壓擠 造成之變形小，又於多層印刷電路板上在200°C以上以加 熱溶融來設置安裝用之焊層及焊接凸塊之時，可防止樹脂 絕緣層的溶融。 ， 以下，針對本發明所使用之聚烯烴系樹脂予以詳述。 聚烯烴樹脂係具有以下結構之樹脂。亦即 (a) 以下構造式(1)所示之一種重複單位所形成之樹脂。 X n 但是，η爲1〜10000 * X爲氫、烷基、苯基、羥基' C2〜C3之不飽和碳氫化 合物、氧基或者是內酯基。 (b) 以下構造式(1)所示之一種重複單位當中由兩種以上 相異之單位共聚合所形成之樹脂。 · 25 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 - -- ϋ ϋ n f I ϋ ϋ I I*- ϋ ϋ JJ Β— - --*-r«J· n - I n n I {請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 &quot;53 1 4 1 [ A7 _B7_ 五、發明說明（為） —^CH—CH2-jjj— · μ )This paper is made in Chinese national standard i | MCNS) A4 size⑵Qx 297 Public Love J Pack --------- Order --------- line (Please read the precautions on the back before filling in this Page) 453 1 4 1 Printed B7 by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (Sichuan) A printed circuit board is characterized by the formation of a selective self-ionization tendency at the surface of the above-mentioned lower conductor circuit. A metal layer made of at least one kind of metal in a group consisting of a metal equal to Sn and less than or equal to A1 and a precious metal, and a roughened layer is formed on the metal layer. At least one metal selected from the group consisting of metals and noble metals with an ionization tendency of Sn equal to or greater than Sn and less than or equal to A1, preferably selected from Al, Cr, Fe, Zn, Ni, Co, Sn, and noble metals At least one metal in the group. The roughened layer is preferably made of a Cu_Ni-P alloy, the interlayer resin insulating layer is preferably provided with a through hole, and the through hole is greater than or equal to sn through the above-mentioned self-ionization tendency and A metal layer made of at least one kind of metal selected from the group consisting of metals and noble metals equal to or less than A1 and the roughened layer are electrically connected to the lower-layer conductor circuit formed on the substrate. ‘The roughened layer is preferably formed by coating with a metal layer or a precious metal layer having a higher ionization tendency than Cu and containing at least one metal below Ti. The above-mentioned through hole is preferably formed by filling with a film. The manufacturing process of the multilayer printed circuit board of the first invention of the tenth group of the present invention is to perform a roughening process after the conductor circuit is formed to form a roughened surface on the conductor circuit. The conductor circuit having the above roughened surface is interlayered. After the resin insulation layer is covered, a conductor circuit composed of a plurality of layers sandwiching an interlayer resin insulation layer is formed on the insulating substrate by continuously repeating the formation process of the openings for through holes, which is characterized in that a rough layer is formed on the conductor circuit. After faceting ', borrowed 19 paper sizes to apply Chinese National Standard (CNS) A4 specifications (210 X 297 public love) I -------- 1 f I! II order · I ---- (Please Read the precautions on the back before filling this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention) Oxidation treatment is applied to make the entire surface of the roughened surface form an oxide film. An interlayer resin insulating layer is formed. After forming the roughened surface of the conductor circuit, it is preferable to perform an oxidation treatment by heating at 80 to 200 ° C for 10 minutes to 3 hours in the atmosphere surrounding the atmosphere, and an oxide film is formed on the entire surface of the roughened surface ^ The multilayer printed circuit board according to the second invention of the tenth group of the present invention is formed on the surface of the substrate on which a conductor circuit composed of a roughened surface is formed to form an interlayer resin insulating layer, and a through hole is formed in the interlayer resin insulating layer. An opening is formed next to a conductive body formed in the opening for the through-hole to form a through-hole 'characterized by the entire surface of the conductor circuit formed of the roughened surface' to form a coating layer made of an oxide film. The thickness of the coating layer composed of the oxide film is preferably 0.01 to 0.2 / z m. [Brief description of drawings] Figures 1 to 2 show cross-sectional views of a part of the manufacturing process of the multilayer printed circuit board of the first group of the present invention. 2 (a) to (e) are cross-sectional views of a part of the manufacturing process of the multilayer printed circuit board of the first group of the present invention. 3 (d) to 3 (d) are cross-sectional views showing a part of the manufacturing process of the multilayer printed circuit board of the first group of the present invention. ‘FIGS. 4 (a) to (d) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board of the second group of the present invention. Figures 5 (a) to (d) are cross-sectional views of a part of the second group of multi-layer printed circuit board manufacturing processes of the present invention. ^ 20 This paper is applicable to China @ 家 标准 (CNS &gt; A4 specification) (210 X 297 mm) ----------- installation --- order --------- line (please read the precautions on the back before filling this page) A7 453141 ___ B7__________ — 'V. Description of the Invention (A) Figures 6 (a) to (d) are cross-sectional views of a part of the manufacturing process of the second group of multi-layer printed circuit boards of the present invention. (c) is a cross-sectional view of a part of the manufacturing process of the multilayer printed circuit board of the second group of the present invention. As shown in (8) to (c) of FIG. 8, it is a multilayer printed circuit of the second group of the present invention A cross-sectional view of a part of the board manufacturing process. · Figures 9 to ⑷ show cross-sectional views of a part of the third group of multilayer printed circuit board manufacturing processes of the present invention. Figures 10 (a) to (d) ) Is a cross-sectional view of a part of a multilayer printed circuit board manufacturing process according to the third group of the present invention. As shown in Figures ⑻ to ⑷, it is a multilayer printed circuit of the third group of the present invention. A cross-sectional view of a part of the manufacturing process of a brushed circuit board. As shown in FIGS. 12 (c) to (c), it is a cross-sectional view of a part of the manufacturing process of the third group of multilayer printed circuit boards of the present invention. Shown is a cross-sectional view of a part of a manufacturing process of a multilayer printed circuit board of the third group of the present invention. Figure Η shows a cross-section of a manufacturing process of another multilayer printed circuit board of the third group of the present invention. Fig. 15 is a cross-sectional view of part of the manufacturing process of the multilayer printed circuit board of the fourth group of the present invention shown in Figs. A cross-sectional view of a part of the manufacturing process of a multilayer printed circuit board. Fig. 17 (d) to (d) are cross-sectional views of a part of the manufacturing process of the fourth group of multilayer printed circuit boards of the present invention. 21 Paper dimensions Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) — — — — — — — — — — I— I- i III {Please read the precautions on the back before filling this page) Property Bureau employee consumer cooperatives seal Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Industrial Consumer Cooperatives 453141 A7 ___B7_____ V. Description of the Invention (/) Figures 18 to (c) are part of the manufacturing process of the fourth group of multilayer printed circuit boards of the present invention. Sectional view. 19 'to' 9 'are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the fifth group of the present invention. Figs. 20 through 20 are cross-sectional views showing a part of a manufacturing process of a multilayer printed circuit board according to the fifth group of the present invention. 21 (d) to 21 (d) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the fifth group of the present invention. 22 (a) and 22 (b) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to a fifth group of the present invention. 23 (f) to 23 (f) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the sixth group of the present invention. 24 (a) to (d) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board of the sixth group of the present invention. ° (d) to (d) of FIG. 25 are the first part of the present invention. A cross-sectional view of part of a six-group multilayer printed circuit board manufacturing process. (A) and (b) of FIG. 26 are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the sixth group of the present invention. (A) and (b) of FIG. 27 are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the sixth group of the present invention. As shown in ⑷ to ⑷ of FIG. 28, it is a cross-sectional view of a part of a manufacturing process of a multilayer printed circuit board according to a seventh group of the present invention. 29 (f) to 29 (f) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the seventh group of the present invention. , 22 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------- β 11! 111-^ I ί (Please read the precautions on the back before filling this page ) Printed by the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 14 1 a? B7 V. Description of the invention (w) As shown in (e) to (e) of Figure 30, this is the seventh group of multilayer printed circuit boards of the present invention. Sectional view of a part of the manufacturing process "As shown in Figs. 31 (a) to (d), it is a cross-sectional view of a part of the manufacturing process of the seventh group of multilayer printed circuit boards of the present invention. 32 (c) to 32 (c) are cross-sectional views showing a part of a manufacturing process of a multilayer printed circuit board according to the seventh group of the present invention. 33 (a) to (d) are cross-sectional views of a part of a manufacturing process of a multilayer brushed circuit board according to the eighth group of the present invention. Figures 34 (a) to (d) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the eighth group of the present invention. 35 (a) to (d) are cross-sectional views of a part of a manufacturing process of a multilayer 91 brushed circuit board according to the eighth group of the present invention. Figs. 36 (a) to (d) are cross-sectional views showing a part of a manufacturing process of a multilayer printed circuit board according to the eighth group of the present invention. 37 (a) to (c) are cross-sectional views of a part of a manufacturing process of a multilayer EP brush circuit board according to the eighth group of the present invention. 38 (a) to (i) are cross-sectional views showing a part of a manufacturing process of a multilayer printed circuit board according to the ninth group of the present invention. Figures 39 (a) to (d) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the ninth group of the present invention. 40 (a) to (i) are cross-sectional views showing a part of a manufacturing process of a multilayer printed circuit board according to the ninth group of the present invention. Figures 41 to VII are cross-sectional views of a part of the ninth group of multilayer printed circuit board manufacturing processes of the present invention. 23 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I------------------------- I --- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453141 A7 B7 V. Description of the invention (π) Figures 42 (a) to (d) show the invention Sectional drawing of part of the ninth group of multilayer printed circuit board manufacturing processes. Figs. 43 (a) and (b) are sectional views showing a part of a manufacturing process of a multilayer printed circuit board according to the ninth group of the present invention. Figs. 44 (a) to (d) are sectional views showing a part of a manufacturing process of a multilayer printed circuit board according to the tenth group of the present invention. 45 (a) to (d) are cross-sectional views showing a part of the manufacturing process of a multilayer printed circuit board according to the tenth group of the present invention. 46 (d) to 46 (d) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the tenth group of the present invention. 47 (a) to (c) are cross-sectional views showing a part of a manufacturing process of a multilayer printed circuit board according to the tenth group of the present invention. 48 (c) to 48 (c) are cross-sectional views of a part of a manufacturing process of a multilayer printed circuit board according to the tenth group of the present invention. 49 (c) to 49 (c) are cross-sectional views showing a process of forming an oxide film in the multi-layer printed circuit board manufacturing method of the tenth group of the present invention. 50 (c) to 50 (c) are cross-sectional views showing a process of forming an oxide film in a conventional method for manufacturing a multilayer printed circuit board. [Detailed disclosure of the invention] The multilayer printed wiring board of the first group of the present invention is characterized by using a polyolefin resin as a resin insulating layer. * As for this polyolefin resin, there are thermosetting polyolefin resins and thermoplastic polyolefin resins, and it is particularly preferable to use thermosetting polyolefin resins. The reason is that the interlayer resin insulation layer is set on the interlayer resin insulation layer. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 cm). ---- II Order.! (Please read the precautions on the back before filling this page) ¢ 53 1 4 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (A) '' In terms of the manufacturing process of the multilayer printed circuit board of the marginal layer If a thermosetting polyolefin resin is used for the interlayer resin insulation layer on the lower layer side, there will be no deformation during heating and extrusion, and the position of the through hole will be small. · On the other hand, in the case of thermoplastic polyolefin resins, its breaking toughness is high during thermal cycling, and it can suppress cracks that occur due to the difference in thermal expansion coefficient between the conductor circuit and the resin. For this thermoplastic polyolefin resin, the melting point is preferably at least 200 ° C. The reason is that if the melting point is above 200 ° C, the deformation caused by heating and compression is small, and the multilayer soldering board is installed at 200 ° C or above by heating to dissolve the solder layer and solder bumps for installation. It prevents the resin insulation layer from melting. Hereinafter, the polyolefin-based resin used in the present invention will be described in detail. The polyolefin resin is a resin having the following structure. That is, (a) a resin formed by a repeating unit represented by the following structural formula (1). X n However, η is 1 to 10000 * X is an unsaturated hydrocarbon, an oxy group, or a lactone group of hydrogen, an alkyl group, a phenyl group, and a hydroxyl group 'C2 to C3. (b) Resin formed by copolymerizing two or more different units among one type of repeating unit shown in the following structural formula (1). · 25 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)--ϋ ϋ nf I ϋ ϋ II *-ϋ ϋ JJ Β —--*-r «J · n-I nn I {Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs &quot; 53 1 4 1 [A7 _B7_ V. Description of the invention (for) — ^ CH—CH2-jjj— · μ)

X 但是，η爲1-10000 X爲氫、烷基、苯基、羥基、C2〜C3之不飽和碳氫化 合物、氧基或者是內酯基。 (c) 以下構造式所示之一種具有重複的單位，又其分子 主鏈中具有雙鍵、氧結構、內酯結構、單環戊二烯結構或 多環戊二烯結構之樹脂。 — -fCH—CH2^;----⑴X is 1-10000, and X is hydrogen, alkyl, phenyl, hydroxyl, C2 to C3 unsaturated hydrocarbon, oxy or lactone. (c) A resin having a repeating unit shown in the following structural formula and having a double bond, an oxygen structure, a lactone structure, a monocyclopentadiene structure, or a polycyclopentadiene structure in its molecular main chain. — -FCH—CH2 ^; ---- ⑴

X 但是，η爲！〜10000 X爲氫、烷基、苯基、羥基、C2〜C3之不飽和碳氫化 合物、氧基或者是內酯基。 (d) 自前述(a)、（b) 、（c)群選出兩種以上樹脂經混合所 成之混合樹脂、自前述(a) 、（b) 、（c)群選出之樹脂與熱 硬化性樹脂所成之混合樹脂，或是自前述(a) 、（b) 、（c)群 選出之樹脂相互交聯所成樹脂。 又本發明之第一群的所說的樹脂，即包括「單體」以 及「低聚物」之槪念。 首先，針對(a) ~(c)的樹脂予以詳述之。 採用前述之含有重複單位之構造的理由，係欲使其破 本紙張尺度適用中國國家標準&lt;CNS)A4規格（210 X 297公釐） -----------農-------—訂---------線 (請先閱讀背面之注意事項再填寫本頁) A7 453 1 4 1 _^B7_ 五、發明說明（〆） 斷韌性値不至降低，則熱硬化性聚烯烴樹脂可滿足此一要 求。 此處，就前述重複單位中之X所採用之烷基而言，較 佳者係擇自甲基、乙基、丙基、異丙基、丁基'異丁基、t 一丁基中至少一種。 就前述重複單位中之X所採用之C2〜C3的碳氫化合物 而言，較佳者係擇自CtL· = CH -、CHsCH = CH -、CH2 = C(CH〇 -、乙炔基中至少一種。 就前述重複單位中之X所採用之氧基而言，較佳者係 環氧基、丙氧基；就內酯基而言，較佳者係擇自β-內酯基 、γ—內酯基' δ—內酯基中至少一種。 又，前述重複單位中之X所採用C2〜C3的碳氫化合物 、氧基、內酯基、氫氧基的理由，係其反應性高，而含有 這些官能基的樹脂(此處係指低聚物)彼此之間交聯容易。 又，η爲1〜10000的理由，係η超過10000時將變成不 溶性溶劑，造成使用上的困難。 於前述(c)的樹脂之中，分子主鏈中之雙鍵結構亦可以 是下述構造式（1)所示之重複單位以及-(CH = CH) m -或是-(CEb - CH = CH - CH2) m -之重複單位聚合所形成者。 此處，m 爲 1-10000。 ~^CH—CH2~j—...⑴ I ηX However, η is! ~ 10000 X is hydrogen, alkyl, phenyl, hydroxyl, C2 ~ C3 unsaturated hydrocarbon, oxy or lactone group. (d) A mixed resin obtained by mixing two or more resins selected from the above (a), (b), and (c) groups, a resin selected from the above (a), (b), and (c) groups and heat-cured A mixed resin made of a flexible resin, or a resin formed by cross-linking resins selected from the aforementioned (a), (b), and (c) groups. The resin of the first group of the present invention includes the idea of "monomer" and "oligomer". First, resins (a) to (c) will be described in detail. The reason for adopting the aforementioned structure containing repeating units is to make the paper size of this paper apply the Chinese National Standard &lt; CNS) A4 specification (210 X 297 mm) ----------- Agriculture- ------ Order --------- Thread (please read the notes on the back before filling this page) A7 453 1 4 1 _ ^ B7_ V. Description of the invention (〆) Toughness at break If it decreases, the thermosetting polyolefin resin can satisfy this requirement. Here, as for the alkyl group used for X in the aforementioned repeating unit, it is preferable to select at least one of methyl, ethyl, propyl, isopropyl, butyl'isobutyl, and t-butyl. One. As for the hydrocarbons of C2 to C3 used for X in the aforementioned repeating unit, it is preferable to select at least one of CtL · = CH-, CHsCH = CH-, CH2 = C (CH〇-, ethynyl As for the oxy group used for X in the aforementioned repeating unit, preferred ones are epoxy and propoxy groups; as for lactone groups, the preferred ones are selected from β-lactone groups and γ-lactones. At least one of ester group δ-lactone group. The reason for the hydrocarbon, oxygen, lactone, and hydroxyl groups of C2 to C3 used for X in the repeating unit is that its reactivity is high, and Resins containing these functional groups (referred to herein as oligomers) are easily cross-linked with each other. The reason why η is 1 to 10,000 is that when η exceeds 10,000, it will become an insoluble solvent, which will cause difficulties in use. In the resin of (c), the double bond structure in the main chain of the molecule may also be a repeating unit represented by the following structural formula (1) and-(CH = CH) m-or-(CEb-CH = CH- CH2) formed by the polymerization of repeating units of m-. Here, m is 1-10000. ~ ^ CH—CH2 ~ j —... ⑴ I η

X 27 I------表--------訂i 1 I-----線 (請先閱讀背面之注意事項再填寫本頁). 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用1f1國國家標準（CNS)A4規格（2〗〇χ 297公S ) A7 d5314 1 _B7_ 五、發明說明（&gt; ) 但是，η爲1〜10〇00 X爲氫、烷基、苯基、羥基' C2〜C3之不飽和碳氫化 合物、氧基或者是內酯基。 前述⑹之樹脂中，就分子主鏈之氧基結構而言，較佳 者係環氧結構。又，就分子主鏈之內酯結構而言，較佳者 係β—內酯、γ—內酯。又，就分子主鏈之單環戊二烯結構 或多環戊二烯結構而言，較佳者係採用擇自環戊二烯及二 環戊二烯。 前述之共聚合，有重複單位如ΑΒΑΒ· · ·般交互聚 合的情形、有重複單位如ΑΒΑΑΒΑΑΑΑΒ · · ·般不規則聚 合的情形、或是如ΑΑΑΑΒΒΒ· · ·般嵌段聚合的情形。 接著，針對(d)之樹脂加以說明。 (d)之樹脂，係擇自前述(a) 、（b) 、（c)群兩種以上樹 脂經混合所成之混合樹脂、擇自前述(a) 、（b) 、（c)群之 樹脂與熱硬化性樹脂所成之混合樹脂，或是擇自前述⑷ 、（b) 、（c)群之樹脂相互交聯所成樹脂。 其中，擇自前述(a) 、（b) 、（c)群兩種以上樹脂進行 混合的情況，係將樹脂粉末溶解於有機溶劑中，或是使其 熱溶融以行混合。 又，擇自前述(a) 、（b) 、（c)群之樹脂與熱硬化性樹 脂進行混合的情況，也是將樹脂粉末溶解於有機溶劑中以 行混合。此時就混合之熱硬化性樹脂而言，較佳者係擇自 熱硬化性聚烯烴樹脂、環氧樹脂、苯酚樹脂、聚醯亞胺樹 脂、雙順丁烯二胺三氮雜苯(BT)樹脂之至少一種加以使用 28 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----- --------------------^ 0 —------ ( (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 4 53141 __B7___ 五、發明說明（A ) 0 再者，擇自前述（a) 、（b) 、（c)群之樹脂相互交聯的 情況，C2〜C3之不飽和碳氫化合物、氧基、內酯基、氫氧 基、以及分子主鏈中之雙鍵、氧結構、內酯結構係做爲交 聯的鍵合部。 又，就使用本發明之熱硬化性聚烯烴樹脂的市售品而 言，可舉出住友3M公司製造之商品名1592。又，就熔點 200°C以上之熱可塑性聚烯烴樹脂的市售品而言，可舉出三 井化學公司製造之商品名TPX(熔點240t)、出光石油化學 公司製造之商品名SPS(熔點270°C)等。TPX中前述重複單 位X係異丁基之樹脂，SPS中X係具有苯基之間同立構構 造的樹脂。 如以上說明之聚烯烴系樹脂，由於其與導體電路之密 接性優，故不需將樹脂絕緣層表面粗化即可形成導體電路 。亦即，可於平坦之樹脂絕緣層表面形成導體電路，尤其 ，只要對此聚烯烴系樹脂引入些許之極性基，其與導體電 路之密接性可獲得大幅的提昇。 又，此種聚烯烴系樹脂，介電常數在3以下，介電耗 損因數在0.005以下皆比環氧樹脂爲低，且高頻率之訊號 亦無傳送延遲。又，聚烯烴系樹脂之耐熱性也不比環氧樹 脂差，於焊接溶融溫度下不會有導體電路的剝離現象。再 者’由於其破斷韌性値亦大，所以不會因熱循環造成以導 體電路與樹脂絕緣層之界面爲起點之龜裂的發生。 接著，本發明之第一群之構成多層印刷電路板的導體 29 k紙張尺度適用中國國家標準（cns3XT規格（210 x 297公釐） ----------I----* 1 I--^0 I---- I--線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 453141 __B7__ 五、發明說明（4 ) 電路，較佳者係透過擇自週期表的第4A族至第1B族之第 4~第7週期的金屬(但是Cu除外）、A1以及Sn之中一種以 上的金屬構成之金屬層而設於樹脂絕緣層上。這些金屬層 與聚烯烴系樹脂的密接性特別的優良’其原因係其具有極 高値之剝離強度1.5〜2.5 kg/cm。 擇自第4A族至第1B族之第4~第7週期的金屬(但是 Cu除外）、A1以及Sii之中一種以上的前述金屬，較佳者係 擇自Ni、Co、Cr、Ti以及貴金屬當中之一種°就貴金屬而 言，較佳者爲Pd、An、Pt。 此金屬層的厚度較佳者爲0.01#ni~0_2ym。其理由， 若使其厚度爲0.01/im以上，則可確保樹脂絕緣層與導體 電路間之密接性，又，若使其厚度爲〇.2^m以下’則可防 止以濺鍍形成金屬層之時的應力之問題而發生龜裂’且於 導體電路形成後已不需要之導體電路間的金屬層亦可利用 蝕刻來輕易除去。 此金屬層，係由無電解鍍敷、電解電鍍、濺鍍、蒸鍍 ' CVD等方法來形成。 又，擇自第4A族至第1B族之第4~第7週期的金屬( 但是Cu除外）、A1以及Sn之中一種以上的金屬構成之前 述金屬層，依需要亦可形成於導體電路的表面。在多層印 刷電路板的情況，必須於導體電路上再形成層間樹脂絕緣 層，而其可改善與層間樹脂絕緣層的密接性。 又，本發明之第一群的多層印刷電路板’較佳者係其 構成乃於基板的內部或表面形成導體電路之多層印刷電路 30 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） II — — — — — — * I I ---- - «111!11[1 {請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消费合作社印製 ^53 1 4 1 A7 -- -B7_— -- 五、發明說明) 板。 以下，就本發明之第一群的多層印刷電路板之製造方 法以多層印刷電路板爲例加以說明。 (1)首先，於基板的表面製作出形成內層銅圖案之電路 基板。 就基板而言，可使用擇自玻璃環氧基板、聚醯亞胺基 板、雙順丁烯二醯胺三氮雜苯基板、氟樹脂基板、聚烯烴 樹脂基板當中至少1種。 對此樹脂基板形成銅圖案時，係將銅面積層板進行蝕 刻。 又，對此基板以鑽頭來打通貫通孔，而於貫通孔的壁 面以及銅箔表面施以無電解鍍敷以形成通孔。就無電解鍍 敷而言以鍍銅爲佳。又，如氟樹脂基板其對電鍍物附著鍍 差的基板而言，可用有機金屬化合物(有機金屬鈉)所成之 前處理液(潤工公司製，商品名：4H)處理、電漿處理等進 行表面改良。 接著，爲使其增厚而進行電解電鎪。就此電解電鍍而 百以鑛銅爲佳。 又，於通孔的內壁以及電解電鍍膜的表面進行粗彳匕處 理亦可。就粗化處理而言，有黑化（氧化）-還原處理、藉 由有機酸及銅錯合物的混合水溶液之噴塗處理、或是藉由 鍍敷Cu-Ni — P針狀合金之處理等。 又，依需要於通孔內塡充導電糊膠，對覆有此導電糊 膠之導體層亦可用無電解鑛敷或電解電鍍來形成之。 31 本紙張尺度適用中國國家標準（CNS)A4规格（210 X 297公釐&gt; — II I I I ----農------- - 訂--------.，線 {請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 53141 A7 _______ B7__ 五、發明說明（V3) (2)在前述（1)製作之電路基板上，形成由聚烯烴系樹脂 所成之樹脂絕緣層。此樹脂絕緣層，其功能係做爲多層印 刷電路板之層間樹脂絕緣層。 此樹脂絕緣層，係先塗佈有未硬化液，再對薄膜狀之 樹脂予以熱壓後積層所形成者.。 接著，於此聚烯烴系樹脂絕緣層中，爲確保與下層導 體電路之電連接而設置開口。 此開口的穿孔，係以雷射光進行。此時，所使用之雷 射光，有二氧化碳雷射、紫外線雷射、準分子雷射等。·此 時，以二氧化碳雷射穿孔之情形則進行去污(desmear)處理 ，此去污處理可使用由鉻酸、過錳酸鹽等之水溶液所成之 氧化劑來進行，又此處理亦可用氧電漿、CR及氧的混合物 電漿或是輝光放電等來進行。特別是Ch及氧的混合物電 漿，樹脂表面引入羥基及羰基等親水性基，使後續之CVD 或PVD容易進行，此爲有利的。 (4)在前述(3)設置開口之聚烯烴樹脂絕緣層的表面， 擇自前述之第4A族至第1B族之第4~第7週期的金屬(但 是Cu除外）、A1以及Sn之中一種以上的金屬所構成之前 述金屬層係以PVD法或CVD法形成之。 就PVD法而言，可舉出濺鍍、離子束濺鍍等之蒸鍍法 。又，就CVD法而言，可具體舉出丙烯基環戊二苯鈀、二 甲基金乙醯醋酸、錫四甲基丙烯腈、二鈷八羧丙烯腈等之 有機金屬(M0)做爲供給材料之PE—CVD (Plasma Enhanced CVD)。 32 本紙張尺度適用巾國國家標準（CNS)A4規格（210 X 297公釐） 义------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消费合作社印製 4 53 1 4 1 A7 _ B7 五、發明說明（Μ ) (5) 接著，在前述(4)所形成之金屬層上，將與以下過程 之無電解鍍敷膜相同的金屬層以濺鍍等形成。此係爲改善 與無電解鍍敷膜間的親和性之故。具體而言，較佳者係以 濺鍍方式來設置銅層。 (6) 接著，在前述(5)所形成之金屬層上施行無電解鍍敷 〇 就無電解鍍敷而言以鍍銅爲最佳。又，無電解鍍敷的 膜厚以0.1〜5ym爲佳。其理由，係由於可不損及在其後進 行之電解電鍍之導體層的特性，而能以蝕刻予以去除之故 〇 (7) 接著’在前述(6)所形成之無電解鍍敷膜上彤成防鍍 膜。 此防鍍膜’係將感光性乾式薄膜進行積層後予以曝光 、顯像處理而形成者。 (8) 接著，將無電解鍍敷膜做爲引導電鍍來進行電解電 鍍’以增厚導體電路。又電解電鍍膜，以5〜3〇#m爲佳。 (9) 接著’在防鍍膜剝離後，將位於防鍍膜下方之無電 解鍍敷膜及擇自第4A族至第1B族之第4〜第7週期的金屬 之中至少一種以上的金屬所構成之金屬層以蝕刻去除，而 得到獨立之導體電路。 就蝕刻液而言，可使用如硫酸一過氧化氫水溶液、過 硫酸氨、過硫酸鈉、過硫酸鉀等之過硫酸鹽水溶液；氯化 鐵、氯化銅之水溶液；鹽酸、硝酸、熱稀硫酸等。 (10) 再者依需要，重複前述(2)〜(9)的過程以得到多層化 33 本紙張尺度適用中國國家標準（CNS)A4規格（2]〇 X 297 ϋ I I I I I I I I n - - 1 . I - d I I I - 一BJI —J n tt I I - - I {請先閱讀背面之注意事項再填寫本頁) A7 4531 4 1 __B7__ 五、發明說明（VL) 之多層印刷電路板。 又，以上的說明，就導體電路的形成方法而言係採用 半加成法但亦可採用全加成法。 此全加成法，係於聚烯烴系樹脂絕緣層表面以CVD或 PVD處理形成薄金屬層後，或積層有感光性乾式薄膜，或 塗佈有液體狀之感光性樹脂，再進行曝光、顯像處理以設 置防鍍膜，接著採用無電解鍍敷以進行增厚，從而形成導 體電路。 本發明之第二群之多層印刷電路板，係於基板上依序 形成導體電路及樹脂絕緣層，又這些導體電路透過通孔連 接而形成多層印刷電路板，其中上述之樹脂絕緣層係由環 烯烴系樹脂所形成者。 依據本發明之第二群之多層印刷電路板，由於上述層 間樹脂絕緣層係由環烯烴系樹脂所構成，相較於環氧樹脂 所成之層間樹脂絕緣層，其介電常數與介電耗損因數大幅 降低之故，乃可防止因訊號傳遞的延遲及訊號的電傳送損 失等造成之訊號錯誤。 又，上述環烯烴系樹脂，由於其機械的特性，特別是 剛性高的緣故，因而可以在堅固的層間樹脂絕緣層上形成 導體電路，也因此，可充分確保導體電路彼此間連接的可 靠度。 又，上述環烯烴系樹脂，由於其與導體電路的密接性 佳，故可防止層間樹脂絕緣層自導體電路剝離的情形，進 而可防止因剝離使得層間樹脂絕緣層之龜裂的發生。 34 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公爱） ---— -^-1 —-----訂----!! 線 (請先閱讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消费合作社印製 經濟邹智慧財產局員工消費合作杜印製 453 1 4 1 A7 --------B7_ 五、發明說明（4 ) 又’上述環嫌煙系樹脂，由於其吸水率亦小，故可使 導體電路間之電氣絕緣性提高，可靠度也提昇。 雖然上述環嫌煙系樹脂的種類並無特別的限定，但於 1GHz之介電常數在0‘3以下，介電損耗因子在〇.〇1以下爲 佳，又上述介電常數在2.4〜2.7間更佳。 藉由使用此種低介電常數之物，可防止因訊號傳遞的 延遲及訊號的電傳送損失等造成之訊號錯誤。 又’上述環烯烴系樹脂以使用2一原菠烷、5-亞乙基 - 2-原疲院或是這些的衍生物所成之單體的單獨聚合物或 是共聚物爲佳。就上述衍生物而言可舉出上述2一原菠烷 等之環烯烴中’藉由用以形成交聯之氨基或無水順式丁烯 二酸殘基或是順式丁烯二酸變性物等所結合之物。 就合成上述共聚物之單體而言，可舉出例如乙烯、丙 烯等。 上述環烯烴系樹脂，可爲上述樹脂之2種以上的混合 物，亦可含有環烯烴系樹脂以外的樹脂。 又，上述環烯烴系樹脂係共聚物的情況，可爲嵌段共 聚物或爲無規共聚物。 又，上述環烯烴系樹脂，以熱硬化性環烯烴系樹脂爲 佳。藉由加熱的進行所形成之交聯，可獲得較高的剛性， 且機械特性也會提昇。 上述環烯烴系樹脂的玻璃轉移溫度（Tg)，較佳爲 130〜20〇r。 上述環烯烴系樹脂，可使用已成形之樹脂層（薄膜）， 35 本紙張尺度適用中國國家標準（CNS)A4規袼（210 X 297公釐） — — — — — — I I I -in I — — I ^»1-----I i I (請λ·閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局貝工消費合作杜印製 4 53 1 4 1 at ____B7__ 五、發明說明（β) 亦可使用單體或是具有一定分子量之低分子量的聚合物， 或是二甲苯，環己烷等分散於溶劑中而呈未硬化溶液的狀 態亦可。 又，就樹脂層而言，亦可使用所謂之RCC(RESIN COATED COPPER :覆樹脂銅范）。 上述環烯烴系樹脂，可爲不含有塡充物等之物，但亦 可爲氫氧化鋁、氫氧化錳、磷酸酯等含有難燃劑之物。 以下’針對使用此種環烯烴系樹脂之多層印刷電路板 的製造方法加以說明。 (1)首先’於樹脂基板表面製作具有下層導體電路之電 路基板。 就樹脂基板而言，以具有無機纖維之樹脂基板爲佳， 具體而言，可舉出例如玻璃纖維環氧基板、玻璃纖維聚醯 亞胺基板、玻璃纖維雙順丁烯二醯胺三氮雜苯樹脂基板、 玻璃纖維氟樹脂基板等。 又，於上述基板之兩面使用貼有銅箔之銅面積層板亦 可。 通常’對此基板以鑽頭來設置貫通孔，而於貫通孔的 壁面以及銅箔表面施以無電解鍍敷以打通貫通孔。就無電 解鍍敷而言以鍍銅爲佳。接著，爲使銅箔增厚亦可進行電 解電鍍。就此電解電鍍而言以鍍銅爲佳。 之後，於通孔的內壁等施行粗化處理，又於通孔內塡 充樹脂糊膠後，對覆於表面之導體層亦可用無電解鍍敷或 電解電鍍來形成之。 36 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） lull.-----I--装--------訂------！，線 {請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 14 1 a? ___B7______ 五、發明說明（vs) 就上述粗化處理的方法而言，例如，可列舉黑化(氧化 )一還原處理、藉由有機酸及銅錯合物的混合水溶液之噴塗 處理、或是藉由電鍍Cu- Ni-P針狀合金之處理等° 經過上述的過程，於全面基板上所形成之銅的圖案上 採先微影技術以形成防鍍膜，接著，藉由蝕刻的進行，形 成下層導體電路。之後，依必要性，將形成導體電路之受 蝕刻的凹陷部分塡充樹脂等亦可。 (2) 其次，於形成之下層導體電路中施行必要之粗化處 理。就粗化處理的方法而言，可採用上述之方法，亦即， 可列舉黑化（氧化）_還原處理、藉由有機酸及銅錯合物的 混合水溶液之噴塗處理' 或是藉由電鍍Cu-Ni — P針狀合 金之處理等。 又，也可不於下層導體電路中施行粗化處理，而將形 成下層導體電路之基板浸漬於溶解有樹脂成分的溶液中， 而於下層導體電路的表面形成樹脂層，以確保與其上形成 之層間樹脂絕緣層的密接性。 (3) 其次，在上述(2)製作之具有下層導體電路之電路基 板的兩面處，形成上述環烯烴系樹脂所成之層間樹脂絕綠 層。 此層間樹脂絕緣層的形成，係採用塗佈環烯烴系樹脂 形成用之未硬化液之後，藉由加熱等使其硬化的方法，或 是將樹脂層於加熱中以真空或是減壓來進行壓合積層的方 法，總之以容易著手的方法對樹脂層進行積層爲宜。此時 之加熱條件，以l〇〇~200°C、0.5〜20分鐘爲宜。 37 本紙張尺度適用中國國家標準（CNS)A4規格&lt;210 X 297公釐） ------------&quot;'HtJ ----- 1 [ I 訂 I I I I---- (請先閱讀背面之注意事項再填寫本頁). 經濟部智慧財產局貝工消费合作杜印製 4 53 1 41 A7 B7 五、發明說明（沙） 其次，藉由對層間樹脂絕緣層進行雷射光的照射以設 置通孔用開口。此時’就可使用之雷射光而言’例如有二 氧化碳(CCh)雷射、紫外線雷射、準分子雷射等’在這些當 中，以準分子雷射及短脈衝之一氧化碳雷射爲佳。 準分子雷射，藉由使用於通孔用開口之形成部分形成 之貫通孔的遮罩等，可一次就形成複數之通孔用開口’而 短脈衝之二氧化碳雷射’則可使開口內之樹脂殘量減少’ 並可減輕對開口周圍之樹脂的所造成的損害。 遮罩的貫通孔必須是正圓，此乃由於爲使雷射光的點 狀成爲正圓之故，所以上述貫通孔之直徑’以左 右爲宜。 以雷射光形成開口之時，特別是使用二氧化碳雷射之 時，較佳者係進行去污處理。上述之去污處理，可使用由 鉻酸、過錳酸鹽等之水溶液所構成之氧化劑來進行，又此 處理亦可用氧電漿、CR及氧的混合物電漿或是輝光放電等 來進行。再者，藉由使用低壓水銀燈照射紫外線以進行表 面的改良亦可。 (5)對層間樹脂絕緣層而言，可不需特別經由粗化處理 等’而於其上面形成金屬層，又，亦可藉由電漿處理或是 酸等處理’對該表面進行粗化後，再形成金屬層。 進行電漿處理時，爲確保做爲上層形成之導體電路與 層間樹脂絕緣層的密接性，亦可形成中間層，而該中間層 係與層間樹脂絕緣層具優異密接性之Ni、Ti、Pd等金屬所 成者。又上述金屬所成之中間層，以濺鍍等物理蒸鍍法 38 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------*裝----Ί I---訂·--------線 (請先閱讀背面之注意事項再填窝本頁) A7 453 1 4 1 __B7_ 五、發明說明（ί/Ι ) (PVD法)形成爲宜，其厚度則以0.1〜2.0μιη爲宜。 (6) 經上述過程後，形成金屬所成之薄膜層。此薄膜層 的材質，以銅或是銅-鎳合金爲佳。又此薄膜層，可藉由 物理蒸鍍法(PVD法)或化學蒸鍍法(CVD法)形成，亦可施 以無電解鍍敷來形成。 就具體之上述PVD法或CVD法而言，可舉出本發明 之第一群記載之方法。 此薄膜之膜厚，以0.1〜5#m爲宜。係因若具有此種膜 厚，不會損害到之後進行之電鍍導體層本身的性能，又可 利用蝕刻去除該薄膜之故。 (7) 在上述(6)形成之無電解鍍敷膜上形成防鍍膜。此防 鍍膜的形成，係將感光性乾式薄膜積層後，進行曝光、顯 像處理所得之。 (8) 其次，將層間樹脂絕緣層上形成之金屬薄膜做爲導 鍍層進行電鍍，以增厚導體電路。又電鍍膜之膜厚，以 5〜30/zm爲宜。 此時，對通孔用開口以電鍍塡充成爲塡孔構造亦可。 (9) 彤成電鍍膜之後，將防鍍膜剝離，又對存在於防鎞 膜下之無電解鍍敷膜及上述中間層以蝕刻去除之，成爲獨 立之導體電路。就上述電鍍而言，以採用鍍銅爲佳。 就蝕刻液而言，可舉出例如硫酸一過氧化氫水溶液、 過硫酸氨、過硫酸鈉、過硫酸鉀等之過硫酸塩水溶液、氯 化鐵、氯化銅之水溶液、鹽酸、硝酸、熱稀硫酸等。又， 亦可使用上述含有銅錯合物與有機酸之蝕刻液，在導體電 39 本紙張尺度適用中國國家標準（CNS&gt;A4規格（210 X 297公釐〉 I -及-----訂.！--線 (請先閱讀背面之;i意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 A7 ^ 53 1 4 1 __B7______ 五、發明說明（0 ) 路間進行蝕刻之同時形成粗化面β (10)之後，重複上述(2Κ9)的過程設置上層的上層導體 電路，於最上層設置防焊層，藉由對該防焊層予以開口而 設置焊接凸塊，例如，可得到單面3層’即雙面6層之多 層印刷電路板。 本發明之第三群之多層印刷電路板’係於設有下層導 體電路的基板上，依序形成有層間樹脂絕緣層及上層導體 電路之多層化的多層印刷電路板，其特徵爲，至少於上述 下層導體電路的表面(以下，簡稱爲導體電路β又，之後所 提到的金屬層，由於其亦可形成於上層導體電路，以下， 在本發明之第三群的說明當中，只要無特別的限定，則導 體電路係包含有下層導體電路及上層導體電路），形成有擇 自Ni、Co、Sn以及貴金屬中至少1種的金屬所成之金屬層 ，又於該金屬層上形成有由Cu-Ni-P所成之粗化層。X 27 I ------ Table -------- Order i 1 I ----- line (please read the precautions on the back before filling this page). Employees' Cooperatives of Intellectual Property Bureau, Ministry of Economic Affairs Printed paper standards are applicable to 1f1 national standard (CNS) A4 specifications (2〗 〇χ 297 公 S) A7 d5314 1 _B7_ V. Description of the invention (&gt;) However, η is 1 ~ 10000 X is hydrogen, alkane Group, phenyl, hydroxy 'C2 ~ C3 unsaturated hydrocarbon, oxy or lactone group. Among the aforementioned fluorene resins, in terms of the oxygen structure of the molecular main chain, an epoxy structure is preferred. As for the lactone structure of the molecular main chain, β-lactone and γ-lactone are preferred. Further, in terms of a monocyclopentadiene structure or a polycyclopentadiene structure of a molecular main chain, it is preferred to use a cyclopentadiene selected from cyclopentadiene and dicyclopentadiene. In the aforementioned copolymerization, there may be cases where repeating units are interactively polymerized like ABA, etc., repeating units such as ΑΑΑΑΒΑΑΑΑΒ ·, ·, irregularly polymerized, or block polymerization, such as ΑΑΑΑΒΒΒ ·. Next, the resin of (d) is demonstrated. (d) The resin is a mixed resin selected from the above-mentioned two or more resins of the groups (a), (b), and (c), and is selected from the resins of the groups (a), (b), and (c). A mixed resin made of a resin and a thermosetting resin, or a resin formed by cross-linking resins selected from the aforementioned ⑷, (b), and (c) groups. Among them, when two or more kinds of resins of the groups (a), (b), and (c) are mixed, the resin powder is dissolved in an organic solvent or it is heat-melted for mixing. When the resins selected from the groups (a), (b), and (c) are mixed with the thermosetting resin, the resin powder is dissolved in an organic solvent and mixed. In this case, the thermosetting resin to be mixed is preferably selected from a thermosetting polyolefin resin, an epoxy resin, a phenol resin, a polyimide resin, and a bis-butenediamine triazabenzene (BT ) At least one kind of resin is used. 28 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ----- ------------------ -^ 0 —------ ((Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 4 53141 __B7___ V. Description of Invention (A) 0 Furthermore, It is selected from the case where the resins of the aforementioned (a), (b), and (c) groups are cross-linked with each other, unsaturated hydrocarbons of C2 to C3, oxygen groups, lactone groups, hydroxyl groups, and A double bond, an oxygen structure, and a lactone structure are used as cross-linked bonding portions. As for a commercially available product using the thermosetting polyolefin resin of the present invention, a trade name of 1592 manufactured by Sumitomo 3M Co., Ltd. is mentioned. In addition, for commercially available thermoplastic polyolefin resins having a melting point of 200 ° C or higher, there are TPX (melting point 240t) manufactured by Mitsui Chemicals Co., Ltd. and Idemitsu The trade name SPS (melting point 270 ° C) manufactured by Oil Chemical Co., Ltd., etc. The aforementioned repeating unit X is isobutyl resin in TPX, X is resin having an isotactic structure between phenyl groups in SPS. Olefin resins, because of their excellent adhesion to conductor circuits, can be used to form conductor circuits without roughening the surface of the resin insulation layer. That is, conductor circuits can be formed on the surface of a flat resin insulation layer. Polyolefin resin introduces a few polar groups, and its adhesion to the conductor circuit can be greatly improved. Moreover, this polyolefin resin has a dielectric constant of 3 or less and a dielectric loss factor of 0.005 or less than epoxy. The resin is low, and there is no transmission delay for high-frequency signals. In addition, polyolefin resins are not less heat resistant than epoxy resins, and there will be no peeling of conductor circuits at the melting temperature of soldering. The fracture toughness is also large, so no cracks will occur from the interface of the conductor circuit and the resin insulation layer due to thermal cycling. Next, the first group of the present invention constitutes a multilayer printed circuit. Conductor 29 k paper size applies to Chinese national standard (cns3XT specification (210 x 297 mm) ---------- I ---- * 1 I-^ 0 I ---- I-- (Please read the notes on the back before filling out this page) Printed by A7 453141 __B7__ of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (4) Circuit, the better one is from Group 4A to A metal layer composed of one or more metals selected from the group consisting of metals (excluding Cu) in the fourth to seventh cycles of Group 1B, and is provided on the resin insulating layer. The reason why these metal layers are particularly excellent in adhesion with the polyolefin resin is that they have extremely high peel strength of 1.5 to 2.5 kg / cm. One or more of the metals selected from the 4th to 7th cycles of Groups 4A to 1B (except Cu), A1 and Sii, preferably Ni, Co, Cr, Ti and precious metals Among them, in terms of precious metals, Pd, An, and Pt are preferred. The thickness of this metal layer is preferably 0.01 # ni ~ 0_2ym. The reason is that if the thickness is 0.01 / im or more, the adhesion between the resin insulating layer and the conductor circuit can be ensured, and if the thickness is 0.2 or less, the formation of a metal layer by sputtering can be prevented. The problem of stress at the time causes cracking, and the metal layer between the conductor circuits that is no longer needed after the conductor circuit is formed can be easily removed by etching. This metal layer is formed by methods such as electroless plating, electrolytic plating, sputtering, and vapor deposition 'CVD. In addition, the aforementioned metal layer composed of one or more metals selected from metals (except Cu) from the 4th to 7th cycles of Group 4A to Group 1B may be formed on conductor circuits as required. surface. In the case of a multilayer printed circuit board, it is necessary to form an interlayer resin insulating layer on the conductor circuit, and it can improve the adhesion with the interlayer resin insulating layer. In addition, the multilayer printed circuit board of the first group of the present invention is preferably a multilayer printed circuit whose composition is to form a conductor circuit inside or on the surface of the substrate. 30 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) II — — — — — — * II -----«111! 11 [1 {Please read the notes on the back before filling out this page) Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives Print Wisdom of the Ministry of Economic Affairs Printed by the Consumer Affairs Cooperative of the Property Bureau ^ 53 1 4 1 A7--B7_--5. Description of the invention). Hereinafter, a method for manufacturing a multilayer printed circuit board according to the first group of the present invention will be described by taking a multilayer printed circuit board as an example. (1) First, a circuit board is formed on the surface of the substrate to form an inner layer copper pattern. As the substrate, at least one selected from a glass epoxy substrate, a polyimide substrate, a biscis butadiamine triazaphenyl plate, a fluororesin substrate, and a polyolefin resin substrate can be used. When a copper pattern is formed on this resin substrate, a copper area laminate is etched. In addition, a drill is used to pass through the through holes on the substrate, and the walls of the through holes and the surface of the copper foil are subjected to electroless plating to form the through holes. For electroless plating, copper plating is preferred. In addition, if the fluororesin substrate has poor adhesion to the plated substrate, it can be treated with a pre-treatment liquid (manufactured by Junko Corporation, trade name: 4H) made of an organometallic compound (organometallic sodium), plasma treatment, or the like. Surface improvement. Next, electrolytic thickening is performed to increase the thickness. For this purpose electroplating is preferred with ore copper. The inner wall of the through hole and the surface of the electrolytic plating film may be roughened. As for the roughening treatment, there are a blackening (oxidation) -reduction treatment, a spray treatment with a mixed aqueous solution of an organic acid and a copper complex, or a treatment with a Cu-Ni-P needle alloy plating. . In addition, a conductive paste is filled in the through hole as needed, and the conductive layer covered with the conductive paste can also be formed by electroless mineral plating or electrolytic plating. 31 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — II III ---- Agriculture --------Order --------., Line { Please read the notes on the back before filling in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53141 A7 _______ B7__ V. Description of the Invention (V3) (2) On the circuit board made in (1) above, the circuit board is formed by Resin insulation layer made of polyolefin resin. The resin insulation layer functions as an interlayer resin insulation layer of a multilayer printed circuit board. This resin insulating layer is formed by first coating an unhardened liquid, and then laminating the thin film resin by hot pressing. Next, an opening is provided in this polyolefin-based resin insulating layer to ensure electrical connection with the underlying conductor circuit. This opening is perforated with laser light. At this time, the laser light used is carbon dioxide laser, ultraviolet laser, excimer laser, and the like. · At this time, in the case of carbon dioxide laser perforation, a desmear treatment is performed. This decontamination treatment can be performed by using an oxidant formed by an aqueous solution of chromic acid, permanganate and the like, and this treatment can also use oxygen Plasma, a plasma of a mixture of CR and oxygen, or glow discharge is performed. Especially for the mixed plasma of Ch and oxygen, the introduction of hydrophilic groups such as hydroxyl groups and carbonyl groups on the resin surface makes subsequent CVD or PVD easy, which is advantageous. (4) The surface of the polyolefin resin insulating layer provided with an opening in (3) above is selected from the metals (except Cu), A1, and Sn from the 4th to 7th periods of the aforementioned Group 4A to 1B. The aforementioned metal layer composed of one or more metals is formed by a PVD method or a CVD method. Examples of the PVD method include vapor deposition methods such as sputtering and ion beam sputtering. In the case of the CVD method, organic metals (M0) such as propenylcyclopentadiphenyl palladium, dimethyl gold acetoacetic acid, tin tetramethacrylonitrile, and dicobalt octacarboxyacrylonitrile can be specifically mentioned as the supply. Material of PE-CVD (Plasma Enhanced CVD). 32 This paper size is applicable to the national standard (CNS) A4 size of the paper towel (210 X 297 mm) Meaning -------- Order --------- line (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 1 4 1 A7 _ B7 V. Description of the Invention (M) (5) Next, the metal layer formed by the above (4) will have nothing to do with the following process. The same metal layer as the electrolytic plating film is formed by sputtering or the like. This is to improve the affinity with the electroless plating film. Specifically, it is preferable to provide a copper layer by a sputtering method. (6) Next, electroless plating is performed on the metal layer formed in (5) above. Copper electroplating is most preferable in terms of electroless plating. The film thickness of electroless plating is preferably 0.1 to 5 μm. The reason is that it can be removed by etching without impairing the characteristics of the conductor layer of the electrolytic plating performed later. (7) Then 'on the electroless plating film formed in (6) above. Into a coating. This anti-plating film 'is formed by laminating a photosensitive dry film and then exposing and developing it. (8) Next, an electroless plating film is used as the lead plating to perform electrolytic plating 'to thicken the conductor circuit. The electrolytic plating film is preferably 5 ~ 30 # m. (9) Next, after peeling off the anti-plating film, the electroless plating film located under the anti-plating film and at least one metal selected from metals in the 4th to 7th cycles selected from Group 4A to Group 1B The metal layer is removed by etching to obtain an independent conductor circuit. As for the etching solution, an aqueous solution of persulfate such as an aqueous solution of sulfuric acid-hydrogen peroxide, ammonia persulfate, sodium persulfate, potassium persulfate, etc .; an aqueous solution of ferric chloride, copper chloride; hydrochloric acid, nitric acid, hot dilute Sulfuric acid and so on. (10) Furthermore, if necessary, repeat the process of (2) ~ (9) above to obtain multiple layers. 33 This paper size applies Chinese National Standard (CNS) A4 specification (2) 0X 297 ϋ IIIIIIII n--1. I -d III-一 BJI —J n tt II--I {Please read the precautions on the back before filling this page) A7 4531 4 1 __B7__ 5. Multilayer printed circuit board of the invention description (VL). In the above description, the method for forming the conductor circuit is a semi-additive method, but a full-additive method may be used. This full-addition method is based on the formation of a thin metal layer on the surface of a polyolefin resin insulation layer by CVD or PVD, or a photosensitive dry film is laminated, or a liquid photosensitive resin is coated, and then exposed, developed An image process is performed to provide a plating resist, and then electroless plating is used to thicken the conductive circuit. The multilayer printed circuit board of the second group of the present invention sequentially forms a conductor circuit and a resin insulation layer on a substrate, and these conductor circuits are connected through a through hole to form a multilayer printed circuit board, wherein the above-mentioned resin insulation layer is formed by a ring Formed by olefin resin. According to the multilayer printed circuit board of the second group of the present invention, since the interlayer resin insulating layer is composed of a cycloolefin resin, its dielectric constant and dielectric loss are compared with the interlayer resin insulating layer made of epoxy resin. The factor is greatly reduced to prevent signal errors caused by delays in signal transmission and loss of electrical transmission of signals. In addition, the above cycloolefin-based resin has a mechanical property, particularly high rigidity, so that a conductor circuit can be formed on a strong interlayer resin insulation layer, and therefore, the reliability of the connection between the conductor circuits can be sufficiently ensured. In addition, since the cycloolefin-based resin has good adhesion to the conductor circuit, it is possible to prevent the interlayer resin insulation layer from being peeled from the conductor circuit, and to prevent cracking of the interlayer resin insulation layer due to peeling. 34 This paper size applies to the national standard (CNS) A4 specification (210 X 297 public love) ------^-1 ------- order ---- !! line (please read the note on the back first) Please fill in this page again for the matter} Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees of the Zou Intellectual Property Bureau Du 453 1 4 1 A7 -------- B7_ V. Description of Invention (4) The above-mentioned smoke-susceptible resins can improve the electrical insulation and reliability of conductor circuits because of their low water absorption. Although the types of the above-mentioned smoke-susceptibility resins are not particularly limited, the dielectric properties at 1 GHz The constant is below 0'3, the dielectric loss factor is preferably below 0.001, and the above-mentioned dielectric constant is more preferably between 2.4 and 2.7. By using such a low dielectric constant, it is possible to prevent signal transmission. The signal error caused by the delay of the signal and the loss of the electrical transmission of the signal. Also, the above-mentioned cyclic olefin resin is made of 2-ortho- spinane, 5-ethylidene-2-ortho-resin, or a derivative of these. It is preferable that the polymer is a single polymer or a copolymer. Examples of the derivative include the above-mentioned 2-ortho- spinane and the like. In olefins, a combination of an amino group used to form a crosslinked amino group, an anhydrous maleic acid residue, or a maleic acid denatured product, etc. As a monomer for synthesizing the aforementioned copolymer, Examples include ethylene, propylene, etc. The cycloolefin-based resin may be a mixture of two or more of the resins described above, and may contain a resin other than the cycloolefin-based resin. In the case of the cycloolefin-based resin copolymer, It is a block copolymer or a random copolymer. The above cycloolefin-based resin is preferably a thermosetting cycloolefin-based resin. Crosslinking formed by heating can obtain high rigidity, and The mechanical properties will also be improved. The glass transition temperature (Tg) of the cycloolefin-based resin is preferably 130 to 200. The cycloolefin-based resin can use a formed resin layer (film). 35 paper sizes are applicable. China National Standard (CNS) A4 Regulations (210 X 297 mm) — — — — — — III -in I — — I ^ »1 ----- I i I (Please read the precautions on the back again (Fill in this page) Shellfish Consumption, Intellectual Property Bureau, Ministry of Economic Affairs Du printed 4 53 1 4 1 at ____B7__ 5. Description of the Invention (β) It is also possible to use monomers or low molecular weight polymers with a certain molecular weight, or xylene, cyclohexane, etc. dispersed in a solvent and presented The state of the unhardened solution is also possible. For the resin layer, a so-called RCC (RESIN COATED COPPER) can also be used. The cycloolefin-based resin may be one that does not contain a filler or the like, However, it may also be a material containing a flame retardant such as aluminum hydroxide, manganese hydroxide, phosphate, etc. The following describes a method for manufacturing a multilayer printed wiring board using such a cycloolefin resin. (1) First, a circuit board having a lower-layer conductor circuit is fabricated on the surface of a resin substrate. The resin substrate is preferably a resin substrate having an inorganic fiber, and specific examples thereof include a glass fiber epoxy substrate, a glass fiber polyimide substrate, and a glass fiber bis-cis-butene diamidine triazapine Styrene resin substrate, glass fiber fluororesin substrate, etc. Alternatively, a copper-area laminate with copper foil applied to both sides of the substrate may be used. Usually, a through-hole is provided with a drill on this substrate, and electroless plating is applied to the wall surface of the through-hole and the surface of the copper foil to open the through-hole. For electroless plating, copper plating is preferred. Then, electrolytic plating may be performed to thicken the copper foil. For this electrolytic plating, copper plating is preferred. After that, the inner wall of the through hole is roughened, and the resin paste is filled in the through hole. The conductive layer covering the surface can also be formed by electroless plating or electrolytic plating. 36 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) lull .----- I--installation -------- order ------! (Please read the notes on the back before filling this page) Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 14 1 a? ___B7______ 5. Description of the invention (vs) As for the above roughening method, for example, Examples include blackening (oxidation) -reduction treatment, spray treatment with a mixed aqueous solution of organic acid and copper complex, or treatment with electroplated Cu-Ni-P needle alloy through the above process. The pattern of copper formed on the full substrate is firstly lithographically formed to form an anti-plating film, and then the underlying conductor circuit is formed by etching. After that, if necessary, the etched recessed portion forming the conductor circuit may be filled with a resin or the like. (2) Secondly, perform necessary roughening in forming the lower-level conductor circuit. As for the method of roughening treatment, the above-mentioned method may be adopted, that is, blackening (oxidation) _reduction treatment, spray treatment with a mixed aqueous solution of an organic acid and a copper complex, or electroplating may be mentioned. Treatment of Cu-Ni — P acicular alloy. Instead of roughening the underlying conductor circuit, the substrate forming the underlying conductor circuit may be immersed in a solution in which a resin component is dissolved, and a resin layer may be formed on the surface of the underlying conductor circuit so as to ensure a space therebetween. Adhesiveness of resin insulation layer. (3) Next, on both sides of the circuit substrate having the lower-layer conductor circuit produced in the above (2), an interlayer resin insulating layer made of the cycloolefin-based resin is formed. This interlayer resin insulating layer is formed by applying an unhardened liquid for forming a cycloolefin-based resin and then hardening it by heating or the like, or by applying a vacuum or reduced pressure to the resin layer while heating. In the method of laminating and laminating, it is preferable to laminate the resin layer by a method that is easy to start. The heating conditions at this time are preferably 100 to 200 ° C and 0.5 to 20 minutes. 37 This paper size applies to China National Standard (CNS) A4 specifications &lt; 210 X 297 mm) ------------ &quot; 'HtJ ----- 1 [I Order III I-- -(Please read the notes on the back before filling out this page). Printed by Shelley Consumer Cooperation, Intellectual Property Bureau, Ministry of Economic Affairs 4 53 1 41 A7 B7 V. Description of the invention (sand) Secondly, by interlayer resin insulation layer The laser light is irradiated to provide an opening for a through hole. At this time, as for the usable laser light, there are, for example, carbon dioxide (CCh) laser, ultraviolet laser, excimer laser, and the like. Among these, an excimer laser and a short-pulse carbon oxide laser are preferred. Excimer lasers can be used to form multiple openings for through-holes at one time by using masks for the through-holes formed in the opening-forming portions of through-holes, while short-pulse carbon dioxide lasers can make Resin residue is reduced 'and damage to the resin around the opening is reduced. The through hole of the mask must be perfectly round. This is because the point shape of the laser light becomes a perfect circle. Therefore, the diameter of the through hole is preferably left to right. When openings are formed with laser light, especially when a carbon dioxide laser is used, it is preferable to perform a decontamination treatment. The above-mentioned decontamination treatment can be performed using an oxidizing agent composed of an aqueous solution such as chromic acid, permanganate, and the like, and the treatment can also be performed using an oxygen plasma, a mixture of CR and oxygen, or a glow discharge. Furthermore, the surface may be improved by irradiating ultraviolet rays using a low-pressure mercury lamp. (5) For the interlayer resin insulating layer, a metal layer may be formed on the interlayer resin insulating layer without special roughening treatment or the like, or the surface may be roughened by plasma treatment or acid treatment. , And then forming a metal layer. When performing plasma treatment, in order to ensure the adhesion between the conductor circuit formed as the upper layer and the interlayer resin insulation layer, an intermediate layer can also be formed, and the intermediate layer is Ni, Ti, Pd with excellent adhesion to the interlayer resin insulation layer. And so on. The intermediate layer made of the above metal is sputtered and other physical evaporation methods. 38 This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) ------ * pack ---- Ί I --- Order · -------- line (please read the notes on the back before filling in this page) A7 453 1 4 1 __B7_ V. Description of the Invention (ί / Ι) (PVD method) is formed as Preferably, the thickness is preferably 0.1 to 2.0 μm. (6) After the above process, a thin film layer made of metal is formed. The material of the thin film layer is preferably copper or a copper-nickel alloy. The thin film layer may be formed by a physical vapor deposition method (PVD method) or a chemical vapor deposition method (CVD method), or may be formed by electroless plating. Specific examples of the PVD method or CVD method include the methods described in the first group of the present invention. The film thickness of this film is preferably 0.1 ~ 5 # m. The reason is that if such a film thickness is used, the performance of the plated conductor layer itself to be performed later will not be impaired, and the film can be removed by etching. (7) A plating resist is formed on the electroless plating film formed in the above (6). This resist is formed by laminating a photosensitive dry film, and then performing exposure and development processes. (8) Next, the metal thin film formed on the interlayer resin insulation layer is used as a conductive plating layer to perform electroplating to thicken the conductor circuit. The thickness of the plated film is preferably 5 to 30 / zm. In this case, the through-hole opening may be filled with a plated hole to form a hole structure. (9) After forming the electroplated film, the anti-plating film is peeled off, and the electroless plating film and the above intermediate layer existing under the anti-rust film are removed by etching to become a separate conductor circuit. For the above-mentioned electroplating, it is preferable to use copper plating. Examples of the etching solution include an aqueous solution of sulfuric acid-hydrogen peroxide, an aqueous solution of ammonium persulfate such as ammonia persulfate, sodium persulfate, and potassium persulfate; an aqueous solution of ferric chloride and copper chloride; hydrochloric acid, nitric acid, and heat. Dilute sulfuric acid and so on. In addition, the above-mentioned etching solution containing copper complex and organic acid can also be used, and the Chinese national standard (CNS &gt; A4 specification (210 X 297 mm) I-and ----- order) can be applied to the paper size of the conductor. .!-Line (please read the back of the page first; I will fill in this page before filling in this page) Consumer Cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs Du printed A7 ^ 53 1 4 1 __B7______ 5. Description of the invention (0) Etching between roads After forming the roughened surface β (10) at the same time, repeat the process of (2KK9) above to set the upper layer of the conductor circuit, set a solder mask on the top layer, and set a solder bump by opening the solder mask, for example, A multilayer printed circuit board with 3 layers on one side, that is, a double-sided layer with 6 layers, can be obtained. The multilayer printed circuit board in the third group of the present invention is formed on a substrate provided with a lower-layer conductor circuit, and an interlayer resin insulation layer and The multilayer printed circuit board of the upper-layer conductor circuit is characterized in that it is at least on the surface of the above-mentioned lower-layer conductor circuit (hereinafter, simply referred to as the conductor circuit β, and the metal layer mentioned later can also be formed on the upper-layer conductor. Circuit, following, In the description of the third group of the present invention, the conductor circuit includes a lower-layer conductor circuit and an upper-layer conductor circuit as long as there is no particular limitation, and is formed of at least one metal selected from Ni, Co, Sn, and precious metals. A metal layer, and a roughened layer made of Cu-Ni-P is formed on the metal layer.

依本發明之第三群的構成，由於在上述導體電路的表 面形成有擇自Ni、Co、Sn以及貴金屬中至少1種的金屬所 成之金屬層(被覆層），當將外露有導體電路表面粗化層的 基板以酸處理之時，由於構成導體電路的銅及Cu - Ni-P 合金間的局部電池反應被抑制，乃可阻止導體電路的溶解 〇 又，上述金屬層的表面，容易析出Cu-Ni-P所成之 合金，故即使鍍液變質，由於不會有電鍍物未析出的情形 ，乃能確實地於導體電路上形成由Cu-Ni-P所成之針狀 合金的粗化層。 40 本紙張尺度適用t國圉家標準（CNS)A4規格（210 X 297公釐） I I I -農---------訂-------- -線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 r 4 53 Μ 1 Α7 ______Β7 _ 五、發明說明（&gt;1) 又，上述金屬層，因其亦具有銅所成之導體電路的蝕 刻遮膜的功能，可防止導體電路的過度蝕刻。 上述金屬層，係形成於導體電路的上面，或是上面及 側面。又，上述金屬層及粗化層不一定要形成於導體電路 的全面上。因此，例如有時於最上層的導體電路上並無形 成上述金屬層及粗化層。 就上述金屬層所使用之金屬而言，除Ni、Co ' Sn以 外，可舉出例如Au、Ag、Pt、Pd等貴金屬。因此，上述金 屬層中，可使用擇自上述金屬及上述貴金屬中至少1種以 上之金屬。 上述金屬層的厚度，以0.1〜3//m爲宜。若未達0.1#m ，則無法抑制局部電池反應，若超過3μπ!的厚度’則導 體電路本身的厚度會增加，由於層間樹脂絕緣層亦增厚之 故，欲形成小直徑的通孔會變得困難。層間樹脂絕緣層的 厚度較薄時，較容易成小直徑的通孔。According to the structure of the third group of the present invention, since a metal layer (coating layer) made of a metal selected from at least one of Ni, Co, Sn, and a noble metal is formed on the surface of the conductor circuit, the conductor circuit is exposed. When the substrate with the roughened surface is treated with an acid, the local battery reaction between copper and Cu-Ni-P alloy constituting the conductor circuit is suppressed, which prevents the dissolution of the conductor circuit. Furthermore, the surface of the metal layer is easy The alloy formed by Cu-Ni-P is precipitated, so even if the plating solution is deteriorated, there is no case where the electroplated substance is not precipitated, and the needle-shaped alloy made of Cu-Ni-P can be reliably formed on the conductor circuit. Coarse layer. 40 This paper size is applicable to the National Standard (CNS) A4 (210 X 297 mm) III-Agricultural --------- Order -------- -Line (Please read the back first Please note this page, please fill in this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed r 4 53 Μ 1 Α7 ______ Β7 _ V. Description of the invention (&gt; 1) Also, the above metal layer Because it also has the function of an etching mask for a conductor circuit made of copper, it can prevent excessive etching of the conductor circuit. The above-mentioned metal layer is formed on the upper surface of the conductor circuit, or on the upper and side surfaces. The metal layer and the roughened layer need not be formed on the entire surface of the conductor circuit. Therefore, for example, the metal layer and the roughened layer may not be formed on the uppermost conductor circuit. Examples of the metal used in the metal layer include, in addition to Ni and Co'Sn, noble metals such as Au, Ag, Pt, and Pd. Therefore, in the metal layer, at least one metal selected from the above metals and the above noble metals can be used. The thickness of the metal layer is preferably 0.1 to 3 // m. If it is less than 0.1 # m, local battery reactions cannot be suppressed. If the thickness exceeds 3μπ !, the thickness of the conductor circuit itself will increase. As the interlayer resin insulation layer is also thickened, the through-holes to be formed with small diameters will change. Got difficult. When the thickness of the interlayer resin insulating layer is thin, it is easier to form a small-diameter through hole.

Cu-Ni - Ρ所成之針狀合金的粗化層，其全體的厚度 以1〜7 jcnri爲宜。 在達到上述厚度的情形下，層間樹脂絕緣層的間隔以 及導體電路的間隔將可比習知之多層印刷電路板小，而能 達成多層印刷電路板的高密度化及輕量化。The thickness of the roughened layer of the needle-like alloy made of Cu-Ni-P is preferably 1 to 7 jcnri. When the thickness is as described above, the distance between the interlayer resin insulating layers and the distance between the conductor circuits can be smaller than that of a conventional multilayer printed circuit board, and the density and weight of the multilayer printed circuit board can be increased.

Cu-Ni-P所成之合金的粗化層的形狀，以針狀及多 孔質狀爲宜。將上述粗化層以電鎞處理而形成之時’上述 粗化層的形狀，會隨界面活性劑的種類而變化’然欲形成 針狀或多孔質狀之粗化層時，則必須對其條件加以選定之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公芨&gt; - -----I---j -農-----II 訂·--I ---i -線 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 d53 1 4 1 A7 ___B7__ 五、發明說明（W) α 又，上述Cu-Ni-Ρ所成之合金之粗化層表面，乃希 望形成離子化傾向較Cu爲高且在D以下之金屬所成之金 屬層，或是形成由貴金屬所成之被覆層(以下，稱爲粗化層 被覆層）。又，此粗化層被覆層的厚度，以爲佳 〇 藉由這些金屬之粗化層被覆層的形成，可防止電解質 容易與粗化層之直接接觸。又，由於這些金屬層本身會被 氧化而形成緻密的氧化膜，乃可防止粗化層或是導體電路 的溶解。 就離子化傾向較Cu爲高且在Ή以下之金屬而言’可 舉出例如 Ti、A卜 Zn、Fe、In、Tl、Co、Ni、Sn、Pb、Bi 等。又，就上述貴金屬而言，可舉出例如Au ' Ag、Pt ' Pd 等。而上述粗化層被覆層即可擇自上述金屬及上述貴金屬 中至少1種來使用。又這些金屬當中，特別以Sn爲所希望 者。因爲Sn經過無電解置換電鍍可形成薄層，故可沿著 粗化層之凹凸處進行析出形成。 使用上述金屬中的Sn時，使用到氟硼化錫一硫脲液或 是氯化錫-硫脲液。此時，藉由Cu—Sn置換反應可形成 0.01~2em左右的Sn層。又，使用貴金屬之時，亦可採用 濺鍍、蒸鍍等方法或藉由簡單的置換形式的電鍍液進行電 鍍處理等方法。 本發明中之導體電路被覆層’可藉由電鍍、無電解鍍 敷、濺鍍、蒸鍍法等形成之。 42 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱&gt; 11 ^ ^ ^ ^ 11- -I n ^ I -II Ϊ ^ .1 ^ ^ ^ ^ ^ I* H I HI, (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局貝工消費合作社印製 4 53141 A7 B7 五、發明說明（Μ ) 在實施無電解鍍鎳之時，可使用10〜50 g/1氯化鎳、 5〜20 g/Ι次亞磷酸鈉、30-60 g/Ι羥基醋酸鈉所成之水溶液， 或是使用10〜50 g/Ι氯化鎳、5~20 g/Ι次亞磷酸鈉、5〜20 g/1 檸檬酸所成之水溶液。 在實施電鍍鎳之時，可使用1〇〇〜300 g/Ι硫酸鎳、 10-60 g/Ι氯化鎳、10〜50 g/Ι硼酸所成之水溶液。 在實施電鍍錫之時，可使用〇.1~〇.5 mol/1檸檬酸鈉、 0.01 〜0.08 mol/1 EDTA、0.0卜0.08 mol/Ι 氯化錫、 0.01〜0.05mol/l氯化鈦所成之水溶液。 在實施電鍍鈷之時，可使用0.1〜1.0 mol/ι氯化鈷、 0.1〜0.5 mol/1次亞磷酸鈉、0.5〜2.0 mol/1酒石酸鈉、0.5~2.0 mol/1氯化氨所成之水溶液β 又，在實施電鍍鈀之時，可使用1〜10 g/l四鈀氯化物 ' 10-50 g/1 EDTA ' 100〜500 g/1 氨、0.1-1.0 g/1 聯氨所成 之水溶液。 接著，針對本發明之第三群中，於導體電路的表面使 Cu - Ni-P所成之合金鍍層析出成長以形成粗化層之電鍵 方法說明之》 本發明之第三群，係將形成有下層導體電路之基板， 浸漬於含有例如錯化劑、銅化合物、鎳化合物、次亞磷酸 塩、含有乙烯之聚氧化乙烯系界面活性劑所成之電鍍水溶 液中，藉由對基板予以振動或搖動的方法，或是供給金屬 離子，以析出成長Cu_Ni-P所成之針狀或多孔質狀合金 ，而形成以被覆層及粗化層構成之合金粗化層。又，電鍍 43 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公釐） 11 -------1--1---------訂·-------線 (請先閱讀背面之注意事項再填寫本頁) A7 B7 453 1 4 1 五、發明說明（&amp;V) 水溶液中，銅離子濃度、鎳離子濃度、次亞磷酸離子濃度 、錯化劑濃度，其分別調整至0.007〜0.160削1/1、 0.001~0.023 mol/1、0‘1〜1.0 mol/1、0.01~0.2 mol/1 爲宜 β 就上述錯化劑而言，可舉出例如檸檬酸、酒石酸、蘋 果酸、EDTA、乙二胺、甘氨酸等。 就含有乙烯之聚氧化乙烯系界面活性劑而言，使用具 有以下(2)式或(3)式構造之物爲最佳。就此界面活性劑而言 ，可舉出例如2，4, 7, 9—四甲基一5—癸院 一4, 7 —二醇 、3, 6—二甲基一 4—辛炔-3, 6 —二醇等炔二醇。就這些的 市售品而言，可舉出例如日信化學工業製造之沙費諾魯 104(多孔質狀）、同440、同465、同485 (皆爲針狀)等。The shape of the roughened layer of the alloy made of Cu-Ni-P is preferably acicular or porous. When the roughened layer is formed by an electric treatment, the shape of the roughened layer may vary depending on the type of the surfactant. However, when a needle-like or porous roughened layer is to be formed, it is necessary to The paper size selected according to the conditions applies to the Chinese National Standard (CNS) A4 specification (210 X 297 males &gt;------ I --- j-Nong ----- II Orders --- I- -i -line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs d53 1 4 1 A7 ___B7__ V. Description of Invention (W) α The surface of the roughened layer of the alloy is intended to form a metal layer made of a metal having a higher ionization tendency than Cu and below D, or a coating layer made of a noble metal (hereinafter, referred to as a roughened layer coating). The thickness of the coating layer of the roughened layer is preferably 0. By forming the coating layer of the roughened layer of these metals, it is possible to prevent the electrolyte from being in direct contact with the roughened layer. Also, because the metal layer itself may Being oxidized to form a dense oxide film can prevent the roughened layer or the dissolution of the conductor circuit. Examples of metals having a higher protonation tendency than Cu and below Ή include, for example, Ti, Ab, Zn, Fe, In, Tl, Co, Ni, Sn, Pb, Bi, and the like. As for the above noble metals, Examples include Au 'Ag, Pt' Pd, etc. The roughened layer coating layer can be selected from at least one of the above metals and the above noble metals. Among these metals, Sn is particularly desirable. Since Sn can be formed into a thin layer by electroless displacement plating, it can be deposited along the rough surface of the roughened layer. When using Sn in the above metals, tin fluoboride-thiourea solution or tin chloride is used- A thiourea solution. At this time, a Sn layer of about 0.01 to 2em can be formed by a Cu-Sn substitution reaction. In addition, when a precious metal is used, sputtering, vapor deposition, or other methods can be used or a simple plating method can be used. The plating method of the conductive circuit in the present invention can be formed by electroplating, electroless plating, sputtering, vapor deposition, etc. 42 This paper size is applicable to China National Standard (CNS) A4 specifications ( 210 X 297 Public Love &gt; 11 ^ ^ ^ ^ 11- -I n ^ I -II Ϊ ^ .1 ^ ^ ^ ^ ^ I * HI HI, (Please read the notes on the back before filling out this page) Printed by Shelley Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs, 4 53141 A7 B7 V. Description of Invention (Μ) When electroless nickel plating An aqueous solution of 10-50 g / 1 nickel chloride, 5-20 g / 1 sodium hypophosphite, 30-60 g / 1 sodium glycolate can be used, or 10-50 g / 1 nickel chloride, An aqueous solution of 5-20 g / 1 sodium phosphite and 5-20 g / 1 citric acid. When nickel plating is performed, an aqueous solution made of 100 to 300 g / 1 nickel sulfate, 10 to 60 g / 1 nickel chloride, and 10 to 50 g / 1 boric acid can be used. When tin plating is performed, 0.1 to 0.5 mol / 1 sodium citrate, 0.01 to 0.08 mol / 1 EDTA, 0.0 to 0.08 mol / l tin chloride, and 0.01 to 0.05 mol / l titanium chloride can be used. The resulting aqueous solution. When cobalt plating is performed, it can be formed by using 0.1 to 1.0 mol / ι cobalt chloride, 0.1 to 0.5 mol / 1 sodium phosphite, 0.5 to 2.0 mol / 1 sodium tartrate, and 0.5 to 2.0 mol / 1 ammonia chloride. The aqueous solution β can be used in the plating of palladium, 1 ~ 10 g / l tetrapalladium chloride '10-50 g / 1 EDTA' 100 ~ 500 g / 1 ammonia, 0.1-1.0 g / 1 hydrazine成 的 水。 Into an aqueous solution. Next, according to the third group of the present invention, a method for forming an alloy bond formed by Cu-Ni-P electroplating on the surface of a conductor circuit to form a roughened layer is described. A third group of the present invention is to form The substrate having the lower-layer conductor circuit is immersed in an electroplating aqueous solution containing, for example, a dissolving agent, a copper compound, a nickel compound, rhenium hypophosphite, and a polyethylene oxide-based surfactant containing ethylene, and the substrate is vibrated or The method of shaking or supplying metal ions to precipitate a needle-like or porous alloy formed by growing Cu_Ni-P to form an alloy roughened layer composed of a coating layer and a roughened layer. In addition, the paper size of 43 paper is applicable to the national standard (CNS) A4 specification (210 X 297 mm). 11 ------- 1--1 --------- Order · --- ---- Line (Please read the precautions on the back before filling this page) A7 B7 453 1 4 1 V. &amp; Invention (&amp; V) Copper ion concentration, nickel ion concentration, hypophosphite ion concentration, The correcting agent concentration is adjusted to 0.007 ~ 0.160 and 1/1, 0.001 ~ 0.023 mol / 1, 0'1 ~ 1.0 mol / 1, and 0.01 ~ 0.2 mol / 1, respectively. As for the above-mentioned correcting agents, Examples thereof include citric acid, tartaric acid, malic acid, EDTA, ethylenediamine, and glycine. As the polyethylene oxide-based surfactant containing ethylene, it is preferable to use a substance having the following formula (2) or (3) structure. Examples of the surfactant include 2,4,7,9-tetramethyl-1,5-decane-1,4,7-diol, 3,6-dimethyl-1,4-octyne-3, 6-diols such as acetylene glycols. These commercially available products include, for example, Safenolol 104 (porous), 440, 465, and 485 (all needle-shaped) manufactured by Nissin Chemical Industry.

Ch〇-(c2h4o)J --------1----袭------—訂-----J --- (諳先閱讀背面之注意事項再填寫本頁) ⑵ ch3 ΌΗCh〇- (c2h4o) J -------- 1 ---- Attack ------- Order ----- J --- (谙 Please read the precautions on the back before filling in this page ) ⑵ ch3 ΌΗ

Rl R2 經濟部智慧財產局員工消费合作社印製Rl R2 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

HO-C-c=C~C-〇H R3 R4 (3) (上述(2)式中，m, 1之和係爲3~30的整數’上述(3)式 中，化及R2係爲烷基，I及1所示係爲氫原子或是低碳 烷基。） 由此種無電解鍍敷液所析出之Cu-Ni-P合金，其表 44 本紙張尺度適用中國國家標平（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 4 53141 a7 __B7___ 五、發明說明（呐） 面係成爲針狀或多孔質狀。就多孔質合金而言，其微孔的 數目，在lcm2爲100,000~1，000,〇〇〇之範圍，而—般爲 3,000,000〜300,000,000之範圍。又，其微孔的直徑，爲 0.01〜100//m之範圍，而一般爲0.1〜l〇#m之範圍。 本發明之第三群中，就於上述導體電路上形成之層間 樹脂絕緣層而言，以使用無電解鍍敷用黏著劑爲佳。此無 電解鍍敷用黏著劑，係爲硬化處理過之酸或是氧化劑中可 溶性的耐熱性樹脂粒子，又以在酸或氧化劑中其分散於難 溶性之未硬化的耐熱性樹脂中所成者爲最佳。藉由對酸或 是氧化劑之溶液的處理，可溶解去除掉耐熱性樹脂粒子， 而可於此黏著劑之表面形成章魚壺狀錨定物構成之粗化面 〇 於上述無電解鍍敷用黏著劑之中，特別是就經過硬化 處理之上述耐熱性樹脂粒子而言、以1)平均粒徑在lOym 以下之耐熱性樹脂粉末、2)由相對平均粒徑大的粒子與相 對平均粒徑小的粒子混合所得之粒子爲佳。其原因係這些 物質可形成更爲複雜的錨定物。 就可使用之耐熱性樹脂而言，可舉出例如環氧樹脂、 聚醯亞胺樹脂、環氧樹脂與熱可塑性樹脂的複合體等◊就 複合之熱可塑性樹脂而言，可舉出例如聚醚磺(PES)等。又 ’就溶解於酸或是氧化劑之溶液的耐熱性樹脂粒子而言， 可舉出例如環氧樹脂(特別以胺系硬化劑使其硬化之環氧樹 脂爲佳）、胺樹脂等。 又’就本發明之第三群所使用之防焊劑而言，可舉出 45 本紙張尺度適用中國國家標举（CNS)A4規格（21〇 X 297公爱） I ----------------— I 訂------I 11½^. (請先M讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消費合作社印製 453 14 1 A； __B7___ 五、發明說明（4) 例如環氧樹脂丙烯酸酯及咪唑硬化劑所成之物。 其次，針對本發明之第三群之多層印刷電路板的製造 方法說明之。 (1) 首先，於核心基板的表面處製作形成有內層銅圖案( 下層導體電路)的電路基板。 此時，可使用本發明之第一群或是本發明之第二群所 記載之方法以相同的方法製作電路基板。 (2) 其次，於上述(1)製作的電路基板上’形成層間樹脂 絕緣層。特別是就本發明之第三群而言，做爲層間樹脂絕 緣層的材料，則以使用前述之無電解鍍敷用黏著劑爲佳。 (3) 將形成之無電解鍍敷用黏著劑層乾燥之後’依其必 要設置通孔形成闬之開口。若爲感光性樹脂，則於曝光、 顯像之後進行熱硬化，而爲熱硬化性樹脂的情形’則於熱 硬化後進行雷射加工，藉此於上述層間樹脂絕緣層設置通 孔形成用之開口。 (4) 其次，將存在於已硬化之上述無電解鍍敷用黏著劑 層(層間樹脂絕緣層)之表面的對酸或氧化劑爲可溶性的樹 脂粒子，藉由酸或氧化劑溶解去除之，以粗化無電解鏟敷 用黏著劑層之表面。 此處，就上述之酸而言，可舉出例如磷酸、鹽酸、硫 酸等無機酸；蟻酸、醋酸等有機酸，特別是以使用有機酸 爲佳。若使用有機酸，則於粗化處理之時，可使自通孔露 出之金屬導體層較難被腐蝕。 另一方面，就上述氧化劑而言，以使用鉻酸、過錳酸 46 本紙張尺度適用中國國家標準（CNS&gt;A4規格（210 X 297公釐） 裝· —. —i訂-------—線 &lt;請先閱讀背面之注意事項再填寫本頁) ^531 4 1 A7 B7____ 五、發明說明（以） 鹽(過錳酸鈣)之水溶液爲佳。 (5) 其次，將已粗化之層間樹脂絕緣層表面的電路基板 賦予觸媒核。 所賦予之觸媒核，以使用貴金屬離子或貴金屬膠體爲 佳，一般而言，係使用氯化鈀或鈀膠體。又’爲固定觸媒 核乃以進行加熱處理爲佳。就此種觸媒核而言則以紀爲佳 〇 (6) 其次，於賦予觸媒核之層間樹脂絕緣層表面施以無 電解鍍敷，而於粗化面的全面上形成無電解鍍敷膜。無電 解鍍敷膜的膜厚，以0.54# m爲佳。 其次，於無電解鏟敷膜上形成防鍍膜。 (7) 其次，於防鍍膜非形成部施以厚度5〜20^m的電鑛 ，以形成上層導體電路及通孔。 此處，就上述電鍍而言，以使用鍍銅爲佳。 又，將金屬層及無電解鍍敷膜蝕刻之時形成有電阻層 之擇自见、Co、Sn以及貴金屬中至少1種的金屬所成之金 屬層。 又，將防鍍膜去除之後，將存在於該防鍍膜下之無電 解鍍敷膜以硫酸及過氧化氫之混合液或過硫酸鈉、過硫酸 氨等水溶液所成之蝕刻液溶解去除，以做爲獨立之導體電 路。 由於擇自Ni、Co、Sn以及貴金屬中至少1種的金屬所 成之金屬層的形成係做爲電阻層之故，由銅所成之上層導 體電路乃不施予蝕刻。 47 本紙張尺度適用t國國家標準（CNS)A4規格（21〇 X 297公爱） I II--I I I ---I I - — — — I — — — ^ i ---I --- (請先Μ讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 B7 4 5 3 14. 五、發明說明（A ) 又，擇自Ni、Co、Sn以及貴金屬中至少1種的金屬所 成之金屬層可在設置獨立之上層導體電路及通孔後，於上 層導體電路及通孔的側面及上面形成之。 (8) 接著，於形成有擇自犯、Co、Sn以及貴金屬中至 少1種的金屬所成之金屬層的上層導體電路上面，形成多 孔質Cu— Ni-P所成之合金的粗化層。 由於上述金屬層的表面容易發生氧化還原反應，故容 易析出Cu — Ni_ P所成之合金。 (9) 其次，就此基板上之層間樹脂絕緣層而言，係形成 無電解鍍敷用黏著劑層。 (10) 再者，重複上述(3)〜(8)的過程設置上層之上層導體 電路，可得到單面3層，即雙面6層之多層印刷電路板。 上述(3H8)的過程中，在設置通孔形成用之開口後， 係將表面以鉻酸粗化，又鉻酸處理亦可防止導體電路的溶 解。 又，以上之說明，其例子雖以所謂之半加成法製造多 層印刷電路板，然亦可於粗化無電解鍍敷用黏著劑層後， 賦予觸媒核、設置防鍍膜，再進行無電解鍍敷以形成導體 電路，即所謂之全加成法亦可適用。 本發明之第四群之多層印刷電路扳的製造方法，係於 樹脂基板上形成有樹脂絕緣層及導體電路之製造方法中， 其特徵爲，上述樹脂絕緣層的表面係設有擇自屬於長週期 型之週期表的第4A族~第1B族範圍之第4〜第7週期的金 屬、A1以及Sn之中至少一種以上的金屬以形成金屬層後 48 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I -------!!-農----- 訂·--1!1_線 (請先®讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消费合作社印製 453 1 4 1 A7 B7 _ 五、發明說明（^) ，將上述金屬層表面以酸洗淨，接著於上述金屬層上形成 導體電路。 依據本發明之第四群知上述的構成，於上述樹脂絕緣 層的表面上形成金屬層後，將上述金屬層表面以酸洗淨而 去除氧化膜。因此，可使金屬層上形成之導體電路與上述 金屬層堅固地密接，而防止導體電路的剝離。 又，由於在上述樹脂絕緣層不需要形成粗化面，故其 表面爲平坦的。因此，由於在樹脂絕緣層上形成之導體電 路的下面不存在有粗化面，而爲平坦之故，不會發生訊號 傳送的延遲。 於上述樹脂絕緣層表面形成金屬層之時，較佳者係使 用擇自 Ni、Cr、Mo、Ti、W、Cu、AL· Sn、Pt、Pd 以及 An 之中至少一種以上的金屬。因此，上述金屬層，可爲上述 金屬之中單一金屬所成之層，亦可爲2種以上金屬所成合 金層。 於本發明之第四群中，就上述金屬層的形成方法而言 ，可舉出例如物理蒸鍍法(PVD法）、化學蒸鍍法(CVD法：) 、電鍍、無電解鍍敷等。 就具體之上述物理蒸鍍法及化學蒸鍍法而言，可舉出 本發明之第一群所記載之方法。 以上述之酸進行洗淨時酸的種類雖無特別之限定，較 佳者係擇自鹽酸、硫酸、醋酸、磷酸之中至少一種以上的 酸或是混酸。 酸的洗淨溫度，由於在25〜60°C其洗淨能力高故爲所 49 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I--------裝 — I — 訂--------線 (請先閱讀背面之泫意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 453 1 4 1 ___B7______ 五、發明說明（αί ) 希望者。 上述合金層的厚度，以0.1〜2.0/im爲佳。若較0.1#m 爲薄時，欲藉由電鍍以形成金屬層會變得困難，又，密接 性的效果也低。另一方面，若超過2.0#πι時，蝕刻會變得 困難。 於本發明之第四群中所形成之樹脂絕緣層，較佳係由 熱硬化性樹脂、熱可塑性樹脂，或是這些的複合樹脂所構 成。 就熱硬化性樹脂而言，較佳者係例如擇自熱硬化性聚 烯烴樹脂、環氧樹脂、聚醯亞胺樹脂、苯酚樹脂、雙順丁 烯二醯胺三氮雜苯樹脂中至少一種加以使用。 就熱可塑性樹脂而言，較佳者係使用例如聚甲基丙烯 (ΡΜΡ)、聚苯乙烯(PS)、聚醚磺(PES)、聚苯醚(ΡΡΕ)、聚苯 撐硫(PPS)等。 於本發明之第四群之多層印刷電路板中，就樹脂基板 而言，係使用於樹脂基板上直接形成導體電路之基板’又 於其上可分別設置1層之樹脂絕緣層及導體電路，或是亦 可設置2層以上。或者，使用不形成導體電路之樹脂基板 ，又於其上可分別設置1層之樹脂絕緣層及導體電路’或 是亦可設置2層以上。又，上述樹脂絕緣層及上述導體電 路，可設置於樹脂基板的單面，亦可設置於樹脂基板的兩 面。 以下，就本發明之第四群之多層印刷電路板的製造方 法的一例加以說明。 50 本紙張尺度適用中國固家標準（CNS)A4規格（2]〇χ 297公芨） — — —— —---- ------------tr----— --- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局貝工消費合作社印製 A7 453 1 4 1 ____B7___ 五、發明說明（叫） (1) 首先，於樹脂基板的表面製作具有下層導體電路的 電路基板。 此時，可使用與本發明之第一群及本發明之第二群記 載之方法相同的方法製作電路基板。 (2) 在上述（1)製作之具有下層導體電路的電路基板的兩 面形成樹脂絕緣層。此樹脂絕緣層之功用係做爲多層印刷 電路板之層間樹脂絕緣層。 此樹脂絕緣層係藉由塗佈未硬化劑，再將薄膜狀之樹 脂熱壓積層所形成者。 (3) 其次，於形成之樹脂絕緣層(以下稱爲層間樹脂絕緣 層）中，爲確保其與下層導體電路的電連接而設置通孔形成 用開口。 此開口穿孔的進行，係以光微影技術之曝光顯像處理 或是雷射光的照射。此時，所使用之雷射光，可舉出例如 二氧化碳雷射、紫外線雷射、準分子雷射等。 若以二氧化碳雷射光穿孔時，則進行去污處理。此去 污處理可使用由鉻酸、過錳酸鹽等之水溶液所成之氧化劑 來進行，又此處理亦可用氧電漿、Ch及氧的混合物電漿或 是輝光放電等來進行。又，藉由使用低壓水銀燈照射紫外 線，亦可進行表面改良。 特別是藉由Ch及氧的混合物電漿進行處理，可於樹 脂表面引入羥基及羰基等親水性基。若於層間樹脂絕緣層 進行上述處理，將可改善與之後形成之金屬層的密接性1 此爲有利的。 51 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 ------装------訂---------線 (請先W讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 _____B7___ 五、發明說明（9)HO-Cc = C ~ C-〇H R3 R4 (3) (In the above formula (2), the sum of m and 1 is an integer from 3 to 30. In the above formula (3), R2 and R2 are alkyl groups. , I and 1 are hydrogen atoms or lower alkyl groups.) For the Cu-Ni-P alloy precipitated by this electroless plating solution, its table 44 is applicable to China National Standards (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53141 a7 __B7___ 5. Description of the invention (na) The surface becomes needle-like or porous. In the case of a porous alloy, the number of micropores is in the range of 100,000 to 1,000, 000, and generally in the range of 3,000,000 to 300,000,000. The diameter of the micropores is in the range of 0.01 to 100 // m, and is generally in the range of 0.1 to 10 # m. In the third group of the present invention, the interlayer resin insulating layer formed on the conductor circuit is preferably an electroless plating adhesive. This adhesive for electroless plating is formed by dissolving heat-resistant resin particles that are soluble in hardened acid or oxidizing agent and dispersing in acid or oxidizing agent in hardly soluble non-hardening heat-resistant resin. For the best. By treating the solution of acid or oxidant, the heat-resistant resin particles can be dissolved and removed, and the roughened surface composed of octopus pot-shaped anchors can be formed on the surface of this adhesive. Adhesion for the above electroless plating Among the agents, especially for the above heat-resistant resin particles that have undergone hardening treatment, 1) the heat-resistant resin powder having an average particle diameter of 10 μm or less, and 2) the particles having a relatively large average particle diameter and a relatively small average particle diameter The particles obtained by mixing the particles are preferred. The reason is that these substances can form more complex anchors. Examples of heat-resistant resins that can be used include epoxy resins, polyimide resins, and composites of epoxy resins and thermoplastic resins. Examples of composite thermoplastic resins include polymer resins. Ether Sulfur (PES), etc. Examples of the heat-resistant resin particles dissolved in a solution of an acid or an oxidizing agent include epoxy resins (especially epoxy resins which are hardened with an amine hardener), amine resins, and the like. Also, as far as the solder resist used in the third group of the present invention is concerned, 45 paper sizes can be cited as applicable to the Chinese National Standards (CNS) A4 specification (21〇X 297 public love) I ------- ---------— Order I ------ I 11½ ^. (Please read the notes on the back before filling in this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs 453 14 1 A; __B7___ 5. Description of the invention (4) For example, made of epoxy acrylate and imidazole hardener. Next, a method for manufacturing a multilayer printed circuit board according to the third group of the present invention will be described. (1) First, a circuit board having an inner layer copper pattern (lower conductor circuit) formed on the surface of the core substrate is prepared. In this case, the circuit board can be produced by the same method using the method described in the first group of the present invention or the second group of the present invention. (2) Next, an interlayer resin insulating layer is formed on the circuit substrate 'produced in the above (1). In particular, in the third group of the present invention, as the material of the interlayer resin insulating layer, it is preferable to use the aforementioned adhesive for electroless plating. (3) After the formed adhesive layer for electroless plating is dried ', an opening for forming a through hole is provided as necessary. In the case of a photosensitive resin, thermal curing is performed after exposure and development, and in the case of a thermosetting resin, 'laser processing is performed after thermal curing, thereby providing through-hole formation for the interlayer resin insulating layer. Opening. (4) Next, the resin particles which are soluble in acid or oxidizing agent, which are present on the surface of the hardened adhesive layer for electroless plating (interlayer resin insulating layer), are dissolved and removed by dissolving the acid or oxidizing agent, and the coarse The surface of the adhesive layer for electroless shovel application. Here, examples of the above-mentioned acids include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; and organic acids such as formic acid and acetic acid. In particular, organic acids are preferably used. If an organic acid is used, the metal conductor layer exposed from the through hole can be hardly corroded during the roughening treatment. On the other hand, as far as the above oxidants are concerned, the use of chromic acid and permanganic acid 46 paper standards are applicable to Chinese national standards (CNS &gt; A4 specifications (210 X 297 mm)). --- line &lt; Please read the precautions on the back before filling this page) ^ 531 4 1 A7 B7____ 5. Description of the invention (to) Aqueous solution of salt (calcium permanganate) is better. (5) Secondly, the circuit board on the surface of the roughened interlayer resin insulating layer is provided with a catalyst core. The catalyst core provided is preferably a noble metal ion or a noble metal colloid. Generally, a palladium chloride or a palladium colloid is used. It is preferable to use a heat treatment as the fixed catalyst core. For this type of catalyst core, the period is better. (6) Next, electroless plating is applied to the surface of the interlayer resin insulation layer provided to the catalyst core, and an electroless plating film is formed on the entire surface of the roughened surface. . The thickness of the electroless plating film is preferably 0.54 # m. Next, a plating resist is formed on the electroless shovel coating. (7) Next, apply a thickness of 5 to 20 ^ m to the non-formed portion of the anti-plating film to form an upper-layer conductor circuit and a via. Here, for the above-mentioned electroplating, it is preferable to use copper plating. In addition, when the metal layer and the electroless plating film are etched, a metal layer made of at least one selected from the group consisting of Co, Sn, and a noble metal is formed as a resistance layer. In addition, after the anti-plating film is removed, the electroless plating film existing under the anti-plating film is dissolved and removed by using an etching solution made of a mixed solution of sulfuric acid and hydrogen peroxide or an aqueous solution such as sodium persulfate and ammonia persulfate to make It is an independent conductor circuit. Since a metal layer made of at least one of Ni, Co, Sn, and a precious metal is used as the resistance layer, the upper conductor circuit made of copper is not etched. 47 This paper size applies to the national standard (CNS) A4 specification (21〇X 297 public love) I II--III --- II----I---^ i --- I --- (Please Read the notes on the back before filling in this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 4 5 3 14. V. Description of the Invention (A) Also select at least 1 of Ni, Co, Sn and precious metals The metal layer formed by the metal can be formed on the side and top of the upper conductor circuit and the via hole after the independent upper conductor circuit and the via hole are provided. (8) Next, a roughened layer of an alloy made of porous Cu—Ni-P is formed on the upper conductor circuit on which a metal layer made of at least one of selective metals, Co, Sn, and precious metals is formed. . Since the surface of the metal layer is liable to undergo a redox reaction, it is easy to precipitate an alloy made of Cu—Ni_P. (9) Next, the interlayer resin insulating layer on the substrate is formed as an adhesive layer for electroless plating. (10) Furthermore, repeat the process of (3) to (8) above to set the upper-layer and upper-layer conductor circuit, to obtain a multilayer printed circuit board with 3 layers on one side, that is, 6 layers on both sides. In the above process (3H8), after the opening for forming the through hole is provided, the surface is roughened with chromic acid, and the chromic acid treatment can also prevent the dissolution of the conductor circuit. In addition, although the above description is an example of manufacturing a multilayer printed circuit board by a so-called semi-additive method, it may be provided with a catalyst core and an anti-plating film after roughening the adhesive layer for electroless plating, and then performing the Electrolytic plating to form conductor circuits, the so-called full-addition method, is also applicable. A method for manufacturing a multilayer printed circuit board according to a fourth group of the present invention is a method for manufacturing a resin insulation layer and a conductor circuit on a resin substrate, characterized in that the surface of the resin insulation layer is provided with a selective length. Periodic Periodic Table Periodic Table 4A to 1B Groups 4 to 7 Period Metals, at least one metal among A1 and Sn to form a metal layer 48 This paper size applies Chinese National Standards (CNS) A4 specification (210 X 297 mm) I ------- !!-Agriculture ----- Order · -1-1 1_line (Please read the precautions on the back before filling this page) Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau 453 1 4 1 A7 B7 _ V. Description of the Invention (^), the surface of the above metal layer is washed with acid, and then a conductor circuit is formed on the above metal layer. According to the fourth group of the present invention, the above-mentioned configuration is described. After the metal layer is formed on the surface of the resin insulating layer, the surface of the metal layer is washed with acid to remove the oxide film. Therefore, the conductor circuit formed on the metal layer can be firmly adhered to the metal layer, and the conductor circuit can be prevented from being peeled off. Since it is not necessary to form a roughened surface on the resin insulating layer, the surface is flat. Therefore, since there is no roughened surface under the conductor circuit formed on the resin insulating layer, and it is flat, there is no delay in signal transmission. When forming a metal layer on the surface of the resin insulating layer, it is preferable to use at least one metal selected from Ni, Cr, Mo, Ti, W, Cu, AL · Sn, Pt, Pd, and An. Therefore, the metal layer may be a layer formed of a single metal among the above metals, or an alloy layer formed of two or more metals. In the fourth group of the present invention, examples of the method for forming the metal layer include a physical vapor deposition method (PVD method), a chemical vapor deposition method (CVD method :), electroplating, and electroless plating. Specific examples of the physical vapor deposition method and the chemical vapor deposition method include the methods described in the first group of the present invention. Although the type of acid used for washing with the above-mentioned acid is not particularly limited, it is preferably selected from at least one acid or mixed acid of hydrochloric acid, sulfuric acid, acetic acid, and phosphoric acid. The cleaning temperature of acid is high because of its high cleaning ability at 25 ~ 60 ° C. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) I -------- Equipment — I — Order -------- line (please read the intention on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 453 1 4 1 ___B7______ V. Description of Invention (αί ) Hope. The thickness of the alloy layer is preferably 0.1 to 2.0 / im. If it is thinner than 0.1 # m, it is difficult to form a metal layer by electroplating, and the effect of adhesion is also low. On the other hand, if it exceeds 2.0 # m, etching will become difficult. The resin insulating layer formed in the fourth group of the present invention is preferably composed of a thermosetting resin, a thermoplastic resin, or a composite resin thereof. The thermosetting resin is preferably at least one selected from a thermosetting polyolefin resin, an epoxy resin, a polyimide resin, a phenol resin, and a bis-butene diamidine triazabenzene resin. Use it. As for the thermoplastic resin, it is preferable to use, for example, polymethyl propylene (PMP), polystyrene (PS), polyethersulfone (PES), polyphenylene ether (PPE), polyphenylene sulfide (PPS), and the like. . In the multilayer printed circuit board of the fourth group of the present invention, as for the resin substrate, it is a substrate used to directly form a conductor circuit on the resin substrate, and a resin insulation layer and a conductor circuit may be provided thereon, respectively. Alternatively, two or more floors may be provided. Alternatively, a resin substrate that does not form a conductor circuit may be used, and one layer of a resin insulation layer and a conductor circuit may be provided thereon, or two or more layers may be provided. The resin insulating layer and the conductor circuit may be provided on one surface of the resin substrate or on both surfaces of the resin substrate. An example of a method for manufacturing a multilayer printed wiring board according to the fourth group of the present invention will be described below. 50 This paper size is applicable to China Solid Standard (CNS) A4 specification (2) 0 × 297 mm. — — — — — — ------------ tr ----— --- (Please read the notes on the back before filling in this page) Printed by the Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 453 1 4 1 ____B7___ 5. Description of the Invention A circuit board having a lower-layer conductor circuit is produced. In this case, the circuit board can be produced by the same method as the method described in the first group of the present invention and the second group of the present invention. (2) A resin insulating layer is formed on both sides of the circuit board having the lower-layer conductor circuit prepared in the above (1). The function of the resin insulating layer is to serve as an interlayer resin insulating layer of a multilayer printed circuit board. This resin insulating layer is formed by applying an unhardening agent and heat-pressing a thin film of resin. (3) Next, in the formed resin insulating layer (hereinafter referred to as an interlayer resin insulating layer), an opening for forming a through hole is provided to ensure its electrical connection with the underlying conductor circuit. The perforation of this opening is performed by the exposure imaging processing of photolithography technology or the irradiation of laser light. In this case, the laser light to be used includes, for example, a carbon dioxide laser, an ultraviolet laser, and an excimer laser. When perforated with carbon dioxide laser light, a decontamination treatment is performed. This decontamination treatment can be performed using an oxidizing agent made of an aqueous solution such as chromic acid, permanganate, and the like, and the treatment can also be performed using an oxygen plasma, a mixture of Ch and oxygen, or a glow discharge. Further, the surface can be improved by irradiating ultraviolet rays with a low-pressure mercury lamp. In particular, treatment with a plasma of a mixture of Ch and oxygen can introduce hydrophilic groups such as hydroxyl groups and carbonyl groups on the surface of the resin. It is advantageous if the above-mentioned treatment is performed on the interlayer resin insulating layer to improve the adhesion with the metal layer formed later1. 51 This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------ installation ------ order --------- line (please read the back first Please pay attention to this page, please fill in this page) Consumption cooperation between employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives of the Ministry of Economic Affairs 453 1 4 1 A7 _____B7___ V. Description of Invention (9)

(4) 在前述(3)設置通孔形成用開口之層間樹脂絕緣層的 表面，形成擇自長週期型之週期表的第4A族至第1B族所 屬範圍之第4週期〜第7週期的金屬元素、A1以及Sn之中 至少一種以上的金屬所構成之金屬層。又此形成係以PVD 法等爲之。 (5) 在上述(4)的過程之後，進行酸處理，以去除金屬表 面的氧化膜。 (6) 其次，在上述(5)形成之金屬層上施以無電解鍍敷。 就無電解鍍敷而言以鍍銅爲最佳。又，無電解鍍敷之 膜厚，以0.1~5^m爲宜。係因若具有此種膜厚，不會損害 到之後進行之電解電鍍導體層本身的性能，又可利用蝕刻 去除該薄膜之故。 又，此無電解鍍敷處理並非必須，可予以省略。 (7) 在上述(6)形成之無電解鍍敷膜上形成防鍍膜。此防 鍍膜的形成，係將感光性乾式薄膜積層後，進行曝光、顯 像處理所得之。 (8) 其次，將無電解鍍敷膜做爲導鍍層進行電解電鍍’ 以增厚導體電路。又電解電鍍膜之膜厚，以5〜30；tzm爲宜 〇 (9)形成電解電鍍膜之後’將防鍍膜剝離’又對存在 於防鍍膜下之無電解鍍敷膜及上述金屬層以蝕刻去除之’ 成爲獨立之導體電路。 就蝕刻液而言，可舉出例如硫酸—過氧化氫水溶液' 過硫酸氨、過硫酸鈉、過硫酸鉀等之過硫酸塩水溶液、氯 52 — if— I — — — — — — — — -II ---- - *lllt I —II (請先Mtl背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 453141 _________B7_____ 五、發明說明（y) 化鐵'氯化銅之水溶液、鹽酸、硝酸、熱稀硫酸等。 又依其必要性，於上層導體電路表面’將擇自屬於長 週期型之週期表的第4A族〜第1B族範圍之第4〜第7週期 的金屬、A1以及Sn之中至少1種的薄金屬層，以電鍍法 、PVD法或CVD法形成之，而重複上述(2)〜(9)的過程之後 ，最後藉由形成防焊層及焊接凸塊以製造多層印刷電路板 〇 又，以上之說明，就導體電路的形成方法而言雖採用 半加成法，但亦可採用全加成法。 本發明之第五群之多層印刷電路板’係於基板之兩面 形成樹脂絕緣層及導體電路之多層印刷電路板，其特徵爲 ’在前述樹脂絕緣層的表面’形成有擇自週期表的第4A 族至第1B族之第4~第7週期之Cu除外的金屬、A1以及 Sn之中一種以上的金屬構成之金屬層，又透過金屬層而設 置上層導體電路。 構成此種金屬層之金屬，由於其與絕緣樹脂之密接性 佳，故於樹脂絕緣層之表面不設置粗化層亦可確保與上層 導體電路之密接性。其結果，樹脂絕緣層的表面被平坦化 ，而導體電路的表面亦被平坦化之故’於傳送高頻率區域 之訊號時不會發生傳送延遲。 又，樹脂基板，與陶瓷基板或金屬基板相異，其不僅 容易板彎且放熱性亦差，而由於積熱之故容易發生銅的遷 移。此點，構成本發明金屬層之前述遷移金屬較銅爲堅固 ，由該遷移金屬所成之金屬層，可抑制層間樹脂絕緣層的 53 ---I I I I--I I I I Λ ^ ----—I — I i 訂·-------- (請先閱讀背面之注意ί項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用卞國國家標準（CNS)A4規格（210 X 297公釐） A7 ^53141 ______B7______ 五、發明說明（&lt;&gt;) 膨脹或收縮，且由於此種金屬層係形成於樹脂基板的兩面 ，故可防止冷熱循環時的板彎、龜裂，再者，可成爲防止 來自銅導體電路之銅離子遷移的障壁，即使於溼度高的條 件下亦可確保層間絕緣。 又，亦可於前述遷移金屬上設置Cu層。若於Cu層上 形成之導體電路爲銅之時，其與遷移金屬之導體電路的密 接性可獲得改善。 於此種本發明之第五群之多層印刷電路板中，構成前 述金屬層之金屬，較佳者係擇自A卜Fe、W、Mo、Sn、Ni 、Co、Cr、Ή以及貴金屬之中至少1種以上的遷移金屬。 又，就貴金屬而言，較佳者係Pd、Au、ΡΜ 由這些遷移金屬所成之金屬層的厚度較佳爲Ο.ΟΙμ m〜0.2&quot;m。其理由’若使其厚度爲〇.01/zm以上，貝[J可確 保樹脂絕緣層與導體電路間之密接性，又，若使其厚度爲 0.2ym以下，則可防止以濺鍍形成金屬層之時的應力之問 題而發生龜裂，且於導體電路形成後已不需要之導體電路 間的金屬層亦可利用蝕刻來輕易除去。 又，於前述遷移金屬之金屬層上所成之Cu層的厚度 較佳爲0.01 〜〇.2/zm。其理由，若使其厚度爲〇〇1 _ 以上，則可確保遷移金屬之金屬層與導體電路間之密接性 ，又，若使其厚度爲以下，則可防止以濺鍍形成金 屬層之時的應力之問題而發生龜裂，且於導體電路形成後 已不需要之導體電路間的Cu靨亦可利用蝕刻來輕易除去 〇 ___54 义張尺度適用中國囡家標準（CNS)A4規格（210 X 29f^J- - - - -- ----，袭'---:----—訂---------線 (靖先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4531 4 1 A7 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明（钧） 於前述金屬層上，乃希望依必要性設置其他種類之金 屬層。具體而言，於樹脂絕緣層上形成鎳層，再藉由於鎳 層上設置銅層，可防止導體電路形成之時電鍍物的未析出 0 前述金屬層，係由無電解鍍敷、電解電鍍、濺鍍、蒸 鍍、CVD等方法來形成。 本發明之第五群所使用之樹脂基板，一般上與陶瓷基 板或金屬基板相異，其不僅容易板彎且放熱性亦差，而由 於積熱之故容易發生銅的遷移。此點，就本發明之第五群 而言’金屬層成爲防止來自銅導體電路之銅離子遷移的障 壁，即使於溼度高的條件下亦可確保層間絕緣。 於本發明之第五群中之上述層間樹脂絕緣層，較佳係 由熱硬化性樹脂、熱可塑性樹脂，或是這些的複合樹脂所 構成。 就熱硬化性樹脂而言，較佳者係例如擇自熱硬化性聚 烯烴樹脂、環氧樹脂、聚醯亞胺樹脂、苯酚樹脂、雙順丁 烯二醯胺三氮雜苯樹脂中至少一種加以使用。 就熱可塑性樹脂而言，較佳者係使用例如聚甲基丙稀 (PMP)、聚苯乙烯(ps)、聚醚磺(PES) '聚苯醚(PPE)、聚苯 撐硫(PPS)等。 於本發明之第五群中之上述層間樹脂絕緣層，以使用 同於本發明之第一群的聚烯烴系樹脂爲最佳。 此種聚烯烴系樹脂，由於其與導體電路之密接性佳， 故於樹脂絕緣層之表面不必粗化亦可形成導體。亦即，可 55 本紙張尺度適用中國國家標準（CNS)A4規格（2〗〇 x 297公釐） ------------------ι — ίβ----I----^ (請先閲讀背面之注$項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 _____B7 ___- 五、發明說明（切） 於平坦的樹脂絕緣層的表面形成導體電路° 又，此種聚烯烴系樹脂，介電常數在3以下，介電耗 損因數在0.005以下皆比環氧樹脂爲低’且高頻率之訊號 亦無傳送延遲。又，聚烯烴系樹脂之耐熱性也不比環氧樹 脂差，於焊接溶融溫度下不會有導體電路的剝離現象°再 者，由於其破斷韌性値亦大，所以不會因熱循環造成以導 體電路與樹脂絕緣層之界面爲起點之龜裂的發生° 以下，就本發明之第五群之多層印刷電路板的製造方 法之一例說明。 ' (1) 首先，於樹脂基板的表面製作形成有內層銅圖案的 電路基板。 此時，可使用本發明之第一群或是本發明之第二群所 記載之方法以相同的方法製作電路基板。 (2) 在上述(1)製作之電路基板的兩面形成樹脂絕緣層。 此樹脂絕緣層之功用係做爲多層印刷電路板之層間樹脂絕 緣層。 此樹脂絕緣層係藉由塗佈未硬化劑，再將薄膜狀之樹 脂熱壓積層所形成者。 (3) 其次，於此樹脂絕緣層中，爲確保其與下層導體電 路的電連接而設置開口。 此開口的穿孔，係以雷射光來進行。此時，所使用之 雷射光，有二氧化碳雷射、紫外線雷射、準分子雷射等。 於是，若以二氧化碳雷射光穿孔時，則進行去污處理。此 去污處理可使用由鉻酸、過錳酸鹽等之水溶液所成之氧化 56 11 — — — — — -----— I— --I---11^. (請先閱讀背面之注意事項再麻寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 經濟部智慧財產局貝工消費合作社印製 A7 B7 五、發明說明（&lt;s) 劑來進行，又此處理亦可用氧電漿、CF4及氧的混合物電發 或是輝光放電等來進行。又，藉由使用低壓水銀燈照射紫 外線，亦可進行表面改良。 特別是藉由CF4及氧的混合物電漿進行處理，可於樹 脂表面引入羥基及羰基等親水性基，以使之後的CVD或 PVD處理易於進行，此爲有利的。 (4) 在前述(3)設置開口之樹脂絕緣層的表面，將擇自第 4A族至第1B族之第4週期~第7週期的金屬元素之中至少 1種之薄金屬層，以電鍍法、PVD法或CVD法等形成。_ 就具體的PVD法及CVD法而言，可舉出本發明之第 一群所記載之方法。 (5) 接著，在前述(4)所形成之金屬層上，將與以下過程 之無電解鍍敷膜相同的金屬層以濺鍍等形成。此係爲改善 與無電解鍍敷膜間的親和性之故。具體而言，以濺鍍方式 來設置銅層爲佳。 (6) 接著，在前述(5)所形成之金屬層上施行無電解鍍敷 〇 就無電解鍍敷而言以鍍銅爲最佳。又，無電解鍍敷的 膜厚以0.1〜爲佳。其理由，係由於可不損及在其後進 行之電解電鍍之導體層的特性，而能以蝕刻予以去除之故 〇 (7) 在前述(6)所形成之無電解鍍敷膜上形成防鍍膜。 此防鍍膜，係將感光性乾式薄膜進行積層後予以曝光 、顯像處理而形成者》 57 本紙張尺度適用中國國家標準（CNS)A4規格（2〗〇 x 297公釐） I I I-------裝·--------訂-------線 (請先M讀背面之注意事項再填寫本頁) A7 4 53 1 4 1 _____B7___ 五、發明說明（4) (8) 接著，將無電解鏟敷膜做爲導電鍍來進行電解電鍍 ，以增厚導體電路。又，電解電鍍膜以5~30/im爲佳。 (9) 接著，在防鍍膜剝離後，將位於防鍍膜下方之無電 解鍍敷膜及擇自第4A族至第1B族之第4〜第7週期的金屬 之中至少一種以上的金屬所構成之金屬層以蝕刻去除，而 得到獨立之導體電路β 就蝕刻液而言，可使用如硫酸-過氧化氫水溶液 '過 硫酸氨、過硫酸鈉、過硫酸鉀等之過硫酸塩水溶液；氯化 鐵、氯化銅之水溶液；鹽酸、硝酸、熱稀硫酸等° (10) 又依其必要性，於導體電路表面’將擇自屬於長 週期型之週期表的第4Α族〜第1Β族範圍之第4~第7週期 的金屬、Α1以及Sn之中至少1種的薄金屬層’以電鍍法 、PVD法或CVD法形成之，再者藉由重複上述⑵~(9)的過 程以得到多層化之印刷電路板。 又，以上之說明，就導體電路的形成方法而言雖採用 半加成法，但亦可採用全加成法。 此全加成法，係於樹脂絕緣層表面以CVD或PVD處 理形成薄金屬層後，或積層有感光性乾式薄膜，或塗佈有 液體狀之感光性樹脂，再進行曝光、顯像處理以設置，接 著採用無電解鑛敷以進行增厚，從而形成導體電路。 或者，於樹脂絕緣層表面形成防鍍膜後，以CVD或 PVD處理設置薄金屬層，或再將附著於防鑛膜表面之此金 屬層以硏磨等去除之，或將防鍍膜本身去除，以此金屬層 做爲觸媒進行無電解鍍敷，亦可形成導體電路。 58 本紙張尺度適用中國囷家標準（CNS)A4規格（2】〇 X 297公釐） I ——!!裝 i — ji —訂·1!1 -線 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B7 五、發明說明（d) 本發明之第六群之多層印刷電路板，其特徵係於樹脂 基板之兩面形成之下層導體電路表面，至少一部份形成有 擇自長週期型之週期表的第4A族至第1B族之第4〜第7週 期的金屬(但是Cu除外）、A1以及Sn之中1種以上的金屬 構成之金屬層。 上述金屬，較佳係使用例如擇自Al、Fe、W、Mo、Sn 、Νι、Co、Cr、Τι以及貴金屬之中的金屬，就貴金屬的例 子而言，較佳者係Pd、Au、Pt。 上述金屬之任何一個皆爲與層間絕緣用樹脂有良好密 接性之物。因此，其具有的性質即使於樹脂基板上發生板 彎的情形導體電路與層間樹脂絕緣層亦不會剝離。並且， 由於對樹脂基板的兩面以對稱的方式形成此種構造之故’ 該基板本身的板彎量亦變小，因此即使於熱循環之時可防 止導體電路與層間樹脂絕緣層的界面附近發生龜裂。 再者，若以這些金屬形成金屬層‘，即使於導體電路的 表面樹脂絕緣層不設置粗化層，仍可確保其與上層導體電 路之必需的密接性，其結果，具有於傳送高頻率區域之訊 號時不會發生傳送延遲的效果。 又，藉由蝕刻形成導體電路之時，前述金屬層係具有 抗蝕層之作用，而可賦予精密圖案的形成。 又，上述金屬層的厚度以0.01 〜0.2爲佳。其理 由爲，若使其厚度爲0.01 以上，則可確保樹脂絕緣層 與導體電路間之密接性，又，若使其厚度爲0.2&quot;m以下， 則可防止以濺鍍形成金屬層之時的應力之問題而發生龜裂 59 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) I I I I---— — 裝------— — 訂------— ·線 (請先《讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 Ml Α7 Β7 五、發明說明（ &lt;&gt;《&gt; ，且於導體電路形成後已不需要之導體電路間的金屬層亦 可利用鈾刻來輕易去除。 又，於前述金屬層上，亦可依必要性形成其他種類之 金屬層。例如，於層間樹脂絕緣層上形成鎳層，在藉由於 鎳層上設置銅層，可防止導體電路形成之時電鍍物的未析 出。再者，這些金屬層’係以無電解鍍敷、電解電鍍、濺 鍍、蒸鍍、CVD等方法來形成。 _ 本發明之第六群所使用之樹脂基板，一般上與陶瓷基 板或金屬基板相異，其不僅容易板彎且放熱性亦差，而由 於積熱之故容易發生銅的遷移。此點，就本發明而言，金 屬層成爲防止來自銅導體電路之銅離子遷移的障壁，即使 於溼度高的條件下亦可確保層間之絕緣。 於本發明之第六群中之上述層間樹脂絕緣層，較佳係 由熱硬化性樹脂、熱可塑性樹脂，或是這些的複合樹脂所 構成。 就熱硬化性樹脂而言，較佳者係例如擇自熱硬化性聚 烯烴樹脂、環氧樹脂、聚醯亞胺樹脂、苯酚樹脂、雙順丁 烯二醯胺三氮雜苯樹脂中至少一種加以使用。 就熱可塑性樹脂而言，較佳者係使用例如聚甲基丙烯 (PMP)、聚苯乙烯(PS)、聚醚磺(PES)、聚苯醚(PPE)、聚苯 撐硫(PPS)等。 於本發明中，就上述層間樹脂絕緣層而言，以使用同 於本發明之第一群的聚烯烴系樹脂爲最佳。 此種聚烯烴系樹脂，由於其與導體電路之密接性佳， 60 本纸張尺度適用中國國家標準（CNS)A4規格（2]0χ297公爱) 11---------— I---11111 ^--I----1 (諝先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 五、發明說明（1) 故不須將內層導體電路表面予以粗化，而可形成平坦之導 體電路。 又，此種聚烯烴系樹脂，介電常數在3以下’介電耗 損因數在0.05以下皆比環氧樹脂爲低’且高頻率之訊號亦 無傳送延遲。又，此聚烯烴系樹脂之耐熱性也不比環氧樹 脂差，於焊接溶融溫度下不會有導體電路的剝離現象。再 者，由於其破斷韌性値亦大，所以不會因熱循環造成以導 體電路與樹脂絕緣層之界面爲起點之龜裂的發生° 以下，就本發明之第六群之多層印刷電路板的製造方 法之一例說明。 (1) 首先，於樹脂基板的表面製作形成有內層銅圖案的 電路基板。 此時，可使用本發明之第一群或是本發明之第二群所 記載之方法以相同的方法製作電路基板。 (2) 在上述(1)製作之電路基板的兩面形成樹脂絕緣層。 此樹脂絕緣層之功用係做爲多層印刷電路板之層間樹脂絕 緣層。 此樹脂絕緣層係藉由塗佈未硬化劑，再將薄膜狀之樹 脂熱壓積層所形成者。 (3) 其次，於此樹脂絕緣層中，爲確保其與下層導體電 路的電連接而設置開口。 此開口的穿孔，係以雷射光來進行。此時，所使用之 雷射光，有二氧化碳雷射、紫外線雷射、準分子雷射等。 於是，若以二氧化碳雷射光穿孔時，則進行去污處理。此 61 -------------裝-----!_訂---------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國囡家標準（CNS)A4規格（2】0 X 297公釐） 經濟部智慧財產局貝工消費合作社印製 4 53 1 4 T A7 _ B7 五、發明說明（w?) 去污處理可使用由鉻酸、過錳酸鹽等之水溶液所成之氧化 劑來進行，又此處理亦可用氧電漿、CF4及氧的混合物電漿 或是輝光放電等來進行。又，藉由使用低壓水銀燈照射紫 外線，亦可進行表面改良。 特別是藉由CF，及氧的混合物電漿進行處理，可於樹 脂表面引入羥基及羰基等親水性基，以使之後的CVD或 PVD處理易於進行，此爲有利的。 (4) 在前述(3)設置開口之樹脂絕緣層的表面，將擇自第 4A族至第1B族之第4週期~第7週期的金屬(但是Cu除外 )、A1及Sn之中至少1種之金屬所成之薄金屬層，以電鍍 法、PVD法或CVD法等形成。 就具體的PVD法及CVD法而言，可舉出本發明之第 一群所記載之方法。 (5) 接著，在前述(4)所形成之金屬層上，將與以下過程 之無電解鍍敷膜相同的金屬層以濺鍍等形成。此係爲改善 與無電解鍍敷膜間的親和性之故。具體而言，以濺鍍方式 來設置銅層爲佳。 (6) 接著，在前述⑸所形成之金屬層上施行無電解鍍敷 〇 就無電解鍍敷而言以鍍銅爲最佳。又，無電解鍍敷的 膜厚以0,1〜5/zm爲佳。其理由，係由於可不損及在其後進 行之電解電鍍之導體層的特性，而能以蝕刻予以去除之故 〇 此無電解鍍敷以及/或者擇自前述第4A族至第1B族之 62 本紙張尺度適用中國國家標準（CNS)A4規袼（210 X 297公釐） ϋ ϋ I I ϋ n I I I I * n - - - - - n-ί-r口、« ϋ ϋ I n n I I (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 14 1 A7 --------- B7 五、發明說明（Μ ) 屬於第4週期〜第7週期的金屬(但是Cu除外）、Al、Sn之 中至少1種之金屬所成之薄金屬層會成爲導體層，而做爲 導電鍍的功用。 (7) 在前述(6)所形成之無電解鍍敷膜上形成防鍍膜。 此防鍍膜，係將感光性乾式薄膜進行積層後予以曝光 、顯像處理而形成者。 (8) 接著，於結束(7)之處理的無電解鍍敷膜上將擇自第 4A族〜第1B族之屬於第4〜第7週期的金屬(但是Cu除外) 、Al、Sn之中至少1種的金屬所成之金屬層，以上述之電 鍍法、PVD法或CVD法形成之。 於此過程之前述金屬層的形成，以無電解鍍敷法來形 成最佳。 之後，將前述無電解鍍敷膜及前述金屬層做爲導電鍍 來進行電解電鍍，以進行導體電路之增厚處理。又，此處 理之無電解鍍敷膜的膜厚以5~30/zm爲佳。 (9) 接著，在上述防鍍膜剝離後，將位於防鍍膜正下方 部分之無電解鍍敷膜及上述金屬層以蝕刻處理去除，而形 成獨立之導體電路。就此過程使用之蝕刻液而言，可使用 如硫酸-過氧化氫水溶液、過硫酸氨、過硫酸鈉、過硫酸 鉀等之過硫酸塩水溶液，氯化鐵、氯化銅之水溶液，鹽酸 、硝酸、熱稀硫酸等。 又，於此蝕刻處理之中，前述金屬層係做爲抗蝕層的 作用，有助於形成如L/S = 15/15//m之獨立導體電路。 (10) 又依其必要性，於上述導體電路表面，將上面所 63 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 111----*4-------I I ------- (請先閲讀背面之注意事項再填寫本頁) A7 45^141 _______B7 __ 五、發明說明（A) 揭載之金屬構成的薄金屬層，以電鍍法、PVD法或CVD法 形成之，再者藉由重複上述(2卜(9)的過程以得到多層化之 雙面印刷電路板。 又，以上之說明，就導體電路的形成方法而言雖採用 半加成法，但亦可採用全加成法。 此全加成法，係於樹脂絕緣層表面以CVD或PVD處 理設置薄金屬層後，或積層有感光性乾式薄膜，或塗佈有 液體狀之感光性樹脂，再進行曝光、顯像處理以設置防鑛 膜’接著採用無電解鍍敷以進行增厚，從而形成導體電路 〇 或者，於樹脂絕緣層表面形成防鍍膜後，以CVD或 PVD處理設置薄金屬層，或再將附著於防鍍膜表面之此金 屬層以硏磨等去除之，再將防鍍膜本身去除，以此金屬層 做爲觸媒進行無電解鑛敷，亦可形成導體電路。 本發明之第七群之第一發明的導體電路形成方法，其 特徵爲至少包含下述(a) ~(c)之過程，亦即 U)於絕緣基板上由Ni、A1等表面形成鈍性膜之金屬 所構成之第1導體層的形成過程； (b) 於上述第1導體層上，較上述Ni、A1等表面形成 鈍性膜之金屬的離子化傾向爲小的金屬構成第2導體層的 形成過程； (c) 使用酸性蝕刻液進行選擇性的蝕刻將特定區域之第 1導體層及第2導體層同時予以蝕刻過程。 上述導體電路的形成方法，係藉由蝕刻首先較表面形 本紙張尺度適用中國國家標準（CNS)A4規格（210X297公釐） 11! -装----：---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 A7 453 1 4 1 ____B7___ 五、發明說明（昀） 成鈍性膜之金屬的離子化傾向爲小的金屬會溶解’使得Ni 、A1等表面形成鈍性膜之金屬外露。若表面形成鈍性膜之 金屬外露，此金屬與較此金屬的離子化傾向爲小的金屬會 由於做爲電解質之酸性蝕刻液(的存在)而發生電池反應’ Ni、A1等形成鈍性膜之金屬將會溶解。 因此，在酸性蝕刻液方面，可使用硫酸水溶液、鹽酸 水溶液或是硫酸-過氧化氫混合水溶液等，而不必使用王 水或硝酸等產量不符合的酸。 又，藉由酸性蝕刻液，可達成習知未有的更快的蝕刻 速度。 於本發明之第七群之中，表面形成之鈍性膜之金屬較 佳者係擇自Ni、Co、Cr、Ti、Nb、Ta、A1之中至少1種。 這些金屬容易構成鈍性膜，而一般的酸性蝕刻液不會將其 溶解。 又，表面形成之鈍性膜之金屬特別以Ni、A1爲佳。這 些金屬與樹脂的密接性良好，就形成印刷電路板的導體電 路而言最爲適當。 以下，基於圖示說明之。在說明中係以Ni、A1彳故爲表 面形成之鈍性膜之金屬的例子。 圖28(a)〜⑹係本發明之導體電路的形成方法中將各過 程模式般表示的剖面圖。 本發明之第七群首先係於絕緣基板上形成由Ni $ W 構成之第1導體層32 (參照圖28(a))。 絕緣基板31的材料並無特別的限定，可爲陶瓷等無^ 65 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I— I — -------1 訂---------線 (請先閱讀背面之注意事項再填寫本頁&gt; 經濟部智慧財產局員工消費合作社印製 453 彳 4 1 A7 B7 經濟部智慧財產局具工消費合作社印製 五、發明說明（MV ) 材料構成之基板，亦可爲樹脂等有機材料構成之基板，但 著重於與形成之導體層的密接性而使用樹脂基板之時，就 可形成與基板的密接性良好之導體層的觀點來看，本發明 主要係以樹脂基板爲對象。 第1導體層32的形成方法並無特別的限定，例如可舉 出如氣相蒸鍍法、電鍍法等，.就可於樹脂基板上形成密接 性優良的導體層來看，則以氣相蒸鍍法，特別是以濺鍍法 爲佳。藉由濺鍍法，而欲形成第1導體層32之時，爲不使 形成之第1導體層32被氧化，較佳者係於減壓之鈍性氣體 周圍氣氛中進行。 其次，於形成第1導體層32之絕緣基板31上，形成 較Ni或A1之離子化傾向爲小的金屬構成之第2導體層33( 參照圖33(b))。 就較Ni之離子化傾向爲小的金屬而言，可舉出例如 Cu、Sn、Pb等》這些金屬，可單獨使用，亦可將2種以上 倂用。亦即，可設置這些金屬的單獨層，亦可設置由這些 金屬構成之複數層。 又，就較A1之離子化傾向爲小的金屬而言，可舉出例 如Cu、Sn、Pb、Fe等。同樣的這些金屬，可單獨使用，亦 可將2種以上倂用。 第2導體層33之形成方法亦無特殊之限定，例如可舉 出如氣相蒸鍍法、電鍍法等，由於連接前面若使用同樣的 方法，能簡單的形成導體層之故，乃希望使用與第1導體 層32之形成方法相同之方法。 66 良紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐 i I I ----訂------- - ·線 (請先閲讀背面之注意事項再填寫本頁) A7 453141 ____B7____ 五、發明說明（〆） 於形成第2導體層33之時，爲避免第1導體層32被 氧化，故於形成第1導體層32之後’使其不要暴露於大氣 周圍氣氛中，迅速地形成第2導體層33爲宜。 於形成第2導體層33之後，藉由使用蝕刻液選擇性地 進行蝕刻，可將特定區域之第1導體層32及第2導體層 33同時地蝕刻，形成導體電路。 選擇性蝕刻的方法無特殊之限定，例如’於由上述2 層構成之導體層上形成抗蝕層之後，將未形成抗蝕層之部 分使用電鍍法等進行增厚，在剝離抗蝕層之後’將原先存 在於抗蝕層之下的導體層予以蝕刻去除以形成導體電路’ 此爲可採用之方法。 此處，係採用前者之方法。又，關於後者之方法’將 在後述之多層印刷電路板之製造方法中詳述之。 亦即，首先於第2導體層33上，採用光微影技術形成 抗蝕層34(參照圖28(c))。之後，將形成抗鈾層部分以外的 部份以蝕刻去除之，形成導體電路β 此時蝕刻的進行可採用酸性蝕刻液。 又，就此酸性蝕刻液而言，可採用例如硫酸水溶液、 鹽酸水溶液或是硫酸-過氧化氬混合水溶液等一般使用上 易於管理之溶液。 若以Ni層爲第1導體層32，以Cu層爲第2導體層33 ，又蝕刻液爲硫酸-過氧化氫混合水溶液之時’其飽刻將 依以下之機構進行。 首先，依照下述(1)及(2)所示之化學式Cu層被触刻著 67 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） !· — !·^·! — !!訂---------線 ί &lt;請先閲讀背面之注意ί項再填寫本頁) 經濟部智慧財產局貝工消費合作社印製 A7 4531 4 1 ________Β7_ 五、發明說明（4 )(4) On the surface of the interlayer resin insulation layer provided with the opening for forming a through hole in (3) above, a fourth cycle to a seventh cycle of the range from Group 4A to Group 1B of the long-period periodic table is formed. A metal layer composed of at least one metal among metal elements, A1, and Sn. This formation is based on the PVD method. (5) After the process of (4) above, an acid treatment is performed to remove the oxide film on the metal surface. (6) Next, electroless plating is performed on the metal layer formed in the above (5). For electroless plating, copper plating is preferred. The thickness of the electroless plating is preferably 0.1 to 5 ^ m. The reason is that if such a film thickness is used, the performance of the electrolytically plated conductor layer itself will not be impaired, and the film can be removed by etching. In addition, this electroless plating process is not necessary, and can be omitted. (7) A plating resist is formed on the electroless plating film formed in the above (6). This resist is formed by laminating a photosensitive dry film, and then performing exposure and development processes. (8) Next, electroless plating is performed using an electroless plating film as a conductive plating layer 'to thicken a conductor circuit. The thickness of the electrolytic plated film is 5 ~ 30; tzm is suitable. (9) After the electrolytic plated film is formed, the stripping of the anti-plating film is performed, and the electroless plated film and the above metal layer existing under the anti-plating film are etched. The 'removed' becomes an independent conductor circuit. Examples of the etching solution include a sulfuric acid-hydrogen peroxide aqueous solution, an ammonium persulfate aqueous solution such as ammonia persulfate, sodium persulfate, and potassium persulfate, and chlorine 52 — if — I — — — — — — — — — II -----* lllt I —II (please note the precautions on the back of Mtl before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) A7 453141 _________B7_____ 5. Description of the invention (Y) Ferric'copper chloride aqueous solution, hydrochloric acid, nitric acid, hot dilute sulfuric acid, etc. According to its necessity, the surface of the upper conductor circuit will be selected from at least one of metals from the 4th to 7th periods of the 4A to 1B range of the long-period periodic table. A thin metal layer is formed by electroplating, PVD, or CVD, and after repeating the above processes (2) to (9), finally, a multilayer printed circuit board is manufactured by forming a solder resist layer and a solder bump. As described above, although the semi-additive method is adopted as the method of forming the conductor circuit, the full-additive method may also be adopted. The multilayered printed circuit board of the fifth group of the present invention is a multilayered printed circuit board on which resin insulation layers and conductor circuits are formed on both sides of a substrate, and is characterized in that a first selective selective periodic table is formed on the surface of the foregoing resin insulation layer. A metal layer composed of one or more of metals other than Cu in the 4th to 7th cycles of the 4A to 1B group, and an upper conductor circuit is provided through the metal layer. Since the metal constituting such a metal layer has good adhesion to the insulating resin, the surface of the resin insulating layer can be provided without a roughened layer to ensure the adhesion to the upper-layer conductor circuit. As a result, the surface of the resin insulating layer is flattened, and the surface of the conductor circuit is also flattened. 'A transmission delay does not occur when transmitting a signal in a high frequency region. In addition, a resin substrate is different from a ceramic substrate or a metal substrate. It is not only easy to bend, but also has poor heat dissipation properties, and copper migration is liable to occur due to accumulated heat. At this point, the aforementioned migrating metal constituting the metal layer of the present invention is stronger than copper, and the metal layer formed by the migrating metal can suppress 53 --- III I--IIII Λ ^ ---- of the interlayer resin insulating layer I — I i Order · -------- (Please read the note on the back before filling in this page) Printed on the paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the national standard (CNS) A4 Specifications (210 X 297 mm) A7 ^ 53141 ______B7______ 5. Description of the invention (&lt; &gt;) Expansion or contraction, and because this metal layer is formed on both sides of the resin substrate, it can prevent plate bending during cold and hot cycling, Cracking, in addition, can serve as a barrier to prevent copper ion migration from copper conductor circuits, ensuring interlayer insulation even under high humidity conditions. A Cu layer may be provided on the migration metal. When the conductor circuit formed on the Cu layer is copper, the adhesion with the conductor circuit of the migrating metal can be improved. In such a fifth group of multi-layer printed circuit boards of the present invention, the metal constituting the aforementioned metal layer is preferably selected from Al, Fe, W, Mo, Sn, Ni, Co, Cr, rhenium, and precious metals. At least one or more migrating metals. In terms of precious metals, Pd, Au, and PM are preferably metal layers made of these migrating metals with a thickness of 0.001 μm to 0.2 &quot; m. The reason 'If the thickness is 0.01 / zm or more, the [J can ensure the adhesion between the resin insulation layer and the conductor circuit, and if the thickness is 0.2 μm or less, the formation of metal by sputtering can be prevented. Cracking occurs due to the stress at the time of the layer, and the metal layer between the conductor circuits that is no longer needed after the conductor circuit is formed can also be easily removed by etching. The thickness of the Cu layer formed on the metal layer of the migration metal is preferably 0.01 to 0.2 / zm. The reason is that if the thickness is 0.001 or more, the adhesion between the metal layer of the migrating metal and the conductor circuit can be ensured, and if the thickness is less than the thickness, the formation of the metal layer by sputtering can be prevented. The problem of stress caused cracks, and Cu 靥 between conductor circuits that are no longer needed after the conductor circuit is formed can also be easily removed by etching. ___54 The scale specification is applicable to the Chinese Standard (CNS) A4 specification (210 X 29f ^ J---------, strike '---: ----- order --------- line (Jing first read the precautions on the back before filling in this page) Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4531 4 1 A7 Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics B7. V. Description of the Invention (Jun) On the aforementioned metal layer, we hope to set up other types of metal layers as necessary. Specifically, a nickel layer is formed on the resin insulating layer, and the copper layer is provided on the nickel layer to prevent the unprecipitated plating material when the conductor circuit is formed. The aforementioned metal layer is formed by electroless plating, electrolytic plating, It is formed by sputtering, vapor deposition, CVD, etc. The fifth group of the present invention The resin substrate used is generally different from a ceramic substrate or a metal substrate. It is not only easy to bend, but also has poor heat dissipation, and it is easy to cause copper migration due to accumulated heat. This point is related to the fifth group of the present invention. The metal layer serves as a barrier to prevent the migration of copper ions from the copper conductor circuit, and can ensure interlayer insulation even under high humidity conditions. The interlayer resin insulating layer in the fifth group of the present invention is preferably made of heat. A thermosetting resin, a thermoplastic resin, or a composite resin of these. The thermosetting resin is preferably selected from thermosetting polyolefin resin, epoxy resin, polyimide resin, and phenol. At least one of resin and bis-cis- butadiene diamine triazabenzene resin is used. As the thermoplastic resin, it is preferable to use, for example, polymethyl propylene (PMP), polystyrene (ps), poly Ether sulfone (PES) 'Polyphenylene ether (PPE), polyphenylene sulfide (PPS), etc. In the above-mentioned interlayer resin insulating layer in the fifth group of the present invention, the same polyolefin as the first group of the present invention is used Resin is the best. Hydrocarbon-based resins have good adhesion to the conductor circuit, so the surface of the resin insulation layer does not need to be roughened to form a conductor. That is, 55 paper sizes are applicable to China National Standard (CNS) A4 specifications (2). x 297 mm) ------------------ ι — ίβ ---- I ---- ^ (Please read the note on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7 ___- V. Description of the invention (cut) The conductor circuit is formed on the surface of a flat resin insulation layer. Moreover, the dielectric constant of this polyolefin resin is below 3, Power loss factors below 0.005 are lower than epoxy resins and high frequency signals have no transmission delay. In addition, polyolefin resins are not inferior in heat resistance to epoxy resins, and there is no peeling of conductor circuits at the melting temperature of soldering. Furthermore, because their fracture toughness is also large, they are not caused by thermal cycling. The occurrence of cracks at the interface between the conductor circuit and the resin insulating layer as a starting point is described below. An example of a method for manufacturing a multilayer printed circuit board according to the fifth group of the present invention will be described below. '(1) First, a circuit board having an inner layer copper pattern formed on the surface of a resin substrate is prepared. In this case, the circuit board can be produced by the same method using the method described in the first group of the present invention or the second group of the present invention. (2) A resin insulating layer is formed on both sides of the circuit board prepared in the above (1). The function of the resin insulating layer is to serve as an interlayer resin insulating layer of a multilayer printed circuit board. This resin insulating layer is formed by applying an unhardening agent and heat-pressing a thin film of resin. (3) Next, an opening is provided in this resin insulating layer to ensure its electrical connection with the underlying conductor circuit. This opening is perforated with laser light. At this time, the laser light used includes carbon dioxide laser, ultraviolet laser, excimer laser, and the like. Then, when it is perforated with carbon dioxide laser light, a decontamination process is performed. This decontamination treatment can use the oxidation of chromic acid, permanganate, etc. 56 11 — — — — — -----— I— --I --- 11 ^. (Please read the back first Note for reprinting this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (&lt; s) Agent, and this treatment can also be carried out using an oxygen plasma, a mixture of CF4 and oxygen, or glow discharge. Also, by using a low-pressure mercury lamp to irradiate ultraviolet rays, the surface can also be improved. Especially by CF4 and Oxygen mixture plasma treatment, it is possible to introduce hydrophilic groups such as hydroxyl groups and carbonyl groups on the resin surface to facilitate subsequent CVD or PVD treatment, which is advantageous. (4) The resin insulation provided with an opening in (3) above The surface of the layer will be a thin metal layer selected from at least one of the metal elements in the fourth to seventh periods from Group 4A to Group 1B by electroplating, PVD, or CVD. For the PVD method and CVD method, the methods described in the first group of the present invention can be cited. (5) Next, on the metal layer formed in (4) above, the same metal layer as that of the electroless plating film in the following process is formed by sputtering or the like. Specifically, it is preferable to provide a copper layer by sputtering. (6) Next, electroless plating is performed on the metal layer formed in (5) above. In terms of electroless plating, Copper plating is the best. The thickness of electroless plating is preferably 0.1 ~. The reason is that it can be removed by etching because it does not damage the characteristics of the conductor layer of the electrolytic plating performed later. Therefore, 〇 (7) forms an anti-plating film on the electroless plating film formed in the above (6). This anti-coating film is formed by laminating a photosensitive dry film and then exposing and developing it. 57 paper size Applicable to China National Standard (CNS) A4 specification (2〗 〇x 297 mm) II I --------- install · -------- order ------- line (please M first Read the notes on the back and fill in this page again) A7 4 53 1 4 1 _____B7___ V. Description of the invention (4) (8) Next, the electroless shovel coating is used as the conductive plating to perform the electricity De-electroplating to thicken the conductor circuit. The electrolytic plating film is preferably 5 ~ 30 / im. (9) Next, after the anti-plating film is peeled off, the electroless plating film located under the anti-plating film and selected from the 4A The metal layer composed of at least one metal among the metals in the 4th to 7th cycles of the group to the group 1B is removed by etching to obtain an independent conductor circuit. For the etching solution, for example, sulfuric acid-peroxidation can be used. Aqueous hydrogen solution: aqueous solution of ammonium persulfate such as ammonia persulfate, sodium persulfate, potassium persulfate, etc .; aqueous solution of ferric chloride, copper chloride; hydrochloric acid, nitric acid, hot dilute sulfuric acid, etc. (10) Depending on its necessity, The surface of the conductor circuit 'will be selected from metals belonging to Groups 4A to 1B of the long-period periodic table, and at least one of A1 and Sn's thin metal layer by electroplating, It is formed by a PVD method or a CVD method, and a multilayered printed circuit board is obtained by repeating the above-mentioned processes (9) to (9). In the above description, although the semi-additive method is used for the method of forming the conductor circuit, the full-additive method may be used. This full-addition method involves forming a thin metal layer on the surface of the resin insulation layer by CVD or PVD treatment, or laminating a photosensitive dry film, or coating a liquid photosensitive resin, and then performing exposure and development processing to Set, followed by thickening with electroless mineral deposits to form a conductor circuit. Alternatively, after the anti-plating film is formed on the surface of the resin insulation layer, a thin metal layer is provided by CVD or PVD treatment, or the metal layer attached to the surface of the anti-mineral film is removed by honing or the like, or the anti-plating film itself is removed to This metal layer is used as a catalyst for electroless plating and can also form a conductor circuit. 58 This paper size is in accordance with China National Standard (CNS) A4 specification (2) 0X 297 mm. I —— !! Install i — ji — order · 1! 1-line (please read the precautions on the back before filling (This page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 453 1 4 1 A7 B7 V. Description of the invention (d) The multilayer printed circuit board of the sixth group of the present invention, its characteristics It is formed on both sides of the resin substrate to form a lower-layer conductor circuit surface, and at least a part of the metal is selected from Group 4A to Group 1B Group 4 to Group 7 (except Cu), A metal layer made of one or more metals among A1 and Sn. The above metals are preferably metals selected from, for example, Al, Fe, W, Mo, Sn, Ni, Co, Cr, Ti, and precious metals. As for the examples of precious metals, Pd, Au, and Pt are preferred. . All of the above metals are those having good adhesion to the resin for interlayer insulation. Therefore, it has the property that the conductor circuit and the interlayer resin insulation layer do not peel off even when a plate bend occurs on the resin substrate. In addition, since this structure is formed symmetrically on both sides of the resin substrate, the amount of plate bending of the substrate itself is also reduced, so that it can prevent the vicinity of the interface between the conductor circuit and the interlayer resin insulation layer even during thermal cycling. Cracked. Furthermore, if the metal layer is formed of these metals, even if the resin insulation layer on the surface of the conductor circuit is not provided with a roughened layer, the necessary tightness with the upper conductor circuit can be ensured. As a result, it has a high-frequency transmission range. The effect of transmission delay does not occur during the signal. When a conductor circuit is formed by etching, the aforementioned metal layer has a function of a resist layer and can provide formation of a precise pattern. The thickness of the metal layer is preferably 0.01 to 0.2. The reason is that if the thickness is 0.01 or more, the adhesion between the resin insulation layer and the conductor circuit can be ensured, and if the thickness is 0.2 or less, the formation of a metal layer by sputtering can be prevented. Cracking occurs due to the problem of stress 59 The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) III I -------------------- Order ----- -— · Line (please read the “Notes on the back side before filling out this page”) 453 Ml Α7 Β7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (&lt; &gt; 《&gt; The metal layer between the conductors and circuits that are no longer needed can be easily removed by uranium etching. Also, other types of metal layers can be formed on the aforementioned metal layer as necessary. For example, nickel is formed on the interlayer resin insulation layer A copper layer is provided on the nickel layer to prevent plating from being deposited when a conductor circuit is formed. Furthermore, these metal layers are formed by electroless plating, electrolytic plating, sputtering, vapor deposition, CVD, etc. Method to form. _ Used by the sixth group of the present invention Grease substrates are generally different from ceramic substrates or metal substrates. They are not only easy to bend and have poor heat dissipation properties, but also cause copper migration due to accumulated heat. At this point, in the present invention, the metal layer prevents Barriers for copper ion migration from copper conductor circuits can ensure interlayer insulation even under high humidity conditions. The interlayer resin insulating layer in the sixth group of the present invention is preferably made of a thermosetting resin, heat A plastic resin or a composite resin of these. For the thermosetting resin, it is preferably selected from, for example, a thermosetting polyolefin resin, an epoxy resin, a polyimide resin, a phenol resin, and bis-cis-butyl. At least one kind of arylenediamine triazabenzene resin is used. As for the thermoplastic resin, it is preferable to use, for example, polymethacryl (PMP), polystyrene (PS), polyethersulfon (PES), Polyphenylene ether (PPE), polyphenylene sulfide (PPS), etc. In the present invention, it is preferable to use the polyolefin-based resin as the first group of the present invention for the interlayer resin insulating layer. This Polyolefin resin, due to Good tightness with conductor circuits, 60 paper sizes are applicable to China National Standard (CNS) A4 specifications (2) 0x297 public love) 11 ----------- I --- 11111 ^-I- --- 1 (谞 Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Therefore, it is not necessary to roughen the inner conductor circuit surface, but it can be formed Flat conductor circuit. In addition, this polyolefin resin has a dielectric constant of 3 or less, a dielectric loss factor of 0.05 or less, which is lower than that of epoxy resin, and high-frequency signals have no transmission delay. The heat resistance of olefin resins is not worse than that of epoxy resins, and there is no peeling of conductor circuits at the solder melting temperature. In addition, since its fracture toughness is also large, cracks from the interface between the conductor circuit and the resin insulation layer as a starting point will not occur due to thermal cycling. Below, the multilayer printed circuit board of the sixth group of the present invention An example of the manufacturing method is explained. (1) First, a circuit board having an inner layer copper pattern formed on the surface of a resin substrate is prepared. In this case, the circuit board can be produced by the same method using the method described in the first group of the present invention or the second group of the present invention. (2) A resin insulating layer is formed on both sides of the circuit board prepared in the above (1). The function of the resin insulating layer is to serve as an interlayer resin insulating layer of a multilayer printed circuit board. This resin insulating layer is formed by applying an unhardening agent and heat-pressing a thin film of resin. (3) Next, an opening is provided in this resin insulating layer to ensure its electrical connection with the underlying conductor circuit. This opening is perforated with laser light. At this time, the laser light used includes carbon dioxide laser, ultraviolet laser, excimer laser, and the like. Then, when it is perforated with carbon dioxide laser light, a decontamination process is performed. This 61 ------------- installation -----! _ Order --------- line (Please read the precautions on the back before filling this page) This paper size Applicable to China National Standard (CNS) A4 specification (2) 0 X 297 mm) Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 1 4 T A7 _ B7 5. Description of invention (w?) An oxidant made of an aqueous solution such as chromic acid, permanganate, etc. is used for the treatment, and the treatment can also be performed with an oxygen plasma, a mixture of CF4 and oxygen plasma, or a glow discharge. Furthermore, the surface can be improved by irradiating ultraviolet rays with a low-pressure mercury lamp. In particular, it is advantageous to use a plasma treatment of a mixture of CF and oxygen to introduce hydrophilic groups such as hydroxyl groups and carbonyl groups on the surface of the resin to facilitate subsequent CVD or PVD treatment. This is advantageous. (4) On the surface of the resin insulating layer provided with an opening in (3) above, at least one of metals (except Cu) from the 4th to 7th cycles of Group 4A to Group 1B is selected. A thin metal layer made of a seed metal is formed by a plating method, a PVD method, or a CVD method. Specific examples of the PVD method and the CVD method include the methods described in the first group of the present invention. (5) Next, on the metal layer formed in the above (4), the same metal layer as that of the electroless plating film in the following process is formed by sputtering or the like. This is to improve the affinity with the electroless plating film. Specifically, it is preferable to provide a copper layer by a sputtering method. (6) Next, electroless plating is performed on the metal layer formed by the aforementioned ⑸. In terms of electroless plating, copper plating is most preferable. The film thickness of electroless plating is preferably from 0.1 to 5 / zm. The reason is because it can be removed by etching without impairing the characteristics of the conductive layer of subsequent electrolytic plating. Therefore, electroless plating and / or selection from 62 to 4A to 1B This paper size applies the Chinese National Standard (CNS) A4 regulations (210 X 297 mm) ϋ ϋ II ϋ n IIII * n-----n-ί-r mouth, «ϋ ϋ I nn II (Please read first Note on the back, please fill out this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 14 1 A7 --------- B7 V. Description of Invention (Μ) Metals belonging to the 4th ~ 7th cycle (Except Cu), a thin metal layer made of at least one kind of metal of Al and Sn will become a conductor layer and be used for conductive plating. (7) A plating resist is formed on the electroless plating film formed in the above (6). This anti-plating film is formed by laminating a photosensitive dry film and then exposing and developing it. (8) Next, the electroless plating film after the process of (7) is selected from the metals belonging to the 4th to 7th cycles (excluding Cu), Al, and Sn from Groups 4A to 1B. A metal layer made of at least one kind of metal is formed by the above-mentioned electroplating method, PVD method, or CVD method. The formation of the aforementioned metal layer in this process is best formed by an electroless plating method. After that, the electroless plating film and the metal layer are used as conductive plating to perform electrolytic plating to thicken the conductor circuit. The thickness of the electroless plated film is preferably 5 to 30 / zm. (9) Next, after the anti-plating film is peeled off, the electroless plating film and the metal layer located directly below the anti-plating film are removed by etching to form an independent conductor circuit. For the etching solution used in this process, an aqueous solution of osmium persulfate such as sulfuric acid-hydrogen peroxide aqueous solution, ammonia persulfate, sodium persulfate, potassium persulfate, etc., an aqueous solution of ferric chloride, copper chloride, hydrochloric acid, nitric acid can be used. , Hot dilute sulfuric acid, etc. In addition, in this etching process, the aforementioned metal layer functions as a resist layer, which is helpful for forming an independent conductor circuit such as L / S = 15/15 // m. (10) According to its necessity, apply the 63 paper sizes on the surface of the above-mentioned conductor circuit to the Chinese National Standard (CNS) A4 (210 X 297 mm) 111 ---- * 4 ----- --II ------- (Please read the precautions on the back before filling this page) A7 45 ^ 141 _______B7 __ V. Description of the invention (A) The thin metal layer composed of the uncovered metal is electroplated, It is formed by the PVD method or the CVD method, and the multilayered double-sided printed circuit board is obtained by repeating the above-mentioned process (2b (9). In addition, as described above, the method for forming the conductor circuit is half. Additive method, but full addition method can also be used. This full addition method is based on the surface of the resin insulation layer after CVD or PVD treatment to set a thin metal layer, or laminated with a photosensitive dry film, or coated with a liquid The photosensitive resin is then subjected to exposure and development processing to provide an anti-mineral film. Then, electroless plating is used to thicken it to form a conductor circuit. Or, after an anti-plating film is formed on the surface of the resin insulating layer, CVD or PVD is used. Treat and set a thin metal layer, or re-attach the metal layer It can be removed by grinding, etc., and then the anti-plating film itself can be removed, and the electroless mineral deposit can be formed by using the metal layer as a catalyst to form a conductor circuit. In order to include at least the following processes (a) to (c), that is, U) the formation process of the first conductor layer composed of a metal with a passive film formed on the surface of Ni, A1, etc. on the insulating substrate; (b) in On the first conductor layer, a metal having a smaller ionization tendency than a metal forming a passive film on the surface such as Ni, A1 and the like constitutes the formation process of the second conductor layer; (c) Selective etching using an acidic etching solution The first conductor layer and the second conductor layer in a specific area are simultaneously etched. The formation method of the above-mentioned conductor circuit is to first apply the Chinese National Standard (CNS) A4 specification (210X297 mm) to the surface shape of the paper by etching. 11! -Packing ----: --- Order ----- ---- Line (Please read the precautions on the back before filling this page) Consumption Cooperation by Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Du A7 453 1 4 1 ____B7___ 5. Description of the Invention (昀) Metal ions forming a passive film The tendency to change is that small metals will dissolve, so that the metal forming a passive film on the surface of Ni, A1, etc. is exposed. If a metal with a passive film is exposed on the surface, this metal and a metal with a smaller ionization tendency than this metal will react with the battery due to the presence of an acidic etchant as an electrolyte. Ni, A1, etc. form a passive film The metal will dissolve. Therefore, in the case of an acidic etchant, a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, or a sulfuric acid-hydrogen peroxide mixed aqueous solution can be used instead of using an acid with an incompatible output such as aqua regia or nitric acid. In addition, by using an acidic etching solution, it is possible to achieve a faster etching rate than previously known. In the seventh group of the present invention, the metal of the passive film formed on the surface is preferably selected from at least one of Ni, Co, Cr, Ti, Nb, Ta, and A1. These metals easily form a passive film, which is not dissolved by a general acid etching solution. The metal of the passive film formed on the surface is particularly preferably Ni or A1. These metals have good adhesion to resin, and are most suitable for forming a conductor circuit of a printed circuit board. The following description is based on the illustration. In the description, an example of a metal with a passive film formed on the surface of Ni and A1 is used. Figs. 28 (a) to 28 are cross-sectional views schematically showing respective processes in the method for forming a conductor circuit of the present invention. The seventh group of the present invention first forms a first conductor layer 32 made of Ni $ W on an insulating substrate (see FIG. 28 (a)). The material of the insulating substrate 31 is not particularly limited, and may be ceramic, etc. ^ 65 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I—I — ------- 1 Order --------- Line (Please read the notes on the back before filling out this page> Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 彳 4 1 A7 B7 Printed by the Consumer ’s Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs System 5. The substrate of the MV material can also be a substrate made of organic materials such as resin. However, when the resin substrate is used with emphasis on the adhesion to the formed conductor layer, the adhesion to the substrate can be formed. From the viewpoint of a good conductive layer, the present invention is mainly directed to a resin substrate. The method for forming the first conductive layer 32 is not particularly limited, and examples thereof include a vapor deposition method and a plating method. In view of the fact that a conductive layer having excellent adhesion can be formed on a resin substrate, a vapor deposition method, particularly a sputtering method is preferred. When the first conductive layer 32 is to be formed by the sputtering method, it is The first conductor layer 32 to be formed is not oxidized, and the pressure is preferably reduced. It is performed in an atmosphere around a inert gas. Next, a second conductor layer 33 made of a metal having a smaller ionization tendency than Ni or A1 is formed on the insulating substrate 31 forming the first conductor layer 32 (see FIG. 33 (b)). ). Examples of metals having a smaller ionization tendency than Ni include metals such as Cu, Sn, and Pb. These metals can be used alone or in combination of two or more. That is, these metals can be provided. It is also possible to provide a plurality of layers made of these metals. Examples of metals having a smaller ionization tendency than A1 include, for example, Cu, Sn, Pb, and Fe. Similar metals may be used. It can be used singly or in combination of two or more types. The method for forming the second conductor layer 33 is not particularly limited, and examples thereof include a vapor deposition method and a plating method. If the same method is used before connection, The reason for the simple formation of the conductor layer is to use the same method as the method for forming the first conductor layer 32. 66 Good paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm i II ---- Order --------· Line (Please read the precautions on the back before filling (Write this page) A7 453141 ____B7____ 5. Description of the invention (〆) When the second conductor layer 33 is formed, in order to prevent the first conductor layer 32 from being oxidized, after the first conductor layer 32 is formed, do not expose it to the atmosphere In the surrounding atmosphere, it is preferable to form the second conductor layer 33 quickly. After the second conductor layer 33 is formed, the first conductor layer 32 and the second conductor layer in a specific region can be selectively etched by using an etchant. 33 Simultaneously etch to form a conductor circuit. There is no particular limitation on the method of selective etching, for example, 'after forming a resist layer on the conductor layer composed of the above two layers, the portion where the resist layer is not formed is performed using a plating method or the like After thickening, after peeling off the resist layer, 'the conductive layer originally existing under the resist layer is etched and removed to form a conductor circuit', this is an available method. Here, the former method is adopted. The latter method will be described in detail in a method for manufacturing a multilayer printed wiring board described later. That is, first, a resist layer 34 is formed on the second conductor layer 33 by a photolithography technique (see Fig. 28 (c)). After that, the portion other than the portion where the uranium-resistant layer is formed is removed by etching to form a conductor circuit β. At this time, the etching can be performed using an acidic etchant. As the acidic etching solution, for example, a solution that is generally easy to manage, such as a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, or a sulfuric acid-argon peroxide mixed aqueous solution, can be used. When the Ni layer is used as the first conductor layer 32, the Cu layer is used as the second conductor layer 33, and the etching solution is a sulfuric acid-hydrogen peroxide mixed aqueous solution ', the saturation is performed by the following mechanism. Firstly, according to the chemical formula Cu layer shown in (1) and (2) below, the paper layer was engraved with 67 paper sizes. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) was applied! · —! · ^ ·! — !! Order --------- line ί &lt; Please read the note on the back before filling in this page) Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 4531 4 1 ________ Β7_ V. Description of the Invention (4)

QQ

Cu + H2O2 CuO + H2O ---(1)Cu + H2O2 CuO + H2O --- (1)

CuO + H2S〇4 — Cu2+ + SO*2. + H2〇· · ·（2) 當Cu層被蝕刻而露出Ni層時，接著，Ni層的蝕刻將 開始。 欲將單獨之Ni層蝕刻之時，大體上，係認爲反應的進 行乃依據下述(3)及(4)所示之化學式。CuO + H2S〇4 — Cu2 + + SO * 2. + H2 (2) When the Cu layer is etched to expose the Ni layer, the etching of the Ni layer will then begin. When the separate Ni layer is to be etched, it is generally considered that the reaction proceeds according to the chemical formulae shown in (3) and (4) below.

Ni + H2〇2 NiO + H2O * * ♦ (3)Ni + H2〇2 NiO + H2O * * ♦ (3)

NiO + H2SO4 Ni2+ + SO42' + H2O · · · (4) 然而’在實際上，由上式(3)所產生之NiO其與mso 的反應’亦即(4)所記載之反應，幾乎不會進行，因此，表 面會爲氧化膜所覆蓋，Ni層幾乎不會遭蝕刻。 另一方面，依據本發明，由於具有Cu層及Ni層之2 層構造，乃形成以Cu層爲陰極、Ni層爲陽極之電池，而 依下述之(5)、（6)式進行反應。NiO + H2SO4 Ni2 + + SO42 '+ H2O (4) However,' In fact, the reaction between NiO and mso produced by the above formula (3) ', that is, the reaction described in (4), will hardly occur As a result, the surface is covered with an oxide film, and the Ni layer is hardly etched. On the other hand, according to the present invention, a two-layer structure having a Cu layer and a Ni layer forms a battery having a Cu layer as a cathode and a Ni layer as an anode. .

Cu2+ — Cu . · ·⑸Cu2 + — Cu. · · ⑸

Ni — Ni2+ · · · (6) 關於Cu，依上述蝕刻之時之氧化反應(離子化反應)與 依電池之還原反應會可逆的來進行，然由於Ni較Cu之離 子化傾向爲大，故就Ni而言，Ni金屬僅會進行成爲Νί離 子之不可逆反應，其結果，Ni於溶液中溶解，而進行著蝕 刻。又，因爲在此反應中不會形成氧化物，Ni乃成爲鈍性 化而反應之進行不會停止，故反應將進行至最後，蝕刻便 得以完成(參照圖28(d))。 68 本紙張尺度適用中國國家標準（CNS)A4規格（210 * 297公釐） ---------— -装------—訂---------線 (請先閲讀背面之注^^項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 B7 453 1 4 五、發明說明Ui ) 其後’藉由進行抗蝕層的剝離，於絕緣基板上形成由 第1導體層32及第2導體層33構成之導體電路(參照圖 28(e))。 本發明之第七群之導體電路的形成方法，係於Ni或 AI構成之第1導體層:32上’形成較Ni或A1之離子化傾向 爲小的金屬構成之第2導體層33之故，乃可採用鹽酸水溶 液等易於管理之酸以進行選擇性的蝕刻。又，由於在絕緣 基板上形成由Ni或A1構成之第1導體層32，特別是當絕 緣基板31係爲樹脂基板之時，因其表面平滑故可與基板形 成密接性良好之導體電路。 其次，針對本發明之第七群之第二發明之多層印刷電 路板的製造方法加以說明。 本發明之第七群之第二發明之多層印刷電路板的製造 方法，係於絕緣基板上，形成樹脂絕緣層與導體電路之多 層印刷電路板的製造方法中，其特徵爲，包含至少下述⑷ ~(e)之過程，亦即 (a) 於絕緣基板上由Ni、Al等表面形成鈍性膜之金屬 所構成之第1導體層的形成過程； (b) 於上述第1導體層上，較上述Ni、A1等表面形成 鈍性膜之金屬的離子化傾向爲小的金屬構成第2導體層的 形成過程； (c) 於上述第2導體層上形成防鍍膜的過程； (d) 於形成有防鍍膜之上述第2導體層上’以電鍰形成 第3導體層的過程； 69 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I! ------装 — ·1— 訂-1!1-線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 d531 4 1 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（β) (e)將防鍍膜剝離之後，使用酸性蝕刻液對存在於防鍍 膜之下的第1導體層及第2導體層同時予以蝕刻的過程。 本發明之第七群之第二發明之多層印刷電路板的製造 方法所使用之較於表面形成鈍性膜之金屬的離子化傾向爲 小的金屬以及酸性蝕刻液，與上述導體電路之形成方法所 採用之物完全相同即可。 又，於上述(e)之過程的蝕刻，係與上述導體電路之形 成方法時相同之機構來進行反應，以將存在於防鍍膜之下 的第1導體層及第2導體層同時予以蝕刻去除之。 又，於本發明之第七群之第二發明之多層印刷電路板 的製造方法中，就絕緣基板而言，係使用於樹脂基板上直 接形成導體電路之基板，又於其上可分別設置1層之樹脂 絕緣層及導體電路，或是亦可設置2層以上。又，使用不 形成導體電路之樹脂基板，而於其上可分別設置1層之樹 脂絕緣層及導體電路，或是亦可設置2層以上。又，上述 樹脂絕緣層及上述導體電路，可設置於樹脂基板的單面， 亦可設置於樹脂基板的兩面。 以下，對本發明之第七群之第二發明之多層印刷電路 板的製造方法的一例更加詳細說明之。 (1) 首先，於樹脂基板的表面製作具有下層導體電路(內 層銅圖案)的電路基板。 此時，可使用本發明之第一群或是本發明之第二群所 記載之方法以相同的方法製作電路基板。 (2) 接著，在上述(1)製作之電路基板的兩面形成樹脂絕 70 本紙張尺度適用中g固家標準（CNS)A4規格（210 X 297公釐） . I---裝--------訂---------線 (請先閲讀背面之;i意事項再填寫本頁) A7 453141 五、發明說明（M) 緣層。此樹脂絕緣層之功用係做爲多層印刷電路板之層間 樹脂絕緣層。 上述樹脂絕緣層，較佳係由熱硬化性樹脂'熱可塑性 樹脂，或是這些的複合樹脂所構成。 就熱硬化性樹脂而言，較佳者係例如擇自熱硬化性聚 烯烴樹脂、環氧樹脂、聚醯亞胺樹脂、苯酚樹脂、雙順丁 烯二醯胺三氮雜苯樹脂中至少一種加以使用。 就熱可塑性樹脂而言，較佳者係使用例如聚甲基丙烯 (PMP)、聚苯乙烯(PS)、聚醚磺(PES)、聚苯醚(PPE)、聚苯 撐硫(PPS)等工程樹脂》 (3) 其次，於此樹脂絕緣層(以下稱爲層間樹脂絕緣層) 中，爲確保與下層導體電路之電連接而設置通孔用開口。 若爲感光性樹脂，則於曝光、顯像之後進行熱硬化， 又，若爲熱硬化性樹脂或聚烯烴樹脂的情形，則藉由雷射 加工，於上述層間樹脂絕緣層設置通孔形成用開口。 就雷射加工時使用之雷射光而言，可舉出例如二氧化 碳雷射、紫外線雷射、準分子雷射等》 (4) 其次，做爲上述⑷之過程而言，於樹脂絕緣層上表 面形成鈍性膜之金屬，係形成例如Ni或A1構成之第1導 體層。 此第1導體層之形成方法雖無特別之限定，在鈍性氣 體之減壓周圍氣氛下，較佳者係藉由濺鍍來進行。上述第 1導體層的厚度以0.〇1〜0.5 爲佳。 藉此，於上述樹脂絕緣層上，可形成平坦而與樹脂絕 71 本紙張尺度適用中0國家標準（CNS)A4規袼&lt;210 X 297公釐） I 1 I — — 裝 ------ - 訂------^線 Λ請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局負工消費合作社印製 經濟部智慧財產局員工消費合作社印製 4 5 3 1 ^ ' A7 _ B7 五、發明說明（π) 緣層之密接性優良之第1導體層》 (5) 其次，做爲上述(b)之過程而言，於上述第1導體層 上，形成較Ni或A1等表面形成鈍性膜之金屬的離子化傾 向爲小的金屬構成之第2導體層。 此第2導體層之形成方法雖無特別之限定，在鈍性氣 體之減壓周圍氣氛下，較佳者係藉由濺鍍來進行。上述第 2導體層的厚度以〇.〇1〜〇.5&quot;m爲佳。 (6) 在上述(5)形成之第2導體層上，做爲上述(c)之過程 ，形成防鍍膜。 · 此防鍍膜之形成方法並無特別之限定，一般係將感光 性乾式薄膜進行積層後予以曝光、顯像處理而形成者。 (7) 其次’做爲上述(d)之過程，將無電解鍍敷膜做爲導 鍍層進行電鍍而形成第3導體層，以增厚導體電路。第3 導體層(電鍍膜)之膜厚，以5~30^m爲宜。 (8) 形成第3導體層之後’做爲上述(e)之過程，將防鍍 膜剝離，使用酸性蝕刻液將存在於防鍍膜之下的第1導體 層及第2導體層蝕刻去除，成爲獨立之導體電路 就酸性蝕刻液而言’可採用例如硫酸水溶液、鹽酸水 溶液或是硫酸_過氧化氫混合水溶液等使用上易於管〗里之 溶液。 (9) 又依必要性，於導體電路表面上，以電鍍法、氣^目 蒸鍍法(PVD法)或化學蒸鍍法(CVD法)形成Ni層，再 由重複上述(2)〜(8)的過程以製造多層化之印刷電路披。 本發明之第八群之第一發明之金屬膜的形成方法，其 72 本紙張尺度適用尹國國家標準（CNS)A4規格（210x297公釐） 裝--------—訂--------.線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453141 五、發明說明（⑴） 特徵係將Ni膜上存在之氧化膜以具有濃度2.0~10.0莫爾/ 升之還原性酸的水溶液去除之後，於上述之Ni膜的表面形 成其他的金屬膜。 只要依此種本發明之第八群之第一發明的構成，藉由 使用上述濃度的還原性酸，可將Ni膜上存在之氧化膜完全 去除之故，若於其上形成其他之金屬膜，2層之金屬層不 會受到氧化膜的阻隔，成爲直接接觸的狀態，因此，可形 成具有優良密接性之導體層的導體電路。 上述Ni膜係於絕緣性基板或金屬層上所形成得到的》 前述絕緣基板的材料並無特別之限定，可爲陶瓷等無機材 料構成之基板，亦可爲樹脂等有機材料構成之基板。又， 就金屬層而言，可使用銅製之導體電路。 又，Ni膜的形成方法並無特別的限定，例如可舉出如 氣相蒸鍍法、電鍍法等；Ni膜形成之後，若此Ni膜係暴 露在空氣中或氧化性之周圍氣氛中的條件下，於其表面容 易形成氧化膜。因而，此情況係適用於本發明中，使用上 述濃度之還原性酸的水溶液可將表面之氧化膜完全去除。 Νί膜的形成部分並無特別的限定，可直接形成於絕緣 基板上，亦可於已形之其他金屬膜上形成之。又，亦可於 絕緣基板上形成1層或2層之金屬膜及樹脂絕緣層，再於 其上形成Ni膜。 又’就於Ni膜上形成之其他的金屬而言，可使用之後 將提到的Cu —Ni —P所成之合金粗化層或金。 上述還原性酸的水溶液並無特別的限定，可採用例如 73 本紙張尺度適用中固國家標準（CNS)A4規格（210 X 297公笼） I •裝-----11--訂·！------線 (請先閲讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消f合作社印製 4 53 1 4 1 A7 B7 五、發明說明（p) 硫酸、硝酸、氫氟酸等。其中，又以使用或管理上簡單之 鹽酸爲佳。 又，於此Ni膜上形成之氧化膜，若使用一般上用以去 除氧化膜之硫酸、磷酸等氧化性之酸來去除是有所困難的 〇 使用之還原性酸的水溶液濃度，係爲2.0〜10_0莫爾/升 〇 上述還原性酸的水溶液濃度，若未達2.0莫爾/升時， 欲將Ni膜上之氧化膜完全去除會有困難，又’若超過10_0 莫爾/升時Ni膜會溶解掉，而不能達到去除氧化膜的效果 〇 較佳之還原性酸的水溶液濃度係爲4,0〜6.0莫爾/升。 又，上述還原性酸的水溶液溫度，以20〜40°C爲佳； 將上述還原性酸的水溶液接觸於Ni膜之時間以1~5分鐘爲 佳。 上述還原性酸的水溶液溫度若未達20°C時，欲將氧化 膜完全去除會有困難’又，若超過40°C時Ni膜會溶解掉’ 而不能達到去除氧化膜的效果。 於上述還原性酸的水溶液中浸漬的時間若未達1分鐘 時，欲將氧化膜完全去除會有困難，另一方面，於上述還 原性酸的水溶液中浸漬的時間達5分鐘時已經足夠，若浸 漬的時間再增加，就效率上來說是不希望見到的。 去除氧化膜之後，於Ni膜上形成之其他金屬的種類並 無特別之限定’可舉出Cu_Ni_P合金等之Ni與其他金屬 74 本纸張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公釐） -----裝---------訂——.——線 (請先閱讀背面之注項再填寫本頁) A7 d 53 1 4 1 ______B7___ 五、發明說明（叻） 構成之合金，Au、Cu等。 如此般，包含於上述Ni膜上形成其他金屬膜的過程’ 於形成之Ni膜上只要爲容易形成氧化膜之金屬膜的形成方 法，不論是哪一種方法皆適用於本發明’例如’下述印刷 電路板之製造方法的粗化層形成過程中’於導體電路設置 Ni膜後，設置Cu-Ni-P合金所構成之合金粗化層時可適 用；另外，於形成焊接凸塊之前的過程中，就用以形成焊 接凸塊的金屬層而言，於Ni膜上形成Au膜之時亦可適用 〇 其次，對本發明之第八群之第二發明之多層印刷電路 板的製造方法說明之。 本發明之第八群的第二發明之多層印刷電路板的製造 方法，爲包含有： (a) 於形成有下層導體電路之基板上設置層間樹脂絕緣 層，而於該層間樹脂絕緣層設置通孔用開口之過程； (b) 於前述層間樹脂絕緣層上形成金屬膜之過程； (c) 於前述金屬膜上形成防鍍膜之過程； (d) 於施行電鍍之後，形成Ni膜而於前述防鍍膜之間 形成電鍍膜及Ni膜之過程： (e) 去除前述防鍍膜之後，將既存於上述防鍍膜下之前 述金屬膜以蝕刻去除之而形成上層導體電路及通孔的過程 :以及 (D於前述上層導體電路上形成由Cu-Ni-P合金所構 成之粗化層的過程。 ______ 75 t張尺度適用中國國&amp;標率（CNS)A4規格（21G χ 297公爱） ' ' I I I--•裝 i—J! — 訂 * — !!·線 {請先閲讀背面之注$項再填窝本頁) 經濟部智慧財產局員工消費合作杜印製 A7 B7 453 1 4 五、發明說明（叫） 其特徵係於前述(e)之過程終:r之後，將存在於前述Ni 膜之氧化膜以具有濃度2.0~10.0獒爾/升的還原性酸的水溶 液予以去除。 只要依此種本發明之第八群之第二發明的構成，藉由 使用上述濃度的還原性酸’可將Ni膜上存在之氧化膜完全 去除之故，若於其上形成Cu-Ni-ρ合金粗化層，2 ‘層之 金屬層不會受到氧化膜的阻隔，成爲直接接觸的狀態，因 此，可形成具有優良密接性之導體層的導體電路。 又，於本發明之第八群之第二發明之多層印刷電路板 中，就樹脂基板而言，係使用於樹脂基板上直接形成導體 電路之基板，又於其上可分別設置1層之樹脂絕緣層及導 體電路，或是亦可設置2層以上。又，使用不形成導體電 路之樹脂基板，而於其上可分別設置2層以上之樹脂絕緣 層及導體電路。又，上述樹脂絕緣層及上述導體電路’可 設置於樹脂基板的單面，亦可設置於樹脂基板的兩面。 以下，對本發明之第八群之第二發明之多層印刷電路 板的製造方法的一例說明之。 (1) 首先，於樹脂基板的表面製作具有下層導體電路的 電路基板。 此時，可使用本發明之第一群或是本發明之第二群所 記載之方法以相同的方法製作電路基板。 (2) 在上述(1)製作之具有下層導體電路的電路基板之兩 面形成樹脂絕緣層·&gt;此樹脂絕緣層之功用係做爲多層印刷 電路板之層間樹脂絕緣層。 76 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐) I 霞i ----訂-------f-線 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 453 14 1 A7 --- B7 五、發明說明（π) 就構成上述樹脂絕緣層（以下稱爲層間樹脂絕緣層）之 材料而言，可舉出例如熱硬化性樹脂、熱可塑性樹脂，或 是這些的複合樹脂等β 本發明之第八群，就上述層間樹脂絕緣層而言，以採 用無電解鍍敷用黏著劑爲佳。此無電解鍍敷用黏著劑係於 硬化處理過之酸或是氧化劑中之可溶性耐熱性樹脂粒子， 又以於酸或氧化劑中分散之由難溶性之未硬化耐熱性樹脂 中所構成者爲最佳。藉由酸或是氧化劑容易的處理，耐熱 性樹脂粒子會被溶解去除，而可於此黏著劑的表面形成章 魚壺狀之錨定物所構成之粗化面。 於上述無電解鍍敷用黏著劑中，特別是就經硬化處理 之上述耐熱性樹脂粒子而言，（a)平均粒徑在ΙΟ/zm以下之 耐熱性樹脂(b)相對平均粒子徑大的粒子與相對平均粒子徑 小的粒子混合所得之粒子乃所希望的。此乃由於可藉由該 等粒子形成更複雜之錨定物之故。 就可使用之耐熱性樹脂而言，可舉出例如環氧樹脂、 聚亞醯胺樹脂、環氧樹脂與熱可塑性樹脂的複合體等。就 複合之熱可塑性樹脂而言，可舉出例如聚醚磺(PES)等。又 ，就溶解於酸或氧化劑溶液中之耐熱性樹脂粒子而言，可 舉出例如環氧樹脂(特別是經由胺系硬化劑硬化之環氧樹脂 爲佳）、胺樹脂等。 (3)其次，於形成之層間樹脂絕緣層，爲確保其與下層 導體電路之電連接而設置通孔用開口。 若使用上述無電解鍍敷用黏著劑時，藉由於曝光、顯 77 本紙張尺度適用令國國家標準（CNS)A4規格（210 X 297公釐) — — 一 — — —------農 — 1!11 訂--------- (請先閲讀背面之注意事項再填寫本頁) A7 4531 4 1 ____B7____ 五、發明說明（4 ) 像之後進行熱硬化：或者，若使用熱硬化性樹脂之時，則 於熱硬化之後藉由雷射加工，而於上述層間樹脂絕緣層設 置通孔用開口。 (4) 其次，將上述層間樹脂絕緣層表面粗化。若使用上 述無電解鍍敷用黏著劑時，將存在於上述層間樹脂絕緣層 表面之在酸或是氧化劑中爲可溶性的樹脂粒子，以酸或是 氧化劑溶解去除，而無電解鍍敷用黏著劑的表面粗化。 此處，就上述之酸而言，可舉出例如磷酸、鹽酸、硫 酸等無機酸；蟻酸、醋酸等有機酸，特別是以使用有機酸 爲佳。若使用有機酸，則於粗化處理之時，可使自通孔外 露之金屬導體層較難被腐蝕。 另一方面，就上述氧化劑而言，以使用鉻酸、過錳酸 鹽(過錳酸鈣)之水溶液爲佳》 (5) 其次，將已粗化之層間樹脂絕緣層表面的電路基板 賦予觸媒核。 所賦予之觸媒核，以使用貴金屬離子或貴金屬膠體爲 佳，一般而言，係使用氯化鈀或鈀膠體。又，爲固定觸媒 核乃以進行加熱處理爲佳。就此種觸媒核而言則以鈀爲佳 〇 (6) 其次，於賦予觸媒核之層間樹脂絕緣層表面施以無 電解鍍敷，而於粗化面的全面上形成無電解鍍敷膜。無電 解鍍敷膜的膜厚，以m爲佳。 其次，於無電解鍍敷膜上形成防鏟膜。 (7) 其次，於防鍍膜非形成部施以厚度5~20μιη的電鍍 78 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — — — !!装·----II 訂!! J ·線 《請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局負工消費合作社印製 經濟部智慧財產局貝工消費合作社印製 ^53 1 41 A7 _ B7 五、發明說明（η ) ，以形成上層導體電路及通孔。 又，於電鍍後，藉由擇自電解鍍鎳、無電解鍵鎳，或 是濺鍍之中至少1種的方法，以形成鎳膜。於上述鎳膜上 ，將易於析出Cu-Ni+-P所構成之電鍍合金。又，由於鎳 膜具有金屬阻膜的作用，故此後即使於蝕刻過程亦可達成 防止過度蝕刻的功效。 此處，就上述電鍍而言，以採用鍍銅爲佳。 再者，於去除防鍍膜之後，將存在於該防鍍膜下之無 電解鍍敷膜以硫酸及過氧化氫之混合液或過硫酸鈉、過硫 酸氨等水溶液所得之蝕刻液溶解去除，成爲獨立之上層導 體電路。 (8) 其次，將存在於上述無電解鍍敷鎳膜上之氧化膜以 具有濃度2.0〜10.0莫爾/升之還原性酸的水溶液去除。以上 述硫酸及過氧化氫之混合液等之蝕刻液，並不能將鎳膜上 之氧化膜去除。 (9) 其次，將去除氧化膜之基板浸漬於電鍍液中，而於 前述上層導體電路上面，形成多孔質Cu —Ni-Ρ合金粗化 層。 (10) 其次，就此基板上之層間樹脂絕緣層而言，例如 形成無電解鍍敷用黏著劑層。 (11) 再者，重複上述(3)〜(9)的過程設置上層之上層導體 電路，可得到例如單面3層，即雙面6層之多層印刷電路 板。 本發明之第九群之多層印刷電路板，係於設有下層導 79 本紙張尺度適用t國國家標準（CNS)A4規格（21〇 X 297公釐) --in---—訂----I I--線 (請先閱讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消費合作社印製 么 5 3 1 4 1 A7 一 B7 五、發明說明（π) 體電路之基板上，層間樹脂絕緣層及上層導體電路被依序 積層形成之多層化的多層印刷電路板，其特徵爲，至少於 上述下層導體電路(以下，僅稱爲導體電路。又，由於之後 的金屬層可形成於上層導體電路上，故於以下之說明，只 要未特別限定則所稱之導體電路係包含上層導體電路及下 層導體電路兩方）表面，形成擇自離子化傾向大於等於Sn 或小於等於A1之金屬及貴金屬群中至少1種的金屬構成之 金屬層，又於該金屬層上形成由Cu- Ni-P合金等構成之 粗化層。 依據此種本發明之第九群的構成，於上述導體電路表 面，因形成擇自離子化傾向大於等於Sn或小於等於A1之 金屬及貴金屬群中至少1種的金屬構成之金屬層之故，將 導體電路表面外露有粗化層之基板藉由酸等處理之時，由 於構成導體電路之銅及Cu — Ni-P合金等粗化層之間的局 部電池反應被抑制，乃可阻止導體電路的溶解。 又，特別在上述金屬層的表面藉由電鏟形成粗化層之 時，由於Cu-Ni- Ρ合金等金屬易於析出，故即使鍍液變 質，不會發生電鍍的未析出，而可確實的於導體電路上形 成由Cu-Ni- P所構成之針狀或多孔質狀的合金等粗化層 〇 又，上述金屬層，因其亦具有銅所成之導體電路的蝕 刻遮膜的功能，可防止導體電路的過度蝕刻。 上述金屬層，係形成於導體電路的上面，或是上面及 側面。又’上述金屬層及粗化層不一定要形成於導體電路 80 本紙張尺度適用中國國家標準（CNSXA4規格（210 X 297公爱) — — — — — — — — — — — ^ 11---J — 訂·!I-線 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消费合作杜印製 453 1 4 1 A7 B7 五、發明說明（1) 的全面上。因此，例如有時於最上層的導體電路上並無形 成上述金屬層及粗化層。 就上述金屬層所使用之金屬而言，可舉出上述A卜Cr 、Fe、Zn、Ni、Co、Sn 等，以及另外例如 Au、Ag、Pt、Pd 等貴金屬。因此，上述金屬層中，可使用擇自上述金屬及 上述貴金屬中至少1種以上之金屬。 上述金屬層的厚度，以0.1〜3/zm爲宜。若未達0.1 ’則無法抑制局部電池反應，若超過3/zm的厚度，則導 體電路本身的厚度會增加，由於層間樹脂絕緣層亦增厚之 故’欲形成小直徑的通孔會變得困難。層間樹脂絕緣層的 厚度較薄時，較容易成小直徑的通孔。Ni — Ni2 + ··· (6) For Cu, the oxidation reaction (ionization reaction) and the reduction reaction according to the battery at the time of the etching will proceed reversibly. However, Ni has a greater ionization tendency than Cu, so In the case of Ni, Ni metal only undergoes an irreversible reaction to become N ions. As a result, Ni is dissolved in the solution and etched. In addition, since no oxide is formed in this reaction, Ni becomes passive and the reaction does not stop, so the reaction proceeds to the end and the etching is completed (see Fig. 28 (d)). 68 This paper size applies to China National Standard (CNS) A4 specification (210 * 297 mm) -----------installed --------- ordered --------- line (Please read the note ^^ on the back before filling out this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 453 1 4 V. Description of the invention Ui) Afterwards, by peeling the resist layer, A conductive circuit including the first conductive layer 32 and the second conductive layer 33 is formed on the substrate (see FIG. 28 (e)). The method for forming the seventh group of the conductor circuit of the present invention is based on the formation of the first conductor layer made of Ni or AI: 32 to form a second conductor layer 33 made of metal having a smaller ionization tendency than Ni or A1. It is possible to use an easily manageable acid such as hydrochloric acid aqueous solution for selective etching. In addition, since the first conductor layer 32 made of Ni or A1 is formed on the insulating substrate, particularly when the insulating substrate 31 is a resin substrate, a conductive circuit with good adhesion to the substrate can be formed because the surface is smooth. Next, a method for manufacturing a multilayer printed circuit board according to the second invention of the seventh group of the present invention will be described. A method for manufacturing a multilayer printed circuit board according to the second invention of the seventh group of the present invention is a manufacturing method of a multilayer printed circuit board formed on an insulating substrate to form a resin insulating layer and a conductor circuit, which includes at least the following The process of ⑷ ~ (e), that is, (a) the formation process of the first conductor layer composed of a metal having a passive film on the surface of Ni, Al, etc. on the insulating substrate; (b) on the first conductor layer The formation process of the second conductor layer formed by a metal having a smaller ionization tendency than that of a metal forming a passive film on the surface such as Ni, A1, etc .; (c) a process of forming a plating resist on the second conductor layer; (d) The process of 'forming the third conductor layer by electromagnetism on the above-mentioned second conductor layer on which the anti-plating film is formed; 69 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) I! ---- --Installation— · 1— Order -1! 1-line (please read the notes on the back before filling out this page) Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs d531 4 1 A7 B7 Employees’ Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printing 5. Description of the invention (β) (e) After peeling off the anti-plating film Using an acid etching solution to the first conductor layer and second conductor layer under the plating film to be present in the anti-etching process simultaneously. The method for manufacturing a multilayer printed circuit board according to the second invention of the seventh group of the present invention uses a metal and an acidic etchant having a lower ionization tendency than a metal having a passive film formed on the surface, and the method for forming the above-mentioned conductor circuit. What is used is exactly the same. In addition, the etching in the step (e) is performed by the same mechanism as in the method of forming the conductor circuit described above, and the first conductor layer and the second conductor layer existing under the anti-plating film are simultaneously etched and removed. Of it. In the method for manufacturing a multilayer printed circuit board according to the second invention of the seventh group of the present invention, the insulating substrate is a substrate directly formed on a resin substrate to form a conductor circuit, and 1 may be provided thereon. Layer of resin insulation layer and conductor circuit, or two or more layers may be provided. Further, a resin substrate on which a conductor circuit is not formed is used, and one layer of a resin insulation layer and a conductor circuit may be provided thereon, or two or more layers may be provided thereon. The resin insulating layer and the conductor circuit may be provided on one surface of the resin substrate or on both surfaces of the resin substrate. Hereinafter, an example of a method for manufacturing a multilayer printed wiring board according to the second invention of the seventh group of the present invention will be described in more detail. (1) First, a circuit board having a lower-layer conductor circuit (inner-layer copper pattern) is prepared on the surface of a resin substrate. In this case, the circuit board can be produced by the same method using the method described in the first group of the present invention or the second group of the present invention. (2) Next, resin 70 is formed on both sides of the circuit board produced in (1) above. The paper size is applicable to the gs standard (CNS) A4 specification (210 X 297 mm). I --- Package --- ----- Order --------- line (please read the back of the page first; I will fill in this page) A7 453141 V. Description of the invention (M) Marginal layer. The function of this resin insulating layer is to serve as an interlayer resin insulating layer of a multilayer printed circuit board. The resin insulating layer is preferably composed of a thermosetting resin, a thermoplastic resin, or a composite resin thereof. The thermosetting resin is preferably at least one selected from a thermosetting polyolefin resin, an epoxy resin, a polyimide resin, a phenol resin, and a bis-butene diamidine triazabenzene resin. Use it. As for the thermoplastic resin, it is preferable to use, for example, polymethyl propylene (PMP), polystyrene (PS), polyether sulfonate (PES), polyphenylene ether (PPE), polyphenylene sulfide (PPS), etc. "Engineering resin" (3) Next, in this resin insulating layer (hereinafter referred to as an interlayer resin insulating layer), openings for through holes are provided to ensure electrical connection with the lower-layer conductor circuit. In the case of a photosensitive resin, thermal curing is performed after exposure and development. In the case of a thermosetting resin or a polyolefin resin, laser processing is used to provide through-hole formation for the interlayer resin insulating layer. Opening. The laser light used in laser processing includes, for example, carbon dioxide laser, ultraviolet laser, excimer laser, etc. (4) Secondly, as the above-mentioned process, on the upper surface of the resin insulation layer The metal forming the passive film forms a first conductor layer made of, for example, Ni or A1. Although the method for forming the first conductor layer is not particularly limited, it is preferably performed by sputtering under a reduced pressure ambient atmosphere of a passive gas. The thickness of the first conductive layer is preferably from 0.01 to 0.5. As a result, the resin insulation layer can be formed to be flat and completely insulated from the resin. The paper standard is applicable to the National Standard (CNS) A4 (<210 X 297 mm) I 1 I — — — --Order ------ ^ Thread ΛPlease read the notes on the back before filling out this page) Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economy Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 4 5 3 1 ^ 'A7 _ B7 V. Description of the invention (π) The first conductor layer with excellent adhesion of the edge layer "(5) Secondly, as for the process of (b) above, the first conductor layer is formed on the first conductor layer. A metal having a passive film on its surface, such as Ni or A1, has a small ionization tendency and is a second conductor layer made of a small metal. Although the method for forming the second conductor layer is not particularly limited, it is preferably performed by sputtering under a reduced-pressure ambient atmosphere of a passive gas. The thickness of the second conductor layer is preferably from 0.001 to 0.5 &quot; m. (6) On the second conductor layer formed in the above (5), as a process of the above (c), a plating resist is formed. · The method for forming the anti-plating film is not particularly limited, and it is generally formed by laminating a photosensitive dry film and then exposing and developing it. (7) Secondly, as the process of (d) above, the electroless plating film is electroplated as a conductive plating layer to form a third conductor layer to thicken the conductor circuit. The thickness of the third conductor layer (plating film) is preferably 5 to 30 ^ m. (8) After the formation of the third conductor layer, as the process of (e) above, the anti-plating film is peeled off, and the first conductor layer and the second conductor layer existing under the anti-plating film are etched and removed using an acidic etchant to become independent As for the conductor circuit of the acidic etching solution, for example, a solution in an easy-to-use tube such as a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, or a sulfuric acid-hydrogen peroxide mixed aqueous solution can be used. (9) According to necessity, the Ni layer is formed on the surface of the conductor circuit by electroplating, gaseous vapor deposition (PVD method) or chemical vapor deposition (CVD method), and the above steps (2) to (2) are repeated. 8) The process of manufacturing multilayer printed circuit boards. The eighth group of the first invention of the first invention of the method of forming a metal film, 72 paper sizes are applicable to the National Standard (CNS) A4 (210x297 mm). ------. Line (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453141 V. Description of the Invention (⑴) The feature is to use the oxide film existing on the Ni film to After the aqueous solution having a reducing acid having a concentration of 2.0 to 10.0 Moore / liter is removed, another metal film is formed on the surface of the Ni film. According to the constitution of the first invention of the eighth group of the present invention, by using a reducing acid having the above concentration, the oxide film existing on the Ni film can be completely removed, and if other metal films are formed thereon Since the two metal layers are not blocked by the oxide film and are in a state of direct contact, a conductor circuit having a conductive layer with excellent adhesion can be formed. The material of the above-mentioned insulating substrate obtained by forming the Ni film on an insulating substrate or a metal layer is not particularly limited, and may be a substrate made of an inorganic material such as ceramics, or a substrate made of an organic material such as resin. As the metal layer, a copper conductor circuit can be used. The method for forming the Ni film is not particularly limited, and examples thereof include a vapor deposition method and a plating method. After the Ni film is formed, if the Ni film is exposed to air or an oxidizing surrounding atmosphere, Under these conditions, an oxide film is easily formed on the surface. Therefore, this case is applicable to the present invention, and the oxide film on the surface can be completely removed by using an aqueous solution of a reducing acid having the above-mentioned concentration. The formation portion of the Νί film is not particularly limited, and it can be formed directly on the insulating substrate, or it can be formed on another formed metal film. Alternatively, one or two metal films and a resin insulating layer may be formed on an insulating substrate, and a Ni film may be formed thereon. As for other metals formed on the Ni film, an alloy roughened layer made of Cu-Ni-P or gold, which will be mentioned later, can be used. The above-mentioned aqueous solution of the reducing acid is not particularly limited, and for example, 73 paper sizes can be applied to the National Solid Standard (CNS) A4 specification (210 X 297 male cage) I • Installation ----- 11--Order ·! ------ line (please read the notes on the back before filling this page) printed by the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the cooperative 4 53 1 4 1 A7 B7 V. Description of the invention (p) Sulfuric acid, nitric acid, Hydrofluoric acid and so on. Among them, hydrochloric acid which is simple to use or manage is preferable. In addition, it is difficult to remove the oxide film formed on the Ni film using oxidizing acids such as sulfuric acid and phosphoric acid, which are generally used to remove the oxide film. The concentration of the aqueous solution of the reducing acid used is 2.0. ～ 10_0 Moore / liter. If the concentration of the above-mentioned reducing acid in the aqueous solution is less than 2.0 Moore / liter, it will be difficult to completely remove the oxide film on the Ni film, and if it exceeds 10_0 Moore / liter, Ni The film will dissolve, and the effect of removing the oxide film cannot be achieved. The preferred aqueous solution concentration of the reducing acid is 4,0 ~ 6.0 Moore / L. The temperature of the aqueous solution of the reducing acid is preferably from 20 to 40 ° C. The time for contacting the aqueous solution of the reducing acid with the Ni film is preferably from 1 to 5 minutes. If the temperature of the aqueous solution of the reducing acid is less than 20 ° C, it will be difficult to completely remove the oxide film ', and if it exceeds 40 ° C, the Ni film will dissolve' and the effect of removing the oxide film cannot be achieved. If the immersion time in the aqueous solution of the reducing acid is less than 1 minute, it may be difficult to completely remove the oxide film. On the other hand, the immersion time in the aqueous solution of the reducing acid is 5 minutes. If the dipping time is further increased, it is undesirable in terms of efficiency. After the oxide film is removed, the types of other metals formed on the Ni film are not particularly limited. Examples include Ni and other metals such as Cu_Ni_P alloy. 74 This paper applies the Chinese National Standard (CNS) A4 specification (2). X 297 mm) ----- install --------- order ——.—— line (please read the note on the back before filling this page) A7 d 53 1 4 1 ______B7___ V. Invention Description (lat) The alloy of Au, Cu, etc. In this way, the process of forming another metal film on the above-mentioned Ni film is included. As long as the method for forming a metal film that is easy to form an oxide film on the formed Ni film, any method is applicable to the present invention. In the process of forming a roughened layer of a printed circuit board manufacturing method, it is applicable when an alloy roughened layer made of a Cu-Ni-P alloy is provided after a Ni film is provided on a conductor circuit; in addition, a process before a solder bump is formed In terms of the metal layer used to form the solder bump, it can also be applied when forming the Au film on the Ni film. Secondly, the method for manufacturing the multilayer printed circuit board of the second invention of the eighth group of the present invention will be described. . A method for manufacturing a multilayer printed circuit board according to the second invention of the eighth group of the present invention includes: (a) providing an interlayer resin insulating layer on a substrate on which a lower-layer conductor circuit is formed; The process of opening for holes; (b) the process of forming a metal film on the aforementioned interlayer resin insulating layer; (c) the process of forming a plating protection film on the aforementioned metal film; (d) the formation of a Ni film and the The process of forming a plating film and a Ni film between the anti-plating films: (e) After removing the aforementioned anti-plating film, the above-mentioned metal film existing under the aforementioned anti-plating film is removed by etching to form an upper-layer conductor circuit and a through hole: and ( D. The process of forming a roughened layer made of Cu-Ni-P alloy on the aforementioned upper conductor circuit. ______ 75 t scales are applicable to China &amp; Standard (CNS) A4 specifications (21G x 297 public love) '' II I-- • Equipment i—J! — Order * — !! · Line {Please read the note on the back of the page before filling in this page) Consumer Cooperation between Intellectual Property Bureau of the Ministry of Economic Affairs, printed by A7 B7 453 1 4 5 2. Description of the invention (called) Its characteristics are described in (e) above Cheng Final: r Then, the oxide film of Ni present in the film to have a concentration of 2.0 to 10.0 mastiff Seoul / liter aqueous solution of a reducing acid to be removed. According to the constitution of the second invention of the eighth group of the present invention, the oxide film existing on the Ni film can be completely removed by using the reducing acid of the above-mentioned concentration. If Cu-Ni- is formed thereon, The rhodium alloy roughened layer, the metal layer of the 2 'layer is not blocked by the oxide film, and is in a state of direct contact. Therefore, a conductor circuit having a conductive layer with excellent adhesion can be formed. Moreover, in the multilayer printed circuit board of the second invention of the eighth group of the present invention, the resin substrate is a substrate used to directly form a conductor circuit on the resin substrate, and one layer of resin may be provided thereon. The insulation layer and the conductor circuit may be provided in two or more layers. In addition, a resin substrate on which a conductor circuit is not formed is used, and two or more resin insulation layers and a conductor circuit may be provided thereon. The resin insulating layer and the conductor circuit 'may be provided on one surface of the resin substrate or on both surfaces of the resin substrate. An example of a method for manufacturing a multilayer printed wiring board according to the second invention of the eighth group of the present invention will be described below. (1) First, a circuit board having a lower-layer conductor circuit is fabricated on the surface of a resin substrate. In this case, the circuit board can be produced by the same method using the method described in the first group of the present invention or the second group of the present invention. (2) A resin insulating layer is formed on both sides of the circuit substrate having the lower-layer conductor circuit produced in the above (1). &Gt; The function of this resin insulating layer is to serve as an interlayer resin insulating layer of a multilayer printed circuit board. 76 This paper size applies to China National Standard (CNS) A4 specification (210 x 297 mm) I Xia i ---- Order ------- f-line (Please read the precautions on the back before filling this page ) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by 453 14 1 A7 --- B7 V. Description of the invention (π) The above resin insulation layer (hereinafter referred to as the interlayer resin insulation layer) For example, materials such as thermosetting resins, thermoplastic resins, or composite resins thereof may be used. For the eighth group of the present invention, for the interlayer resin insulating layer, electroless plating is used. Adhesives are preferred. The adhesive for electroless plating is based on soluble heat-resistant resin particles in hardened acid or oxidizing agent, and is composed of hardly soluble non-hardened heat-resistant resin dispersed in acid or oxidizing agent. good. Through the easy treatment with acid or oxidant, the heat-resistant resin particles will be dissolved and removed, and a roughened surface made of octopus-shaped anchors can be formed on the surface of this adhesive. Among the above-mentioned adhesives for electroless plating, particularly for the above heat-resistant resin particles subjected to hardening treatment, (a) the heat-resistant resin having an average particle diameter of 10 / zm or less (b) has a relatively large average particle diameter. Particles obtained by mixing particles with particles having a relatively small average particle diameter are desirable. This is because more complex anchors can be formed by these particles. Examples of the heat-resistant resin that can be used include epoxy resins, polyurethane resins, composites of epoxy resins and thermoplastic resins, and the like. Examples of the composite thermoplastic resin include polyethersulfonic acid (PES). Examples of the heat-resistant resin particles dissolved in an acid or an oxidant solution include epoxy resins (especially epoxy resins hardened by an amine-based hardener), amine resins, and the like. (3) Secondly, in the formed interlayer resin insulating layer, openings for through holes are provided to ensure the electrical connection with the lower-layer conductor circuit. If the above-mentioned adhesive for electroless plating is used, due to exposure, the paper size of 77 papers is applicable to the national standard (CNS) A4 specification (210 X 297 mm). — — — — — ———-- Nong — 1! 11 Order --------- (Please read the notes on the back before filling this page) A7 4531 4 1 ____B7____ V. Description of the invention (4) Thermal curing after the image: Or, if using In the case of a thermosetting resin, after the thermosetting, a through hole opening is provided in the interlayer resin insulating layer by laser processing. (4) Next, roughen the surface of the interlayer resin insulating layer. If the above-mentioned adhesive for electroless plating is used, the resin particles that are soluble in acid or oxidant existing on the surface of the interlayer resin insulating layer are dissolved and removed with acid or oxidant, and the adhesive for electroless plating is removed. Roughened surface. Here, examples of the above-mentioned acids include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; and organic acids such as formic acid and acetic acid. In particular, organic acids are preferably used. If an organic acid is used, the metal conductor layer exposed from the through hole can be hardly corroded during the roughening treatment. On the other hand, as for the above oxidizing agent, it is better to use an aqueous solution of chromic acid and permanganate (calcium permanganate). (5) Next, the circuit board surface of the roughened interlayer resin insulating layer is provided with a contact Media core. The catalyst core provided is preferably a noble metal ion or a noble metal colloid. Generally, a palladium chloride or a palladium colloid is used. In addition, it is preferable to heat-treat the catalyst core. For this type of catalyst core, palladium is preferred. (6) Next, electroless plating is applied to the surface of the interlayer resin insulation layer provided to the catalyst core, and an electroless plating film is formed on the entire surface of the roughened surface. . The thickness of the electroless plated film is preferably m. Next, an anti-shovel film is formed on the electroless plated film. (7) Secondly, apply a thickness of 5 to 20 μm to the non-formed part of the anti-plating film. The paper size is 78. This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). — — — — — — !! --- Order II! J · Line "Please read the notes on the back before filling out this page) Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Shell Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 53 1 41 A7 _ B7 V. Description of the invention (η) to form upper-layer conductor circuits and vias. After plating, a nickel film is formed by selecting at least one of electrolytic nickel plating, non-electrolytic bond nickel, or sputtering. On the above-mentioned nickel film, a plating alloy composed of Cu-Ni + -P will be easily precipitated. In addition, since the nickel film functions as a metal barrier film, the effect of preventing over-etching can be achieved even after the etching process. Here, for the above-mentioned electroplating, it is preferable to use copper plating. Furthermore, after the anti-plating film is removed, the electroless plating film existing under the anti-plating film is dissolved and removed with a mixed solution of sulfuric acid and hydrogen peroxide or an aqueous solution such as sodium persulfate and ammonia persulfate, and becomes independent. Upper conductor circuit. (8) Next, the oxide film existing on the above electroless plated nickel film is removed with an aqueous solution having a reducing acid having a concentration of 2.0 to 10.0 mol / liter. The above etching solution such as a mixed solution of sulfuric acid and hydrogen peroxide cannot remove the oxide film on the nickel film. (9) Next, the substrate from which the oxide film is removed is immersed in a plating solution, and a porous Cu-Ni-P alloy roughened layer is formed on the upper conductor circuit. (10) Next, as an interlayer resin insulating layer on the substrate, for example, an adhesive layer for electroless plating is formed. (11) Furthermore, by repeating the above steps (3) to (9) and setting the upper-layer and upper-layer conductor circuit, for example, a multilayer printed circuit board having three layers on one side, that is, six layers on both sides can be obtained. The multi-layer printed circuit board of the ninth group of the present invention is provided with a lower layer guide 79. The paper size is applicable to the national standard (CNS) A4 specification (21〇X 297 mm) --in ----- order-- --I I-- line (Please read the notes on the back before filling in this page) Is it printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs? 5 3 1 4 1 A7 A B7 V. Description of the invention (π) The multilayer printed circuit board in which the interlayer resin insulating layer and the upper conductor circuit are sequentially laminated on the substrate is characterized in that it is at least lower than the above-mentioned lower conductor circuit (hereinafter, simply referred to as a conductor circuit.) The layer can be formed on the upper conductor circuit, so in the following description, as long as it is not particularly limited, the so-called conductor circuit includes both the upper conductor circuit and the lower conductor circuit.) The surface is formed with a selective ionization tendency greater than or equal to Sn or less than A metal layer composed of at least one of the metals of the metal A1 and the precious metal group, and a roughened layer composed of a Cu-Ni-P alloy or the like is formed on the metal layer. According to the structure of the ninth group of the present invention, a metal layer composed of at least one metal selected from the group consisting of a metal having an ionization tendency of Sn or higher and A1 or less and a precious metal group is formed on the surface of the conductor circuit. When a substrate with a roughened layer exposed on the surface of a conductor circuit is treated with an acid or the like, the local battery reaction between the roughened layers such as copper and Cu—Ni-P alloy constituting the conductor circuit is suppressed, which can prevent the conductor circuit. Of dissolution. In addition, especially when a roughened layer is formed on the surface of the metal layer by an electric shovel, metals such as Cu-Ni-P alloy are easily precipitated. Therefore, even if the plating solution is deteriorated, unprecipitated plating does not occur. A roughened layer such as a needle-like or porous alloy made of Cu-Ni-P is formed on a conductor circuit. The above metal layer also functions as an etching mask for a conductor circuit made of copper. Prevents excessive etching of conductor circuits. The above-mentioned metal layer is formed on the upper surface of the conductor circuit, or on the upper and side surfaces. Also, the above-mentioned metal layer and roughened layer do not have to be formed on the conductor circuit. J — Order ·! I-line (please read the precautions on the back before filling this page) Du Cooperation of Intellectual Property Bureau, Ministry of Economic Affairs, employee printing 453 1 4 1 A7 B7 5. The comprehensive description of invention (1). Therefore For example, the above-mentioned metal layer and roughened layer may not be formed on the uppermost conductor circuit. Examples of the metal used in the above-mentioned metal layer include the above-mentioned Cr, Fe, Zn, Ni, Co, and Sn. And other precious metals such as Au, Ag, Pt, and Pd. Therefore, the above metal layer can use at least one metal selected from the above metals and the above noble metals. The thickness of the above metal layer is 0.1 to 3 / zm is suitable. If it is less than 0.1 ', local battery reaction cannot be suppressed. If it exceeds 3 / zm, the thickness of the conductor circuit itself will increase. Because the interlayer resin insulation layer is also thickened, it is intended to form a small-diameter Holes can become difficult. Interlayer resin When the thickness of the edge layer is thin, relatively easily as a through-hole of a small diameter.

Cu - Ni- P構成之針狀或多孔質狀合金的粗化層，其 全體的厚度以l〜7#m爲宜。 在達到上述厚度的情形下，層間樹脂絕緣層的間隔以 及導體電路的間隔將可比習知之多層印刷電路板小，而能 達成多層印刷電路板的高密度化及輕量化。The roughened layer of a needle-like or porous alloy made of Cu-Ni-P preferably has a thickness of 1 to 7 # m as a whole. When the thickness is as described above, the distance between the interlayer resin insulating layers and the distance between the conductor circuits can be smaller than that of a conventional multilayer printed circuit board, and the density and weight of the multilayer printed circuit board can be increased.

Cu—m-p合金等粗化層的形狀，以針狀及多孔質狀 爲宜。將上述粗化層以電鍍處理而形成之時，上述粗化層 的形狀，會隨界面活性劑的種類而變化，然欲形成針狀或 多孔狀之粗化層時，則必須對其條件加以選定之51 就本發明之第九群之粗化層而言，除了 Cu-Ni-P所 構成之針狀或多孔質狀合金之外，亦可形成Cu-Ce-P所 構成之電鍍凹凸或電鍍銅塊。 於形成電鍍銅塊之時，就鍍液而言’可使用例如 81 本紙張尺度適用中國國家栋準（CNS)A4規格（210 X 297公釐) — II 11-----裝·!—訂·！-線 (請先閱讀背面之注意事項再填寫本頁) A7 453141 _____B7___ 五、發明說明（紗） 22〜38 g/Ι之銅化合物、10〜20 g/Ι之錯化劑、150~250 g/Ι之 焦磷酸鹽、5~10 g/Ι硝酸鹽、1〜3 g/Ι氨、10〜25 g/1??之水溶 液。就錯化劑而言，可使用EDTA或酒石酸鉀鈉。 就本發明之第九群，係於Cu- Νι-Ρ合金粗化層的表 面，乃希望形成離子化傾向較Cu爲高且在Ti以下之金屬 ，或是由貴金屬所構成之被覆層(以下，稱爲粗化層被覆層 )。又，此粗化層被覆層的厚度，以〇.l~2;zm爲佳。 藉由這些金屬之粗化.層被覆層的形成，可防止電解質 溶液與粗化層之直接接觸。又，由於這些金屬層本身會被 氧化而形成緻密的氧化膜，乃可防止粗化層或是導體電路 的溶解。 就離子化傾向較Cu爲高且在Ti以下之金屬而言，可 舉出例如 Ti、Al、Zn、Fe、In、Ή、Co、Ni、Sn、Pb、Bi 等。又，就上述貴金屬而言，可舉出例如Au、Ag、Pt、Pd 等。因此，上述粗化層被覆層即可擇自上述金屬及上述貴 金屬中至少1種來使用。又這些金屬當中，特別以Sn爲所 希望者。因爲Sn經過無電解置換電鍍可形成薄層，故可 沿著粗化層之凹凸處進行析出形成。 使用上述金屬中的Sn時，使用到氟硼化錫一硫脲液或 是氯化錫-硫腺液。此時，藉由Cu-Sn置換反應可形成 0.01〜左右的Sn層。又，使用貴金屬之時，可採用濺 鍍、蒸鍍等方法或藉由簡單之置換形式的電鍍液的電鍍處 理方法。 本發明之第九群之中於導體電路表面形成之金屬層’ 82 . 本紙張尺度適用中國國家標準（CNS&gt;A4規格（210 X 297公釐） ----— II 訂·！------ (請先閱讀背面之注意事項再填寫本頁〕 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 4 53 1 4 1 A7 B7 五、發明說明（？丨） 可藉由電鍍、無電解鍍敷'濺鍍、蒸鍍法等形成之。 實施無電解鍍鎳、電鍍鎳、無電解鍍錫、無電解鍍銘 ，以及無電解鍍鈀時，可使用與本發明相同之方法。 實施電解鍍鉻之時，係將含有250〜350 g/Ι之無水鉻酸 、12〜20 g/Ι之氟矽化鈉以及0.1〜0.5 g/Ι之硫酸之水溶液做 爲鍍浴，將基板浸漬於此鍍浴之後，以1〇~30 A/dm2的電流 密度通電即可。 又，於形成由A1構成之上述金屬層之時，因電鍍的進 行有困難，故以濺鍍形成上述金屬層。 實施無電解鍍鋅之時，係使用含有1〇〇〜800 g/Ι之氫氧 化鈉以及50〜200 g/Ι之氧化鋅的水溶液，以常溫實施電鍍 處理。 實施電鍍鐵之時，係將含有100-400 g/Ι之硫酸亞鐵以 及50-200 g/l之硫酸氨的水溶液做爲鍍浴，將基板浸漬於 此鍍浴之後，以6〜10 A/dm2的電流密度通電即可。 其次，於本發明之第九群，針對在導體電路的表面使 Cu-Ni —P合金之電鍍層等析出成長，而用以形成粗化層 之電銨方法加以說明。 本發明之第九群，係將形成有下層導體電路之基板， 浸漬於含有錯化劑、銅化合物、鎳化合物、次亞磷酸塩、 乙烯之聚氧化乙烯系界面活性劑所成之電鍍水溶液中，藉 由對基板予以振動或搖動，或是供給金屬離子，以析出成 長Cu-Ni-Ρ所成之多孔質合金，而形成被覆層及粗化層 構成之合金的粗化層。又，電鍍水溶液中，銅離子濃度、 83 本紙張尺度適用中國因家標準（CNS&gt;A4規格（210 X 297公茇） ^----------------- {請先A3讀背面之注意事項再填ic本頁) 經濟部智慧財產局員工消费合作社印製 4 5314 1 A7 B7 五、發明說明（卜） 鎳離子濃度、次亞磷酸離子濃度、錯化劑濃度’其分別調 整至 0.007〜0.160 mol/卜 0·001~0·023 mol/1、0.1 〜1.0 mol/卜 0.01 〜0.2 mol/1 爲宜。 就上述錯化劑而言，可舉出例如檸檬酸、酒石酸、蘋 果酸、EDTA，乙二胺、甘氨酸等。 就含有乙烯之聚氧化乙烯系界面活性劑而言’使用具 有上述(2)式或(3)式構造之物爲最佳。就此界面活性劑而言 ，可舉出例如2, 4, 7, 9一四甲基一5—癸烷 一4, 7—二醇 、3, 6—二甲基—4一辛炔一 3, 6 —二醇等烯二醇。就這些的 市售品而言，可舉出例如日信化學工業製造之沙費諾魯 104(多孔質狀）、同440、同465、同485 (皆爲針狀)等。 由此種無電解鍍敷液所析出之Cu-Ni-P合金’其表 面係成爲針狀或多孔質狀。就多孔質合金而言，其微孔的 數目，在lcm2爲100,〇〇(M,000,000之範圍內，而一般包含 之範圍爲3,000,000~300,000,000。又，其微孔的直徑，爲 0.01〜100/im之範圍，而一般包含之範圍爲0.1~1〇νπιβ 本發明之第九群之多層印刷電路板中，就於上述導體 電路上形成之層間樹脂絕緣層而言，以使用無電解鍍敷用 黏著劑爲佳。此無電解鍍敷用黏著劑，係在硬化處理過之 酸或是氧化劑中之可溶性的耐熱性樹脂粒子，又以在酸或 氧化劑中其分散於難溶性之未硬化的耐熱性樹脂中所成者 爲最佳。藉由以酸或是氧化劑之溶液的處理，可溶解去除 掉耐熱性樹脂粒子，而可於此黏著劑之表面形成章魚壺狀 錨定物構成之粗化面。 84 本紙張尺度適用中國國家標準&lt;CNS&gt;A4規格（2】0 X 297公釐) I 1--------t-------訂---------線 (請先閱讀背面之注意事項再洗穷本頁) Α7 Β7 經濟部智慧財產局員工消费合作社印製 453 1 4 1 五、發明說明（？）） 於上述無電解鍍敷用黏著劑之中，特別是就經過硬化 處理之上述耐熱性樹脂粒子而言、以1)平均粒徑在10/im 以下之耐熱性樹脂粉末、2)由相對平均粒徑大的粒子與相 對平均粒徑小的粒子混合所得之粒子爲佳。其原因係這些 物質可形成更爲複雜的錨定物。 就可使用之耐熱性樹脂而言，可舉出例如環氧樹脂、 聚醯亞胺樹脂 '環氧樹脂與熱可塑性樹脂的複合體等。就 複合之熱可塑性樹脂而言，可舉出例如聚醚磺(PES)等。又 ，就溶解於酸或是氧化劑之溶液的耐熱性樹脂粒子而言， 可舉出例如環氧樹脂(特別以胺系硬化劑使其硬化之環氧樹 脂爲佳）、胺樹脂等。 又，就本發明之第九群所使用之防焊劑而言，可舉出 例如環氧樹脂丙烯酸酯及咪唑硬化劑所成之物。 其次，針對本發明之第九群之多層印刷電路板的製造 方法說明之。 (1)首先，於核心基板的表面製作形成有內層銅圖案(下 層導體電路)的電路基板。 對此核心基板之下層導體電路的形成，係藉由蝕刻銅 面積層板來進行，或是，係依照下面的方法來進行。亦即 ，於玻璃環氧基板、聚醯亞胺基板、陶瓷基板、金屬基板 等之基板上形成無電解鍍敷用黏著劑層，接著，將此黏著 劑層表面粗化之後，以電解電鍍形成導體層，再將此導體 層蝕刻以形成下層導體電路。 又，於核心基板中形成通孔，而透過此通孔表裡面之 85 本紙張尺度適用中國囤家標準（CNS)A4規格（210 χ 297公釐） 1— II------^-------— It---------線 (請先閱讀背面之注意事項再填寫本頁) 4531 4 1 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（叫） 電路層得以電連接。 又’可於舰及核心、顏之下層導賴路卩 以保持平滑性。 特別於本發明之第九群中，對核心基板之下層 路表面具有之通孔的焊墊表面’形成捧自上述&amp;、 、Zn、N!、C。、Sn以及貴金屬中至少丨種的金屬構^之^ 屬層，又於該金屬層上形成針狀或多孔質狀的Cu__ 合金等構成之粗化層。再者’依必要性，於上述^化~層上P 形成前述粗化層被覆層。 (2) 其次’於上述α)製作的電路基板上，形成層間樹脂 絕緣層。特別是就本發明而目’做爲餍間樹脂絕緣層的材 料，則以使用前述之無電解鑛敷用黏著劑爲佳。 (3) 將形成之無電解鏟敷用黏著劑層乾燥之後，依其必 要設置通孔形成用開口。若爲感光性樹脂時，則於曝光、 顯像之後進行熱硬化，而爲熱硬化性樹脂的情形，則於熱 硬化後進行雷射加工，藉此於上述層間樹脂絕緣層設置通 孔形成用開口。 (4) 其次，將存在於已硬化之上述無電解鍍敷用黏著劑 層（層間樹脂絕緣層)表面之對酸或氧化劑爲可溶性的樹脂 粒子，藉由酸或氧化劑溶解去除之，以粗化無電解鍍敷用 黏著劑層之表面。 此處，就上述之酸而言，可舉出例如磷酸、鹽酸、硫 酸等無機酸；蟻酸、醋酸等有機酸，特別是以使用有機酸 爲佳。若使用有機酸，則於粗化處理之時，可使自通孔外 86 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝—-----訂---------線 (請先閲讀背面之注意事項再填寫本頁) A7 453141 ____B7_ 五、發明說明（打） 露之金屬導體層較難被腐蝕。 另一方面，就上述氧化劑而言，以使用鉻酸、過錳酸 鹽(過錳酸鈣)之水溶液爲佳。 (5) 其次，將已粗化之層間樹脂絕緣層表面的電路基板 賦予觸媒核。 所賦予之觸媒核，以使用貴金屬離子或貴金屬膠體爲 佳，一般而言，係使用氯化鈀或鈀膠體。又，爲固定觸媒 核乃以進行加熱處理爲佳。就此種觸媒核而言則以鈀爲佳 〇 (6) 其次，於賦予觸媒核之層間樹脂絕緣層表面施以無 電解鍍敷，而於粗化面的全面上形成無電解鍍敷膜。無電 解鍍敷膜的膜厚，以0.5~5//ιη爲佳。 其次，於無電解鍍敷膜上形成防鍍膜。 (7) 其次，於防鍍膜非形成部施以厚度的電鍍 ，以形成上層導體電路及通孔。 此處，就上述電鍍而言，以使用鍍銅爲佳。 再者，將金屬層及無電解鍍敷膜蝕刻之時做爲阻蝕層 係形成擇自Α卜Cr、Fe、Zn、Ni、Co、Sn以及貴金屬中至 少1種的金屬構成之金屬層。 又，將防鑛膜去除之後，將存在於該防鍍膜下之無電 解鍍敷膜以硫酸及過氧化氫之混合液或過硫酸鈉、過硫酸 氨等水溶液所成之蝕刻液溶解去除，以成爲獨立之導體電 路。 又，由於在銅構成之上層導體電路形成有擇自Ai、Cf 87 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） I---I --------- I---訂 I ! - &lt;請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消.f合作杜印製 453 Μ 1 五、發明說明（#) 、Fe、Zn、Ni、Co、Sn以及貴金屬中至少1種的金屬所成 之金屬層其做爲電阻層之故，不會受到蝕刻。 又，擇自Al、Cr、Fe、Zn、Ni、Co、Sn以及貴金屬中 至少1種的金屬構成之金屬層可在設置獨立之上層導體電 路及通孔後，於上層導體電路及通孔的側面及上面形成之 〇 ⑻接著，於形成有擇自Al、Cr、Fe、Zn、Ni、Co、Sn 以及貴金屬中至少1種的金屬所成之金屬層的上層導體電 路上面，形成Cu — Ni — P合金所成之粗化層。 由於上述金屬層的表面容易發生氧化還原反應’故容 易析出Cu —Ni-P所成之電鍍合金。 (9) 其次，於Cu-Νί-Ρ合金的表面，形成離子化傾向 較Cu爲高且在Ti以下之金屬或是貴金屬所構成之粗化層 被覆層。 (10) 之後，於形成有上述上層導體電路之基板上’做 爲層間樹脂絕緣層，乃形成無電解鍍敷用黏著劑層。 (11) 再者，重複上述(3)〜(10)的過程設置上層之上層導 體電路，可得到例如單面3層，即雙面6層之多層印刷電 路板。 上述(3)〜(10)的過程中，於設置通孔形成用之開口後， 係將表面以鉻酸粗化’又鉻酸處理亦可防止導體電路的溶 解。 ..又，以上之說明，其例子雖以所謂之半加成法製造多 層印刷電路板，然亦可將無電解鍍敷用黏著劑層粗化後’ 88 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 I . ---------I — ------I-- t請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 d5314 1 A7 _____B7___ 五、發明說明（巧） 賦予觸媒核、設置防鍍膜，再進行無電解鍍敷以形成導體 電路，即所謂之全加成法亦可適用。 本發明之第十群之多層印刷電路板的製造方法，係於 形成導體電路後施以粗化處理而於導體電路上形成粗化面 ，具有上述粗化面之導體電路以層間樹脂絕緣層被覆之後 藉由通孔用開口之形成過程不斷的重複，於絕緣性基板上 夾有層間樹脂絕緣層之複數層所成之導體電路的形成，其 特徵爲，於導體電路上形成粗化面後，藉由施以氧化處理 ，以使得上述粗化面之表面整體形成氧化膜，之後，形成 層間樹脂絕緣層。 依本發明之第十群之構成，於導體電路上形成粗化面 之後，藉由將基板加熱處理等簡單的方式，而可於此整體 表面形成氧化膜，並可將多層印刷電路板之製造過程簡略 化，再者，可形成與下層導體電路有良好密接性之通孔， 而可製造充分確保通孔與導體電路之連接可靠度的多層印 刷電路板。 圖49(a)〜(c)係表示本發明之氧化膜的形成過程之剖面 圖，圖50(a)〜(c)係表示習知之氧化膜的形成過程之剖面圖 〇 於本發明之第十群，如圖49所示般，於導體電路105 上形成粗化層111之後(參照圖49(a))，於粗化層111(粗化 面)之整體表面形成氧化膜118(參照圖49(b))，之後再形成 層間樹脂絕緣層102及通孔1〇6(參照圖49(c))。 藉由上述過程形成之氧化膜118,由於在以層間樹脂 89 -I I I I ---裝· ！11!訂!1 — ! (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規袼（2】0 X 297公釐） A7 4 53 1 4 1 _______B7_ 五、發明說明（Μ ) 絕緣層覆蓋之部分及自層間樹脂絕緣層外露之部分皆已覆 蓋該氧化膜，即使與粗化液接觸亦不會發生局部電池反應 。因此，相對於氧化劑等將具有耐腐蝕性，即使於之後過 程在酸洗淨等當中於導體電路表面與酸性溶液等接觸之時 ，亦不會發生導體電路105表面(粗化層)溶解及空孔等的 情形。 又，習知亦是於導體電路105上形成粗化層111之後( 參照圖50(a))，在此導體電路105上形成層間樹脂絕緣層 102,接著設置通孔用開口 106(參照圖50(b))，而爲了將層 間樹脂絕緣層102完全硬化乃以150°C使其熱硬化。 然而，欲使此種層間樹脂絕緣層102硬化之時的加熱 ，由於僅通孔用開口 106被氧化而形成氧化膜Π8，若粗 化液自層間樹脂絕緣層102滲透，氧化膜118及導體電路 105之間將發生局部電池反應，於是發生空孔H9(參照圖 50(c))。 就導體電路上形成粗化面的方法而言並無特別之限定 ，可舉出蝕刻處理、黑化還原處理、電鍍處理等。 就上述蝕刻處理方法而言，可舉出例如將銅錯合物與 有機酸構成之蝕刻液以氧共存化使之作用的方法，就電鍍 處理方法而言，可舉出例如藉由無電解鍍敷以形成由Cu-Ni-P合金構成之針狀或是多孔質狀的粗化層。 藉由上述電鍍處理或蝕刻處理等方法於導體電路上形 成粗化面之後，就於上述粗化面之表面形成氧化膜的方法 而言並無特別的限定，雖可採用含有氧化劑等溶液使其與 90 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝·！---—訂 -------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作钍印製 經濟部智慧財產局員工消費合作社印製 4531 4 1 A7 __B7 ____ 五、發明說明（^ ) 導體電路表面接觸之方法，但亦可將經過上述過程之基板 ，於大氣周圍氣氛下，藉由以80~200°C加熱10分鐘〜3小 時，而施以氧化處理，於上述粗化面之整體表面形成氧化 膜的方法，其具有簡單、可形成緻密氧化膜等特點，故爲 所希望採用之法。 氧化處理的溫度以130~160°C爲佳，氧化處理的時間 則以10〜180秒爲佳。 藉由上述氧化處理，0.01~0.2#ιη左右厚度之氧化膜將 於其表面形成，而粗化層的形狀則大致保持其原狀。- 又，由於此氧化膜對氧化劑等具有耐腐蝕性，即使於 導體電路表面設置Sn等金屬被覆膜，於之後過程對基板行 酸洗淨之時，或是對設有通孔用開口之層間樹脂絕緣層表 面以鉻酸等進行粗化處理之時，亦不會發生導體電路表面 溶解及空孔等的情形。 因此，於表面形成有氧化膜的導體電路上，可形成與 該導體電路具有良好密接性之層間樹脂絕緣層。 又，於此層間樹脂絕緣層形成通孔用開口之後，此形 成之通孔其與下面之導體電路具有良好之密接性。 本發明之第十群之多層印刷電路板，係於其表面以粗 化面構成之形成有導體電路之基板上形成層間樹脂絕緣層 ，而於上述層間樹脂絕緣層形成通孔用開口，接著，於上 述通孔用開口形成導電體以構成通孔之多層印刷電路板之 中，其特徵爲，於上述以粗化面構成之導體電路表面整體 ，形成有由上述氧化膜所成之被覆層。 91 本紙張尺度適用中國國家標準（CNS)A4規格（2]0 X 297公釐〉 — II---If—-----------I-- (請先閲讀背面之注意事項再填寫本頁) A7 4 53 1 4 1 _____B7___ 五、發明說明（p ) 依本發明之第十群的構成，於以上述粗化面構成之導 體電路表面，係形成有上述氧化膜所成之被覆層，由於此 氧化膜係導體電路表面之全體氧化所形成緻密之物，即使 於具有此氧化膜之導體電路上形成通孔’氧化膜亦不會剝 離。 因此，於此導體電路上形成之通孔’其與該導體電路 之密接性優異，對熱循環等溫度的變化亦具有耐久性，而 不會發生剝離的現象。 其次，就本發明之第十群之多層印刷電路板的製造方 法以半加成法爲例說明之。 (1)首先，於核心基板的表面製作形成有內層銅圖案(下 層導體電路)的電路基板。 對此核心基板形成下層導體電路之時’係將銅面積層 板以形成特定圖案狀之蝕刻方法，於玻璃環氧基板、聚醯 亞胺基板、陶瓷基板、金屬基板等之基板上形成無電解鍍 敷用黏著劑層，將此無電解鍍敷用黏著劑層表面粗化成爲 粗化面之後，採用無電解鍍敷方法，或是，於上述粗化面 全體施以無電解鍍敷形成防鍍膜，而於防鍍膜之非形成部 份施以電解電鍍後，去除防鍍膜，再進行鈾刻處理，形成 由電解電鍍膜及無電解鍍敷膜構成導體電路’此爲亦可採 用之方法(半加成法）。 通常，於基板上形成導體電路後’於通孔及基板之導 體電路間塡充雙酚醛F型環氧樹脂等低黏度之樹脂塡充劑 後’可藉由硏磨樹脂層及導體電路以確保樹脂層及導體電 ___ 92 _ 氏張尺度適用中國國家標準（CNS)A4規格（210 κ 297公蹵） I —ill ^ I I I I I 1 I · I I I J n I ϋ )SJall — ΙΕ — — — (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（幻） 路的平滑性’但於塡充上述樹脂塡充劑之前在導體電路表 面須形成粗化面。 又，亦可於核心基板中形成通孔，而透過此通孔使表 裡面之電路層得以電連接。 上述粗化面之形成以硏磨處理、飩刻處理、黑化還原 處理以及電鍍處理之其中任一方法爲佳》 於這些處理之中，進行黑化還原處理之時，以使用含 有 NaOH(20 g/1)、NaClCh(50 g/1)、Na3P〇4(15.0 g/Ι)水溶液所 得之黑化浴(氧化浴），以及含有NaOH (2.7 g/丨）、NaBH4(1.0 g/1)水溶液所得之還原浴來形成粗化面之方法爲佳。 又’藉由電鍍處理而形成粗化層之時，以含有硫酸銅 (1〜40 g/Ι)、硫酸鎳(0·1~6.0 g/Ι)、檸檬酸(10~20 g/Ι)、次亞磷 酸鈉（10~100 g/1)、硼酸（10〜40 g/I)、界面活性劑（日信化學 工業公司製，沙費諾魯465)(0.01〜10 g/Ι)之pH=9的無電解 鍍敷浴施以無電解鍍敷，形成Cu-Ni-P合金構成的粗化 層之方法爲所希望者β 由於在此範圍析出之被膜的結晶構造爲針狀構造，其 具有良好之錨定物效果。於此無電解鍍敷浴除上述化合物 外亦可加入錯化劑及添加劑。 就上述蝕刻處理方法而言，可舉出使含有銅錯合物及 有機酸之蝕刻液以氧共存化方式使其反應，將導體電路表 面粗化之方法。 此時，藉由下述之式(7)及式(8)的化學反應進行蝕刻》 93 本紙張尺度適用令國國家標準（CNS&gt;A4規格（210 X 297公釐） I i I ----- i 11 訂 11 —----- (請先閱讀背面之注意事項再填寫本頁) Α7 Β7 453 Μ 1 五、發明說明)The shape of the roughened layer such as Cu-m-p alloy is preferably needle-like or porous. When the roughened layer is formed by electroplating, the shape of the roughened layer varies depending on the type of the surfactant. However, when a roughened layer having a needle shape or a porous shape is to be formed, the conditions must be adjusted. Selected 51 As for the roughened layer of the ninth group of the present invention, in addition to needle-like or porous alloys composed of Cu-Ni-P, electroplated bumps or Electroplated copper blocks. When forming electroplated copper blocks, as far as the plating solution is concerned, '81 paper sizes can be used, such as China National Building Standard (CNS) A4 (210 X 297 mm) — II 11 ----- packed !! — Order! -Line (please read the precautions on the back before filling in this page) A7 453141 _____B7___ V. Description of the invention (yarn) Copper compound of 22 ~ 38 g / l, Modification agent of 10 ~ 20 g / l, 150 ~ 250 g / I of pyrophosphate, 5-10 g / 1 nitrate, 1 ~ 3 g / 1 ammonia, 10 ~ 25 g / 1 ?? aqueous solution. In the case of a scrambler, EDTA or potassium sodium tartrate can be used. According to the ninth group of the present invention, the surface of the roughened layer of the Cu-Nm-P alloy is intended to form a metal having a higher ionization tendency than Cu and less than Ti, or a coating layer composed of a precious metal (hereinafter , Called the roughening layer coating). The thickness of the coating layer of the roughened layer is preferably from 0.1 to 2; zm. The formation of a coating layer of these metals can prevent direct contact between the electrolyte solution and the roughened layer. In addition, since these metal layers are oxidized to form a dense oxide film, the roughened layer or the conductor circuit can be prevented from being dissolved. Examples of metals having a higher ionization tendency than Cu and below Ti include Ti, Al, Zn, Fe, In, rhenium, Co, Ni, Sn, Pb, and Bi. Examples of the noble metals include Au, Ag, Pt, and Pd. Therefore, the roughened layer coating layer can be selected from at least one of the metals and the precious metals and used. Among these metals, Sn is particularly desirable. Since Sn can be formed into a thin layer by electroless displacement plating, it can be formed by depositing along the unevenness of the roughened layer. When Sn is used in the above metals, tin fluoboride-thiourea solution or tin chloride-sulfur gland solution is used. At this time, an Sn layer of about 0.01 to about 0.01 can be formed by a Cu-Sn substitution reaction. When a precious metal is used, a method such as sputtering, vapor deposition, or a plating method using a simple replacement plating solution can be used. The metal layer formed on the surface of the conductor circuit among the ninth group of the present invention '82. The paper size is applicable to the Chinese national standard (CNS &gt; A4 specification (210 X 297 mm) -------- II Order ·! --- --- (Please read the notes on the back before filling out this page) Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 1 4 1 A7 B7 V. Description of the invention (? 丨) Can be formed by electroplating, electroless plating, sputtering, vapor deposition, etc. When electroless nickel plating, electroplated nickel, electroless tin plating, electroless plating, and electroless palladium plating can be used, The same method of the present invention. When electrolytic chromium plating is carried out, an aqueous solution containing 250 to 350 g / l of anhydrous chromic acid, 12 to 20 g / l of sodium fluorosilicide, and 0.1 to 0.5 g / l of sulfuric acid is used as the plating. After the substrate is immersed in the plating bath, the current may be applied at a current density of 10 to 30 A / dm2. In addition, when the above-mentioned metal layer composed of A1 is formed, it is difficult to perform plating, so it is spattered. The above-mentioned metal layer is formed by electroplating. 〇〇 ～ 800 g / 1 of sodium hydroxide and 50 ~ 200 g / 1 of zinc oxide in water are subjected to electroplating at normal temperature. When iron plating is carried out, it contains 100-400 g / 1 of ferrous sulfate and A 50-200 g / l ammonia sulfate aqueous solution is used as the plating bath. After the substrate is immersed in the plating bath, it can be energized at a current density of 6 to 10 A / dm2. Second, in the ninth group of the present invention, A method of forming a roughened layer by electroplating a Cu-Ni-P alloy plating layer on the surface of a conductor circuit and the like will be described. A ninth group of the present invention is a substrate on which a lower-layer conductor circuit is formed. It is immersed in an electroplating aqueous solution made of a polyoxyethylene-based surfactant containing an activator, a copper compound, a nickel compound, rhenium hypophosphite, and ethylene, and the substrate is vibrated or shaken, or metal ions are supplied to The porous alloy formed by growing Cu-Ni-P is precipitated to form a roughened layer of the alloy consisting of a coating layer and a roughened layer. In addition, in the electroplating aqueous solution, the copper ion concentration and 83 paper standards are applicable to Chinese standards ( CNS &gt; A4 size (210 X 297 (Public note) ^ ----------------- {Please read the notes on the back of A3 before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 5314 1 A7 B7 V. Description of the invention (b) Nickel ion concentration, hypophosphite ion concentration, and concentration of the modifier are adjusted to 0.007 ~ 0.160 mol / bu 0 · 001 ~ 0 · 023 mol / 1, 0.1 ~ 1.0 mol / bu 0.01 to 0.2 mol / 1 is preferred. Examples of the disabling agent include citric acid, tartaric acid, malic acid, EDTA, ethylenediamine, and glycine. As for the polyethylene oxide-based surfactant containing ethylene, it is preferable to use a substance having the structure of the formula (2) or (3). Examples of the surfactant include 2, 4, 7, 9-tetramethyl-5-decane-4, 7-diol, 3, 6-dimethyl-4-octyne-3, 6-ene glycols such as diols. These commercially available products include, for example, Safenolol 104 (porous), 440, 465, and 485 (all needle-shaped) manufactured by Nissin Chemical Industry. The surface of Cu-Ni-P alloy 'precipitated by this electroless plating solution is needle-like or porous. For porous alloys, the number of micropores is in the range of 100,000,000 (M, 000,000, lcm2), and the general range is 3,000,000 to 300,000,000. In addition, the diameter of the micropores is 0.01 to 100 / im range, but generally included in the range of 0.1 ~ 1〇νπιβ In the multilayer printed circuit board of the ninth group of the present invention, as for the interlayer resin insulating layer formed on the above conductor circuit, electroless plating is used It is better to use an adhesive. The adhesive for electroless plating is a soluble heat-resistant resin particle in a hardened acid or an oxidant, and it is dispersed in an acid or an oxidant in a hardly soluble non-hardened The one made of heat-resistant resin is the best. By treating with acid or oxidant solution, the heat-resistant resin particles can be dissolved and removed, and a thick octopus pot-shaped anchor can be formed on the surface of this adhesive. The surface of this paper is 84. The paper size is in accordance with Chinese National Standard &lt; CNS &gt; A4 (2) 0 X 297 mm. I 1 -------- t ------- Order ----- ---- Line (Please read the precautions on the back before washing this page) Α7 Β7 Printed by the Bureau's Consumer Cooperative 453 1 4 1 V. Description of the Invention (?)) Among the above-mentioned adhesives for electroless plating, especially for the heat-resistant resin particles that have undergone hardening treatment, the average particle size is 1) A heat-resistant resin powder having a diameter of 10 / im or less, and 2) particles obtained by mixing particles having a relatively large average particle diameter and particles having a relatively small average particle diameter are preferred. The reason is that these substances can form more complex anchors. Examples of the heat-resistant resin that can be used include epoxy resins, polyimide resins, and composites of epoxy resins and thermoplastic resins. Examples of the composite thermoplastic resin include polyethersulfonic acid (PES). Examples of the heat-resistant resin particles dissolved in a solution of an acid or an oxidizing agent include epoxy resins (preferably epoxy resins cured by an amine hardener), amine resins, and the like. The solder resist used in the ninth group of the present invention includes, for example, an epoxy resin acrylate and an imidazole hardener. Next, a method for manufacturing a multilayer printed circuit board according to the ninth group of the present invention will be described. (1) First, a circuit substrate having an inner layer copper pattern (lower conductor circuit) formed on the surface of a core substrate is prepared. The formation of the underlying conductor circuit on this core substrate is performed by etching a copper area laminate, or it is performed according to the following method. That is, an adhesive layer for electroless plating is formed on a substrate such as a glass epoxy substrate, a polyimide substrate, a ceramic substrate, a metal substrate, etc., and then the surface of this adhesive layer is roughened and then formed by electrolytic plating. A conductor layer, and the conductor layer is etched to form a lower conductor circuit. In addition, through-holes are formed in the core substrate, and the 85 paper sizes on the inside of the through-hole table conform to the Chinese Standard (CNS) A4 (210 χ 297 mm) 1— II ------ ^- ------— It --------- line (Please read the precautions on the back before filling this page) 4531 4 1 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Called) The circuit layer is electrically connected. It ’s also possible to guide the road below the ship, the core, and the bottom to maintain smoothness. In particular, in the ninth group of the present invention, the pad surface ′ of the through-holes provided on the surface of the layer under the core substrate is formed from the above &amp;, Zn, N !, and C. A metal layer of at least one of the metal structures of Sn, Sn, and precious metals, and a roughened layer composed of a needle-like or porous Cu__ alloy and the like is formed on the metal layer. Furthermore, as necessary, the aforementioned roughened layer coating layer is formed on the above-mentioned layers. (2) Next, an interlayer resin insulating layer is formed on the circuit board prepared in the above-mentioned α). In particular, in the present invention, it is preferable to use the above-mentioned material for the interlayer resin insulating layer by using the aforementioned electroless mineral deposit adhesive. (3) After drying the formed adhesive layer for electroless shovel, an opening for through-hole formation is provided as necessary. In the case of a photosensitive resin, thermal curing is performed after exposure and development, and in the case of a thermosetting resin, laser processing is performed after thermal curing, thereby providing through-hole formation for the interlayer resin insulating layer. Opening. (4) Secondly, the resin particles which are soluble in acid or oxidant, which are present on the surface of the hardened surface of the above-mentioned electroless plating adhesive layer (interlayer resin insulation layer), are dissolved and removed by dissolving the acid or oxidant to roughen The surface of the adhesive layer for electroless plating. Here, examples of the above-mentioned acids include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; and organic acids such as formic acid and acetic acid. In particular, organic acids are preferably used. If an organic acid is used, it can be used from the outside of the through hole 86 paper sizes to apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ------ Wire (Please read the precautions on the back before filling this page) A7 453141 ____B7_ V. Description of the invention (type) The exposed metal conductor layer is more difficult to be corroded. On the other hand, the oxidizing agent is preferably an aqueous solution using chromic acid or permanganate (calcium permanganate). (5) Secondly, the circuit board on the surface of the roughened interlayer resin insulating layer is provided with a catalyst core. The catalyst core provided is preferably a noble metal ion or a noble metal colloid. Generally, a palladium chloride or a palladium colloid is used. In addition, it is preferable to heat-treat the catalyst core. For this type of catalyst core, palladium is preferred. (6) Next, electroless plating is applied to the surface of the interlayer resin insulation layer provided to the catalyst core, and an electroless plating film is formed on the entire surface of the roughened surface. . The film thickness of the electroless plating film is preferably 0.5 to 5 // ιη. Next, a plating resist is formed on the electroless plating film. (7) Next, a thick plating is applied to the non-formed portion of the anti-plating film to form upper-layer conductor circuits and through holes. Here, for the above-mentioned electroplating, it is preferable to use copper plating. In addition, the metal layer and the electroless plated film are etched as a corrosion resisting layer to form a metal layer composed of at least one metal selected from ACr, Fe, Zn, Ni, Co, Sn, and a noble metal. In addition, after removing the anti-ore film, the electroless plating film existing under the anti-film is dissolved and removed with an etching solution made of a mixed solution of sulfuric acid and hydrogen peroxide or an aqueous solution such as sodium persulfate and ammonia persulfate to Become a separate conductor circuit. In addition, because the upper conductor circuit is formed of copper, it is selected from Ai and Cf 87. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love). I --- I -------- -I --- Order I!-&Lt; Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs. F Cooperation Du printed 453 Μ 1 5 2. Description of the Invention (#) A metal layer made of at least one of Fe, Zn, Ni, Co, Sn, and a precious metal is used as a resistive layer and will not be etched. In addition, a metal layer made of a metal selected from at least one of Al, Cr, Fe, Zn, Ni, Co, Sn, and a noble metal can be provided with an independent upper-layer conductor circuit and a through-hole, and then can be formed on the upper-layer conductor circuit and the through-hole. 〇 及 formed on the side surface and the upper surface, and then Cu—Ni is formed on the upper-layer conductor circuit on which a metal layer made of a metal selected from at least one of Al, Cr, Fe, Zn, Ni, Co, Sn, and a noble metal is formed. — Roughened layer made of P alloy. Since the surface of the metal layer is liable to undergo a redox reaction ', a plating alloy made of Cu-Ni-P is easily precipitated. (9) Secondly, on the surface of Cu-Nί-P alloy, a roughened coating layer composed of a metal or noble metal having a higher ionization tendency than Cu and less than Ti is formed. (10) Thereafter, on the substrate on which the above-mentioned upper conductor circuit is formed, as an interlayer resin insulating layer, an adhesive layer for electroless plating is formed. (11) Furthermore, by repeating the above steps (3) to (10), setting the upper-layer and upper-layer conductor circuits, for example, a multilayer printed circuit board with three layers on one side, that is, six layers on both sides can be obtained. In the processes (3) to (10), after the openings for forming the through holes are provided, the surface is roughened with chromic acid, and the chromic acid treatment can also prevent the dissolution of the conductor circuit. .. Moreover, although the above description is an example of a multilayer printed circuit board manufactured by the so-called semi-additive method, the adhesive layer for electroless plating can also be roughened. 88 This paper is sized to the Chinese National Standard (CNS ) A4 specification (210 X 297 mm) I. --------- I — ------ I-- tPlease read the notes on the back before filling this page) Intellectual Property Bureau, Ministry of Economic Affairs Printed by the employee consumer cooperative d5314 1 A7 _____B7___ 5. Description of the Invention (Clever) The catalyst core is provided, an anti-plating film is provided, and then electroless plating is performed to form a conductor circuit. The so-called full addition method can also be applied. A method for manufacturing a multi-layer printed circuit board according to the tenth group of the present invention is to form a roughened surface on a conductor circuit by forming a roughened surface after forming the conductor circuit. The conductor circuit having the roughened surface is covered with an interlayer resin insulating layer. After that, the process of forming through-hole openings is continuously repeated, and the formation of a conductor circuit formed by interposing a plurality of layers of interlayer resin insulation layers on an insulating substrate is characterized by forming a roughened surface on the conductor circuit. An oxidation treatment is performed to form an oxide film on the entire surface of the roughened surface, and then an interlayer resin insulating layer is formed. According to the structure of the tenth group of the present invention, after forming a roughened surface on a conductor circuit, an oxide film can be formed on the entire surface by a simple method such as heat treatment of the substrate, and a multilayer printed circuit board can be manufactured. The process is simplified, and furthermore, it is possible to form through-holes with good adhesion to the underlying conductor circuit, and it is possible to manufacture a multi-layer printed circuit board that fully ensures the reliability of the connection between the through-hole and the conductor circuit. 49 (a) to (c) are cross-sectional views showing a process of forming an oxide film of the present invention, and Figs. 50 (a) to (c) are cross-sectional views showing a process of forming a conventional oxide film. Ten groups, as shown in FIG. 49, after forming the roughened layer 111 on the conductor circuit 105 (see FIG. 49 (a)), an oxide film 118 is formed on the entire surface of the roughened layer 111 (roughened surface) (see FIG. 49). 49 (b)), and then an interlayer resin insulating layer 102 and a through hole 106 are formed (see FIG. 49 (c)). The oxide film 118 formed by the above-mentioned process, since the interlayer resin 89 -I I I I --- is installed! 11! Order! 1 —! (Please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS) A4 Regulations (2) 0 X 297 mm A7 4 53 1 4 1 _______B7_ 5 2. Description of the Invention (M) The part covered by the insulating layer and the part exposed from the interlayer resin insulating layer have been covered with the oxide film, and no local battery reaction will occur even in contact with the roughening solution. Therefore, it has corrosion resistance with respect to oxidants and the like. Even when the surface of the conductor circuit comes into contact with an acidic solution or the like during a subsequent process such as acid cleaning, the surface (roughened layer) of the conductor circuit 105 does not dissolve and empty. Holes, etc. It is also known to form a roughened layer 111 on the conductor circuit 105 (see FIG. 50 (a)), and then to form an interlayer resin insulating layer 102 on the conductor circuit 105, and then provide a through-hole opening 106 (see FIG. 50). (b)), and in order to completely harden the interlayer resin insulating layer 102, it is thermally hardened at 150 ° C. However, in order to heat the interlayer resin insulating layer 102 when it is hardened, only the through-hole opening 106 is oxidized to form an oxide film Π8. If the roughening solution penetrates from the interlayer resin insulating layer 102, the oxide film 118 and the conductor circuit A local battery reaction occurs between 105, so that a void H9 occurs (see FIG. 50 (c)). The method for forming a roughened surface on a conductor circuit is not particularly limited, and examples thereof include an etching treatment, a blackening reduction treatment, and a plating treatment. Examples of the etching method include a method in which an etching solution composed of a copper complex and an organic acid is coexisted with oxygen, and examples of the plating method include electroless plating. Apply to form a needle-like or porous roughened layer made of Cu-Ni-P alloy. After the roughened surface is formed on the conductor circuit by the above-mentioned plating process or etching process, the method of forming an oxide film on the surface of the roughened surface is not particularly limited, although a solution containing an oxidizing agent or the like may be used to make it With 90 paper sizes applicable to China National Standard (CNS) A4 (210 X 297 mm) Packing! ----- Order ------- Line (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption 钍 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 4531 4 1 A7 __B7 ____ V. Description of the Invention (^) The method of contacting the surface of a conductor circuit, but the substrate after the above process can also be heated at 80 ~ 200 ° C for 10 minutes to 3 hours in the ambient atmosphere. The method of forming an oxide film on the entire surface of the roughened surface by an oxidation treatment has the characteristics of being simple and capable of forming a dense oxide film, and is therefore a desirable method. The temperature of the oxidation treatment is preferably 130 to 160 ° C, and the time of the oxidation treatment is preferably 10 to 180 seconds. Through the above-mentioned oxidation treatment, an oxide film having a thickness of about 0.01 to 0.2 # m will be formed on the surface thereof, and the shape of the roughened layer will be substantially maintained as it is. -Since this oxide film has corrosion resistance to oxidants, etc., even if a metal coating film such as Sn is provided on the surface of the conductor circuit, when the substrate is acid-washed in a later process, or if an opening for a through hole is provided, When the surface of the interlayer resin insulating layer is roughened with chromic acid or the like, the surface of the conductor circuit does not dissolve, and voids do not occur. Therefore, an interlayer resin insulating layer having good adhesion to the conductor circuit can be formed on the conductor circuit having an oxide film formed on the surface. Further, after the through-hole opening is formed in the interlayer resin insulating layer, the formed through-hole has good adhesion to the underlying conductor circuit. The multilayer printed circuit board of the tenth group of the present invention is to form an interlayer resin insulating layer on a substrate on which a conductor circuit is formed with a roughened surface, and to form an opening for a through hole in the interlayer resin insulating layer. In the multilayer printed circuit board in which a conductive body is formed in the opening for the through hole to constitute the through hole, a coating layer made of the oxide film is formed on the entire surface of the conductive circuit having the roughened surface. 91 This paper size applies to China National Standard (CNS) A4 (2) 0 X 297 mm> — II --- If —--------------- (Please read the note on the back first Please fill in this page again for details) A7 4 53 1 4 1 _____B7___ 5. Description of the invention (p) According to the tenth group of the present invention, the surface of the conductor circuit composed of the roughened surface is formed by forming the above oxide film. The coating layer is a dense substance formed by the entire oxidation of the surface of the conductor circuit. Even if a through-hole 'oxide film is formed on a conductor circuit having the oxide film, it will not peel off. Therefore, it is formed on the conductor circuit. The through-holes are excellent in adhesion with the conductor circuit, and are durable against changes in temperature such as thermal cycling without peeling. Second, the manufacture of the multilayer printed circuit board of the tenth group of the present invention The method is described by taking the semi-additive method as an example. (1) First, a circuit substrate with an inner layer copper pattern (lower conductor circuit) is formed on the surface of the core substrate. Copper area laminates to form specific patterns In an etching method, an adhesive layer for electroless plating is formed on a substrate such as a glass epoxy substrate, a polyimide substrate, a ceramic substrate, or a metal substrate, and the surface of the adhesive layer for electroless plating is roughened to become rough. After the surface is formed, the electroless plating method is adopted, or the entire surface of the roughened surface is subjected to electroless plating to form an anti-plating film, and the non-formed part of the anti-plating film is subjected to electrolytic plating, and then the anti-plating film is removed, and then Carry out uranium engraving to form a conductor circuit composed of electrolytic plating film and electroless plating film. This is a method that can also be used (semi-additive method). Generally, after forming a conductor circuit on a substrate, Conductor circuits are filled with low-viscosity resins such as bisphenol F-type epoxy resin, and the resin layer and conductor circuits can be honed to ensure the resin layer and conductor electricity. 92 92 _ The scale of the scale is applicable to Chinese national standards (CNS) A4 Specification (210 κ 297 cm) I —ill ^ IIIII 1 I · IIIJ n I ϋ) SJall — ΙΕ — — — (Please read the notes on the back before filling out this page) Employees, Intellectual Property Office, Ministry of Economic Affairs consumption Printed by the agency 453 1 4 1 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (the magic) The smoothness of the road 'but the surface of the conductor circuit must be roughened before being filled with the above resin and filler surface. In addition, a through hole can also be formed in the core substrate, and the circuit layer on the surface can be electrically connected through the through hole. The above-mentioned roughened surface is formed by any one of honing, engraving, blackening reduction, and electroplating. Among these treatments, when the blackening reduction treatment is performed, a solution containing NaOH (20 g / 1), NaClCh (50 g / 1), Na3P04 (15.0 g / 1) aqueous blackening bath (oxidation bath), and containing NaOH (2.7 g / 丨), NaBH4 (1.0 g / 1) A method for forming a roughened surface by using a reduction bath obtained from an aqueous solution is preferred. In addition, when a roughened layer is formed by electroplating, it may contain copper sulfate (1 to 40 g / 1), nickel sulfate (0.1 to 6.0 g / 1), and citric acid (10 to 20 g / 1). , Sodium hypophosphite (10 ~ 100 g / 1), Boric acid (10 ~ 40 g / I), Surfactant (manufactured by Nissin Chemical Industry Co., Ltd., Safenoru 465) (0.01 ~ 10 g / Ι) The method of applying electroless plating to pH = 9 to form a roughened layer made of Cu-Ni-P alloy is desirable. Since the crystal structure of the film deposited in this range is a needle-like structure, It has a good anchor effect. In addition to the above compounds, the electroless plating bath can also be added with an erroneous agent and an additive. Examples of the above-mentioned etching treatment method include a method of reacting an etching solution containing a copper complex and an organic acid with oxygen in a coexistent manner to roughen the surface of a conductor circuit. At this time, etching is performed by the chemical reaction of the following formulae (7) and (8). "93 This paper size applies national standards (CNS &gt; A4 specifications (210 X 297 mm) I i I --- -i 11 Order 11 ------- (Please read the notes on the back before filling in this page) Α7 Β7 453 Μ 1 5. Description of the invention)

Cu + Cu(n)AP— 2Cu(I)Ap/2. · ·⑺ 1Cu + Cu (n) AP— 2Cu (I) Ap / 2. · · ⑺ 1

2Cu(I)A^+p/4〇2 + pAH 2Cu(n) AP + p/2H2〇· · ·（8) (式中，A爲錯化劑(做爲鰲合劑使用)），p爲配位數） 就上述銅錯合物而言，以唑類之銅錯合物爲佳。此唑 類之銅錯合物其作用係將金屬銅等氧化而做爲氧化劑用。 就唑類而言，可舉出例如二唑、三唑、四唑等。其中，又 以咪唑、2—甲基咪唑、2 —乙基咪唑、2_乙基一4一甲基 咪唑、2—苯基咪唑、2-H^ —烷咪唑等。上述蝕刻液中唑 類之銅錯合物的含有量以1〜15 重量％爲佳。除了在溶解 性及安定性上優良之外，又，亦可使構成觸媒核之Pd等貴 金屬溶解。 又，爲溶解氧化銅，則將有機酸調配至唑類之銅錯合 物中。就上述有機酸的具體例而言，可舉出例如蟻酸、醋 酸、丙基酸、酪酸、戊酸、苯偶姻肟酸、丙烯酸、巴豆酸 、硝酸、丙二酸、琥珀酸、戊二酸、馬來酸、安息香酸、 乙二酸、乳酸、蘋果酸、氨磺醯酸等。在使用上，可將其 單獨使用，亦可將2種以上倂用。 蝕刻液中有機酸之含有量，以〇.卜30重量％爲佳。不 但可維持被氧化之銅的溶解性，亦可確保溶解安定性。如 上述式（8)所示，產生之亞銅錯合物，藉由酸的作用溶解， 其與氧結合成爲銅錯合物，而再提供爲將銅氧化之物。 爲輔助銅的溶解或唑類的氧化作用，亦可將_素離子 ____ 94 、張尺度適用_國國家標準（CNS)A4規格（2】〇 κ 297公® ~ I-- --袭·！！11 訂·1!! 線 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 d531 4 1 ____B7___ 五、發明說明（Μ ) 例如氟離子、氯離子 '溴離子等加入上述蝕刻液之中。又 ，藉由添加鹽酸、氯化鈉等，可提供鹵素離子。蝕刻液中 之鹵素離子的含有量以0.01〜20重量％爲佳。其理由爲可 使形成之粗化面及層間樹脂絕緣層有良好之密接性。 於調製蝕刻液之時，將唑類之銅錯合物及有機酸(依必 要性使用具有鹵素離子之物)溶解於水中。又，做爲上述之 蝕刻液，就市售之蝕刻液而言，係使用例如美克公司製造 之商品名「美克Η棒德」。使用上述蝕刻液之時蝕刻量以 1〜ΙΟμιη爲佳》若蝕刻量超過l〇/im，形成之粗化面與通 孔導體間會產生連接不良的情形，另一方面，若蝕刻量未 達Ιμιη，其與在上面形成之層間樹脂絕緣層的密接性會變 得不足。 以上述方法形成之粗化面，一般係留下側面進行硏磨 ，以確保樹脂層及導體電路的平滑性。 (2) 接著，將經過上述(1)過程之基板放入加熱裝置中， 於大氣周圍氣氛下，以100〜200°C加熱10分鐘〜3小時，藉 此實施氧化處理，而於以蝕刻形成之導體電路的粗化面上 ，或於以電鍍等形成之導體電路上之粗化層表面，形成氧 化膜。 (3) 其次，在以上述(2)製作之基板上，對含有有機溶劑 之粗化面形成用樹脂組成物進行塗佈、乾燥以設置粗化面 形成用樹脂組成物之層。 上述粗化面形成用樹脂組成物，對於擇自酸、鹼以及 氧化劑之中至少1種構成之粗化液爲難溶性未硬化之耐熱 95 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1ΙΙΙΙΙΙΙ1ΙΪΙ — I J II ϊ I I I — — If— — — — (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 453 1 4 1 ____B7 五、發明說明（Μ) 性樹脂基體中，乃希望對擇自酸、鹼以及氧化劑之中至少 1種構成之粗化液分散有可溶性物質。 &lt;請先閲讀背面之注意事項再填寫本頁) 又，於本發明使用「難溶性」、「可溶性」一語，係 針對在同一粗化液中浸漬相同時間的情況下，將相對之溶 解速度較快之物權宜地稱爲「可溶性」，而將相對之溶解 速度較慢之物權宜地稱爲「難溶性」。 就上述熱性樹脂基體而言，可使用例如熱硬化性樹脂 ，或是熱硬化性樹脂(包含熱硬化基的一部份感光化之物) 熱可塑性樹脂之複合體。 就上述熱硬化性樹脂而言，可舉出環氧樹脂、苯酚樹 脂、聚醯亞胺樹脂、熱硬化性聚烯烴樹脂等。又，爲將上 述熱硬化性樹脂感光化，可使用異丁烯酸或丙烯酸，以將 熱硬化基異丁烯(丙烯)化。特別以環氧樹脂之異丁烯(丙烯) 酯爲最適者。 就上述環氧樹脂而言，可使用例如線型環氧樹脂、脂 環式環氧樹脂等。 就上述熱可塑性樹脂而言，可使用例如聚醚磺、聚磺 類、聚苯磺、聚苯撐硫、聚苯醚、聚醚醯亞胺等。 經濟部智慧財產局貝工消費合作社印製 對於上述擇自酸、鹼以及氧化劑之中至少1種所成之 粗化液爲可溶性物質而言，以擇自無機粒子、樹脂粒子、 金屬粒子、橡膠粒子、液相樹脂以及液相橡膠中至少1種 爲佳。 就上述無機粒子而言，可舉出例如二氧化矽、氧化鋁 、碳酸鈣、雲母、白雲母等。這些粒子，可單獨使用，亦 96 本紙張又度適用中國國家標準（CNS)A4規格（2〗〇χ 297公釐） 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B7 五、發明說明) 可將2種以上倂用之β 上述氧化鋁粒子可用氫氟酸溶解去除之’而碳酸鈣則 可用鹽酸溶解去除之。又’含有鈉之二氧化矽或白雲母可 用鹼性水溶液溶解去除之。 就上述樹脂粒子而言，可舉出胺樹脂(三聚氰醯胺樹脂 、尿素樹脂、三聚氰二胺樹脂等）、環氧樹脂、雙順丁烯二 胺三氮雜苯樹脂等。這些樹脂，可單獨使用，亦可將2種 以上倂用之。 又，上述環氧樹脂係可溶解於酸或氧化劑之物，或將 對酸或氧化劑爲難溶解性之物藉由選用低聚物之種類或硬 化劑而可任意製造之。例如，將雙酚醛Α型環氧樹脂以胺 系硬化劑硬化之樹脂，其極易於溶解於鉻酸中，然將甲酚 線型環氧樹脂以咪唑硬化劑硬化之樹脂，其不易溶解於鉻 酸中。 對上述樹脂粒子有必要事先予以硬化處理。若不事先 將其硬化，則上述樹脂粒子將會溶解於使樹脂基體溶解之 溶劑中而造成均一的混合，造成欲以酸或氧化單將樹脂粒 子選擇性地溶解去除上有所困難。 就上述金屬粒子而言，可舉出例如金、銀、銅、錫、 鋅' 不銹鋼、鋁等。這些金屬粒子，可單獨使用，亦可將 2種以上倂用之。 就上述橡膠粒子而言，可舉出例如丙烯腈-丁二烯橡 膠、聚氯丁二烯橡膠、聚異丙烯橡膠、丙烯腈橡膠、聚硫 剛性橡膠、氟橡膠、聚氨酯橡膠、矽橡膠、ABS樹脂等。 97 本纸張尺度適用令國國家標準（CNS)A4規格（210 X 297公釐) ! !11 1 ! --------I I I I I f請先閲讀背面之注意事項再填寫本頁) 453141 A7 經濟部智慧財產局負工消費合作社印製 B7 五、發明說明（科） 這些橡膠粒子，可單獨使用，亦可將2種以上併用之。 就上述液相樹脂而言，可使用上述熱硬化性樹脂之未 硬化溶液，而就此種液相樹脂的具體例而言，則可舉出未 硬化之環氧低聚物及胺系硬化劑之混合液等。 就上述液相橡膠而言，可使用例如上述橡膠之未硬化 溶液等- 於使用上述液相樹脂或液相橡膠調製上述感光性樹脂 組成物之時，爲使耐熱性樹脂基體與可溶性物質不要均一 地相溶（亦即達到相分離），故有必要對這些物質進行選擇 〇 藉由將依據上述基準所選擇之耐熱性樹脂基體與可溶 性物質加以混合，則於上述耐熱性樹脂基體的「海」中， 液相樹脂或液相橡膠處於「島」的分散狀態，或者是，於 液相樹脂或液相橡膠的「海」中，耐熱性樹脂基體處於「 島」的分散狀態，藉此，可調製感光性樹脂組成物。 接著，將處於此狀態之感光性樹脂組成物硬化之後， 藉由去除「海」或者是「島j的液相樹脂或液相橡膠而可 形成粗化面。 就做爲上述粗化液使用之酸而言，可舉出例如磷酸、 鹽酸、硫酸；或是蟻酸、醋酸等有機酸，其中又以使用有 機酸爲佳。若使用有機酸，則於粗化處理之時，可使自通 孔露出之金屬導體層較難被腐蝕。 就上述氧化劑而言，以使用例如鉻酸、鹼性過錳酸鹽( 過錳酸鈣)之水溶液爲佳。 98 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐 -!111 — ！1 — -裝· 一 ---—訂------I — (請先閱讀背面之注意事項再填寫本頁). A7 453141 _ B7_ 五、發明說明（η ) 另外，就鹼而言，則以氫氧化鈉、氫氧化鈣等之水溶 液爲佳。 於本發明中，在使用上述無機粒子、上述金屬粒子以 及上述樹脂粒子之時，其平均粒徑以l〇vm以下爲佳。 又，特別是對於平均粒徑未達2#m的情形，藉由將 相對平均粒徑大的粗粒子與相對平均粒徑小的微粒子之混 合粒子加以組合使用，則可去除無電解鍍敷膜之溶解殘渣 ，並減少防鍍膜下之鈀觸媒量，再者，可淺層形成複雜之 粗化面。於是，藉由形成此複雜之粗化面，則淺層粗化面 亦可維持實用上之剝離強度。 藉由搭配上述之粗粒子及微粒子，而可淺層地形成複 雜之粗化面，係由於使用之粒子徑在粗粒子的平均粒徑未 達2/zm之故，即使將這些粒子溶解去除而形成之錨定物 亦會變淺，又，由於去除之粒子係相對粒徑大的粗粒子與 相對粒徑小的微粒子之混合粒子，故所形成之粗化面也會 成爲複雜之面。 又，此時所使用之粒子徑，由於粗粒子之平均粒徑未 達之故，不會由於粗化進行過度而發生空孔，從而 形成之層間樹脂絕緣層具有優異之層間絕緣性。 又上述粗粒子之平均粒徑以超過0.8//m而未達2.0ym 、微粒子之平均粒徑以0.1~0.8/zm爲佳。 於此範圍內，粗化面之深度大槪成爲Rmax = 3jtnn左 右，故以半加成法不但可將無電解鍍敷膜輕易蝕刻去除之 ，亦可將於無電解鍍敷膜下之鈀觸媒簡單去除掉；又，可 99 本紙張尺度適用令國國家標準&lt;CNS)A4規格（210 X 297公釐） I 1 — I I ίι_ 農--------—訂---------線 (請先Μ讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 4 53 1 4 1 A7 B7 五'發明說明（时） 維持實用上之剝離強度1.0〜1.3kg /cm。 上述粗化面形成用樹脂組成物中之有機溶劑的含有量 ，以10重量％以下爲佳。 在進行粗化面形成用樹脂組成物的塗佈之時，可使用 轅軋機或幕塗機等。 (4) 將上述(3)形成之粗化面形成用樹脂組成物層予以乾 燥而呈半硬化狀態之後，設置通孔用開口。 當粗化面形成用樹脂組成物層處於乾燥之狀態，則導 體電路圖案上之上述樹脂組成物層的厚度薄，而起因於具 有大面積之平面層上之層間樹脂絕緣層的厚度變厚，或是 導體電路與導體電路非形成部之凹凸，會使得層間樹脂絕 緣層中常有凹凸之發生，故乃希望使用金屬板或金屬輥筒 ，於一邊加熱時一邊進行壓合，以將層間樹脂絕緣層的表 面平坦化。 通孔用開口的形成，係於粗化面形成用樹脂組成物層 使用紫外線曝光後進行顯像處理所得者。又，於進行曝光 顯像處理之時，係在相當於前述通孔用開口之部分，將描 繪有黑圓圖案之光罩（以玻璃基板爲佳）之黑圓圖案描繪側 以與粗化面形成用樹脂組成物層呈密接狀態的方式裝設其 上，進行曝光、顯像處理。 (5) 其次，使該粗化面形成用樹脂組成物層硬化之以成 爲層間樹脂絕緣層，在將此層間樹脂絕緣層粗化。 於粗化處理時，對於存在於上述層間樹脂絕緣層表面 之擇自無機粒子、樹脂粒子、金屬粒子、橡膠粒子、液相 100 本紙張尺度適用中國國家標準（CNS)A4規格&lt;210 X 297公釐) -------------M ill—---^ i I------^ (請先M讀背面之ii意事項再填窝本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 a7 __JB7_ 五、發明說明（”） 樹脂以及液相橡膠中至少1種之可溶性物質，雖可用上述 之酸、氧化劑、鹼等粗化液將其去除之，然此時對在導體 電路表面形成之氧化膜則應採避免其遭蝕刻的條件來施以 粗化處理。因而，使用之粗化液，以ltMOOO g/ι之鉻酸水 溶液或是0.卜10 mol/ι過錳酸鹽之鹼性水溶液爲佳。又，於 上述層間樹脂絕緣層形成之粗化面的深度，以1〜5/zm左 右爲佳。 (6) 其次，將已粗化之層間樹脂絕緣層表面賦予觸媒核 。所賦予之觸媒核，以使用貴金屬離子或貴金屬膠體爲佳 ，一般而言，係使用氯化鈀或鈀膠體。又，爲固定觸媒核 乃以進行加熱處理爲佳。就此種觸媒核而言則以鈀爲佳。 (7) 其次，於粗化面全面形成無電解鍍敷膜。就上述無 電解鍍敷液而言，係使用下述之無電解鍍敷液。 就鍍液之組成而言，以含有EDTA(50 g/Ι)、硫酸銅(1〇 g/1)、HCHO(8 ml/1)、NaOH(10 g/丨)之水溶液爲佳。又無電解 鍍敷膜之厚度以0.1〜5/zm爲佳，其中又以0.5~3vm更佳 〇 (8) 接著，於無電解鍍敷膜上積層感光性樹脂膜(乾燥膜 )，再將描繪有防鍍膜圖案之光罩(以玻璃基板爲佳)密接於 感光性樹脂膜而載設其上，藉由進行曝光、顯像處理，以 形成防鍍膜圖案。 (9) 其次，於防鍍膜非形成部實施電解電鍍，形成導體 電路及通孔。 此處，就上述電解電鍍而言，以使用鍍銅爲佳，而其 101 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) !!!展 -----訂-------I 線 (請先閱讀背面之注意事項再填寫本頁} 453141 A7 _B7____ 五、發明說明（/Μ) 厚度則以0.5〜3/zm爲佳。 (10) 再者，於去除防鍍膜之後，可藉由硫酸與過氧化 氫之混合液或過硫酸鈉、過硫酸氨、氯化鐵、氯化銅等餓 刻液將鍍膜溶解去除，成爲獨立之導體電路。之後，依必 要性，可以鉻酸等將鈀觸媒核溶解去除之。 (11) 其次，於導體電路之表面形成粗化面，此時，以 藉由上述之硏磨處理、蝕刻處理、黑化還原處理以及電鍍 處理等其中任一之方法形成爲佳。 之後，藉由與上述(2)相同方法，於導體電路表面形成 氧化膜。 (12) 其次，於此基板上，使用上述粗化面形成用樹脂 組成物，以與上述方法相同之方法形成層間樹脂絕緣層。 (13) 其次，重複⑷气⑵的過程並設置上層導體電路等 ，又於其上形成具有焊墊功用之平板狀的導體底座或通孔 等。最後藉由形成防焊劑層以及焊接凸塊以完成多層印刷 電路板的製造。又，以下之方法雖採用半加成法，但亦可 採用全加成法。 [爲實施發明之最佳形態] [實施例1] (1)在由厚度〇.8mm的BT(雙順丁烯二胺三氮雜苯)樹脂 構成之基板的兩面，積層有厚度的銅箔2，而將以 此形成之BT樹脂銅面積層板(三菱氣體化學製造，商品名 :HL830 —C，8T12D)做爲起始材料(參照圖1U))。首先，將 此銅面積層板鑽孔(參照圖1(b))，其次’附著上Pd—Sn膠 102 本紙張尺度適用中國團家標準（CNS)A4規格（2〗0 X 297公釐〉 (請先閲讀背面之注意事項再填寫本頁&gt; 装-----訂-----!1 &quot;^ 經濟部智慧財產局員工消費合作社印製 A7 4 53 1 4 1 __B7_ 五、發明說明（β丨） 體，以下述組成之無電解鍍敷水溶液、下述條件實施無電 解鍍敷，於基板全面形成0.7/zm之無電解鍍敷膜。 [無電解鍍敷水溶液]2Cu (I) A ^ + p / 4〇2 + pAH 2Cu (n) AP + p / 2H2 (8) (where A is a dislocation agent (used as a chelating agent)), and p is Coordination number) As for the above-mentioned copper complexes, copper complexes of azoles are preferred. The copper complex of azoles acts as an oxidant by oxidizing metallic copper and the like. Examples of the azoles include diazoles, triazoles, and tetrazoles. Among them, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-H ^ -alkylimidazole and the like. The content of the copper complex of azoles in the etching solution is preferably 1 to 15% by weight. In addition to being excellent in solubility and stability, it is also possible to dissolve noble metals such as Pd constituting the catalyst core. To dissolve copper oxide, an organic acid is blended into a copper complex of azoles. Specific examples of the organic acid include formic acid, acetic acid, propyl acid, butyric acid, valeric acid, benzoin hydroxamic acid, acrylic acid, crotonic acid, nitric acid, malonic acid, succinic acid, and glutaric acid. , Maleic acid, benzoic acid, oxalic acid, lactic acid, malic acid, sulfasal acid, etc. They can be used alone or in combination of two or more. The content of the organic acid in the etching solution is preferably at least 30% by weight. Not only can maintain the solubility of the oxidized copper, but also ensure the stability of dissolution. As shown in the above formula (8), the produced cuprous complex is dissolved by the action of an acid, which is combined with oxygen to form a copper complex, and is further provided as a substance that oxidizes copper. In order to assist the dissolution of copper or the oxidation of azoles, it is also possible to apply _ prime ion ____ 94 and Zhang scale _ National Standard (CNS) A4 specifications (2) 〇κ 297 公 ® ~ I-- ！ 11 Order · 1 !! Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 d531 4 1 ____B7___ V. Description of the invention (M) For example, fluoride ion, chloride ion 'Bromide ions and the like are added to the above-mentioned etching solution. Moreover, by adding hydrochloric acid, sodium chloride, etc., halogen ions can be provided. The content of halogen ions in the etching solution is preferably 0.01 to 20% by weight. The reason is that The formed roughened surface and the interlayer resin insulation layer have good adhesion. When preparing an etching solution, a copper complex of azoles and an organic acid (using halogen ions if necessary) are dissolved in water. In addition, as the above-mentioned etching solution, a commercially available etching solution is, for example, a brand name "Mike Bard" manufactured by Meike Co., Ltd. When the above-mentioned etchant is used, the etching amount is preferably 1 to 10 μm. 》 If the etching amount exceeds 10 / im, the roughened surface and Poor connection may occur between the hole conductors. On the other hand, if the etching amount does not reach 1 μm, the adhesion with the interlayer resin insulation layer formed thereon will be insufficient. The roughened surface formed by the above method is generally retained. Honing the lower side to ensure the smoothness of the resin layer and the conductor circuit. (2) Next, put the substrate after the above (1) process in a heating device, and heat it at 100 ~ 200 ° C in the atmosphere around the atmosphere. From 10 minutes to 3 hours, an oxidation treatment is performed to form an oxide film on the roughened surface of the conductor circuit formed by etching or on the surface of the roughened layer of the conductor circuit formed by electroplating or the like. (3) Next On the substrate prepared in the above step (2), the resin composition for forming a roughened surface containing an organic solvent is coated and dried to provide a layer of the resin composition for forming a roughened surface. The resin for forming a roughened surface. The composition is hardly soluble and unhardened for the roughened liquid selected from at least one of acid, alkali and oxidizing agent. Heat-resistance 95 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 1ΙΙΙΙΙΙΙΙΙΙΙΙ — IJ II ϊ III — — If — — — — (Please read the notes on the back before filling out this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 453 1 4 1 ____B7 V. Description of Invention (Μ) In the resin matrix, it is desirable to dissolve a soluble substance in a roughened liquid selected from at least one of an acid, an alkali, and an oxidizing agent. &Lt; Please read the precautions on the reverse side before filling out this page). In the present invention, " The terms "insoluble" and "soluble" refer to the material that is relatively fast to dissolve relatively quickly when it is immersed in the same roughening solution for the same time, and the relative dissolution is slower. The property is expediently called "insoluble." As the above-mentioned thermosetting resin matrix, for example, a thermosetting resin or a composite of a thermosetting resin (a photosensitized part containing a thermosetting base) and a thermoplastic resin can be used. Examples of the thermosetting resin include epoxy resin, phenol resin, polyimide resin, and thermosetting polyolefin resin. Further, in order to sensitize the thermosetting resin, methacrylic acid or acrylic acid may be used to make the thermosetting isobutylene (propylene). In particular, isobutylene (propylene) esters of epoxy resins are the most suitable. As the epoxy resin, for example, a linear epoxy resin, an alicyclic epoxy resin, or the like can be used. As the thermoplastic resin, for example, polyethersulfonic acid, polysulfonic acids, polybenzenesulfonic acid, polyphenylene sulfide, polyphenylene ether, polyetherimine, and the like can be used. Printed by the Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For the above roughened liquid selected from at least one of acid, alkali and oxidant as a soluble substance, it is selected from inorganic particles, resin particles, metal particles, and rubber. At least one of particles, liquid resin and liquid rubber is preferred. Examples of the inorganic particles include silica, alumina, calcium carbonate, mica, muscovite, and the like. These particles can be used alone, and 96 papers are also applicable to the Chinese National Standard (CNS) A4 specification (2〗 〇χ297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 A7 B7 V. Invention Explanation) Two or more kinds of β alumina particles can be removed by dissolving hydrofluoric acid and calcium carbonate can be removed by dissolving hydrochloric acid. Also, sodium dioxide or muscovite containing sodium can be removed by dissolving it in an alkaline aqueous solution. Examples of the resin particles include amine resins (melamine resins, urea resins, melamine diamine resins, etc.), epoxy resins, and dicis-butenediamine triazabenzene resins. These resins may be used alone or in combination of two or more kinds. The epoxy resin is a substance that can be dissolved in an acid or an oxidizing agent, or a substance that is hardly soluble in an acid or an oxidizing agent can be arbitrarily produced by selecting the type of oligomer or a hardener. For example, a resin hardened with a bisphenol A epoxy resin with an amine hardener is extremely soluble in chromic acid, while a resin hardened with a cresol novolak epoxy resin with an imidazole hardener is not easily soluble in chromium In acid. It is necessary to harden the resin particles in advance. If it is not hardened in advance, the above-mentioned resin particles will be dissolved in a solvent that dissolves the resin matrix, resulting in uniform mixing, which makes it difficult to selectively dissolve and remove the resin particles by acid or oxidation. Examples of the metal particles include gold, silver, copper, tin, zinc, stainless steel, and aluminum. These metal particles may be used alone or in combination of two or more kinds. Examples of the rubber particles include acrylonitrile-butadiene rubber, polychloroprene rubber, polyisopropylene rubber, acrylonitrile rubber, polysulfide rigid rubber, fluorine rubber, polyurethane rubber, silicone rubber, and ABS. Resin, etc. 97 This paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm)!! 11 1! -------- IIIII f Please read the precautions on the back before filling this page) 453141 A7 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. B7 V. Description of Invention (Section) These rubber particles can be used alone or in combination of two or more. As the liquid resin, an uncured solution of the thermosetting resin may be used, and as a specific example of the liquid resin, an uncured epoxy oligomer and an amine-based hardener may be used. Mixing liquid and so on. For the liquid-phase rubber, for example, an uncured solution of the rubber can be used. When the liquid-phase resin or the liquid-phase rubber is used to prepare the photosensitive resin composition, the heat-resistant resin matrix and the soluble substance should not be uniform. It is compatible with the ground (that is, phase separation is achieved), so it is necessary to select these substances. By mixing the heat-resistant resin matrix selected according to the above-mentioned standards with soluble substances, the "sea" of the above-mentioned heat-resistant resin matrix is mixed. In this case, the liquid resin or liquid rubber is in the "island" dispersed state, or in the "sea" of the liquid resin or liquid rubber, the heat-resistant resin matrix is in the "island" dispersed state. A photosensitive resin composition is prepared. Then, after the photosensitive resin composition in this state is hardened, a roughened surface can be formed by removing the "sea" or "island j liquid resin or liquid rubber." The roughened liquid is used as the above-mentioned roughened liquid. Examples of the acid include phosphoric acid, hydrochloric acid, and sulfuric acid; and organic acids such as formic acid and acetic acid. Among them, it is preferable to use an organic acid. If an organic acid is used, self-through holes can be made during roughening treatment. The exposed metal conductor layer is harder to be corroded. As for the above oxidizing agent, it is better to use an aqueous solution of, for example, chromic acid and alkaline permanganate (calcium permanganate). 98 The paper size applies to the Chinese National Standard (CNS) A4 specifications (210 x 297 mm-! 111 —! 1 — -install · one ----- order ------ I — (Please read the precautions on the back before filling this page). A7 453141 _ B7_ V. Description of the invention (η) In addition, in terms of alkali, an aqueous solution of sodium hydroxide, calcium hydroxide, etc. is preferred. In the present invention, when the inorganic particles, the metal particles, and the resin particles are used, The average particle diameter is preferably 10 vm or less. When the average particle diameter is less than 2 # m, by using a combination of coarse particles with a relatively large average particle size and fine particles with a relatively small average particle size, the dissolved residue of the electroless plating film can be removed, and Reduce the amount of palladium catalyst under the anti-plating film, and further, it can form a complex roughened surface in a shallow layer. Therefore, by forming this complex roughened surface, the shallow roughened surface can also maintain practical peel strength. By combining the above coarse particles and fine particles, a complex roughened surface can be formed in a shallow layer, because the used particle diameter is less than 2 / zm of the average diameter of the coarse particles. Even if these particles are dissolved and removed, The formed anchors will also become shallower, and because the removed particles are a mixture of coarse particles with a relatively large particle size and fine particles with a relatively small particle size, the roughened surface formed will also become a complex surface. The particle diameter used at this time is because the average particle diameter of the coarse particles is not reached, and voids will not occur due to excessive roughening, so the interlayer resin insulating layer formed has excellent interlayer insulation. particle The average particle diameter is more than 0.8 // m and less than 2.0ym, and the average particle diameter of the fine particles is preferably 0.1 to 0.8 / zm. Within this range, the depth of the roughened surface is approximately Rmax = 3jtnn, so it is half The addition method can not only easily remove the electroless plating film, but also simply remove the palladium catalyst under the electroless plating film; in addition, it can apply 99 national paper standards to the national standard &lt; CNS) A4 size (210 X 297 mm) I 1 — II ί_ Agriculture ------------ Order --------- line (please read the notes on the back before filling this page) Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau and printed by the Consumer Cooperatives of the Ministry of Economics and Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 1 4 1 A7 B7 5 'Description of the Invention (at the time) Maintain a practical peel strength of 1.0 ~ 1.3kg / cm. The content of the organic solvent in the resin composition for forming a roughened surface is preferably 10% by weight or less. When the resin composition for forming a roughened surface is applied, a honing mill or a curtain coater can be used. (4) After the resin composition layer for forming a roughened surface formed in the above (3) is dried to a semi-hardened state, an opening for a through hole is provided. When the resin composition layer for forming a roughened surface is in a dry state, the thickness of the resin composition layer on the conductor circuit pattern is thin, and the thickness of the interlayer resin insulation layer on a planar layer having a large area is increased, Or the unevenness of the conductor circuit and the non-formed part of the conductor circuit will cause unevenness in the interlayer resin insulation layer. Therefore, it is desirable to use a metal plate or a metal roller and press-fit while heating to insulate the interlayer resin. The surface of the layer is flattened. The formation of the openings for the through-holes is based on the resin composition layer for forming a roughened surface, which is obtained by performing development processing after exposure to ultraviolet rays. When performing the exposure and development processing, the black circle pattern drawing side of a mask (preferably a glass substrate) on which a black circle pattern is drawn is formed on the portion corresponding to the opening for the through hole to match the roughened surface. The resin composition layer for formation is mounted on the resin composition layer in an intimate state, and exposed and developed. (5) Next, the roughened surface-forming resin composition layer is cured to form an interlayer resin insulating layer, and the interlayer resin insulating layer is roughened. In the roughening treatment, the choice of inorganic particles, resin particles, metal particles, rubber particles, and liquid phase for the existence of the above-mentioned interlayer resin insulating layer is 100. The paper size applies the Chinese National Standard (CNS) A4 specification &lt; 210 X 297 (Mm) ------------- Mill —----- ^ i I ------ ^ (please read the ii meaning on the back before filling in this page) Ministry of Economic Affairs Printed by the Intellectual Property Bureau employee consumer cooperative 453 1 4 1 a7 __JB7_ V. Description of the invention (") At least one soluble substance in resin and liquid rubber, although it can be removed by the above-mentioned roughening solution of acid, oxidant, alkali, etc. However, at this time, the oxide film formed on the surface of the conductor circuit should be roughened under conditions that prevent it from being etched. Therefore, the roughening solution used should be a chromic acid aqueous solution of ltMOOO g / ι or 0. A 10 mol / ι permanganate alkaline aqueous solution is preferred. The depth of the roughened surface formed on the interlayer resin insulating layer is preferably about 1 to 5 / zm. (6) Second, the The surface of the roughened interlayer resin insulation layer is given a catalyst core. The given catalyst core is made of precious metal ions or precious gold. Colloids are preferred. Generally speaking, palladium chloride or palladium colloids are used. In addition, it is better to heat the catalyst core to fix it. For this type of catalyst core, palladium is preferred. (7) Secondly, An electroless plating film is formed on the roughened surface. The electroless plating solution described above uses the following electroless plating solution. The composition of the plating solution contains EDTA (50 g / 1) The aqueous solution of copper sulfate (10g / 1), HCHO (8 ml / 1), NaOH (10 g / 丨) is preferred. The thickness of the electroless plating film is preferably 0.1 ~ 5 / zm, of which 0.5 to 3 vm is better. (8) Next, a photosensitive resin film (dry film) is laminated on the electroless plating film, and a photomask (preferably a glass substrate) on which the anti-plating pattern is drawn is adhered to the photosensitivity. A resin film is placed thereon, and then exposed and developed to form a plating resist pattern. (9) Next, electrolytic plating is performed on the non-plating resist forming portion to form a conductor circuit and a through hole. Here, as described above For electrolytic plating, it is better to use copper plating, and its 101 paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) !!! ----- Order ------- I line (Please read the precautions on the back before filling in this page} 453141 A7 _B7____ 5. Description of the invention (/ Μ) The thickness is preferably 0.5 ~ 3 / zm. (10) Furthermore, after the anti-plating film is removed, the plating film can be dissolved and removed by using a mixed solution of sulfuric acid and hydrogen peroxide or a hungry etching solution such as sodium persulfate, ammonia persulfate, ferric chloride, and copper chloride to become independent After that, if necessary, palladium catalyst nuclei can be dissolved and removed by chromic acid or the like. (11) Next, a roughened surface is formed on the surface of the conductor circuit. At this time, it is preferably formed by any one of the above-mentioned honing treatment, etching treatment, blackening reduction treatment, and plating treatment. Thereafter, an oxide film is formed on the surface of the conductor circuit by the same method as in the above (2). (12) Next, on this substrate, an interlayer resin insulating layer is formed in the same manner as described above by using the resin composition for forming a roughened surface. (13) Secondly, the process of tritium gas is repeated, and the upper conductor circuit is set, and a flat-shaped conductor base or through hole with a pad function is formed thereon. Finally, a multi-layer printed circuit board is manufactured by forming a solder resist layer and solder bumps. Although the following method uses a semi-additive method, a full-additive method may be used. [The best form for implementing the invention] [Example 1] (1) On both sides of a substrate made of a BT (biscisbutadienetriazine) resin having a thickness of 0.8 mm, a copper foil having a thickness is laminated. 2. The BT resin copper area laminate (Mitsubishi Gas Chemical Co., Ltd., trade name: HL830-C, 8T12D) thus formed was used as a starting material (see FIG. 1U). First, drill this copper area laminate (refer to Figure 1 (b)), and secondly, attach Pd—Sn glue 102. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2) 0 X 297 mm> (Please read the precautions on the back before filling in this page &gt; Loading ----- Order -----! 1 &quot; ^ Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 4 53 1 4 1 __B7_ V. DESCRIPTION OF THE INVENTION The (β 丨) body is subjected to electroless plating with an electroless plating aqueous solution of the following composition and the following conditions to form a 0.7 / zm electroless plating film on the entire substrate. [Electrolytic plating aqueous solution]

EDTA 150 gA 硫酸銅20g/l HCHO 30 ml/1EDTA 150 gA copper sulfate 20g / l HCHO 30 ml / 1

NaOH 40 g/1 α，α ’ 一聯二[1比B定 80 mg/1 PEG 0.1 g/1 [無電解鍍敷條件] 7〇t：之液溫，30分鐘。 再者，以下述組成之電解電鍍水溶液、下述條件實施 電解鍍銅，形成厚度15/zm之電解鍍銅膜(參照圖1(c))。 [電解電鍍水溶液] 硫酸 180 g/1NaOH 40 g / 1 α, α ′ one pair [1 than B fixed 80 mg / 1 PEG 0.1 g / 1 [electroless plating conditions] 70t: liquid temperature, 30 minutes. Furthermore, electrolytic copper plating was performed using an electrolytic plating aqueous solution having the following composition and the following conditions to form an electrolytic copper plating film having a thickness of 15 / zm (see Fig. 1 (c)). [Aqueous electrolytic solution] Sulfuric acid 180 g / 1

硫酸銅 80 gA 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 1 ml/1 [電解電鍍條件] 電流密度 1 A/dm2 時間 30分鐘 溫度 室溫 (2)對如此般形成有內層銅圖案(包含通孔3)之基板進 行水洗，而乾燥之後，在氧化浴（黑化浴）上係使用 103 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（/θ)Copper sulfate 80 gA additive (manufactured by Attic Japan, trade name: Capalaseide GL) 1 ml / 1 [electrolytic plating conditions] current density 1 A / dm2 time 30 minutes temperature room temperature (2) The substrate with the inner copper pattern (including the through hole 3) is generally washed with water, and after drying, it is used on an oxidation bath (blackening bath) 103. This paper size applies to Chinese National Standard (CNS) A4 (210 X 297) (Mm) Packing -------- Order --------- line (please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 453 1 4 1 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (/ θ)

Na〇H(20 g/1)、NaClCb(50 g/1)、Na3P〇4(15.0 g/1)的水溶液； 在還原浴上係使用NaOH(2.7 g/l)、NaBH4(1.0 g/丨)的水溶液 ，以供給做爲氧化還原處理’而於導體電路、通孔全表面 設置粗化層4(參照圖1(d))。 (3) 將含有銅粒子之導電糊劑5藉由網版印刷塡充至通 孔3內，使之乾燥、硬化。接著’將導體上面之粗化層4 及自通孔3溢出之導電糊劑5，利用#400的帶式硏磨紙(三 共理化學製造)而藉由帶式硏磨機將該等之物硏磨去除之， 又爲了將由於此帶式硏磨機造成的損傷去除，乃進行拋光 硏磨，將基板表面平坦化(參照圖1(e))。 (4) 在上述(3)平坦化之基板表面，依一般方法賦予鈀膠 體觸媒，而藉由實施無電解鍍敷以形成厚度0.6mm之無電 解鍍銅膜6(參照圖1(f))。 (5) 接下來，以下面之條件施以電解鍍銅，形成厚度15 μm的電解鍍銅膜7，以將成爲導體電路9的部分增厚，並 形成將塡充於通孔3之導電糊劑5覆蓋的導體層(覆鍍層 )10部分。 [電解電鍍水溶液] 硫酸 180 g/1 硫酸銅 80gn 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德(}乙） 1 ml/1 [電解電鍍條件] 電流密度 1 A/dm2 1----J I---訂·----I----線 ί請先閱讀背面之注意事項再填寫本頁v 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公釐） A7 4 5314 1 _B7_ 五、發明說明（/Λ) 時間 30分鐘 溫度 室溫 (6) 於用以形成導體電路9及導體層10部分之基板的 兩面，將市售之感光性乾燥膜張貼上去，進而裝設光罩， 再以100 m〗/cm2進行曝光、0.8%碳酸氫鈉進行顯像處理， 從而形成厚度15#m之抗蝕層8 (參照圖2(a))。 (7) 接著，將未形成抗蝕層8部分之鍍膜，使用硫酸及 過氧化氫的水溶液採蝕刻方式溶解去除之，又，將抗蝕層 8以5%KOH剝離去除，乃形成獨立之導體電路9以及覆有 導電糊劑5之導體層(以下，將此導體層簡稱爲覆鍍層)10 ( 參照圖2(b))。 (8) 其次，於包含導體電路9及覆鍍層10側面的全表 面形成由Cu-Ni —P合金構成之厚度爲的粗化層( 凹凸層)11，再於此粗化層11的表面設置厚度0.3/zm的Sn 層(參照圖2(c)，而Sn層則未予圖示）。 其形成方法如以下所述。亦即，對基板進行酸性脫脂 而行軟蝕刻，其次，以由氯化鈀及有機酸構成之觸媒溶液 進行處理，而賦予鈀觸媒，將此觸媒活性化之後，藉由硫 酸銅(8 g/Ι)、硫酸鎳(0.6 g/i)、檸檬酸(15 g/丨）、次亞磷酸鈉 (29 g/Ι)、硼酸(31 g/Ι)、界面活性劑（日信化學工業製造之沙 費諾魯465)0.1 g/Ι之水溶液構成之pH = 9的無電解鍍敷浴 來實施電鍍，而於導體電路9及覆鍍層10的全表面設置 Cu-Ni-P合金之粗化層。接著，使用氟硼化錫0.1 mol/1 ，硫脲1.0m〇l/l之水溶液，以溫度50°C、pH = 1,2之條件 105 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝----------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 _ B7 五、發明說明（叫） 進行Cu-Sn置換反應，而於粗化層11的表面設置厚度0.3 /z m的Sn層。（Sn層未予圖示） (9) 於基板的兩面，將厚度50#m的熱硬化型聚烯烴樹 脂層(住友3M製造，商品名：1592)，在進行溫度50〜180°C 昇溫的同時以壓力10 kg/cm2予以積層，而設置由聚烯烴系 樹脂構成之層間樹脂絕緣層12(參照圖2(d))。 (10) 以波長10.4wm的C〇2氣體雷射於聚烯烴系樹脂所 構成之層間樹脂絕緣層12設置直徑80jcim的通孔用開口。 再者，藉由氧電漿處理，以進行去污。又，電漿處理條件 ，係電力500W、氣壓500mToir，時間10分鐘。 (11) 採用沁濺鍍靶，在氣壓〇.6Pa、溫度80°C、電力 200W ’以及時間5分鐘的條件下進行濺鍍，則Ni薄膜將 於聚烯烴系樹脂絕緣層12的表面形成。此時，所形成之 Ni金屬層之厚度爲O.lym。 又*用以濺鍍之裝置，係使用日本真空技術股份有限 公司製造之SV — 4540。 (12) 對結束前述（11)處理之基板，再進行濺鍍以形成厚 度0.05 的Cu層。此時濺鍍之條件，係以Cu濺鑛靶在 氣壓0.6Pa、溫度80°C、電力200W，以及時間2分鐘進行 濺鍍。接著’實施前述(1)之無電解鍍敷，而形成厚度0.7# m的無電解鍍敷膜14(參照圖3(a))。 (13) 於前述(12)形成無電解鍍敷膜14之基板兩面，貼 上市售之感光性乾式薄膜，進而裝設光罩，再以1〇〇 mJ/cm2進行曝光、0.8%碳酸鈉進行顯像處理，從而設置厚 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚) 装----！| 訂------- _ 線--- (請先Μ讀背面之注$項再填寫本頁) 經濟部智慧財產局員工消费合作社印製 453 1 4 1 A7. ___B7___ 五、發明說明（ 度15//m之防鍍膜16 (參照圖3(b))。 (14) 再者，實施前述(1)之電解電鍍，以形成厚度15〆 m之電解電鍍膜15，除了增厚導體電路9之部分，尙可對 通孔17之部分進行電鍍塡充(參照圖3(c))。 (15) 又，將防鍍膜16以5%之KOH剝離去除之後，再 將位於該防鍍膜16下方之Ni膜以及無電解鍍敷膜14以硫 酸與過氧化氫之混合液、以及硝酸與鹽酸之混合液藉由蝕 刻溶解去除之，而形成由無電解鍍敷膜14及電解鍍銅膜 15所構成之厚度16之導體電路9(包含通孔17)，從而製造 出多層印刷電路板(參照圖3(d))。 [實施例2] 於本實施例，就聚烯烴系樹脂而言，係使用三井化學 製造之TPX(商品名），藉由氧電漿處理而進行去污以及表 面改良。依此表面改良，可確認絕緣層表面係具有羥基以 及羰基等極性基。 於本實施例除了再將Ni以氣壓0.6Pa、溫度80°C、電 力200W，以及時間1分鐘的條件附著至聚烯烴系樹脂絕緣 層，其餘則係與實施例1相同之方法製造多層印刷電路板 〇 [實施例3] 於本實施例，就聚烯烴系樹脂而言，係使用出光石油 化學製造之SPS(商品名），藉由氧電漿處理而進行去污以及 表面改良。依此表面改良，可確認絕緣層表面係具有羥基 以及羰基等極性基。 107 ^----------^--------- (請先閱讀背面之注意事項再填寫本真&gt; 本紙張尺度適用中國國家標準（CNS&gt;A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作杜印製 ^53 1 4 1 A7 B7 五、發明說明（μ) 於本實施例，例除了再將Pt以氣壓〇.6Pa、溫度80°C 、電力200W，以及時間1分鐘的條件附著至聚烯烴系樹脂 絕緣層，其餘則係與實施例1相同之方法製造多層印刷電 .路板。 [實施例4] 於本實施例，將前述重複單位之構造式X係CH2 = CH 一、Η、苯基等單體分別聚合以形成聚烯烴低聚物，而該 等低聚物彼此間係以過氧化苯醯爲起始劑、CH2 = CH-爲 鍵合部，形成具有交聯構造之樹脂以做爲聚嫌烴系樹脂來 使用。具體上係使用以下述之合成例來合成聚烯烴低聚物 薄膜，而用與實施例1相同之方法製造多層印刷電路板。 但是，於本實施例係以All來替代Ni ’而將Au以氣壓 0.6Pa、溫度80°C、電力200W ’以及時間2分鐘的條件附 著至聚烯烴系樹脂絕緣層。 又，本合成例所合成之聚烯烴低聚物係熱硬化型之物 。因此，此聚烯烴低聚物於熱壓時將由於發生交聯反應而 硬化。 [合成例] (a) 於500ml正庚烷中，溶解苯乙烯104重量份以及鋰 丁烷10.8重量份，於70°C加熱3小時。 (b) 於進行過前期(a)處理之溶液中，在灌入容量比苯乙 烯：丁二烯=3 : 1混合氣體的同時’於70°C放置5小時 〇 (c) 添加12以loot放置1小時則可去除正庚烷。 108 本紙張尺度適用中國圈家標準（CNS)A4規格（21〇 X 297公釐） I - ! I I I ^ ----- --- (請先Η讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B7 五、發明說明（&lt;。1) (d) 以丙酮洗淨生成物來去除未反應物及Lil。 (e) 將所得之生成物50重量份再度溶解於500ml正庚院 中*又溶入1重量份之過氧化苯醯，將其薄塗於聚對苯二 甲酸乙酯薄膜上。 (f) 自50°C以1°C/分的速度緩慢地昇溫，直到100°C方 停止加熱，再放置30分鐘，藉由去除溶劑乃可獲得厚度 50#m之半硬化性狀態之聚烯烴低聚物薄膜β又，聚烯烴 低聚物薄膜之熔點爲ll〇°C。 [實施例5] 於本實施例，將前述重複單位之構造式X係環氧基、 Η、苯基等單體分別聚合以形成聚烯烴低聚物，而該等低 聚物彼此間係以過氧化苯醯爲起始劑、環氧基爲鍵合部’ 形成具有交聯構造之樹脂以做爲聚烯烴系樹脂來使用。具 體上係使用以下述之合成例來合成聚烯烴低聚物薄膜’而 用與實施例1相同之方法製造多層印刷電路板。但是，於 本實施例係以Ti來替代Ni，而將Ti以氣壓0.6Pa、溫度80 °C '電力200W，以及時間5分鐘的條件附著至聚烯烴系樹 脂絕緣層。 又，本合成例所合成之聚烯烴低聚物係熱硬化型之物 。因此，此聚烯烴低聚物於熱壓時將由於發生交聯反應而 硬化。 [合成例] (a)於500ml正庚烷中，溶解苯乙烯104重量份以及鋰 丁烷10.8重量份，於70°C加熱3小時。 109 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I -裳·！-----訂--------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 a? B7 五、發明說明（/。尤） (b)於進行過前期⑻處理之溶液中，在灌入容量比苯乙 烯：丁二烯=3 : 1混合氣體的同時，於7〇°C放置5小時 〇 (C)添加12以100°C放置1小時則可去除正庚烷。 (d) 以丙酮洗淨生成物來去除未反應物及Lil ° (e) 將前述⑷之生成物20重量份添加環己醇’於含有 60重量％硫酸、0.5重量％過氧化氫之水溶液中懸膠’而在 室溫放置2小時。 (f) 以THF(四氫吡喃)提取生成物’而將該提取液保持 於，同時持續將乙烯酮灌入10分鐘。 (g) 藉由將前述⑴之反應液分散於聚對苯二甲酸乙酯上 ，以室溫其自然乾燥而去除THF以及乙烯酮，可獲得未交 聯之聚烯烴低聚物薄膜。又，聚烯烴低聚物薄膜的熔點係 105°C。 ' [實施例7] 於本實施例，將前述重複單位之構造式X係Η、苯基 等單體以及分子主鏈中具有_(CH2—CH = CH—(：沁&gt;構造 之單體，分別聚合以形成聚烯烴低聚物，而該等低聚物彼 此間係以過氧化苯醯爲起始劑，將伴隨內酯基脫碳酸之縮 合反應具有交聯構造之樹脂，做爲聚烯烴系樹脂來使用。 具體上係使用以下述之合成例來合成聚烯烴低聚物薄膜， 而用與實施例1相同之方法製造多層印刷電路板。但是， 於本實施例係以Cr來替代Ni，而將Cr以氣壓0.6Pa、溫度 80°C、電力200W，以及時間3分鐘的條件附著至聚烯烴系 110 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公釐) -装--------訂·--------線 (請先Μ讀背面之注意事項再填寫本頁) A7 453 1 4 1 _____B7_____ 五、發明說明（,。*|) 樹脂絕緣層。 又，本合成例所合成之聚烯烴低聚物係熱硬化型之物 。因此，此聚烯烴低聚物於熱壓時將由於發生交聯反應而 硬化。 [合成例] (a) 於500ml正庚烷中，溶解苯乙烯104重量份，又灌 入容量比苯乙烯：丁二烯=3 : 1之混合氣體70°C加熱3 小時。 (b) 在灌入混合氣體的同時使4重量份之過氧化苯醯溶 解，於70°C放置3小時。 (c) 於100°C加熱1小時以去除正庚烷。 (d) 以丙酮洗淨生成物，而去除丙酮之後，再度將此生 成物500重量份溶解於正庚烷中，又，再溶解過氧化苯醯 3重量份。 、 (e) 將上述溶液薄薄地分散於聚對苯二甲酸乙酯薄膜上 ，以It：/分自50°C昇溫至100°C。再放置30分鐘，而獲得 呈半硬化狀態之聚烯烴低聚物薄膜。又，所得之聚烯烴低 聚物薄膜的熔點係78°C。 [實施例8] 於本實施例，將前述重複單位之構造式X係OH、以 及分子主鏈中具有內酯構造之聚烯烴低聚物分別合成，而 此等低聚物彼此間係以OH基、內酯基做爲鍵合部來交聯 ，而將具有此構造之樹脂，做爲聚烯烴系樹脂來使用。具 體上係使用以下述之合成例來合成聚烯烴低聚物薄膜，而 ____ in 九張尺度適用令國國豕標準（CNS)A4規格（210 x 297公爱） II — — — — — — - 11 I I I--訂--II--- -- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 A7 4 53141 __B7____ 五、發明說明（||D ) 用與實施例1相同之方法製造多層印刷電路板。 [合成例] (a) 於500ml之3-正庚烷中，使少量之1〇〇重量份丙 烯腈酸溶解，又於灌入丁二烯氣體之同時，使2重量份之 過氧化苯醯溶解，於50°C放置1小時，接著，將體積比苯 乙烯：丁二烯=3 : 1之混合氣體灌入的同時於70°C放置3 小時。 (b) 在以150°C、2小時的時間來去除3-正庚烷，並以 丙酮去除未反應物。 (c) 將上述生成物20重量份添加至環己醇中’而於60% 硫酸水溶液中懸膠，於室溫下放置2小時，以乙酸乙酯抽 取生成物。 (d) 於此抽取液中添加氯化亞硫醯，於室溫放置2小時 。之後，將乙酸乙酯以及其他低分子量之物減壓去除之， 而以丙酮再度洗淨。 (e) 另一方面，於二甲苯中溶解Ziegler型觸媒(A1 (Et)3 + Co擔體)與乙醛，於灌入苯乙烯氣體的同時於50°C反應 之。 (f) 於150°C、30分鐘的加熱去除二甲苯之後，以希鹽 酸及丙酮洗淨之，而殘留之物及爲生成物。將其溶入正庚 烷中，再將自前述(d)所得之生成物溶解其中而廣布於聚 對苯二甲酸乙酯薄膜上’自50°C以1°C/分的速率昇溫至 100°C，再放置30分鐘’藉此’可獲得呈半硬化狀態之聚 烯烴薄膜。又，所得之聚烯烴薄膜的熔點係21CTC。 112 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I --!装----)I--訂·! ---.線 (請先閱讀背面之注意事項再填窵本頁) 經濟部智慧財產局員工消費合作杜印製 經濟部智慧財產局員工消費合作社印製 4 53141 A7 B7 五、發明說明（i丨丨） [實施例9] [嵌段共聚合的例子] 於本實施例，將前述重複單位之構造式X係苯基之單 體、以及分子主鏈中具有一（CH2 — CH = CH — CH〇m構造之 單體共聚合彤成之聚烯烴低聚物，使其彼此間交聯，而將 具有此構造之樹脂，做爲聚烯烴系樹脂來使用。具體上係 使用以下述之合成例來合成之聚烯烴低聚物薄膜，而用與 實施例1相同之方法製造多層印刷電路板。 [合成例] (a) 於500ml正庚烷中，溶解苯乙烯104重量份，而於 該溶液中灌入丁二烯氣體，再將BF;灌入10分鐘。 (b) 其次，在僅灌入丁二烯氣體的情況下，於70°C反應 2小時。 (c) 將此溶液薄薄地廣布於聚對苯二甲酸乙酯上，以 100°C、30分鐘的時間去除正庚烷，而獲得未硬化之聚烯烴 薄膜。又，所得之聚烯烴薄膜的熔點係ioo°c。又，將該 硬化薄膜置於液態氮中破壞，該截面在經由電子顯微鏡以 及ESCA觀察後，發現係爲聚苯乙烯以及聚丁二烯的嵌段 共聚物。各嵌段約爲〇.5~2em。 [實施例10] (聚合物合金：熱可塑型聚烯烴+熱硬化型聚烯烴） 使用以下述合成例合成之聚烯烴薄膜而採用與實施例 1相同的方法製造多層印刷電路板。 [合成例] 113 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) A7 453 1 4 1 _____B7 __ 五、發明說明（ (a) 於500ml正庚烷中，溶解苯乙烯1〇4重量份以及鋰 丁烷10.8重量份，於70°C加熱3小時。 (b) 於進行過前期⑷處理之溶液中’在灌入容量比苯乙 烯：丁二烯=3 : 1混合氣體的同時，於7〇°C放置5小時 〇 (C)添加12以100°c放置1小時則可去除正庚烷。 (d) 以丙酮洗淨生成物來去除未反應物及LH。 (e) 另一方面，將熱可塑型聚烯烴之出光石油化學公司 製造的SPS(商品名)溶解於二甲苯中。 (f) 將前述(d)及⑹混合，自50至150爲止以1分的速 率昇溫來去除溶劑，而得到未硬化之聚烯烴薄膜。 [實施例11] (聚合物合金：熱可塑型聚烯烴+熱硬化型性樹脂） 使用以下述合成例合成之聚烯烴薄膜而採用與實施例 1相同的方法製造多層印刷電路板。 [合成例] U)正庚烷中，使聚甲基丙烯(三井化學公司製造，商品 名：TPX)溶解於其中，而雙酚醛F型環氧樹脂及咪唑硬化 劑（四國化成公司製造，2E4MZ — CN)及TPP(三苯基磷化氫) 係以下述之組成混合。 TPX 80重量份 雙酚醛F型環氧樹脂 15重量份 咪唑硬化劑 5重量份 TPP 0.1重量份 114 本纸張尺度適用中國固家標準（CNS)A4規格（21〇 X 297公t ) --------------------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 Μ 1 Α7 Β7 經濟部智慧財產局員工消费合作社印製 五、發明說明。Λ) (b) 將前述溶液以輥軋機塗佈於聚對苯二甲酸乙酯薄膜 上，以70°C、30分鐘加熱以去除溶劑。 (c) 以180°C、5小時使之完全熱硬化，而得到聚烯烴薄 膜。 [比較例1] 於本比較例，做爲層間絕緣用樹脂除了使用氟樹脂以 外，其餘皆與實施例1相同來製造多層印刷電路板。 層間樹脂絕緣層的形成係藉由將厚度25/zm之鐵氟龍 層(杜邦製造，商品名：鐵氟龍FEP)於溫度200°C、壓力20 kg/cm2予以積層，而以300°C退火的方式來進行之。 [比較例2] 於本比較例，做爲層間絕緣用樹脂除了使用環氧丙烯 酯樹脂以外，其餘皆與實施例1相同來製造多層印刷電路 板。 層間樹脂絕緣層的形成，可藉由塗佈甲醛酚醛淸漆樹 脂環氧丙烯酯樹脂（共榮社製造，CNA — 25)，於120°C、3 小時加熱硬化來進行。 就此種方式之實施例及比較例所得之多層印刷電路板 ，乃實施剝離強度、於-55°C〜125°C(各3分鐘)以1000循環 的條件之熱循環試驗、介電常數，以及焊接耐熱性試驗等 〇 其結果，就剝離強度而言，於實施例1之電路板係2.4 Kg/cm，於實施例2之電路板係2.0 Kg/cm，於實施例3之 電路板係1·5 Kg/cm，於實施例4之電路板係1·7 Kg/cm， 115 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公爱) 裝.--------訂---------線 (請先Μ讀背面之注意事項再填窝本頁) 453141 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（叫） 於實施例5之電路板係1·5 Kg/cm，於實施例6之電路板係 1.8 Kg/cm ’於實施例7之電路板係2.1 Kg/cm，於實施例8 之電路板係1_6 Kg/cm，於實施例9之電路板係1.3 Kg/cm ’於實施例10之電路板係1.2 Kg/Cm，於實施例11之電路 板係 1.4 Kg/cm。 如此般，依據將聚烯烴系樹脂做爲層間樹脂絕緣層使 用之關於本發明的電路板，即使未於層間樹脂絕緣層設置 粗化面，亦可確保實用上之剝離強度。 相對於此’於比較例1之電路板，其剝離強度〇.7 Kg/cm係相同條件之實施例的1/2。 就熱循環試驗而言’於實施例1〜實施例11的電路板 ’其中並未發現層間樹脂絕緣層有龜裂的現象。 又’關於將聚烯烴系樹脂做爲層間樹脂絕緣層使用之 實施例1之電路基板的介電常數，於10MHz、100MHz、 500MHz，以及 1GHz 之時，其分別爲 2.8、2.7、2.6、2.5。 而介電耗損因數則爲0.001。 再者，於焊接耐熱性試驗(260°c、30秒浸漬）中並未觀 察到剝離的發生。 [實施例12] (1)於厚度lmm之玻璃環氧樹脂或是BT(聚對苯二甲酸 乙酯)樹脂構成之基板101的兩面積層有18#m銅箔108， 而以此銅面積層板做爲起始材料(參照圖4(a))。首先，對此 銅面積層板進行鑽削孔，接著於形成防鍍膜之後，於此基 板施以無電解鍍敷處理以形成通孔109，接著，將銅箔藉 116 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 11-------- ------------I — — (請先Μ讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消費合作杜印製 453 14 1 A7 B7 五、發明說明（γ) 由一般方法進行圖案狀的蝕刻’而於基板兩面形成內層銅 圖案(下層導體電路）1〇4 ° (2) 將形成下層導體電路104的基板水洗之’而於乾燥 後，將蝕刻液對基板的兩面以噴塗器噴附上去’藉由對下 層導體電路104表面以及通孔109的焊墊表面及其內壁進 行蝕刻，於下層導體電路全表面形成粗化面⑺如、109a(參 照圖4(b))。就蝕刻液而言，係使用咪唑銅（Π)錯合物10重 量份。乙二酸7重量份、氯化轉5重量份’以及離子交換 水78重量份混合所得之物。 (3) 將以環烯烴系樹脂做爲主成分之樹脂塡充劑110， 藉由使用印刷機而塗佈至基板的雨面’使得下層導體電路 104間或是通孔109內塡充該物，再進行加熱乾燥。亦即 ，藉由此過程，樹脂塡充劑係塡充於下層導體電路104間 或是通孔109之內(參照圖4(c))。 (4) 將結束上述(3)處理之基板的單面，藉由使用帶式硏 磨機(三共理化學公司製造)進行帶式硏磨，使得下層導體 電路104表面或通孔109之焊墊表面以不留下樹脂塡充劑 110的方式予以硏磨，接著，爲去除因上述帶式硏磨所造 成之磨損乃進行拋光硏磨。此一連串的硏磨亦於基板的另 一面進行。然後，將塡充之樹脂塡充劑110加熱硬化之(參 照圖4(d))。 藉此，將塡充於通孔109等之樹脂塡充劑110之表層 部以及下層導體電路HH上面之粗化層104a去除使得基板 的兩面平滑化，樹脂塡充劑110與下層導體電路104側面 117 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — II ----裝-----ί — 訂- ----·線 &lt;請先閲讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消費合作社印製 I ^ 453 1 4 1 A7 B7 五、發明說明（扑） 透過粗化層104a而強固的密接著，又通孔109的內壁面與 樹脂塡充劑110則透過粗化面109a強固地密接而得到此電 路基板。 (5) 於結束前述(4)處理之基板的兩面，將與上述(2)使用 之蝕刻液相同之蝕刻液以噴塗器嘖附其上，將一度平坦化 之下104之表面及通孔109之焊墊表面藉由蝕刻的進行， 而於下層導體電路104的全表面形成粗化面l〇4a、109a (參 照圖5(a))。 (6) 其次，於經過上述過程之基板的兩面，將厚度50μ m之熱硬化性環烯烴系樹脂層自50~150°C昇溫的同時以壓 力5kg/cm2進行真空壓合積層’以設置由環烯烴系樹脂而成 之層間樹脂絕緣層102(參照圖5(b))。真空壓合時之真空度 係 10 mmHg 〇 (7) 其次’以波長10_2/zm之CCh氣體雷射，而於光束 直徑5mm、極熱模式(top hot mode)、脈衝寬度50//秒、先 罩孔徑0.5mm、3次照射的條件下於環烯烴系樹脂所構成 之層間樹脂絕緣層102中設置直徑80#m之通孔用開口 1〇6(參照圖5(c))。之後，使用酵素電漿進行去污處理。 (8) 其义’使用日本真空技術股份有限公司製造之SV - 4540進行電漿處理，以將層間樹脂絕緣層1U)2表面粗化 (參照圖5(d))。此時，使用鈍性氣體之氬氣，而於電力 200W、氣壓0.6Pa、溫度70°C的條件下，進行2分鐘之電 漿處理。 (9) 其次’使用相同之裝置，將內部以氬氣置換之後， 118 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝-----彥—訂-------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 53141 A7 ----------§Z_ 五、發明說明（.οΊ ) 以Ni-Cu合金爲濺鍍靶，於氣壓〇.6Pa、溫度80°C、電力 200W、時間5分鐘的條件下進行濺鍍，於是Ni- Cu合金 層112便於聚烯烴系層間樹脂絕緣層102之表面形成。此 時，所形成之Ni_Cu合金層112的厚度係0.2# m(參照圖 6(a))。 (10) 於結束上述處理之基板的兩面，貼附上市售之感 光性乾式薄膜，再裝設光罩薄膜，於1〇〇 m〗/cm2曝光後’ 以0.8%碳酸鈉進行顯像處理，從而形成厚度之防鍍 膜103的圖案(參照圖6(b))。 (11) 其次，以下述之條件實施電鍍，而形成厚度15μιη 之電鍍膜113(參照圖6(c))。又’藉由此電鍍膜I〗3 ’乃成 爲進行後述過程之形成導體電路105部分的增厚以及形成 通孔107部分的電鑛塡充等。又，電鍍水溶液中之添加劑 ，係亞特提克日本公司製造之卡帕拉夕德HL ° [電解電鍍水溶液] 硫酸 2.24 mol/1 硫酸銅 0.26 mol/1 添加劑 19.5 ml/1 [電解電鍍條件] 電流密度 1 A/dm2 時間 65分鐘NaOH (20 g / 1), NaClCb (50 g / 1), Na3P〇4 (15.0 g / 1) in water; NaOH (2.7 g / l), NaBH4 (1.0 g / 丨) An aqueous solution of) is supplied as a redox treatment, and a roughened layer 4 is provided on the entire surface of the conductor circuit and the through hole (see FIG. 1 (d)). (3) The conductive paste 5 containing copper particles is filled into the through hole 3 by screen printing, and dried and hardened. Next, 'the roughened layer 4 on the conductor and the conductive paste 5 overflowing from the through hole 3, use a # 400 tape honing paper (manufactured by Sankyo Ricoh Chemical Co., Ltd.) and use a tape honing machine to put these things In order to remove the honing, in order to remove the damage caused by the belt honing machine, polishing honing is performed to flatten the substrate surface (see FIG. 1 (e)). (4) A palladium colloid catalyst is applied to the surface of the substrate (3) flattened according to a general method, and electroless plating is performed to form an electroless copper-plated film 6 having a thickness of 0.6 mm (see FIG. 1 (f)). ). (5) Next, electrolytic copper plating is applied under the following conditions to form an electrolytic copper plating film 7 with a thickness of 15 μm to thicken the portion that becomes the conductor circuit 9 and form a conductive paste that fills the through hole 3 10 portions of the conductor layer (plating layer) covered by the agent 5. [Aqueous solution for electrolytic plating] Sulfuric acid 180 g / 1 Copper sulfate 80gn additive (made by Attic Japan Co., Ltd., trade name: Kapalacide (} B) 1 ml / 1 [Electrolytic plating conditions] Current density 1 A / dm2 1 ---- J I --- Order · ---- I ---- Line ί Please read the notes on the back before filling in this page v The paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm) A7 4 5314 1 _B7_ V. Description of the invention (/ Λ) Time 30 minutes Temperature room temperature (6) On both sides of the substrate used to form the conductor circuit 9 and the conductor layer 10, commercially available photosensitivity The dried film was put on, and then a photomask was installed, and then exposed at 100 m / cm2 and developed with 0.8% sodium bicarbonate to form a resist layer 8 with a thickness of 15 # m (see FIG. 2 (a)). (7) Next, the plating film of the portion where the resist layer 8 is not formed is dissolved and removed by an etching method using an aqueous solution of sulfuric acid and hydrogen peroxide, and the resist layer 8 is peeled and removed at 5% KOH to form an independent layer. Conductor circuit 9 and a conductor layer (hereinafter, this conductor layer is simply referred to as a plating layer) 10 covered with a conductive paste 5 (see FIG. 2 (b)). (8) Next, A roughened layer (concavo-convex layer) 11 made of Cu-Ni-P alloy is formed on the entire surface of the side surface of the conductor circuit 9 and the plating layer 10, and a thickness of 0.3 / zm is set on the surface of the roughened layer 11 Layer (refer to FIG. 2 (c), and the Sn layer is not shown). The formation method is as follows. That is, the substrate is subjected to acid degreasing and soft etching, and secondly, palladium chloride and organic acid are used. The formed catalyst solution is processed to give a palladium catalyst. After activating this catalyst, copper sulfate (8 g / 1), nickel sulfate (0.6 g / i), and citric acid (15 g / 丨) are used. Electroless solution consisting of 0.1 g / 1 aqueous solution of sodium hypophosphite (29 g / 1), boric acid (31 g / 1), surfactant (Safinollu 465 manufactured by Nissin Chemical Industry) at pH = 9 A plating bath is used for electroplating, and a roughened layer of a Cu-Ni-P alloy is provided on the entire surface of the conductor circuit 9 and the plating layer 10. Next, 0.1 mol / 1 of tin borofluoride and 1.0 mol of thiourea are used. l Aqueous solution at a temperature of 50 ° C and a pH of 1,2. 105 This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm). Packing ---------- Order- -------- Line (Please read first Note on the back, please fill out this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 A7 _ B7 V. Description of the Invention (called) Cu-Sn substitution reaction, An Sn layer having a thickness of 0.3 / zm is provided on the surface of the roughened layer 11. (Sn layer is not shown) (9) On both sides of the substrate, a heat-curable polyolefin resin layer (manufactured by Sumitomo 3M, trade name: 1592) with a thickness of 50 # m was heated at a temperature of 50 to 180 ° C. At the same time, they were laminated with a pressure of 10 kg / cm2, and an interlayer resin insulating layer 12 made of a polyolefin-based resin was provided (see FIG. 2 (d)). (10) An interlayer resin insulation layer 12 made of a polyolefin resin with a CO2 gas having a wavelength of 10.4 wm is provided with a through hole opening having a diameter of 80 jcim. Furthermore, it is decontaminated by an oxygen plasma treatment. In addition, the plasma treatment conditions are 500W electric power and 500mToir air pressure, and the time is 10 minutes. (11) Using a Qin sputtering target and performing sputtering under the conditions of a pressure of 0.6 Pa, a temperature of 80 ° C, a power of 200 W ', and a time of 5 minutes, a Ni film is formed on the surface of the polyolefin-based resin insulating layer 12. At this time, the thickness of the Ni metal layer formed was O.lym. Also * The device used for sputtering is SV-4540 manufactured by Japan Vacuum Technology Co., Ltd. (12) For the substrate on which the above-mentioned (11) processing has been completed, sputtering is performed to form a Cu layer having a thickness of 0.05. The sputtering conditions at this time were performed using a Cu sputtering target at a pressure of 0.6 Pa, a temperature of 80 ° C, a power of 200 W, and a time of 2 minutes. Next, the aforementioned (1) electroless plating is performed to form an electroless plated film 14 having a thickness of 0.7 # m (see FIG. 3 (a)). (13) On the two sides of the substrate on which the electroless plating film 14 is formed in (12), a commercially-available photosensitive dry film is attached, and a photomask is installed, and then exposed at 100 mJ / cm2 and 0.8% sodium carbonate. Development processing, so as to set the size of the thick paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 cm). Order ------- _ Line --- (please read the note $ on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 A7. ___B7___ V. Description of the Invention (Anti-plating film 16 with a degree of 15 // m (refer to FIG. 3 (b)). (14) Furthermore, the electrolytic plating of the above (1) is performed to form an electrolytic plating film 15 having a thickness of 15 μm, except for thickening the conductor. For the part of the circuit 9, the part of the through hole 17 can be electroplated (refer to FIG. 3 (c)). (15) After removing the anti-plating film 16 by 5% KOH, the anti-plating film is located there The Ni film underneath 16 and the electroless plating film 14 are removed by etching and dissolving in a mixed solution of sulfuric acid and hydrogen peroxide and a mixed solution of nitric acid and hydrochloric acid to form an electroless plating film 14 and an electrolytic copper plating film. A conductor circuit 9 (including a through hole 17) having a thickness of 16 and a thickness of 15 is used to manufacture a multilayer printed circuit board (see FIG. 3 (d)). [Example 2] In this example, a polyolefin resin It uses TPX (trade name) manufactured by Mitsui Chemicals to perform decontamination and surface modification by oxygen plasma treatment. Based on this surface improvement, the insulation layer can be confirmed The surface has polar groups such as hydroxyl and carbonyl. In this example, except that Ni was attached to the polyolefin resin insulation layer under the conditions of a pressure of 0.6Pa, a temperature of 80 ° C, a power of 200W, and a time of 1 minute, the rest are related to In the same manner as in Example 1, a multilayer printed circuit board was manufactured. [Example 3] In this example, as for the polyolefin-based resin, SPS (trade name) manufactured by Idemitsu Petrochemical was used. Decontamination and surface improvement. Based on this surface improvement, it can be confirmed that the surface of the insulating layer has polar groups such as hydroxyl groups and carbonyl groups. 107 ^ ---------- ^ --------- (Please Please read the notes on the back before filling in the authenticity.> This paper size applies the Chinese national standard (CNS)> A4 size (210 X 297 mm). Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs on consumer cooperation. DU 53 1 4 1 A7 B7 5 Explanation of the invention (μ) In this embodiment, except that Pt is attached to the polyolefin resin insulation layer under the conditions of air pressure 0.6 Pa, temperature 80 ° C, power 200 W, and time of 1 minute, the rest are implemented with The same method as in Example 1 was used to make multilayer printed circuits. [Example 4] In this example, monomers such as the structural formula X of the aforementioned repeating unit, CH2 = CH1, fluorene, and phenyl, were polymerized to form a polyolefin oligomer, and the oligomers are related to each other. A resin having a cross-linked structure was formed using benzene hydrazone as a starter and CH2 = CH- as a bonding part, and was used as a polyhydrocarbon resin. Specifically, a polyolefin was synthesized using the following synthesis example An oligomer film was produced in the same manner as in Example 1 to produce a multilayer printed circuit board. However, in this embodiment, All is used instead of Ni ', and Au is attached to the polyolefin-based resin insulating layer under the conditions of a pressure of 0.6 Pa, a temperature of 80 ° C, a power of 200 W', and a time of 2 minutes. The polyolefin oligomer synthesized in this synthesis example is a thermosetting type. Therefore, this polyolefin oligomer will harden due to a crosslinking reaction during hot pressing. [Synthesis example] (a) In 500 ml of n-heptane, 104 parts by weight of styrene and 10.8 parts by weight of lithium butane were dissolved, and heated at 70 ° C for 3 hours. (b) In the solution that has been treated in the previous stage (a), while injecting a mixture of styrene: butadiene = 3: 1, let it stand at 70 ° C for 5 hours. (c) Add 12 to loot Leave it for 1 hour to remove n-heptane. 108 This paper size is in accordance with China Standards Standard (CNS) A4 (21〇X 297mm) I-! III ^ ----- --- (Please read the precautions on the back before filling this page) Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau 453 1 4 1 A7 B7 V. Description of the invention (&lt; 1) (d) Wash the product with acetone to remove unreacted substances and Lil. (e) Dissolve 50 parts by weight of the obtained product in 500 ml of Zheng Gengyuan * and dissolve 1 part by weight of phenylhydrazone peroxide, and thinly coat the film on polyethylene terephthalate. (f) Slowly increase the temperature from 50 ° C at a rate of 1 ° C / minute, stop heating until 100 ° C, and leave it for 30 minutes. By removing the solvent, a semi-hardened polymer with a thickness of 50 # m can be obtained. The olefin oligomer film β has a melting point of 110 ° C. [Example 5] In this example, monomers such as the structural formula X-based epoxy group, fluorene, and phenyl groups of the aforementioned repeating units were polymerized to form polyolefin oligomers, and the oligomers were Phenylperoxide is used as an initiator and epoxy group is used as a bonding portion. A resin having a crosslinked structure is formed and used as a polyolefin resin. Specifically, a polyolefin oligomer film was synthesized using the following synthesis example, and a multilayer printed wiring board was produced in the same manner as in Example 1. However, in this example, Ti was used instead of Ni, and Ti was attached to the polyolefin resin insulating layer under the conditions of an air pressure of 0.6 Pa, a temperature of 80 ° C '200 W, and a time of 5 minutes. The polyolefin oligomer synthesized in this synthesis example is a thermosetting type. Therefore, this polyolefin oligomer will harden due to a crosslinking reaction during hot pressing. [Synthesis example] (a) In 500 ml of n-heptane, 104 parts by weight of styrene and 10.8 parts by weight of lithium butane were dissolved, and heated at 70 ° C for 3 hours. 109 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) I -Shang ·! ----- Order -------- line (please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 a? B7 V. Description of the invention ( (B) In a solution that has been subjected to a preliminary treatment, a mixture of styrene: butadiene with a volume ratio of 3: 1 is filled, and it is left at 70 ° C for 5 hours. (C) is added 12Remove n-heptane by leaving it at 100 ° C for 1 hour. (d) Wash the product with acetone to remove unreacted materials and Lil ° (e) Add 20 parts by weight of the above-mentioned product of hydrazone to cyclohexanol 'in an aqueous solution containing 60% by weight sulfuric acid and 0.5% by weight hydrogen peroxide Suspend the gel and leave it at room temperature for 2 hours. (f) The product was extracted with THF (tetrahydropyran) and the extract was kept while the ketene was continuously poured for 10 minutes. (g) By dispersing the aforementioned reaction solution of rhenium onto polyethylene terephthalate, and naturally drying it at room temperature to remove THF and ketene, an uncrosslinked polyolefin oligomer film can be obtained. The melting point of the polyolefin oligomer film is 105 ° C. '[Example 7] In this example, monomers such as the structural formula X-series fluorene, phenyl, and the like in the repeating unit as well as monomers having a _ (CH2—CH = CH— (: Qin &gt; structure) in the main chain of the molecule are described. , Respectively, to form a polyolefin oligomer, and these oligomers are each based on benzene peroxide as a starter, and a resin having a crosslinked structure accompanying the condensation reaction of lactone group decarbonation is used as a polymer An olefin resin is used. Specifically, a polyolefin oligomer film is synthesized by the following synthesis example, and a multilayer printed circuit board is manufactured by the same method as in Example 1. However, in this embodiment, Cr is used instead. Ni, and Cr is attached to the polyolefin series 110 at a pressure of 0.6Pa, a temperature of 80 ° C, a power of 200W, and a time of 3 minutes. This paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm). -Install -------- Order · -------- Line (please read the precautions on the back before filling this page) A7 453 1 4 1 _____B7_____ 5. Description of the invention (,. * | ) Resin insulation layer. The polyolefin oligomer synthesized in this synthesis example is a thermosetting type. Therefore, this polyolefin is low. The material will harden due to the cross-linking reaction during hot pressing. [Synthesis example] (a) In 500 ml of n-heptane, 104 parts by weight of styrene is dissolved, and the capacity ratio of styrene: butadiene = 3: 1 The mixed gas is heated at 70 ° C for 3 hours. (B) 4 parts by weight of phenylhydrazone peroxide is dissolved while the mixed gas is poured, and left at 70 ° C for 3 hours. (C) heated at 100 ° C for 1 hour to Removal of n-heptane. (D) Wash the product with acetone. After removing the acetone, 500 parts by weight of this product was dissolved in n-heptane, and 3 parts by weight of phenylhydrazone peroxide was redissolved. ) The above solution was thinly dispersed on a polyethylene terephthalate film, and it was heated from 50 ° C to 100 ° C at It: / min. It was left for 30 minutes to obtain a polyolefin oligomer in a semi-hardened state. The melting point of the obtained polyolefin oligomer film was 78 ° C. [Example 8] In this example, the structural formula X-type OH of the aforementioned repeating unit and the lactone structure in the molecular main chain were used. Polyolefin oligomers are synthesized separately, and these oligomers are crosslinked with OH group and lactone group as the bonding part, The resin with this structure is used as a polyolefin-based resin. Specifically, polyolefin oligomer films are synthesized using the following synthesis examples, and ____ in nine standards are applicable to the national standard (CNS) A4 specification (210 x 297 public love) II — — — — — —-11 II I--Order --II ----(Please read the notes on the back before filling out this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumption cooperation Du printed A7 4 53141 __B7____ 5. Description of the invention (|| D) A multilayer printed circuit board was manufactured in the same way as in Example 1. [Synthesis example] (a) In 500 ml of 3-n-heptane, a small amount of 100 parts by weight of acrylonitrile acid was dissolved, and at the same time as butadiene gas was poured, 2 parts by weight of benzene peroxide Dissolve and leave it at 50 ° C for 1 hour. Then, inject a mixed gas with a volume ratio of styrene: butadiene = 3: 1 and leave it at 70 ° C for 3 hours. (b) Remove 3-n-heptane at 150 ° C for 2 hours and remove unreacted material with acetone. (c) 20 parts by weight of the above product was added to cyclohexanol ', and the suspension was suspended in a 60% sulfuric acid aqueous solution, and allowed to stand at room temperature for 2 hours, and the product was extracted with ethyl acetate. (d) Add thionyl chloride to this extraction solution and leave at room temperature for 2 hours. After that, ethyl acetate and other low molecular weight substances were removed under reduced pressure, and washed again with acetone. (e) On the other hand, a Ziegler-type catalyst (A1 (Et) 3 + Co support) and acetaldehyde are dissolved in xylene and reacted at 50 ° C while injecting styrene gas. (f) After the xylene was removed by heating at 150 ° C for 30 minutes, it was washed with citric acid and acetone, and the residue was the product. It was dissolved in n-heptane, and the product obtained from the above (d) was dissolved therein and widely spread on the polyethylene terephthalate film. The temperature was raised from 50 ° C at a rate of 1 ° C / min. At 100 ° C, it is left to stand for 30 minutes, and the polyolefin film can be obtained in a semi-hardened state. The melting point of the obtained polyolefin film was 21 CTC. 112 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) I-! Loading ----) I--Order ·! ---. (Please read the precautions on the back first Fill out this page) Consumption cooperation with employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 4 53141 A7 B7 V. Description of the invention (i 丨 丨) [Example 9] [Block copolymerization Example] In this embodiment, a monomer of the structural formula X-based phenyl of the aforementioned repeating unit and a monomer having a (CH2 — CH = CH — CHOM structure) in the molecular main chain are copolymerized into a polyolefin. The oligomer is crosslinked with each other, and the resin having this structure is used as a polyolefin resin. Specifically, a polyolefin oligomer film synthesized by the following synthesis example is used, and A multilayer printed circuit board was manufactured in the same manner as in Example 1. [Synthesis example] (a) In 500 ml of n-heptane, 104 parts by weight of styrene was dissolved, and butadiene gas was poured into the solution, and then BF was filled; (B) Next, react with 70 ° C for 2 hours with only butadiene gas. c) The solution was spread thinly on polyethylene terephthalate, and n-heptane was removed at 100 ° C for 30 minutes to obtain an unhardened polyolefin film. In addition, the obtained polyolefin film was The melting point is ioo ° C. The hardened film was destroyed by being placed in liquid nitrogen. After observation of the cross section through an electron microscope and ESCA, it was found to be a block copolymer of polystyrene and polybutadiene. Each block Approximately 0.5 to 2em. [Example 10] (Polymer alloy: thermoplastic polyolefin + thermosetting polyolefin) A polyolefin film synthesized in the following synthesis example was used to produce the same method as in Example 1. [Multi-layer printed circuit board.] [Synthesis example] 113 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm). Please read the notes on the back before filling this page) A7 453 1 4 1 _____B7 __ V. Description of the invention ((a) In 500ml n-heptane, dissolve 104 parts by weight of styrene and 10.8 parts by weight of lithium butane. Heat at 70 ° C for 3 hours. (B) In the solution that has been subjected to the preliminary limulus treatment, 'fill the volume ratio of phenylethyl : Butadiene = 3: 1 mixed gas, and left at 70 ° C for 5 hours. (C) Add 12 and leave at 100 ° C for 1 hour to remove n-heptane. (D) Wash the product with acetone (E) On the other hand, SPS (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. of thermoplastic polyolefin is dissolved in xylene. (F) (d) and rhenium are mixed From 50 to 150, the temperature was increased at a rate of 1 minute to remove the solvent, and an unhardened polyolefin film was obtained. [Example 11] (Polymer alloy: thermoplastic polyolefin + thermosetting resin) A multilayer printed wiring board was produced in the same manner as in Example 1 using a polyolefin film synthesized in the following Synthesis Example. [Synthesis example] U) Polymethyl propylene (manufactured by Mitsui Chemicals, trade name: TPX) was dissolved in n-heptane, and bisphenol F-type epoxy resin and imidazole hardener (manufactured by Shikoku Chemical Co., Ltd., 2E4MZ — CN) and TPP (triphenylphosphine) are mixed with the following composition. TPX 80 parts by weight bisphenol F-type epoxy resin 15 parts by weight imidazole hardener 5 parts by weight TPP 0.1 parts by weight 114 This paper size is applicable to China Solid Standard (CNS) A4 specification (21〇X 297g t) --- ----------------- ^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 Μ 1 Α7 Β7 Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives V. Invention Description. Λ) (b) The foregoing solution was coated on a polyethylene terephthalate film by a roll mill, and heated at 70 ° C for 30 minutes to remove the solvent. (c) Completely heat-harden it at 180 ° C for 5 hours to obtain a polyolefin film. [Comparative Example 1] In this Comparative Example, a multilayer printed wiring board was manufactured in the same manner as in Example 1 except that a fluororesin was used as the resin for interlayer insulation. The interlayer resin insulation layer is formed by laminating a Teflon layer (manufactured by DuPont, trade name: Teflon FEP) with a thickness of 25 / zm at a temperature of 200 ° C and a pressure of 20 kg / cm2, and the temperature is 300 ° C. This is done by annealing. [Comparative Example 2] In this Comparative Example, a multilayer printed wiring board was produced in the same manner as in Example 1 except that an epoxy propylene resin was used as the resin for interlayer insulation. The formation of the interlayer resin insulating layer can be performed by coating with formaldehyde novolac resin epoxy acrylic resin (manufactured by Kyoeisha, CNA-25) and heating and curing at 120 ° C for 3 hours. The multilayer printed circuit boards obtained in the examples and comparative examples in this manner were subjected to a thermal cycle test, a dielectric constant, and a peel strength of -55 ° C to 125 ° C (3 minutes each) at 1,000 cycles, and Solder heat resistance test, etc. As a result, in terms of peel strength, the circuit board system of Example 1 was 2.4 Kg / cm, the circuit board system of Example 2 was 2.0 Kg / cm, and the circuit board system of Example 3 was 1. · 5 Kg / cm, the circuit board system in Example 4 is 1 · 7 Kg / cm, 115 paper sizes are applicable to China National Standard (CNS) A4 specification (210 χ 297 public love) .------------ -Order --------- Line (please read the notes on the back before filling in this page) 453141 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (called) In the Examples The circuit board of 5 is 1.5 Kg / cm, the circuit board of Example 6 is 1.8 Kg / cm 'the circuit board of Example 7 is 2.1 Kg / cm, and the circuit board of Example 8 is 1_6 Kg / cm The circuit board in Example 9 is 1.3 Kg / cm ', the circuit board in Example 10 is 1.2 Kg / Cm, and the circuit board in Example 11 is 1.4 Kg / cm. As described above, according to the circuit board of the present invention using a polyolefin-based resin as an interlayer resin insulating layer, even if a roughened surface is not provided on the interlayer resin insulating layer, practical peel strength can be secured. In contrast, the peeling strength of the circuit board of Comparative Example 1 was 0.7 Kg / cm, which was 1/2 of that of the Example under the same conditions. Regarding the thermal cycle test, 'the circuit boards of Examples 1 to 11' did not show any cracks in the interlayer resin insulating layer. The dielectric constants of the circuit substrate of Example 1 using a polyolefin resin as an interlayer resin insulating layer were 2.8, 2.7, 2.6, and 2.5 at 10 MHz, 100 MHz, 500 MHz, and 1 GHz, respectively. The dielectric loss factor is 0.001. In addition, no peeling was observed in the soldering heat resistance test (260 ° C, 30 second immersion). [Example 12] (1) There are 18 # m copper foil 108 on two areas of a substrate 101 made of glass epoxy or BT (polyethylene terephthalate) resin with a thickness of 1mm, and the copper area layer The plate is used as a starting material (see FIG. 4 (a)). First, drill holes in this copper area laminate, and then after forming an anti-plating film, apply electroless plating to this substrate to form through-holes 109. Next, borrow copper foil from 116 paper standards to Chinese national standards (CNS) A4 specification (210 X 297 mm) 11 -------- ------------ I — — (Please read the precautions on the back before filling in this page ) Consumption Cooperation by Employees of Intellectual Property Bureau, Ministry of Economic Affairs, Du Printed 453 14 1 A7 B7 V. Description of the Invention (γ) Pattern-shaped etching by general method to form inner layer copper patterns (lower conductor circuits) on both sides of the substrate 104 ° (2) The substrate forming the lower-layer conductor circuit 104 is washed with water, and after drying, the etchant is sprayed on both sides of the substrate with a sprayer, and the surface of the lower-layer conductor circuit 104 and the pad surface of the through-hole 109 are sprayed on. Its inner wall is etched to form a roughened surface such as 109a on the entire surface of the lower-layer conductor circuit (see FIG. 4 (b)). For the etching solution, 10 parts by weight of copper (II) complex was used. 7 parts by weight of oxalic acid, 5 parts by weight of chlorination and 78 parts by weight of ion-exchanged water were mixed. (3) A resin filler 110 containing a cycloolefin-based resin as a main component is applied to the rain surface of the substrate by using a printer, so that the lower conductor circuit 104 or the through-hole 109 is filled with the substance. , And then heat drying. That is, by this process, the resin filler is filled between the lower-layer conductor circuits 104 or the through-holes 109 (see FIG. 4 (c)). (4) One side of the substrate on which the above (3) processing is to be performed, by using a belt honing machine (manufactured by Sankyo Ricoh Chemical Co., Ltd.) to perform belt honing, so that the surface of the lower conductor circuit 104 or the pad of the through-hole 109 The surface is honed in such a manner that the resin honing filler 110 is not left. Next, polishing honing is performed to remove the wear caused by the belt honing described above. This series of honing is also performed on the other side of the substrate. Then, the resin-filled resin filler 110 is heat-hardened (see FIG. 4 (d)). With this, the surface layer portion of the resin filler 110 filled in the through hole 109 and the roughened layer 104a on the lower conductor circuit HH is removed to smooth both sides of the substrate, and the resin filler 110 and the side of the lower conductor circuit 104 are smoothed. 117 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) — II ---- installation ----- ί — order----- · line &lt; Please read the note on the back first Matters are re-filled on this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs I ^ 453 1 4 1 A7 B7 V. Description of the Invention (Fluff) Strongly adhered through the roughened layer 104a, and the inner wall surface of the through hole 109 The resin substrate 110 is strongly adhered to the roughened surface 109a to obtain the circuit board. (5) Attach the same etching solution as the etching solution used in the above (2) with a sprayer on both sides of the substrate on which the above (4) treatment is finished, and flatten the surface of the lower 104 and the through hole 109 once. The surface of the pad is etched to form roughened surfaces 104a and 109a on the entire surface of the lower-layer conductor circuit 104 (see FIG. 5 (a)). (6) Next, on both sides of the substrate that has undergone the above process, a thermosetting cycloolefin-based resin layer having a thickness of 50 μm is heated from 50 to 150 ° C and vacuum-laminated and laminated at a pressure of 5 kg / cm2 to set a layer. An interlayer resin insulating layer 102 made of a cycloolefin-based resin (see FIG. 5 (b)). The degree of vacuum during vacuum lamination is 10 mmHg 〇 (7) Secondly, using a CCh gas laser with a wavelength of 10_2 / zm, and a beam diameter of 5mm, top hot mode, pulse width 50 // s, first Under the conditions of a cover aperture of 0.5 mm and three irradiations, an opening 10 for a through hole having a diameter of 80 #m is provided in the interlayer resin insulating layer 102 made of a cycloolefin resin (see FIG. 5 (c)). After that, the enzyme plasma is used for decontamination. (8) Its meaning 'uses SV-4540 manufactured by Japan Vacuum Technology Co., Ltd. for plasma treatment to roughen the surface of the interlayer resin insulating layer 1U) 2 (see FIG. 5 (d)). At this time, an inert gas such as argon was used, and plasma treatment was performed for 2 minutes under the conditions of an electric power of 200 W, an air pressure of 0.6 Pa, and a temperature of 70 ° C. (9) Secondly, after using the same device to replace the inside with argon, 118 paper sizes are applicable to China National Standard (CNS) A4 (210 X 297 mm). ---- Line (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 53141 A7 ---------- §Z_ V. Description of the Invention (.οΊ) The Ni-Cu alloy was used as a sputtering target, and the sputtering was performed under the conditions of a pressure of 0.6 Pa, a temperature of 80 ° C, a power of 200 W, and a time of 5 minutes. The Ni-Cu alloy layer 112 facilitated the polyolefin-based interlayer resin insulating layer 102. The surface is formed. At this time, the thickness of the Ni_Cu alloy layer 112 to be formed is 0.2 # m (see FIG. 6 (a)). (10) On both sides of the substrate on which the above-mentioned processing has been completed, a commercially available photosensitive dry film is attached, and a photomask film is installed, and after exposure at 100 m / cm2, development processing is performed with 0.8% sodium carbonate, As a result, a pattern of the plating resist 103 is formed (see FIG. 6 (b)). (11) Next, plating was performed under the following conditions to form a plating film 113 having a thickness of 15 μm (see FIG. 6 (c)). In addition, the plating film I [3] is used to increase the thickness of the portion where the conductor circuit 105 is formed as described later, and the electric charging of the portion where the via hole 107 is formed. In addition, the additives in the electroplating aqueous solution are Kapalashide HL ° manufactured by Attic Japan Co., Ltd. [Electrolytic electroplating aqueous solution] 2.24 mol / 1 sulfuric acid / 1 0.26 mol / 1 copper sulfate 19.5 ml / 1 [electrolytic plating conditions] Current density 1 A / dm2 time 65 minutes

溫度 22±2°C (12) 接著，將防鍍膜103以5%NaOH剝離去除後，對 存在於該防鑛膜103下的Ni—Cu合金層112使用硝酸、硫 119 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — - I I ί I ί 訂 — (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B7 五、發明說明（ίί〇 酸及過氧化氫的混合液以蝕刻方式溶解去除之，而形成由 電鍍銅膜113構成之厚度16//m之導體電路105(包含通孔 107)(參照圖 6(d))。 (13) 接著，藉由重複上述⑸〜(12)的過程，再形成上層 導體電路(參照圖7(a)-圖8(b))。 (14) 其次，藉由將甲酚酚醛型環氧樹脂（日本化藥公司 製造）之環氧基50%丙烯化之感光性賦予的低聚物(分子量 :4000)46.67重量份以成爲濃度60重量％般的方式溶解於 甘醇二甲醚(DMDG)中、溶解於甲基乙基酮之80重量％的 雙酚醛A型環氧樹脂(油化謝魯公司製造，商品名：環氧樹 脂1001)15重量份、咪唑硬化劑（四國化成公司製造，商品 名：2E4MZ-CN)1.6重量份、感光性單體之多官能丙烯單 體（日本化藥公司製造，商品名：R604)3重量份、以及多價 丙烯單體(共榮化學公司製造，商品名：DPE6A)1.5重量份 、分散系消泡劑(三能普克公司製造*商品名：S —65)0.71 重量份裝入容器中，進行攪拌、混合以調製混合組成物， 對此混合組成物加入做爲光聚合起始劑之苯酚(關東化學公 司製造)2,0重量份、做爲光增感劑之米蚩酮(關東化學公司 製造)0.2重量份，而得到於25°C調整爲黏度2.0Pa s之阻焊 劑組成物(有機樹脂絕緣材料）。 又，黏度測定係依據B型黏度計(東京計量儀器公司製 造，DVL-B型)於60rpm時採用迴轉器編號4、而於6rpm 時採用迴轉器編號3。 (15) 其次，於多層電路基板的兩面，將上述阻焊劑組 120 本紙張尺度適用中國國家標準（CNS)A4規格（210 * 297公釐） 11 —!裝 — 1111 訂—-------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 41 at B7 五、發明說明（Μ) 成物塗佈20/zm之厚度，以於70°C下20分鐘、於70°C下 30分鐘的條件進行乾燥處理之後，將描繪有防焊層開口部 圖案的厚度5mm之光罩使其密接於防焊層，而以1〇〇〇 mJ/cm2的紫外線進行曝光，再以DMTG溶液予以顯像處理 ，從而形成直徑200#m的開口。 再者，以80°C1小時、100°C1小時、120°C1小時、150 °C3小時的條件分別進行加熱處理使防焊層硬化，形成焊 墊部分開口之厚度之防焊層(有機樹脂絕緣層)114。 (16) 其次，將形成有防焊層(有機樹脂絕緣層)1M之基 板，於包含氯化鎳(2.3X10·1 mol/1)、次亞磷酸鈉（2.8&gt;&lt;10_1 mol/1)、檸檬酸鈉(1.6X10.1 m〇m )之pH = 4.5的無電解鍍鎳 液中浸漬20分鐘，而於開口部形成厚度5ym之鍍鎳層 115。再者，將該基板於包含氰化金鈣(7.6XUT3 mol/l)、氯 化銨(1.9X10·1 mol/1)、檸檬酸鈉（lJxliT1 mol/1)、次亞磷酸鈉 (1.7X10·1 moi/1)之無電解鍍敷液中以80〇C的條件浸漬7_5分 鐘，而於鍍鎳層115上形成厚度〇.〇3//m之鍍金層116。 (17) 之後，於防焊層114之開口印刷焊接糊劑，於200 °C藉由迴焊(reflow)形成焊接凸塊(焊接體）117，而製造具有 焊接凸塊117之多層印刷電路板(參照圖8(c))。 針對所得之多層印刷電路板，乃測量其介電常數、介 電耗損因數以及剝離強度，並於128°C實施48小時之加熱 處理實驗，以及於-55°C〜125°C實施1〇〇〇次熱循環試驗。再 者，於上述加熱處理實驗之後，以及於上述熱循環試驗之 後，就層間樹脂絕緣層與下層導體電路間的剝離' 通孔部 121 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------訂·！----！線 〈請先閱讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消費合作杜印製 53 141 A7 __B7______ 五、發明說明（〖W) 分之電阻變化率測量之。其結果示於下面的表1中。 [實施例13] 除了不進行過程(5)的導體電路之蝕刻以及過程(8)層間 樹脂絕緣層的粗化處理之外，其餘皆與上述實施例12相同 ，來製造多層印刷電路板。接著，就所得之多層印刷電路 板，進行與實施例12相同之試驗及評價。其結果係示於下 面的表1中》 [比較例3] 就用以形成層間樹脂絕緣層的樹脂而言，除了使用熱 硬化型線狀聚烯烴系樹脂（住友3M公司製造，商品名： 1592)，其餘皆與上述實施例12相同，來製造多層印刷電 路板。接著，就所得之多層印刷電路板，進行與實施例12 相同之試驗及評價。其結果係示於下面的表1中》 表1 介電常數⑷ 介電耗損因 數細δ) 剝離強度 (kg/cm) 加熱試驗 熱循環試驗 實施例12 2.5 0.008 1.0 無剝離，電 阻變化率0% 無剝離，電 阻變化率〇% 實施例13 2.8 0.008 1.0 無剝離，電 阻變化率0% 無剝離，電 阻變化率〇% 比較例3 3.1 0.1 0.3 電阻變化率 30% 電阻變化率 30% 由上述表1之結果可淸楚地看到，實施例之多層印刷 電路板，即使進行加熱試驗或熱循環試驗之後，其體電路 及通孔間的電阻變化率小，而相較於實施例中未見到導體 122 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先閲讀背面之注意事項再填寫本X ) 訂.. --線_ 經濟部智慧財產局員工消費合作社印製 53 1 4 ΐ Α7 ____Β7___ 五、發明說明（丨〉 電路與層間樹脂絕緣層有剝離的發生，則比較例之多層印 刷電路板’其電阻變化率大》又，於試驗後會發生剝離現 象。 [實施例14] A. 無電解鍍敷用黏著劑的調製 (a) 甲酚酚醛型環氧樹脂（日本化藥公司製造，分子量： 2500)之25%丙烯化物35重量份、感光性單體(東亞合成公 司製造’阿羅尼克斯M325)3.15重量份、消泡劑0.5重量份 ，以及N—甲基吡咯烷酮(NMP)3.6重量份裝入容器中，進 行攪拌、混合以調製混合組成物。 (b) 將聚醚磺(PES)12重量份、環氧樹脂粒子(三洋化成 公司製造，聚合物保羅)平均粒徑之物7.2重量份與 平均粒徑O+5/zm之物3.09重量份裝入別的容器中，進行攪 拌、混合之後，再添加NMP30重量份，以硏磨機攪拌混 合，以調製另外之混合組成物。 (c) 將咪唑硬化齊[](四國化成公司製造，2E4MZ — CN)2 重量份、光起始劑之苯酚2重量份、光增感劑之米蚩酮0.2 重量份以及NMP1.5重量份再裝入別的容器中，進行攪拌 、混合，以調製混合組成物。 接著，將於(a)、（b)及(c)所調製之混合組成物藉混合而 得到無電解鍍敷用黏著劑。 B, 多層印刷電路板之製造方法 (1)於厚度1mm之玻璃環氧樹脂或是BT(聚對苯二甲 酸乙酯)樹脂構成之基板101的兩面積層有銅箔108 123 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I i I --------^-----I — — (請先閱讀背面之注f項再填窝本頁) 4531 4 1 A7 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明（ ，而以此銅面積層板做爲起始材料(參照圖9(a))。首先，對 此銅面積層板進行鑽削孔，接著於形成防鍍膜之後，於此 基板施以無電解鍍敷處理以形成通孔109，再者，將銅箔 藉由一般方法進行圖案狀的蝕刻，而於基板兩面形成內層 銅圖案(下層導體電路)1〇4。 將形成下層導體電路104之基板予以水洗、乾燥之後 ，以含有 NaOH(10 g/1)、NaCl〇2(40 g/1)、Na3PCM6 g/Ι)之水 溶液爲氧化浴(黑化浴)進行氧化浴處理，而於包含通孔109 之下層導體電路104的全表面形成粗化面104a、109a(參照 圖 9(b))。 (2) 將以環氧樹脂做爲主成分之樹脂塡充劑11〇，藉由 使用印刷機而塗佈至基板的兩面，使得下層導體電路104 間或是通孔109內塡充該物，再進行加熱乾燥。亦即，藉 由此過程，樹脂塡充劑係塡充於下層導體電路104間或是 通孔109之內(參照圖9(c))。 (3) 將結束上述(2)處理之基板的單面，藉由使用帶式硏 磨機（三共理化學公司製造)進行帶式硏磨，使得下層導體 電路104表面或通孔1〇9之焊墊表面以不留下樹脂塡充劑 110的方式予以硏磨，接著，爲去除因上述帶式硏磨所造 成之磨損乃進行拋光硏磨。此一連串的硏磨亦於基板的另 一面進行。然後，將塡充之樹脂塡充劑110加熱硬化之(參 照圖9(d))。 藉此，將塡充於通孔109等之樹脂塡充劑110之表層 部以及下層導體電路104上面之粗化層104a去除使得基板 124 本紙張尺度適用中國國家榡準（CNS)A4規格（210x297公釐） ^--------β--------- &lt;請先Μ讀背面之注意事項再填寫本頁〕 A7 453141 ___B7___ 五、發明說明（的） 的兩面平滑化，樹脂塡充劑110與下層導體電路104側面 透過粗化層104a而強固的密接著’又通孔109的內壁面與 樹脂塡充劑110則透過粗化面109a強固地密接而得到此電 路基板。 (4) 將經過上述（3)過程之基板，浸漬於包含氯化鎳（30 g/Ι)、次亞磷酸鈉（10 g/Ι)、檸檬酸鈉⑽gA )之水溶液(9〇°C) 的無電解鍍鎳液中，而於而於下層導體電路104的上面及 通孔109的焊墊上面形成厚度1.2^ηι之鎳被覆層111a。 (5) 再者，於外露之導體電路104以及通孔109的焊墊 上面的鎳層上，形成厚度2/zm之由Cu_Ni —P構成的多 孔質合金粗化層111b，再於此粗化層111b的表面設置厚度 0.3//m之Sn層(參照圖10(a))。然而，對於Sn層並未予圖 示0 該粗化層111b的形成方法係如下所述。亦即’對基板 進行鹼性脫脂而行軟蝕刻，其次，以由氯化鈀及有機酸構 成之觸媒溶液進行處理，而賦予鈀觸媒，將此觸媒活性化 之後，於硫酸銅(3.2 X 10_2 m〇l/l)、硫酸鎳(2_4 X ·1/1) 、檸檬酸(5.2 X10_2mol/1)、次亞磷酸鈉(2.7 XlC^mol/l)、 硼酸(5.0 X10·1 mol/1)、界面活性劑（日信化學工業製造之沙 費諾魯465)(1.0 g/Ι)之水溶液構成之pH = 9的無電解鍍敷銅 浴中置入基板，於浸漬2分鐘後開始以1秒1次的速率於 縱方向使其振動，而於銅導體電路104及通孔1〇9的焊墊 表面的鎳層上設置厚度5μιη的由Cu-Ni-P構成之針狀 合金的粗化層111b。再者，於含有氟硼化錫〇·1 m〇l/l、硫 125 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） --裝-----1**訂-----I---線 (請先閲讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消費合作社印製 A7 453 1 4 1 B7 五、發明說明（、&gt;1V) 脲1.0 mol/I，溫度35°c，pH = 1.2的條件下進行Cu—Sn置 換反應，而於粗化層的表面設置厚度〇.3#m的Sn層(未圖 示）。 (6) 於基板的兩面，將上述A記載之組成的無電解鍍敷 用黏著劑使用輥軋機塗佈其上2次，而於水平狀態下放置 20分鐘之後，於60°C乾燥300分鐘(參照圖10(b))。又，於 圖10(b)以後，由於要將鎳被覆層111a及粗化層mb個別 圖示有所困難，乃將其合倂而賦予符號111。 (7) 於上述(6)形成之無電解鍍敷用黏著劑層之基板的兩 面，將印刷有直徑85;zm黑圓的光罩薄膜密接於其上，藉 由超高壓水銀燈產生的500 nJ/cm2強度來進行曝光。將此 藉由甘醇二甲醚(DMDG)溶液進行噴塗顯影，以使該黏著劑 層形成直徑85/zm之通孔所成之開孔。又，將該基板以超 高壓水銀燈產生的3000 mJ/cm2強度來進行曝光（100°C，1 小時），之後藉由於15(TC、5小時的加熱處理，乃形成具 有開孔(通孔形成用開口 106)之厚度18#m的層間樹脂絕緣 層102(102a、102b)(參照圖10(c))。其中，該開孔的尺寸精 度係相當於光罩薄膜般優異。. (8) 將形成有通孔形成用開孔106的基板浸漬於73°C之 鉻酸水溶液中20分鐘，以溶解去除存在於層間樹脂絕緣層 102表面之環氧樹脂粒子，而將其表面粗化’以得到粗化 面。之後，浸漬於中和溶液(西普雷公司製造）中並水洗之( 參照圖10(d))。 再者，於經過粗化面處理之該基板的表面’藉由賦予 126 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） - -----裝--------訂---------線 (請先聞讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 4 53141 A7 B7 五、發明說明（Μ) 鈀觸媒(亞特提克公司製造），而於層間樹脂絕緣層102表 面及通孔用開孔106的內壁面附著觸媒核。 (9) 其次，將基板浸漬予以下組成之無電解鍍銅水溶液 中，而於粗化面全體形成厚度〇.8#rn之無電解鍍銅膜112( 參照圖11(a))。 [無電解鍍敷水溶液] EDTA 50 g/1 硫酸銅 10 g/1 HCHO 10 ml/1Temperature 22 ± 2 ° C (12) Next, after removing the anti-plating film 103 with 5% NaOH, use Nitric Acid and Sulfur 119 for the Ni-Cu alloy layer 112 existing under the anti-mineral film 103. This paper is applicable to Chinese countries Standard (CNS) A4 Specification (210 X 297 mm) — — — —-II ί I ί Order — (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs 453 1 4 1 A7 B7 V. Description of the Invention (The mixed solution of acid and hydrogen peroxide is dissolved and removed by etching to form a conductor circuit 105 (including through hole 107) with a thickness of 16 // m composed of an electroplated copper film 113 ( (Refer to Fig. 6 (d)). (13) Next, the upper-layer conductor circuit is formed by repeating the above-mentioned processes from (12) to (12) (refer to Fig. 7 (a)-Fig. 8 (b)). (14) Next, An oligomer (molecular weight: 4000) that imparts a sensitivity of 60% by weight to an oligomer (molecular weight: 4000) of 50% acryl-based epoxy group of a cresol novolac-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) so that the concentration becomes 60% by weight 80% by weight of bisphenol A epoxy resin (oil) dissolved in glycol dimethyl ether (DMDG) and methyl ethyl ketone Manufactured by Xielu Company, trade name: epoxy resin 1001) 15 parts by weight, imidazole hardener (manufactured by Shikoku Chemical Co., Ltd., trade name: 2E4MZ-CN) 1.6 parts by weight, photosensitive monomer, polyfunctional propylene monomer (Japan 3 parts by weight of chemical company, R604) and 1.5 parts by weight of polyvalent propylene monomer (manufactured by Kyoei Chemical Co., Ltd., product name: DPE6A). Name: S —65) 0.71 parts by weight is put into a container, and the mixture is stirred and mixed to prepare a mixed composition. To the mixed composition, 2,0 parts by weight of phenol (manufactured by Kanto Chemical Co., Ltd.) is added as a photopolymerization initiator. 2. 0.2 parts by weight of mirenone (manufactured by Kanto Chemical Co., Ltd.) as a photosensitizer, and a solder resist composition (organic resin insulation material) adjusted to a viscosity of 2.0 Pa s at 25 ° C. Also, the viscosity measurement system According to a type B viscometer (manufactured by Tokyo Metrology Instruments Co., Ltd., DVL-B), a gyrator number 4 is used at 60 rpm, and a gyrator number 3 is used at 6 rpm. (15) Next, on both sides of the multilayer circuit board, the above 120 solder masks China National Standard (CNS) A4 Specification (210 * 297 mm) 11 —! Pack — 1111 Order —------- Line (Please read the precautions on the back before filling this page) Staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 453 1 41 at B7 V. Description of the invention (M) The finished product is coated to a thickness of 20 / zm, dried at 70 ° C for 20 minutes, and dried at 70 ° C for 30 minutes. A mask with a thickness of 5 mm with a pattern of the opening portion of the solder resist layer is closely adhered to the solder resist layer, and exposed to ultraviolet light at 1000 mJ / cm2, and then developed with a DMTG solution to form a 200 # diameter. m's opening. Furthermore, heat treatment was performed under conditions of 80 ° C for 1 hour, 100 ° C for 1 hour, 120 ° C for 1 hour, and 150 ° C for 3 hours to harden the solder resist layer to form a solder resist layer (organic resin insulation) with a thickness of the opening of the pad portion. Layer) 114. (16) Next, a 1M substrate with a solder resist (organic resin insulating layer) formed on the substrate containing nickel chloride (2.3X10 · 1 mol / 1) and sodium hypophosphite (2.8 &gt; &lt; 10_1 mol / 1) ), Sodium citrate (1.6 × 10.1 m 0 m) in an electroless nickel plating solution having a pH of 4.5 and immersed for 20 minutes to form a nickel plating layer 115 having a thickness of 5 μm at the opening. In addition, the substrate contains gold calcium cyanide (7.6XUT3 mol / l), ammonium chloride (1.9X10 · 1 mol / 1), sodium citrate (1JxliT1 mol / 1), and sodium hypophosphite (1.7X10). · 1 moi / 1) of electroless plating solution was immersed at 80 ° C. for 7-5 minutes to form a gold plating layer 116 having a thickness of 0.03 // m on the nickel plating layer 115. (17) After that, a solder paste is printed on the opening of the solder resist 114, and a solder bump (welded body) 117 is formed by reflow at 200 ° C to manufacture a multilayer printed circuit board having the solder bump 117 (Refer to FIG. 8 (c)). For the obtained multilayer printed circuit board, the dielectric constant, dielectric loss factor and peel strength were measured, and a heat treatment experiment was performed at 128 ° C for 48 hours, and at 100 ° C from -55 ° C to 125 ° C. 〇 Thermal cycle test. In addition, after the above heat treatment experiment and after the above thermal cycle test, the peeling between the interlayer resin insulation layer and the lower conductor circuit was performed. The through-hole portion 121 This paper is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- Order! ----! Line (Please read the precautions on the back before filling in this page) Du Yin printed by the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs 53 141 A7 __B7______ 5. The invention description (〖W) measures the resistance change rate. The results are shown in Table 1 below. [Example 13] Except that the conductor circuit etching in the process (5) and the roughening treatment of the interlayer resin insulating layer in the process (8) were not performed, the rest were the same as those in the above-mentioned Example 12 to manufacture a multilayer printed circuit board. Next, the obtained multilayer printed wiring board was subjected to the same tests and evaluations as in Example 12. The results are shown in Table 1 below. [Comparative Example 3] Except for the resin used to form the interlayer resin insulating layer, a thermosetting linear polyolefin resin (manufactured by Sumitomo 3M, trade name: 1592) was used. ), And the rest are the same as those in the above-mentioned Embodiment 12 to manufacture a multilayer printed circuit board. Next, the obtained multilayer printed wiring board was subjected to the same tests and evaluations as in Example 12. The results are shown in Table 1 below. Table 1 Dielectric constant 细 Dielectric loss factor is fine δ) Peel strength (kg / cm) Heat test Thermal cycle test Example 12 2.5 0.008 1.0 No peel, resistance change rate 0% No peeling, resistance change rate 0% Example 13 2.8 0.008 1.0 No peeling, resistance change rate 0% No peeling, resistance change rate 0% Comparative Example 3 3.1 0.1 0.3 Resistance change rate 30% Resistance change rate 30% From Table 1 above As a result, it can be clearly seen that even after the multilayer printed circuit board of the embodiment is subjected to a heating test or a thermal cycle test, the resistance change rate between the body circuit and the through-hole is small, which is not compared with that in the embodiment. Conductor 122 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) (Please read the notes on the back before filling in this X) Order .. --line _ Printed by the Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative Regulation 53 1 4 ΐ Α7 ____ Β7 ___ 5. Description of the invention (丨> The circuit and the interlayer resin insulation layer are peeled off, then the multilayer printed circuit board of the comparative example has a large rate of change in resistance. Also, peeling will occur after the test. [Example 14] A. Preparation of adhesive for electroless plating (a) 35 parts by weight of 25% acryl compound of cresol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 2500), photosensitivity 3.15 parts by weight of a monomer (Aronix M325, manufactured by Toa Synthesis Co., Ltd.), 0.5 parts by weight of an antifoaming agent, and 3.6 parts by weight of N-methylpyrrolidone (NMP) were placed in a container, and stirred and mixed to prepare a mixed composition (B) 7.2 parts by weight of polyethersulfonate (PES), 7.2 parts by weight of epoxy resin particles (manufactured by Sanyo Chemical Co., Ltd., polymer Paul) and 3.09 of average particle size O + 5 / zm Put weight parts into another container, stir and mix, then add 30 parts by weight of NMP, stir and mix with a honing machine to prepare another mixed composition. (C) Harden imidazole [] (Shikoku Chemical Co., Ltd.) Manufacturing, 2E4MZ — CN) 2 parts by weight, 2 parts by weight of phenol as a photoinitiator, 0.2 parts by weight of stilbone of photosensitizer, and 1.5 parts by weight of NMP, and then put into another container, and stir and mix. To mix the composition. Next, it will be prepared by (a), (b) and (c) The mixed composition is mixed to obtain an adhesive for electroless plating. B. Manufacturing method of a multilayer printed circuit board (1) It is made of glass epoxy resin or BT (polyethylene terephthalate) resin with a thickness of 1 mm. Copper foil 108 123 is applied to the two areas of the substrate 101. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) I i I -------- ^ ----- I — — ( Please read the note f on the back before filling in this page) 4531 4 1 A7 Printed by B7 of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives V. Description of the invention (, and the copper area laminate as the starting material (see figure) 9 (a)). First, drill holes in this copper area laminate, and then, after forming an anti-plating film, apply electroless plating to this substrate to form through-holes 109, and then pattern the copper foil by a general method. By etching, an inner layer copper pattern (lower conductor circuit) 104 is formed on both sides of the substrate. The substrate on which the lower-layer conductor circuit 104 is formed is washed with water and dried, and then an aqueous solution containing NaOH (10 g / 1), NaClO2 (40 g / 1), and Na3PCM6 g / 1 is used as an oxidation bath (blackening bath). The oxidation bath treatment forms roughened surfaces 104a and 109a on the entire surface of the lower-layer conductor circuit 104 including the through hole 109 (see FIG. 9 (b)). (2) A resin filler 11 containing epoxy resin as a main component is applied to both sides of the substrate by using a printing machine, so that the lower conductor circuit 104 or the through hole 109 is filled with the object. It was then heated and dried. That is, by this process, the resin filler is filled between the lower-layer conductor circuits 104 or the through-holes 109 (see Fig. 9 (c)). (3) The single side of the substrate on which the above (2) processing is finished is subjected to a belt honing by using a belt honing machine (manufactured by Sankyo Ricoh Chemical Co., Ltd.), so that the surface of the lower-layer conductor circuit 104 or the through hole 10 The pad surface is honed in such a manner that the resin honing filler 110 is not left. Next, polishing honing is performed to remove abrasion caused by the belt honing described above. This series of honing is also performed on the other side of the substrate. Then, the resin-filled resin filler 110 is heat-hardened (see Fig. 9 (d)). In this way, the surface layer of the resin filler 110 filled in the through hole 109 and the roughened layer 104a on the lower conductor circuit 104 are removed, so that the substrate 124 is in accordance with China National Standard (CNS) A4 (210x297). (Mm) ^ -------- β --------- &lt; Please read the notes on the back before filling in this page] A7 453141 ___B7___ 5. The two sides of the description of the invention are smooth The circuit between the resin filler 110 and the lower conductor circuit 104 is strongly adhered through the roughened layer 104a. The inner wall surface of the through hole 109 and the resin filler 110 are firmly adhered through the roughened surface 109a to obtain this circuit Substrate. (4) The substrate subjected to the above (3) process is immersed in an aqueous solution (90 ° C) containing nickel chloride (30 g / 1), sodium hypophosphite (10 g / 1), and sodium citrate gA). In a non-electrolytic nickel plating solution, a nickel coating layer 111a having a thickness of 1.2 μm is formed on the upper surface of the lower conductor circuit 104 and the pads of the through holes 109. (5) Furthermore, a porous alloy roughened layer 111b made of Cu_Ni-P with a thickness of 2 / zm is formed on the nickel layer on the exposed conductive circuit 104 and the pad of the through-hole 109, and then roughened there. An Sn layer having a thickness of 0.3 // m is provided on the surface of the layer 111b (see FIG. 10 (a)). However, the Sn layer is not illustrated. The method for forming the roughened layer 111b is as follows. That is, the substrate is subjected to alkaline degreasing for soft etching, and then treated with a catalyst solution composed of palladium chloride and an organic acid to give a palladium catalyst. 3.2 X 10_2 mol / l), nickel sulfate (2_4 X · 1/1), citric acid (5.2 X10_2mol / 1), sodium hypophosphite (2.7 XlC ^ mol / l), boric acid (5.0 X10 · 1 mol / 1). Surfactant (Shafenuru 465 manufactured by Nissin Chemical Industry Co., Ltd.) (1.0 g / 1) in an electroless copper plating bath with a pH of 9 composed of an aqueous solution, and the substrate was placed there. After immersion for 2 minutes Started to vibrate in the longitudinal direction at a rate of 1 second, and a 5 μm thick needle-like alloy made of Cu-Ni-P was placed on the nickel layer on the surface of the copper conductor circuit 104 and the pad of the through hole 109. Roughened layer 111b. In addition, the paper standards containing tin fluoboride 0.1 mmol / l and sulfur 125 are applicable to China National Standard (CNS) A4 specifications (210 X 297 public love)-installed ----- 1 ** Order ----- I --- line (please read the notes on the back before filling in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 453 1 4 1 B7 V. Description of the invention (&gt; 1V ) Urea 1.0 mol / I, temperature 35 ° c, pH = 1.2, Cu-Sn substitution reaction is performed, and a Sn layer (not shown) with a thickness of 0.3 # m is provided on the surface of the roughened layer. (6) On both sides of the substrate, apply the adhesive for electroless plating of the composition described in A above twice using a roll mill, leave it in a horizontal state for 20 minutes, and dry it at 60 ° C for 300 minutes ( (See Fig. 10 (b)). In addition, after FIG. 10 (b), since it is difficult to separately illustrate the nickel coating layer 111a and the roughened layer mb, the symbols 111 are given by combining them. (7) On both sides of the substrate of the adhesive layer for electroless plating formed in the above (6), a mask film with a black circle diameter 85; zm printed thereon was adhered thereto, and 500 nJ generated by an ultra-high pressure mercury lamp. / cm2 intensity for exposure. This was spray-developed with a diglyme (DMDG) solution to make the adhesive layer an opening formed by a through hole having a diameter of 85 / zm. In addition, the substrate was exposed at an intensity of 3000 mJ / cm2 generated by an ultra-high pressure mercury lamp (100 ° C, 1 hour), and then formed with an opening (through-hole formation) by a heat treatment of 15 (TC, 5 hours). An interlayer resin insulating layer 102 (102a, 102b) with a thickness of 18 # m using an opening 106) (see FIG. 10 (c)). The dimensional accuracy of the opening is excellent as a mask film. (8) The substrate on which the through-hole openings 106 were formed was immersed in a chromic acid aqueous solution at 73 ° C for 20 minutes to dissolve and remove the epoxy resin particles existing on the surface of the interlayer resin insulating layer 102, and roughen the surface. A roughened surface is obtained. Then, it is immersed in a neutralization solution (manufactured by Shipley Corporation) and washed with water (see FIG. 10 (d)). Furthermore, the surface of the substrate subjected to the roughened surface treatment is given by 126 The size of this paper applies to China National Standard (CNS) A4 (210 X 297 mm)-------------------------- (Read the notes on the back and fill in this page again.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 4 53141 A7 B7 5. Description of the invention (M) Palladium catalyst (manufactured by Attic), and a catalyst core is attached to the surface of the interlayer resin insulation layer 102 and the inner wall surface of the through-hole opening 106. (9) Second The substrate was immersed in an electroless copper plating aqueous solution having the following composition, and an electroless copper plating film 112 having a thickness of 0.8 # rn was formed on the entire roughened surface (see FIG. 11 (a)). [Electroless plating aqueous solution ] EDTA 50 g / 1 copper sulfate 10 g / 1 HCHO 10 ml / 1

NaOH 6 g/1 α , α ’ —聯二卩比卩定 80 mg/1 聚乙二醇(PEG) 0.1 g/1 [無電解鍍敷條件] 70°C之液體溫度，15分鐘。 (10) 將市售之感光性乾式膜112張貼上去，進而裝設 光罩，再以100 m〗/cm2進行曝光、0.8%碳酸氫鈉進行顯像 處理，從而設置防鍍膜103 (參照圖11(b))。 (11) 再者，以下述條件實施電解鍍銅，形成厚度13&quot; m之電解鍍銅膜113(參照圖11(c))。 [電解電鍍水溶液] 硫酸 180 g/1 硫酸銅 80 g/1 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 1 ml/1 127 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I 1 I I I I --------訂· ----線 (請先閱讀背面之注意事項再填寫本頁) 453 1 4 1 A7 B7 經濟部智慧財產局員工消費合作杜印製 五、發明說明（) [電解電鍍條件] 電流密度 1 A/dm2 時間 30分鐘 溫度 室溫 (12) 將防鍍膜103以5%之KOH水溶液剝離去除之後， 再將位於該防鍍膜103下方之無電解鍍敷膜112以硫酸與 過氧化氫之混合液藉由蝕刻處理溶解去除之，而形成由無 電解鍍銅膜112及電解鍍銅膜113所構成之L/S = 28/28之 厚度ll#m之上層導體電路1〇5(包含通孔107)。 再者，於氯化鎳(30 g/Ι)、次亞磷酸鈉（10 g/Ι)、檸檬酸 鈉（10 g/Ι )之水溶液(90°C)的無電解鍍鎳液中浸漬，而於導 體電路全面以及通孔焊墊全面形成厚度1.2ym的鎳被覆層 llla(參照圖 11(d))。 (13) 對形成有上層導體電路105及鎳被覆層111a的基 板進行相同於上述(5)的處理，而於上層導體電路105的表 面形成厚度2#m之由Cu-Ni-P構成之合金粗化層lllb( 參照圖12(a))。又，於含有氟硼化錫0.1 mol/1、硫脲1.0 mol/1，溫度35°C，pH = 1.2的條件下進行Cu—Sn置換反應 ，而於粗化層的表面設置厚度0.3 #ιη的Sn層(未圖示）。 (14) 藉由重複上述(6H13)的過程，再形成上層導體電 路(參照圖12〇?)~圖13(d))，此處雖未予圖示，最後係形成 具有開孔之防焊層，而在進行鍍金處理之後，形成焊接凸 塊，而得到具有焊接凸塊之多層印刷電路板。又，於圖 12(1&gt;)~圖13(d)中，亦將鎳被覆層111a與粗化層111b兩層 128 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公藿） !1裝------1·訂---------線 (請先閲續背面之注意事項再填寬本頁) A7 B7 53 1 4 五、發明說明（y ) 合在一起而賦予符號111。 [實施例15] 雖與實施例Η大致相同’但於過程（12)以下則有所變 更。 (12)在實施電解鍍銅之後’再進一步’將基板浸漬於 硫酸鎳(240 g/Ι)、氯化鎳(45 g/Ι)、硼酸(30 g/Ι)之水溶液所構 成之pH = 4.5的鑛浴’而於溫度55 ±5°C、電流密度 4A/dm2的條件下，對做爲陽極的Νι板施以電鍍鎳，而形成 厚度0.8/im的鎳被覆層。 再者，將防鍍膜103以5%之KOH水溶液剝離去除之 後，再將位於該防鍍膜103下方之無電解鍍敷膜112以硫 酸與過氧化氫之混合液藉由蝕刻處理溶解去除之’而形成 由無電解鍍銅膜112及電解鍍銅膜113所構成之L/S = 28/28之厚度Π/zm之上層導體電路1〇5(包含通孔107)(參 照圖14)。 [比較例4] 除了未予形成鎳被覆層，其餘皆與實施例14的力'法丰目 同來製造多層印刷電路板。 [實施例16] 除了不形成鎳層而改以無電解鍍敷形成厚度之 錫層外，其餘皆與實施例14的方法相同來製造多層印刷電1 路板。電鍍液之組成如下：NaOH 6 g / 1 α, α ′ -bipyridine ratio 80 mg / 1 polyethylene glycol (PEG) 0.1 g / 1 [electroless plating conditions] liquid temperature at 70 ° C for 15 minutes. (10) Put a commercially available photosensitive dry film 112 on it, and then install a photomask, and then expose it at 100 m / cm2 and develop processing with 0.8% sodium bicarbonate. (b)). (11) Furthermore, electrolytic copper plating was performed under the following conditions to form an electrolytic copper plating film 113 having a thickness of 13 m (see FIG. 11 (c)). [Aqueous solution for electroplating] Sulfuric acid 180 g / 1 Copper sulfate 80 g / 1 Additive (manufactured by Attic Japan, trade name: Capalaseide GL) 1 ml / 1 127 This paper size applies to Chinese national standards (CNS ) A4 specification (210 X 297 mm) I 1 IIII -------- Order · ---- Line (Please read the precautions on the back before filling this page) 453 1 4 1 A7 B7 Ministry of Economy Wisdom Printed by Du Bureau of Consumer Property Co., Ltd. 5. Description of the invention () [Electrolytic plating conditions] Current density 1 A / dm2 Time 30 minutes Temperature Room temperature (12) After removing the anti-plating film 103 with 5% KOH aqueous solution, remove The electroless plated film 112 located under the anti-plating film 103 is dissolved and removed by etching with a mixed solution of sulfuric acid and hydrogen peroxide to form an L / composed of an electroless copper plated film 112 and an electrolytic copper plated film 113. S = 28/28 thickness ll # m of the upper layer conductor circuit 105 (including the through hole 107). Furthermore, immersion in an electroless nickel plating solution of an aqueous solution (90 ° C) of nickel chloride (30 g / 1), sodium hypophosphite (10 g / 1), and sodium citrate (10 g / 1), On the entire conductor circuit and through-hole pads, a nickel coating layer 11a with a thickness of 1.2 μm is formed (see FIG. 11 (d)). (13) The substrate on which the upper-layer conductor circuit 105 and the nickel coating layer 111a are formed is subjected to the same treatment as in the above (5), and an alloy made of Cu-Ni-P with a thickness of 2 # m is formed on the surface of the upper-layer conductor circuit 105. The roughened layer 111b (see FIG. 12 (a)). In addition, Cu—Sn substitution reaction was performed under the conditions of 0.1 mol / 1 tin borohydride, 1.0 mol / 1 thiourea, temperature 35 ° C, and pH = 1.2, and a thickness of 0.3 # ιη was set on the surface of the roughened layer. Sn layer (not shown). (14) By repeating the above (6H13) process, the upper-layer conductor circuit is formed (refer to Figure 12?) To Figure 13 (d)). Although not shown here, a solder mask with an opening is formed at the end. After the gold plating process is performed, solder bumps are formed to obtain a multilayer printed circuit board having solder bumps. In addition, in Fig. 12 (1 &gt;) to Fig. 13 (d), the nickel coating layer 111a and the roughened layer 111b are also two layers of 128. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 cm). ! 1 pack ----- 1 · order --------- line (please read the precautions on the back of the page before filling this page) A7 B7 53 1 4 V. Description of the invention (y) Together to give the symbol 111. [Embodiment 15] Although it is almost the same as the embodiment Η, it is changed after the procedure (12). (12) After electrolytic copper plating is performed, the substrate is immersed in an aqueous solution of nickel sulfate (240 g / 1), nickel chloride (45 g / 1), and boric acid (30 g / 1). 4.5 ore bath ', and under the conditions of temperature 55 ± 5 ° C and current density 4A / dm2, the Ni plate as the anode was electroplated with nickel to form a nickel coating layer with a thickness of 0.8 / im. Furthermore, after the anti-plating film 103 is stripped and removed with a 5% KOH aqueous solution, the electroless plating film 112 located below the anti-plating film 103 is dissolved and removed by etching in a mixed solution of sulfuric acid and hydrogen peroxide. An upper-layer conductor circuit 105 (including a through hole 107) having a thickness L / S = 28/28 composed of the electroless copper-plated film 112 and the electrolytic copper-plated film 113 is formed (see FIG. 14). [Comparative Example 4] A multilayer printed wiring board was manufactured in the same manner as in Example 14 except that the nickel coating layer was not formed. [Example 16] A multilayer printed circuit board was produced in the same manner as in Example 14 except that the nickel layer was not formed and the tin layer was formed by electroless plating. The composition of the plating solution is as follows:

檸檬酸鈉 0.34mol/I EDTA 0.04 mol/1 129 _____ ^纸張尺度過用中國國家標準（CNS)A4規格（210 X 297公釐） 1 I I I------- - - -----!| 訂·！一 —--— &lt;請先Μ讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消費合作社印製 453141 A7 B7 、發明說明（ μη 氯化錫 0.04 mol/1 醋酸鈉 0.12 mol/1 氯化欽 0.029 mol/1 液溫 70~90〇C [實施例17] 除了不形成鎳層而改以無電解鍍敷形成鈷層外，其餘 皆與實施例14的方法相同來製造多層印刷電路板。無電解 鍍敷之條件如下= 氯化鈷 次亞磷酸鈉 酒石酸鈉 氯化銨 pH 液溫 [實施例18] 除了不形成鎳層而改以無電解鍍敷形成鈀層外，其餘 皆與實施例14的方法相同來製造多層印刷電路板。無電解 鍍敷之條件如下=Sodium citrate 0.34mol / I EDTA 0.04 mol / 1 129 _____ ^ Paper size used Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1 II I ------------ -! | Order ·! I ----- &lt; Please read the notes on the back before filling in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453141 A7 B7, Description of the invention (μηtin chloride 0.04 mol / 1 sodium acetate 0.12 mol / 1 Chlorin chloride 0.029 mol / 1 Liquid temperature 70 ~ 90 ° C [Example 17] Except that instead of forming a nickel layer, a non-electrolytic plating is used to form a cobalt layer, the rest are the same as the method of Example 14 to produce a multilayer Printed circuit board. The conditions for electroless plating are as follows = cobalt chloride sodium hypophosphite sodium tartrate ammonium chloride pH liquid temperature [Example 18] Except that instead of forming a nickel layer, electroless plating is used to form a palladium layer. The multilayer printed circuit board was manufactured in the same manner as in Example 14. The conditions for electroless plating were as follows =

0.60 mol/1 0.26 mol/1 0.90 mol/1 1.30 mol/1 8-10 90-100°C 敦--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製0.60 mol / 1 0.26 mol / 1 0.90 mol / 1 1.30 mol / 1 8-10 90-100 ° C Tun -------- Order --------- line (Please read the Please fill in this page for attention) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

四鈀膠體 5.4 g/1 EDTA鈉鹽 33.6 g/1 氨 350 g/1 聯氨 0.3 g/1 液溫 90°C 關於上述實施例與比較例所得之電路板，其截面係藉 130 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作杜印製 53 1 4 1 A7 _B7_ 五、發明說明（4 ) 由光學顯微鏡觀察，以觀察導體電路的溶解以及Cu-Ni-P粗化層的未析出。 在實施例14 ~18，未見到導體電路的溶解，但於比較 例4，則在電源層(平面層)的一部份見到溶解的現象。 又，在實施例Η〜18，於進行Cu—Ni—P構成之針狀 合金的電鍍處理時，即使經過10次轉動亦未有電鍍未析出 的發生，但在比較例4，則於3次轉動時便發生電鍍未析 出的現象。 再者，關於可形成之圖案寬度(L/S)，在實施例14〜18 ，可形成5/15//m之窄的圖案寬度，但在比較例，只能形 成30/30之寬的圖案寬度。 [實施例19] (1)在由厚度〇.8mm的BT(雙順丁烯二胺三氮雜苯)樹脂 構成之厚度1.0mm之基板1的兩面，積層有厚度18#m的 銅箔2，而將以此形成之BT樹脂銅面積層板(三菱氣體化 學製造，商品名：HLS30—1.0T12D)做爲起始材料（參照圖 15(a))。首先，將此銅面積層板鑽孔形成貫通孔（參照圖 15(b))，其次，於表面附著上Pd—Sii膠體，以下述組成之 無電解鍍敷水溶液、下述條件實施無電解鍍敷，於基板全 面形成0.7 μ m之無電解鍍敷膜。 [無電解鍍敷水溶液] EDTA 60 g/1 硫酸銅 10 g/1 HCHO 8 ml/1 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 131 裝--------訂---------線 (請先閱讀背面之注意事項再填窝本頁) 4 經濟部智慧財產局員工消費合作社印製 53 1 4 1 A7 __B7____ 五、發明說明（…）Tetrapalladium colloid 5.4 g / 1 EDTA sodium salt 33.6 g / 1 Ammonia 350 g / 1 Hydrazine 0.3 g / 1 Liquid temperature 90 ° C About the circuit boards obtained in the above examples and comparative examples, the cross-sections are based on 130 paper sizes Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, employee printing Du 1 53 1 4 1 A7 _B7_ V. Description of the invention (4) Observation by optical microscope Dissolution and no precipitation of the Cu-Ni-P roughened layer. In Examples 14 to 18, no dissolution of the conductor circuit was observed, but in Comparative Example 4, dissolution was seen in a part of the power supply layer (planar layer). In Examples Η to 18, when electroplating of a needle-shaped alloy made of Cu—Ni—P was performed, no plating and precipitation did not occur even after 10 rotations. However, in Comparative Example 4, it was performed 3 times. When rotating, plating does not precipitate. Furthermore, regarding the pattern width (L / S) that can be formed, in Examples 14 to 18, a narrow pattern width of 5/15 // m can be formed, but in the comparative example, only a 30/30 width can be formed. Pattern width. [Example 19] (1) On both sides of a substrate 1 having a thickness of 1.0 mm and consisting of a BT (biscis- butadiene diamine triazabenzene) resin having a thickness of 0.8 mm, a copper foil 2 having a thickness of 18 #m was laminated. The BT resin copper area laminate (Mitsubishi Gas Chemical Co., Ltd., trade name: HLS30—1.0T12D) thus formed was used as a starting material (see FIG. 15 (a)). First, this copper area laminate was drilled to form a through hole (see FIG. 15 (b)). Second, a Pd-Sii colloid was adhered to the surface, and electroless plating was performed using an electroless plating aqueous solution of the following composition and the following conditions. Electroless plating film was formed on the entire surface of the substrate with a thickness of 0.7 μm. [Aqueous solution without electroplating] EDTA 60 g / 1 copper sulfate 10 g / 1 HCHO 8 ml / 1 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 131 Packing --- --Order --------- line (please read the notes on the back before filling in this page) 4 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 53 1 4 1 A7 __B7____ V. Description of the invention (… )

NaOH 10 g/1 α，α ’ —聯—卩定 80 mg/1 聚乙二醇(PEG) 0.1 g/1 [無電解鍍敷條件] 70°C之液溫，10分鐘。 再者，以下述組成之電解電鍍水溶液、下述條件實施 電解鍍銅，形成厚度15/zm之電解鍍銅膜。 [電解電鍍水溶液] 硫酸 170~200 g/1 硫酸銅 50~70 g/1 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 20-40 ml/l [電解電鍍條件]NaOH 10 g / 1 α, α ′ -co-dioxine 80 mg / 1 polyethylene glycol (PEG) 0.1 g / 1 [electroless plating conditions] at a liquid temperature of 70 ° C for 10 minutes. Furthermore, electrolytic copper plating was performed under an electrolytic plating aqueous solution having the following composition and under the following conditions to form an electrolytic copper plating film having a thickness of 15 / zm. [Aqueous solution for electrolytic plating] Sulfuric acid 170 ~ 200 g / 1 Copper sulfate 50 ~ 70 g / 1 Additive (made by Attic Japan Co., Ltd., trade name: Capalaseide GL) 20-40 ml / l [Electrolytic plating conditions ]

電流密度 1.5〜2.3 A/dVCurrent density 1.5 ~ 2.3 A / dV

溫度 23〜26°C (2) 對以上述過程於基板全面形成導體層3(包含通孔 3a)之基板進行水洗，而乾燥之後，使用含有NaOH(20 g/1) 、NaClCh(50 g/1)、Na3PCM15.0 g/1)之水溶液而成之氧化浴( 黑化浴），以及，使用含有NaOH(2_7 g/1)、NaBIMl.O g/1)的 水溶液而成之還原浴，以供給做爲氧化還原處理’而於包 括有通孔3a之導體層3的全表面設置粗化層4(參照圖 15(d))。 (3) 其次，將含有平均粒徑I5#m之銅粒子的金屬粒子 糊劑(達自達電線公司製造’ DD糊劑：非導電性塡孔銅糊 132 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝--------訂iii!線 (請先閱讀背面之注意事項再填窝本頁) 經濟部智慧財產局員工消費合作社印製 4 53 1 4 1 A7 B7 五、發明說明（Θ丨） 劑)藉由網板印刷塡充至通孔3a內，於100°C30分鐘、180 °C2小時的條件下使之乾燥、硬化。接著，將導體層3表 面形成之粗化層4及自通孔3a溢出之金屬粒子糊劑5，利 用#400的帶式硏磨紙(三共理化學製造)而藉由帶式硏磨機 將該等之物硏磨去除之，又爲了將由於此帶式硏磨機造成 的磨損去除，乃藉由AhCb硏磨或SiC硏磨顆粒進行拋光硏 磨，將基板表面平坦化(參照圖15(e))。 (4) 在上述(3)平坦化之基板表面，依一般方法賦予鈀膠 體觸媒，而藉由實施無電解鍍敷以形成厚度〇.6mm之無電 解鍍銅膜6(參照圖15(f))。 (5) 接下來，以下面之條件施以電鍍銅，形成厚度 m的電鍍銅膜7，於後述圖（16)之過程中’乃進行成爲下層 導體電路9部分的增厚，以及進行將塡充於通孔3a之金屬 粒子糊劑5覆蓋的成爲導體層10之部分的形成。 [電解電鍍水溶液] 硫酸 170〜200 g/l 硫酸銅 50〜70 g/1 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 20-40 ml/1 [電解電鍍條件] 電流密度 1.5〜2.3 A/dm2Temperature 23 ~ 26 ° C (2) Wash the substrate on which the conductor layer 3 (including the through hole 3a) is completely formed on the substrate by the above process, and then dry it using NaOH (20 g / 1), NaClCh (50 g / 1), an oxidation bath (blackening bath) made of an aqueous solution of Na3PCM 15.0 g / 1), and a reduction bath made using an aqueous solution containing NaOH (2_7 g / 1), NaBIM 1.0 g / 1), The roughening layer 4 is provided on the entire surface of the conductor layer 3 including the through hole 3a with the supply as a redox process (see FIG. 15 (d)). (3) Secondly, a metal particle paste containing copper particles with an average particle diameter of I5 # m (made by Dazda Electric Wire Co., Ltd. DD paste: non-conductive countersunk copper paste 132) This paper applies Chinese national standards ( CNS) A4 size (210 X 297 mm) Packing -------- Order iii! Line (Please read the precautions on the back before filling in this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives 4 53 1 4 1 A7 B7 V. Description of the invention (Θ 丨) The agent is filled into the through hole 3a by screen printing and dried and hardened at 100 ° C for 30 minutes and 180 ° C for 2 hours. Next, the roughened layer 4 formed on the surface of the conductor layer 3 and the metal particle paste 5 overflowing from the through-hole 3a were passed through a belt honing paper (manufactured by Sankyo Ricoh Chemical Co., Ltd.) using a # 400 belt honing machine. These objects are removed by honing, and in order to remove the wear caused by the belt honing machine, the substrate surface is flattened by AhCb honing or SiC honing particles to planarize the substrate surface (see FIG. 15 ( e)). (4) A palladium colloid catalyst is provided on the substrate surface flattened by the above (3) according to a general method, and electroless plating is performed to form an electroless copper plating film 6 having a thickness of 0.6 mm (see FIG. 15 (f )). (5) Next, electroplated copper is applied under the following conditions to form an electroplated copper film 7 with a thickness of m. In the process of FIG. 16 (described later), the thickness of the portion that becomes the lower-layer conductor circuit 9 is increased, and Formation of the portion to be the conductor layer 10 covered by the metal particle paste 5 filled in the through hole 3a. [Aqueous solution for electrolytic plating] Sulfuric acid 170 ~ 200 g / l Copper sulfate 50 ~ 70 g / 1 Additive (manufactured by Attic Japan Co., Ltd., trade name: Capalaseide GL) 20-40 ml / 1 [Electrolytic plating conditions ] Current density 1.5 ~ 2.3 A / dm2

溫度 23~26°C (6) 於形成導體電路9及導體層10之部分的基板兩面 處，將市售之感光性乾式薄膜張貼上去’進而裝設光罩’ 133 本紙張尺度適用中國國家標準（CNS&gt;A4規格（2]0 X 297公釐） — — — — — — — — — — —I· · I I I I I —1111 — 11- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 a? B7 五、發明說明（π) 再以100 m〗/cm2進行曝光、0.8%碳酸氫鈉進行顯像處理’ 從而形成厚度15/zm之抗蝕層8 (參照圖16(a))。 (7) 接著，將未形成抗蝕層8之部分的鍍膜’使用硫酸 及過氧化氫的水溶液採蝕刻方式溶解去除之’又’將抗蝕 層8以5%KOH剝離去除’乃形成獨立之導體電路9以及 覆有金屬粒子糊劑5之導體層10 (參照圖16(b))。 (8) 其次，於下層導體電路9及覆有金屬粒子糊劑5之 導體層10的表面形成由Cu-Ni-P合金構成之厚度爲2_5 Mm的粗化層(凹凸層)11 ’再於此粗化層11的表面設置厚 度0.3/zm的Sn層(參照圖16(c))，該等層之形成方法係如 下所述。又，於圖16(c)中Sn層未予圖示。 亦即，對基板予以酸性脫脂而進行軟蝕刻’其次’以 由氯化鈀及有機酸構成之觸媒溶液進行處理使鈀觸媒附著 其上，將此觸媒活性化之後’藉由包含硫酸銅(8 W1)、硫酸 鎳(0.6 g/Ι)、檸檬酸（15 g/Ι)、次亞磷酸鈉(29 g/D、硼酸(31 g/Ι)、界面活性劑（日信化學工業製造之沙費諾魯扣讯0·1 g/Ι)之水溶液構成的pH = 9的無電解鍍敷浴來實施無電解 鍍敷，而於導體電路的全表面形成由Cu-Ni-P合金所構 成之粗化層11(凹凸層）。接著’將其浸漬於包含氟硼化錫 (0.1 mol/丨)以及硫脲(l.Omol/1)之水溶液(pH = U、溫度5〇°C) 的無電解錫置換鍍浴中，而於上述粗化層的表面設置厚度 0.3 /nn 的 Sn 層 ° (9) 將甲酚酚醛型環氧樹脂（日本化藥公司製造’分子量 :2500)之25%丙烯化物35重量份、感光性單體(東亞合成 134 本纸張尺度適用中國國家標準（CNS)A4規格（210〆297公釐) *Λ--------訂---------線 &lt;請先閱讀背面之注意事項再填寫本頁) A7 4531 4 1 ___B7___ _ 五、發明說明（\Vj) 公司製造，商品名：阿羅尼克斯M325)3.15重量份、消泡 劑（三能普克公司製造，商品名：S-65)0.5重量份、咪哩 硬化劑（四國化成公司製造，商品名：2E4MZ-CN)2重量份 、光起始劑之苯酚2重量份、光增感劑之米蚩酮0.2重量 份，以及N—甲基毗咯烷酮(NMP)1.5重量份裝入容器中’ 藉由進行攪拌、混合以調製環氧樹脂之丙烯腈酯組成物。 其次，將此環氧樹脂之丙烯腈酯組成物以輥軋機塗佈 至基板的兩面，而形成由層間樹脂絕緣層12而成之樹脂層 120 (參照圖 16(d))。 ' (10) 形成樹脂層120之後，於80eC進行10分鐘之預先 烘烤處理，接著，以紫外線曝光、進行顯像處理，從而設 置通孔形成用開孔13。再者，以150°C、小時的條件進行 熱硬化以做爲層間樹脂絕緣層12 (參照圖16(e)) »層間樹脂 絕緣層12在熱硬化後之厚度爲18/zm。 (11) 採用Ni濺鍍靶，在氣壓〇.8Pa、溫度80°C、電力 200W，以及時間20分鐘的條件下進行濺鍍，則厚度〇,以 m之Ni金屬層14將於層間樹脂絕緣層π的表面形成(參 照圖17(a))。又，用以濺鍍之裝置，係使用日本真空技術 股份有限公司製造之SV- 4540。 (12) 於前述（11)形成金屬層14之基板兩面，貼上市售 之感光性乾式薄膜，進而裝設光罩，再以1〇〇 m〗/cm2進行 曝光、0.8%碳酸鈉進行顯像處理，從而形成厚度30ym之 防鍍膜16 (參照圖17(b))。 (13) 再者，使用含有硫酸（150 g/Ι)之酸，以溫度40°C、 135 本紙張尺度適用中國國家標準（CNS)A4規格（2〗〇 X 297公爱） X---1 I---訂---------線！ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 ^53 I 4 1 A7 B?Temperature 23 ~ 26 ° C (6) On both sides of the substrate where the conductor circuit 9 and the conductor layer 10 are formed, a commercially-available photosensitive dry film is posted 'and then a photomask' is installed. 133 This paper is in accordance with Chinese national standards (CNS &gt; A4 specification (2) 0 X 297 mm) — — — — — — — — — — — —I · IIIII —1111 — 11- (Please read the precautions on the back before filling this page) Wisdom of the Ministry of Economy Printed by the Consumer Cooperative of the Property Bureau 453 1 4 1 a? B7 V. Description of the invention (π) Exposure at 100 m / cm2 and development treatment with 0.8% sodium bicarbonate to form a 15 / zm thickness resist Layer 8 (see Fig. 16 (a)). (7) Next, the plating film of the portion where the resist layer 8 is not formed is dissolved and removed using an aqueous solution of sulfuric acid and hydrogen peroxide by etching, and the resist layer 8 is removed. Stripping and removing with 5% KOH is to form a separate conductive circuit 9 and a conductive layer 10 coated with a metal particle paste 5 (see FIG. 16 (b)). (8) Next, the lower conductive circuit 9 and the metal particles are coated. The surface of the conductor layer 10 of the paste 5 is formed of a Cu-Ni-P alloy with a thickness of 2-5 Mm. Layer (concave-convex layer) 11 'An Sn layer having a thickness of 0.3 / zm is provided on the surface of the roughened layer 11 (see FIG. 16 (c)), and the formation method of these layers is as follows. In addition, FIG. 16 ( The Sn layer in c) is not shown. That is, the substrate is subjected to an acid degreasing and soft etching is performed 'second', and a catalyst solution composed of palladium chloride and an organic acid is processed to attach a palladium catalyst thereon. After the catalyst is activated, the catalyst contains copper sulfate (8 W1), nickel sulfate (0.6 g / 1), citric acid (15 g / 1), sodium hypophosphite (29 g / D, boric acid (31 g / 1) ), Surface active agent (Safenoru Kouxun 0.1 · 1 g / l manufactured by Nissin Chemical Industry) with an electroless plating bath at pH = 9 to perform electroless plating, and A roughened layer 11 (concavo-convex layer) composed of a Cu-Ni-P alloy is formed on the entire surface. Then, it is dipped in a layer containing tin fluoroboride (0.1 mol / 丨) and thiourea (1.0 mol / 1). In an electroless tin replacement plating bath with an aqueous solution (pH = U, temperature 50 ° C), a Sn layer having a thickness of 0.3 / nn is provided on the surface of the roughened layer. (9) A cresol novolac epoxy resin ( Made by Nippon Kayaku Co., Ltd. Molecular weight: 2500) 35% by weight of acryl compound, 35 parts by weight of photosensitive monomers (East Asia Synthetic 134) The paper size applies to China National Standard (CNS) A4 specifications (210〆297 mm) * Λ ------- -Order --------- Threads &lt; Please read the notes on the back before filling in this page) A7 4531 4 1 ___B7___ _ V. Description of the invention (\ Vj) Made by the company, trade name: Aronix M325) 3.15 parts by weight, defoaming agent (manufactured by Sanneng Puke Co., Ltd., trade name: S-65), 0.5 parts by weight, miric hardener (manufactured by Shikoku Chemical Co., Ltd., trade name: 2E4MZ-CN), 2 parts by weight, 2 parts by weight of phenol as a photoinitiator, 0.2 parts by weight of stilbone as a photosensitizer, and 1.5 parts by weight of N-methylpyrrolidone (NMP) were placed in a container. 'By stirring, mixing to prepare Acrylonitrile ester composition of epoxy resin. Next, the acrylonitrile composition of this epoxy resin is applied to both sides of the substrate by a roll mill to form a resin layer 120 composed of an interlayer resin insulating layer 12 (see FIG. 16 (d)). '(10) After the resin layer 120 is formed, a pre-baking treatment is performed at 80 eC for 10 minutes, followed by exposure to ultraviolet light and development processing, so that the through-hole forming openings 13 are provided. Furthermore, heat curing was performed at 150 ° C for one hour as the interlayer resin insulating layer 12 (see FIG. 16 (e)). The thickness of the interlayer resin insulating layer 12 after thermal curing was 18 / zm. (11) Using a Ni sputtering target, sputtering is performed under the conditions of a pressure of 0.8 Pa, a temperature of 80 ° C, a power of 200 W, and a time of 20 minutes. The Ni metal layer 14 having a thickness of 0 m will be insulated by the interlayer resin. The surface of the layer π is formed (see FIG. 17 (a)). The sputtering device used was SV-4540 manufactured by Japan Vacuum Technology Co., Ltd. (12) On the two sides of the substrate on which the metal layer 14 is formed in (11), a commercially available photosensitive dry film is attached, and then a photomask is installed, and then exposed at 100 m / cm2 and developed with 0.8% sodium carbonate. Processing to form a plating resist 16 having a thickness of 30 μm (see FIG. 17 (b)). (13) Furthermore, using an acid containing sulfuric acid (150 g / 1) at a temperature of 40 ° C, 135 paper standards are applicable to China National Standard (CNS) A4 specifications (2〗 〇 × 297 public love) X --- 1 I --- Order --------- Line! (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employee Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 53 I 4 1 A7 B?

五、發明說明GvO 時間5分鐘的條件對金屬層Μ進行酸處理’以去除表面之 氧化層。 (14) 其次，以記載於前述（Π之條件相同的條件實施之 電解電鍍，以形成厚度之電解電鍍膜15。又’藉由 此電解電鍍膜15，則可增厚導體電路9之部分，且可對通 孔17部分進行電鍍塡充(參照圖17(c))。 (15) 又，將防鍍膜16以5%之NaOH剝離去除之後，再 將存在於該防鍍膜16下方之Ni金屬層14以含有40°C之過 硫酸鈉水溶液蝕刻去除之，而形成由Ni金屬層14及電解 鍍銅膜15所構成之厚度16/zm的上層導體電路19(包含通 孔Π)(參照圖17(d))。 (16) 之後，藉由重複(9H15)之過程以進行多層化。又 ，於圖18之中，於具有圖17(d)所形成之上層導體電路19 等基板上，重複(9)〜(15)之過程，則分別形成1層的層間樹 脂絕緣層12與上層導體電路19(參照圖18(a))，相同於實 施例12(14)於調製完阻焊劑組成物之後，於其上形成以下 般之防焊層(參照圖18(b卜（c))。 (Π)亦即，於多層電路基板的兩面，將上述阻焊劑組 成物塗佈2〇vm之厚度，而進行乾燥處理之後，將描繪有 防焊層開口部圖案的光罩使其密接於防焊層，而以1000 mJ/cm2的紫外線進行曝光，再以DMTG溶液予以顯像處理 ，從而形成開口。再者，以80°C1小時、l〇(TC 1小時' 12〇 °C1小時、150°C3小時的條件分別進行加熱處理使防焊層 硬化，而形成具有開孔21、厚度20ym之阻焊圖案層18( 136 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公;g ) ϊ I I ^ I I I — f I ^ ^ · ί I ! I I — 』6J I ] —a »1 I I ϋ I (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention The metal layer M is subjected to acid treatment 'under the condition of a GvO time of 5 minutes to remove the oxide layer on the surface. (14) Next, electrolytic plating is performed under the same conditions as described in the above (Π) to form a thick electrolytic plating film 15. Also, by using this electrolytic plating film 15, the portion of the conductor circuit 9 can be thickened, In addition, electroplating can be performed on the portion of the through hole 17 (see FIG. 17 (c)). (15) After removing the anti-plating film 16 by 5% NaOH, the Ni metal existing under the anti-plating film 16 is removed. The layer 14 is removed by etching with an aqueous solution of sodium persulfate containing 40 ° C to form a 16 / zm upper conductor circuit 19 (including a through hole Π) with a thickness of 16 / zm composed of the Ni metal layer 14 and the electrolytic copper plating film 15 (refer to the figure) 17 (d)). (16) Thereafter, the process of (9H15) is repeated to perform multi-layering. Also, in FIG. 18, on a substrate having an upper-layer conductor circuit 19 formed in FIG. 17 (d), Repeating the process from (9) to (15), one layer of the interlayer resin insulation layer 12 and the upper conductor circuit 19 are formed (see FIG. 18 (a)), which is the same as that in Example 12 (14) after the solder resist composition is completed. After the object is formed, the following solder resist layer is formed thereon (see FIG. 18 (bb (c)). (Π) That is, on both sides of the multilayer circuit substrate, The solder resist composition is applied to a thickness of 20 vm, and after the drying process is performed, a photomask with a pattern of the opening portion of the solder resist layer is brought into close contact with the solder resist layer, and exposed to ultraviolet light of 1000 mJ / cm2, The DMTG solution was used to develop an image to form an opening. Further, the solder resist was hardened by heating at 80 ° C for 1 hour, 10 ° C for 1 hour, 120 ° C for 1 hour, and 150 ° C for 3 hours. To form a solder mask pattern layer 18 with openings 21 and a thickness of 20 μm (136 paper sizes are applicable to China National Standard (CNS) A4 specifications (2) 0 X 297 male; g) ϊ II ^ III — f I ^ ^ · ί I! II — 』6J I] —a» 1 II ϋ I (Please read the notes on the back before filling this page)

五、發明說明（，#) 經濟部智慧財產局員工消費合作社印製 參照圖18(b))。 (18) 其次，將形成有阻焊圖案層18之基板’於鎮*化錬 (30 g/Ι)、次亞磷酸鈉⑽g川、檸檬酸鈉(丨〇 S /Π構成之成 =5的無電解鍍鎳液中浸漬20分鐘’而於開孔21之底部开夕 成厚度5//m之鍍鎳層。 再者，將該基板於氰化金鈣(2 gA)、氯化鉉(75 g/1\' 檸檬酸鈉(50 g/ι)、次亞磷酸鈉（10 g/1)構成之無電解鑛敷'液 中以93°C的條件浸漬23秒，而於鍍鎳層上形成厚度0.03# m之鍍金層22。又’於圖18(c)之中， 係將形成之鍍鎳層及 鍍金層合倂而賦予符號22。 (19) 之後，於阻焊圖案層18之開孔印刷焊接糊劑，於 200°C藉由迴焊(reflow)形成焊接凸塊(焊接體)23，而製造具 有焊接凸塊23之多層印刷電路板(參照圖18(c))。 [實施例20] 除了使用Cr濺鍍靶，於氣壓〇.9Pa · s、濺鍍時間20 分鐘的條件下進行濺鍍，形成厚度之Cr金屬層之 外，其餘皆與實施例19相同來製造多層印刷電路板。 [實施例21] 除了使用Pd濺鍍靶而形成Pd金屬層之外，其餘皆與 實施例19相同來製造多層印刷電路板。 [實施例22] 除了使用Ti濺鍍靶而形成Ti金屬層之外，其餘皆與 實施例19相同來製造多層印刷電路板。 [比較例5] 137 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閲讀背面之注意事項搏填寫本頁&gt; 裏-------- 線. 453 1 41 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（) 除了在形成Ni金屬層之後不進行酸洗淨之外，其餘皆 與實施例19相同來製造多層印刷電路扳。 針對以上實施例19~22以及比較例5所得之多層印刷 電路板，乃進行剝離強度之測定。又’使用光學顯微鏡來 觀察金屬層與電解鍍銅膜之間有無剝離旳發生β其結果示 於下述之表2。 表 2 _______ 實施例19 實施例20 實施例21 實施例22 比較例5 1.3 1.1 1.2V. Description of the invention (, #) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (see Figure 18 (b)). (18) Secondly, the substrate with the solder resist pattern layer 18 formed thereon is composed of yttrium (30 g / 1), sodium hypophosphite, sodium citrate, sodium citrate (丨 〇S / Π composition = 5) After being immersed in the electroless nickel plating solution for 20 minutes, a nickel plating layer having a thickness of 5 // m is formed on the bottom of the opening 21. Further, the substrate is coated with gold calcium cyanide (2 gA), rhenium chloride ( 75 g / 1 \ 'sodium citrate (50 g / ι) and sodium hypophosphite (10 g / 1) in an electroless mineral deposit solution immersed at 93 ° C for 23 seconds, and then nickel-plated A gold-plated layer 22 having a thickness of 0.03 # m is formed thereon. Also in FIG. 18 (c), the formed nickel-plated layer and gold-plated layer are combined to give the symbol 22. (19) After that, the solder resist pattern layer 18 is formed. The solder paste is printed by opening printing, and a solder bump (solder body) 23 is formed by reflow at 200 ° C to manufacture a multilayer printed circuit board having the solder bump 23 (see FIG. 18 (c)). [Example 20] Except that a Cr sputtering target was used and sputtering was performed under the conditions of a pressure of 0.9 Pa · s and a sputtering time of 20 minutes to form a Cr metal layer having a thickness, the rest were manufactured in the same manner as in Example 19. [Multilayer printed circuit board] [Example 21] Except Except that a Pd metal layer was formed using a Pd sputtering target, the rest were the same as in Example 19 to manufacture a multilayer printed circuit board. [Example 22] Except for forming a Ti metal layer using a Ti sputtering target, the rest were implemented. Example 19 was used to make a multilayer printed circuit board. [Comparative Example 5] 137 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back first and fill in this page> -------- Line. 453 1 41 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention () Except that the Ni metal layer is not pickled, the rest are implemented. The multilayer printed circuit board was manufactured in the same manner as in Example 19. For the multilayer printed circuit boards obtained in Examples 19 to 22 and Comparative Example 5, the peel strength was measured. The optical layer was also used to observe the metal layer and the electrolytic copper-plated film. The results are shown in Table 2 below. Table 2 _______ Example 19 Example 20 Example 21 Example 22 Comparative Example 5 1.3 1.1 1.2

U 1.2 剝離強度(kg/cm)U 1.2 Peel strength (kg / cm)

由上述表2可明顯地看出’於層間樹脂絕緣層上形成 金屬層之後，藉由進行酸洗淨去除金屬靨表面之氧化膜， 乃使得金屬層與電解鍍銅膜具有良好之密接性，從而防止 電解鍍銅膜的剝離。 [實施例23] (1)在由BT(雙順丁烯一I女二氮雜笨）樹脂構成之厚度 O.Srmn之基板1的兩面’積層有厚度l8&amp;m的銅涪2，而 將以此形成之BT樹脂銅面積層板(三獒氣體化學製造，商 品名：HL830-0.8T12D)做爲起始材料(參照圖19(a))。首先 '將此銅面積層板鑽孔形成貫通孔(參照圖19(b)),其次， 於表面附著上Pd-Sn膠體，以下述組成之無電解鍍敷水溶 液、下述條件實施無電解鍍敷’於基板全面形成0.7 之From Table 2 above, it can be clearly seen that after the metal layer is formed on the interlayer resin insulating layer, the oxide film on the surface of the metal is removed by acid cleaning, so that the metal layer and the electrolytic copper plating film have good adhesion. This prevents peeling of the electrolytic copper plating film. [Example 23] (1) On both sides of a substrate 1 having a thickness of 0.1 mm and consisting of BT (biscis- butene-1 female diazabenzyl) resin, copper cymbals 2 having a thickness of 18 m were laminated, and A BT resin copper area laminate (manufactured by Mikasa Gas Chemical Co., Ltd., trade name: HL830-0.8T12D) was used as a starting material (see FIG. 19 (a)). First, this copper area laminate was drilled to form a through hole (see Fig. 19 (b)). Second, Pd-Sn colloid was adhered to the surface, and electroless plating was performed using an electroless plating solution with the following composition and the following conditions Apply 'on the substrate to the full formation of 0.7

If X-----1--訂---------線 (請先閱讀背面之注意事項再填寫本頁) 138 本紙張尺度適用中國國家標準（CNS)A4規袼（2〗0 X 297公釐） 453141 A7 _B7 五、發明說明（) 無電解鍍敷膜。 [無電解鍍敷水溶液] EDTA 150 g/1 硫酸銅 20 g/1 HCHO 30 ml/1 NaOH 40 g/1 α，α’—聯二吡啶 80 mg/1 聚乙二醇(PEG) 0.1 g/1 [無電解鍍敷條件] --------------X--- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 7(TC之液溫，30分鐘。 再者，以下述組成之電解電鍍水溶液、下述條件實施 電解鍍銅，形成厚度15/zm之電解鍍銅膜(參照圖19(c))。 [電解電鍍水溶液] 硫酸 180 g/1 硫酸銅 80 g/1 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 1 ml/1 [電解電鍍條件] 電流密度 1 A/dm2 時間 30分鐘 溫度 室溫 (2)將如此般形成內層銅圖案(包含通孔3a)之基板進行 水洗，而乾燥之後，就氧化浴（黑化浴)而言，係使用含有 Na〇H(20 g/1)、NaCl〇2(50 g/1)、Na3PCM15.0 g/Ι)之水溶液， 139 ,. :線- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 4 53 1 4 1 _____B7__ 五、發明說明（W ) 就還原浴而言，係使用含有NaOH(2.7 g/1)、NaBH^l.O g/1) 的水溶液，以供給做爲氧化還原處理，而於導體電路、通 孔之全表面設置粗化層4(參照圖19(d))。 (3) 將含有銅粒子的導電糊劑藉由網板印刷塡充至通孔 3內，使之乾燥、硬化。接著，將導體上面之粗化層4以 及自通孔3溢出之導電糊劑，使用#400的帶式硏磨紙(三 共理化學製造)而藉由帶式硏磨機將之硏磨去除，又爲了將 由於此帶式硏磨機造成的磨損去除，乃進行拋光硏磨，將 基板表面平坦化(參照圖19(e))。 (4) 在上述(3)平坦化之基板表面，依一般方法賦予鈀膠 體觸媒，而藉由實施無電解鍍敷以形成厚度0.6mm之無電 解鍍銅膜6(參照圖19(f))。 (5) 接下來，以下面之條件施以電鍍銅，形成厚度15/z m的電鍍銅膜7，再進行成爲導體電路9部分的增厚，以 及進行將塡充於通孔3之導電糊劑5覆蓋的成爲導體層(覆 鍍層)10的部分的形成。 [電解電鍍水溶液] 硫酸 180 g/1 硫酸銅 80 g/1 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 1 ml/1 [電解電鍍條件] 電流密度 1 A/dm2 時間 30分鐘 140 I--A---- ---It·!------^ I ( (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（2〗〇 X 297公釐） 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 ___ B7 五、發明說明（、V)) 溫度 室溫 (6) 於形成導體電路9及導體層10部分之基板的兩面 處，貼上市售之感光性乾式薄膜，進而裝設光罩，再以 100 mJ/cm2進行曝光、0.8%碳酸氫鈉進行顯像處理，從而 形成厚度15/zm之抗蝕層8 (參照圖20(a))。 (7) 接著’將未形成抗蝕層8之部分的鍍膜，使用硫酸 及過氧化氫的混合液採蝕刻方式溶解去除之，又，將抗触 層8以5%KOH剝離去除，乃形成獨立之導體電路9以及 覆有導電糊劑5之導體層（以下，簡稱此導體層爲覆鑛層) 10 (參照圖 20(b))。 (8) 其次，於包含導體電路9及覆鍍層1〇側面的全表 面形成由Cu-Ni-P合金構成之厚度爲2.5//m的粗化層( 凹凸層)11 ’再於此粗化層11的表面設置厚度的Sn 層(參照圖20(c)，Sn層未予圖示）。 其形成方法係如下所述。亦即，對基板予以酸性脫脂 而進行軟蝕刻，其次，以由氯化鈀及有機酸構成之觸媒溶 液進行處理以賦予鈀觸媒，將此觸媒活性化之後，藉由@ 酸銅8 g/Ι、硫酸鎳0.6 g/Ι '檸檬酸15 g/Ι、次亞瞵酸納29 g/Ι、硼酸31 g/Ι、界面活性劑（日信化學工業製造之沙費諾 魯465)0.1 g/Ι之水溶液構成的pH = 9的無電解鍍敷浴來實 施電鍍，而於導體電路9以及覆鍍層10的全表面形 Cn—Ni-P合金所構成之粗化層11。接著，使用氟棚化錫 (0.1 mol/1)以及硫脲（l.〇mol/l)之水溶液，以溫度5〇t、pH = 1.2的條件進行Cu-Sn置換反應，而於粗化層u的表面設 141 本紙張尺度適用中國國家標準（CNS)A4規格（2〗0 X 297公釐） i n ϋ n ϋ ϋ I i n^-eJ n *^1 ϋ n I (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 53 1 41 A/ __ B7 五、發明說明（从。） 置厚度0.3//m的Sn層(Sn層未予圖示）。 (9) 於基板的兩面，將厚度50//m的熱硬化型聚烯烴樹 脂層(住友3M製造，商品名：1592)，在進行溫度50〜18trc 昇溫的同時以壓力10 kg/cm2予以熱壓積層，而設置由聚烯 烴系樹脂構成之層間樹脂絕緣層12(參照圖20(d))。 (10) 以波長10.4vm的C〇2氣體雷射於聚烯烴系樹脂所 構成之層間樹脂絕緣層12設置直徑8〇Am的通孔用開口 13。再者，藉由Ch及氧混合氣體的電漿處理，以進行去 污及聚烯烴系樹脂絕緣層表面的改良。依此改良之表面當 中，確認具有OH基、羰基或COOH基等親水性基。 又，氧電漿處理條件，係電力800W、氣壓500mTon: ，時間20分鐘。 (11) 採用Ni濺鍍靶，在氣壓0.6Pa、溫度80°C、電力 200W，以及時間5分鐘的條件下進行濺鍍，則Ni薄膜將 於聚烯烴系樹脂絕緣層12的表面形成。此時，所形成之 Ni金屬層之厚度爲O.lem» 又，於Ni金屬層上，再以同樣的條件而利用濺鏟方式 形成厚度0.1 Am的銅層。又，用以濺鍍之裝置，係使用日 本真空技術股份有限公司製造之SV-4540。 (12) 對結束前述（11)處理之基板，再施以前述（1)之無電 解鍍敷，而形成厚度〇.7#m的無電解鍍敷膜14(參照圖 21(a))。 (13) 以前述（12)形成之無電解鍍敷膜14之基板兩面， 貼上市售之感光性乾式薄膜，進而裝設光罩，再以100 142 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) .—1--------訂··--------線 (請先閱讀背面之注意事項再填冩本頁) 經濟部智慧財產局員工消費合作社印製 4 53 14 1 A7 B7 五、發明說明（叫丨〉 mJ/cm2進行曝光、0.8%碳酸鈉進行顯像處理’從而設置厚 度15/zm之防鍍膜16 (參照圖21(b)) ° (14) 再者，實施前述(1)之電解電鍍’以形成厚度15# m之電解電鍍膜15 ’藉此增厚導體電路9之部分’並對通 孔17之部分進行電鑛塡充(參照圖21(c))。 (15) 又，將防鍍膜16以之剝離去除之後’再 將位於該防鍍膜16下方之Ni膜以及無電解鍍敷膜14 ’以 硝酸以及硫酸/過氧化氫之混合液藉由蝕刻溶解去除之’而 形成由Ni膜、無電解鍍銅膜14及電解鍍銅膜15所構成之 厚度16ym之導體電路(包含通孔17)(參照圖21(d))。 (16) 再者，藉由重複前述(8)~(15)過程而得到多層電路 板(參照圖22(a))。又’與實施例12的(14)相同般得到抗蝕 劑組成物。 (17) 將在前述(16)得到之多層電路基板於垂直的直立狀 態下使其夾在一對塗佈用輥軋機的中間，以塗佈厚度20// m之抗蝕劑組成物。 (18) 其次，進行70°C20分鐘、70°C30分鐘的乾燥處理 之後，以1000 mJ/cm2的紫外線進行曝光，再進行DMTG顯 像處理。 再者，以80°C1小時、l〇〇°Cl小時、120°C1小時、150 °C3小時的條件進行加熱處理，而於通孔、焊墊、格子狀 電源層上面的一部份形成具有開口（開口直徑20 μ m)之防焊 層(厚度 20/im)18。 (19) 其次，將形成有防焊層18之基板，於氯化鎳30 143 本紙張尺度適用中國國家標準（CNS〉A4規格（210 X 297公釐) ------------I I ΪΑ--I (請先閱讀背面之注旁筆項再填寫本頁&gt; L'SJ_ 線！ Δ 53 1 ^ ' a? B7 五、發明說明（，ίμ) g/ι、次亞磷酸鈉10 g /1、檸檬酸鈉10 g /1構成之pH = 5的 無電解鍍鎳液中浸漬20分鐘，而於開口部形成厚度5/zm 之鑛鎳層19。再者，將該基板於氰化金鈣2 g/1、氯化銨75 g/Ι、檸檬酸鈉50 g/Ι、次亞磷酸鈉10 g/Ι之水溶液構成之無 電解鍍金液中以93°C的條件浸漬23秒，而於鍍鎳層上形成 厚度0.03/zm之鍍金層20。 (20)之後，於防焊層18之開口部印刷焊接糊劑，於 200°C藉由迴焊形成焊接凸塊21，而製造具有焊接凸塊21 之多層印刷電路板(參照圖22(b))。 [實施例24] 於本實施例，就聚烯烴系樹脂而言，係使用三井化學 製造之TPX(商品名），藉由與實施例23相同的氧電漿條件 進行去污，接著藉由低壓水銀燈照射30~60秒之紫外線來 進行表面改良，以導入ΟΗ基以及羰基。 於本實施例除了再將Pd以氣壓〇.6Pa、溫度100t、 電力200W，以及時間2分鐘的條件附著厚度0.1/zm至聚 烯烴系樹脂絕緣層以外，其餘則係與實施例23相同之方法 製造多層印刷電路板。 [實施例25] 於本實施例，就聚烯烴系樹脂而言，除了使用出光石 油化學製造之SPS(商品名），而將Ti以氣壓0.6Pa、溫度 l〇〇°C、電力200W ’以及時間5分鐘的條件附著厚度0_1// m至聚烯烴系樹脂絕緣層以外’其餘則係與實施例23相同 之方法製造多層印刷電路板。 144 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------- I X - I I (請先閱讀背面之注意事項再填寫本頁) · .線· 經濟部智慧財產局員工消費合作社印*1^ 經濟部智慧財產局員工消費合作杜印製 d 53 1 4 1 A7 B7 五、發明說明（叫） [實施例26] 於本實施例，除了依據以下所述方法形成導體電路以 外，其餘則係與實施例23相同之方法製造多層印刷電路板 〇 亦即，於實施上述實施例23之(8)〜(9)之後’於聚烯烴 系樹脂構成之層間樹脂絕緣層上貼上市售之感光性乾式薄 膜，進而裝設光罩，再以100 m】/cm2進行曝光、0.8%碳酸 鈉進行顯像處理，從而設置厚度l〇gm之防鏟膜。接著， 以氣壓〇.6Pa、溫度100°C、電力200W，以及時間2分鐘的 條件濺鍵Co而形成厚度0.1/zm之Co層後，將防鍍膜以 5%之KOH剝離去除，再將Co做爲觸媒而依據實施例23 進行無電解鍍銅，乃形成厚度l〇#m之導體電路。 [實施例27] 於本實施例，除了替代掉Ni而以Al、Cr、Sn、Mo、 W、Fe進行濺鍍之外，其餘則係與實施例23相同之方法製 造多層印刷電路板。 又，濺鍍的進行係於氣壓0.6Pa、溫度100°C、電力 200W，以及時間2分鐘的條件下於聚烯烴系樹脂絕緣層表 面附著厚度Ο.Ι/zm之物。 針對以此製造之有關實施例之多層印刷電路板，測定 其剝離強度。 又，.將電路板於128°C放置48小時之後測定板彎量之 增加率。又，將電路板以-55°C〜125°C進行500循環之試驗 〇 145 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） --------------文--- (請先閱讀背面之注意事項再填寫本頁) .. ··線. A7 4531 4 1 _ B7_ 五、發明說明（•⑽） 另外，於組裝1C晶片之後，於相對溼度100%之周圍 氣氛下，於室溫驅動100小時之後對遷移的有無進行評價 。遷移的有無，係依據層間導通的有無來判斷。其結果示 於表3。 表3 剝離強度 (kg/cm) 增加率（％) 遷移 龜裂 實施例23(Ni) 2.4 1 输 實施例24(Pd) 2.0 1 frrr Mil: 夕l、、 M j 1 實施例25(Ti) 1.5 1 iffi i t An* ΤΤΓΓ i 1 \\ 實施例26(Co) 2.0 1 te /1 SN 4rrr JILL /1 w 實施例27-l(Cr) 2.0 1 -fm·. &amp; &gt; n\ 實施例27-2(Sn) 2.0 1 &gt;»w fte &gt; M V 實施例27·3(Μο) 1.8 1 /nr, 7ΤΓΓ i 1 w M 實施例27-4(W) 1.5 1 te /S\\ JITT： 實施例27-5(Α1) 1.6 1 int /1 由表3所示之結果可明顯地看出，有關實施例之電路 板，不管其是否於層間樹脂絕緣層設置粗化面，皆可確保 充分之剝離強度。 又，有關實施例之電路板，不管其放熱性是否不佳， 由於藉由m、Pd等金屬來抑制銅的擴散，故不會發生遷移 而可確保層間絕緣性。 亦即，於樹脂基板的兩面形成增厚層，又，透過直接 設置於樹脂絕緣層表面之擇自週期表4A族到4B族之第1B 族中第4〜第7週期的金屬(除了 Cu之外)之中至少1種的金 屬所構成之金屬層，而形成有導體層，藉此乃使本發明之 146 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I I 農--------訂.--------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 453141 _B7_ 五、發明說明（㈣） 第五群得以奏效。 [實施例28] (1)就核心基板而言，係由BT(雙順丁烯二胺三氮雜苯) 樹脂構成之厚度〇.8mm之基板1的兩面積層厚度18vm之 銅箔2，而以此BT樹脂銅面積層板(三菱氣體化學製造， 商品名：HL830 — 0.8T12D)做爲起始材料(參照圖23(a))。首 先，將此銅面積層板鑽孔(參照圖23(b))，其次，附著上Pd - Sn膠體，以下述組成之無電解鍍敷水溶液、下述條件實 施無電解鍍敷，於基板全面形成0.7 μ m之無電解鍍敷膜。 [無電解鍍敷水溶液] EDTA 150 g/1 硫酸銅 20 g/1 HCHO 30 ml/1If X ----- 1--Order --------- Line (Please read the precautions on the back before filling in this page) 138 This paper size applies Chinese National Standard (CNS) A4 Regulations (2 〖0 X 297 mm） 453141 A7 _B7 V. Description of the invention () Electroless plating film. [Aqueous electroless plating solution] EDTA 150 g / 1 copper sulfate 20 g / 1 HCHO 30 ml / 1 NaOH 40 g / 1 α, α'-bipyridine 80 mg / 1 polyethylene glycol (PEG) 0.1 g / 1 [Electroless plating conditions] -------------- X --- (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 7 (Liquid temperature of TC, 30 minutes. In addition, electrolytic copper plating was performed under an electrolytic plating aqueous solution having the following composition and under the following conditions to form an electrolytic copper plating film having a thickness of 15 / zm (see FIG. 19 (c)). [Electrolytic plating Aqueous solution] Sulfuric acid 180 g / 1 Copper sulfate 80 g / 1 Additive (manufactured by Attic Japan, trade name: Capalaseide GL) 1 ml / 1 [Electrolytic plating conditions] Current density 1 A / dm2 Time 30 Minute temperature, room temperature (2) The substrate on which the inner layer copper pattern (including the through hole 3a) was formed was washed with water, and after drying, the oxidation bath (blackening bath) was used with NaOH (20 g). / 1), NaCl〇2 (50 g / 1), Na3PCM15.0 g / l) in water, 139,.:: Line-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) A7 4 53 1 4 1 _____B7__ V. Hair Explanation (W) As far as the reduction bath is concerned, an aqueous solution containing NaOH (2.7 g / 1), NaBH ^ lO g / 1) is used as a redox treatment, and it is applied to the entire surface of the conductor circuit and the through hole. A roughening layer 4 is provided (see FIG. 19 (d)). (3) Fill the through hole 3 with a conductive paste containing copper particles by screen printing, and dry and harden it. Next, the roughened layer 4 on the conductor and the conductive paste overflowing from the through hole 3 were honed and removed by a belt honing machine using # 400 belt honing paper (manufactured by Sankyo Ricoh Chemical). In order to remove abrasion caused by the belt honing machine, polishing and honing are performed to flatten the substrate surface (see FIG. 19 (e)). (4) A palladium colloid catalyst is applied to the flattened substrate surface as described in (3) above, and electroless plating is performed to form an electroless copper-plated film 6 having a thickness of 0.6 mm (see FIG. 19 (f)). ). (5) Next, copper plating is applied under the following conditions to form a copper plating film 7 having a thickness of 15 / zm, and then thickening the portion of the conductor circuit 9 and conducting paste filling the through hole 3 Formation of the part covered by 5 to become the conductor layer (plating layer) 10. [Aqueous solution for electrolytic plating] Sulfuric acid 180 g / 1 Copper sulfate 80 g / 1 Additive (manufactured by Attic Japan, trade name: Capalaseide GL) 1 ml / 1 [Electrolytic plating conditions] Current density 1 A / dm2 time 30 minutes 140 I--A ---- --- It ·! ------ ^ I ((Please read the precautions on the back before filling out this page) The paper size of the paper is in accordance with China National Standard (CNS) A4 (2) 0 × 297 mm. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 A7 ___ B7 V. Description of the invention (, V)) Temperature chamber (6) On both sides of the substrate forming the conductor circuit 9 and the conductor layer 10, a commercially-available photosensitive dry film is pasted, a photomask is installed, and exposure is performed at 100 mJ / cm2 and 0.8% sodium bicarbonate. The developing process is performed to form a resist layer 8 having a thickness of 15 / zm (see FIG. 20 (a)). (7) Next, the plating film of the part where the resist layer 8 is not formed is dissolved and removed by using a mixed solution of sulfuric acid and hydrogen peroxide, and the anti-contact layer 8 is peeled off at 5% KOH to form an independent layer. The conductive circuit 9 and the conductive layer 5 (hereinafter, this conductive layer is referred to as an ore-covered layer) 10 (see FIG. 20 (b)). (8) Secondly, a roughened layer (concavo-convex layer) 11 'formed of Cu-Ni-P alloy and having a thickness of 2.5 // m is formed on the entire surface including the side surfaces of the conductor circuit 9 and the plating layer 10, and then roughened there. A Sn layer having a thickness is provided on the surface of the layer 11 (refer to FIG. 20 (c), the Sn layer is not shown). The formation method is as follows. That is, the substrate is subjected to acid degreasing to perform soft etching. Next, the substrate is treated with a catalyst solution composed of palladium chloride and an organic acid to give a palladium catalyst. After activating the catalyst, the substrate is treated with @ 酸 铜 8 g / Ι, nickel sulfate 0.6 g / 1, citric acid 15 g / 1, sodium hypophosphite 29 g / 1, boric acid 31 g / 1, surfactant (Safinoru 465 manufactured by Nissin Chemical Industry) The electroless plating bath having a pH of 9 composed of a 0.1 g / 1 aqueous solution is used for electroplating, and the roughened layer 11 composed of the Cn-Ni-P alloy on the entire surface of the conductor circuit 9 and the plating layer 10 is formed. Next, a Cu-Sn substitution reaction was performed using an aqueous solution of tin fluoride (0.1 mol / 1) and thiourea (1.0 mol / l) at a temperature of 50 t and a pH of 1.2, and the roughened layer was The surface of u is set to 141. The paper size is applicable to Chinese National Standard (CNS) A4 (2) 0 X 297 mm in in n ϋ ϋ I in ^ -eJ n * ^ 1 ϋ n I (Please read the note on the back first Please fill out this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 1 41 A / __ B7 V. Description of the invention (from.) Sn layer with thickness of 0.3 // m (Sn layer is not shown). (9) On both sides of the substrate, a heat-curable polyolefin resin layer (manufactured by Sumitomo 3M, trade name: 1592) with a thickness of 50 // m was heated at a temperature of 50 to 18 trc while applying a pressure of 10 kg / cm2. An interlayer resin insulating layer 12 made of a polyolefin-based resin is laminated on the laminated layer (see FIG. 20 (d)). (10) An interlayer resin insulating layer 12 made of a polyolefin resin with a CO2 gas having a wavelength of 10.4 vm is provided with a through-hole opening 13 having a diameter of 80 Am. In addition, plasma treatment of a mixed gas of Ch and oxygen is used to perform decontamination and improve the surface of the polyolefin-based resin insulating layer. It has been confirmed that the modified surface has a hydrophilic group such as an OH group, a carbonyl group, or a COOH group. The oxygen plasma treatment conditions are 800 W of electric power, 500 mTon of air pressure, and a time of 20 minutes. (11) Using a Ni sputtering target, sputtering is performed under the conditions of a pressure of 0.6 Pa, a temperature of 80 ° C, a power of 200 W, and a time of 5 minutes, and a Ni film is formed on the surface of the polyolefin-based resin insulating layer 12. At this time, the thickness of the Ni metal layer formed was O.lem », and a copper layer with a thickness of 0.1 Am was formed on the Ni metal layer by a sputtering method under the same conditions. The sputtering equipment used was SV-4540 manufactured by Japan Vacuum Technology Co., Ltd. (12) An electroless plating film 14 (see FIG. 21 (a)) having a thickness of 0.7 # m is formed on the substrate that has undergone the above-mentioned (11) treatment and then subjected to the non-electrolytic plating of the above-mentioned (1). (13) The two sides of the substrate of the electroless plating film 14 formed in the above (12) are pasted with a commercially available photosensitive dry film, and then a photomask is installed, and the Chinese national standard (CNS) A4 is applied to the paper size of 100 142 Specifications (210 X 297 mm) .—1 -------- Order ·· -------- Line (Please read the notes on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the employee consumer cooperative 4 53 14 1 A7 B7 V. Description of the invention (called 丨> mJ / cm2 for exposure and 0.8% sodium carbonate for development processing 'to set a 15 / zm thickness anti-coating film 16 (refer to Figure 21 (b )) ° (14) Furthermore, the above-mentioned (1) electrolytic plating is performed to form an electrolytic plating film 15 'with a thickness of 15 # m, thereby thickening a portion of the conductor circuit 9 and performing electro-mineralization on the portion of the through-hole 17 Filling (refer to Figure 21 (c)). (15) After removing the anti-plating film 16 by peeling it off, the Ni film and the electroless plating film 14 located below the anti-plating film 16 are treated with nitric acid and sulfuric acid / The mixed solution of hydrogen peroxide is dissolved and removed by etching to form a conductor having a thickness of 16 μm composed of a Ni film, an electroless copper plating film 14, and an electrolytic copper plating film 15. (Including through hole 17) (refer to FIG. 21 (d)). (16) Furthermore, a multilayer circuit board is obtained by repeating the above-mentioned (8) to (15) (refer to FIG. 22 (a)). The resist composition was obtained in the same manner as in (14) of Example 12. (17) The multilayer circuit board obtained in the above (16) was sandwiched between a pair of coating rollers in a vertical upright state, A resist composition having a thickness of 20 // m is applied. (18) Next, after drying at 70 ° C for 20 minutes and 70 ° C for 30 minutes, exposure is performed with ultraviolet light at 1000 mJ / cm2, and then DMTG is developed. In addition, heat treatment was performed under the conditions of 80 ° C for 1 hour, 100 ° C for 1 hour, 120 ° C for 1 hour, and 150 ° C for 3 hours. Form a solder mask (thickness 20 / im) 18 with an opening (opening diameter 20 μm). (19) Next, the substrate with solder mask 18 will be formed on nickel chloride 30 143. This paper size applies to Chinese national standards (CNS> A4 specification (210 X 297 mm) ------------ II ΪΑ--I (Please read the note next to the note on the back before filling in this page> L'SJ_ line! Δ 53 1 ^ 'a? B 7 V. Description of the invention (, ί) g / ι, sodium hypophosphite 10 g / 1, sodium citrate 10 g / 1, pH = 5 in an electroless nickel plating solution immersed for 20 minutes, and formed in the opening Mineral nickel layer 19 with a thickness of 5 / zm. Further, the substrate was placed in an electroless gold plating solution composed of an aqueous solution of 2 g / 1 gold calcium cyanide, 75 g / 1 ammonium chloride, 50 g / 1 sodium citrate, and 10 g / 1 sodium hypophosphite. Dipping at 93 ° C for 23 seconds, a gold plating layer 20 having a thickness of 0.03 / zm was formed on the nickel plating layer. (20) After that, a solder paste is printed on the opening of the solder resist layer 18, and a solder bump 21 is formed by reflow at 200 ° C to manufacture a multilayer printed circuit board having the solder bump 21 (see FIG. 22 (b). )). [Example 24] In this example, as for the polyolefin-based resin, TPX (trade name) manufactured by Mitsui Chemicals was used, and decontamination was performed under the same oxygen plasma conditions as in Example 23, followed by low pressure. The mercury lamp is irradiated with ultraviolet rays for 30 to 60 seconds to perform surface modification, so as to introduce an oxo group and a carbonyl group. In this example, except that Pd was adhered to the polyolefin resin insulating layer with a thickness of 0.1 / zm at a pressure of 0.6 Pa, a temperature of 100 t, a power of 200 W, and a time of 2 minutes, the rest were the same as in Example 23. Manufacture of multilayer printed circuit boards. [Example 25] In this example, in the case of polyolefin resin, in addition to using SPS (trade name) manufactured by Idemitsu Petrochemical, Ti was set at a pressure of 0.6 Pa, a temperature of 100 ° C, and an electric power of 200 W 'and A thickness of 0_1 // m to a thickness of 0_1 // m outside the polyolefin-based resin insulating layer was applied under the condition of 5 minutes. The rest was manufactured in the same manner as in Example 23 to produce a multilayer printed circuit board. 144 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) ------------- IX-II (Please read the precautions on the back before filling this page) · .Line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs * 1 ^ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs d 53 1 4 1 A7 B7 V. Description of the Invention (called) [Embodiment 26] In this embodiment, Except for forming a conductor circuit according to the method described below, the rest is a method of manufacturing a multilayer printed circuit board in the same manner as in Example 23. That is, after the implementation of (8) to (9) of the above-mentioned Example 23, the method A commercially available photosensitive dry film is affixed to the interlayer resin insulation layer made of resin, and then a photomask is installed, and then exposed at 100 m] / cm2 and developed with 0.8% sodium carbonate to provide a thickness of 10 gm. Shovel film. Next, the Co layer was sputtered with a pressure of 0.6 Pa, a temperature of 100 ° C, a power of 200 W, and a time of 2 minutes to form a Co layer with a thickness of 0.1 / zm. Then, the resist was peeled off with 5% KOH, and then Co As a catalyst, electroless copper plating was performed according to Example 23 to form a conductor circuit with a thickness of 10 # m. [Example 27] In this example, a multilayer printed circuit board was manufactured in the same manner as in Example 23 except that instead of Ni, sputtering was performed using Al, Cr, Sn, Mo, W, and Fe. In addition, sputtering was performed under conditions of a pressure of 0.6 Pa, a temperature of 100 ° C, an electric power of 200 W, and a time of 2 minutes to attach a substance having a thickness of 0.1 / zm to the surface of the polyolefin resin insulating layer. The multilayer printed wiring board of the related example thus manufactured was measured for its peel strength. After the circuit board was left at 128 ° C for 48 hours, the increase rate of the amount of bending of the board was measured. In addition, the circuit board is tested for 500 cycles at -55 ° C ~ 125 ° C. 145 This paper is in accordance with the Chinese National Standard (CNS) A4 specification (210 x 297 mm) ---------- ---- Article --- (Please read the precautions on the back before filling in this page) .. · Line. A7 4531 4 1 _ B7_ V. Description of the Invention (• ⑽) In addition, after assembling the 1C chip, In a surrounding atmosphere with a relative humidity of 100%, the presence or absence of migration was evaluated after driving at room temperature for 100 hours. The presence or absence of migration is judged based on the presence or absence of continuity between layers. The results are shown in Table 3. Table 3 Peel strength (kg / cm) Increasing rate (%) Migration and cracking Example 23 (Ni) 2.4 1 Loss Example 24 (Pd) 2.0 1 frrr Mil: Xi, Mj 1 Example 25 (Ti) 1.5 1 iffi it An * ΤΤΓΓ i 1 \\ Example 26 (Co) 2.0 1 te / 1 SN 4rrr JILL / 1 w Example 27-1 (Cr) 2.0 1 -fm ·. &Amp; &gt; n \ Example 27-2 (Sn) 2.0 1 &gt; »w fte &gt; MV Example 27 · 3 (Μο) 1.8 1 / nr, 7ΤΓΓ i 1 w M Example 27-4 (W) 1.5 1 te / S \\ JITT : Example 27-5 (Α1) 1.6 1 int / 1 From the results shown in Table 3, it can be clearly seen that the circuit board of the related example can ensure whether or not a roughened surface is provided on the interlayer resin insulation layer. Full peel strength. Regarding the circuit board of the embodiment, regardless of whether or not its heat dissipation is not good, since the diffusion of copper is suppressed by metals such as m and Pd, migration does not occur and interlayer insulation can be ensured. That is, a thickened layer is formed on both sides of the resin substrate, and the metals selected from the 4th to 7th periods in Group 1B of the Periodic Table 4A to 4B Group (except Cu Outer), a metal layer composed of at least one of the metals, and a conductive layer is formed, so that the 146 paper size of the present invention is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). II Agriculture -------- Order .-------- Line (Please read the notes on the back before filling this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 453141 _B7_ V. Description of the invention ( Ii) The fifth group works. [Example 28] (1) As for the core substrate, a copper foil 2 with a thickness of 18 vm and a two-layer layer of a substrate 1 having a thickness of 0.8 mm and made of BT (biscis- butene diamine triazabenzene) resin, and This BT resin copper area laminate (manufactured by Mitsubishi Gas Chemical, trade name: HL830 — 0.8T12D) was used as a starting material (see FIG. 23 (a)). First, this copper area laminate was drilled (refer to FIG. 23 (b)). Second, Pd-Sn colloid was adhered, and electroless plating was performed with an electroless plating aqueous solution with the following composition and the following conditions, and the entire substrate was An electroless plated film of 0.7 μm was formed. [Aqueous electroless plating solution] EDTA 150 g / 1 copper sulfate 20 g / 1 HCHO 30 ml / 1

NaOH 40 g/1 α，α’-聯二卩比11 定 80mg/l PEG 0.1 g/1 [無電解鍍敷條件] 70t之液溫，30分鐘。 再者，以下述組成之電解電鍍水溶液、下述條件實施 電解鍍銅，形成由厚度15vm之電解鍍銅膜構成之內層導 體電路2以及通孔3(參照圖23(c))。 [電解電鍍水溶液] 硫酸 180 g/1 硫酸銅 80 g/1 147 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） X- - ------- 訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 Λ„ A/ B7 五、發明說明（w) 添加劑(亞特提克日本公司製造’商品名：卡帕拉錫德GL) 1 ml/1 [電解電鍍條件] 電流密度 1 A/dm2 時間 30分鐘 溫度 室溫 (2) 將如此般形成內層銅圖案(包含通孔3a)之基板進行 水洗，而乾燥之後，就氧化浴(黑化浴)而言’係使用含有 NaOH(20 g/1)、NaCKM50 g/1)、Na3PCM15.0 g/Ι)之水溶液’ 就還原浴而言，係使用含有NaOH(2.7 g/1)、NaBH4(1.0 g/1) 的水溶液，以供給做爲氧化還原處理，而於內層導體電路 2、通孔3之全表面設置粗化層4(參照圖23(d)) 〇 (3) 其次，將含有銅粒子的導電糊劑藉由網板印刷塡充 至通孔3內，使之乾燥、硬化。接著，將內層導體電路2 上面之粗化層4以及自通孔3溢出之導電糊劑5，使用#400 的帶式硏磨紙(三共理化學製造)而藉由帶式硏磨機將之硏 磨去除，又爲了將由於此帶式硏磨機造成的磨損去除，乃 進行拋光硏磨，將基板表面平坦化(參照圖23(e))。 經濟部智慧財產局員工消費合作社印製 — — — — — — — I — It i ^ I I 1?^ * II I &lt;請先Μ讀背面之注意事項再填寫本頁) —線_ (4) 在前述(3)平坦化之基板表面，依一般方法賦予鈀膠 體觸媒，而藉由實施無電解鍍敷以形成厚度〇.6μπι之無電 解鍍銅膜6(參照圖23(f))。 (5) 接下來，以下面之條件施以電鍍銅，形成厚度15# m的電鏟銅膜7，再進行成爲導體電路9部分的增厚，以 及進行將塡充於通孔3之導電糊劑5覆蓋的成爲導體層(覆 148 本紙張尺度適用_國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作杜印製 453 1 4 1 A7 ____ B7 五、發明說明（叫） 鍍層)1〇的部分的形成(參照圖24(b))。 [電解電鍍水溶液]NaOH 40 g / 1 α, α'-bipyridine ratio 11 fixed 80mg / l PEG 0.1 g / 1 [electroless plating conditions] liquid temperature of 70t for 30 minutes. Furthermore, electrolytic copper plating was performed under an electrolytic plating aqueous solution having the following composition and under the following conditions to form an inner layer conductor circuit 2 and a through hole 3 composed of an electrolytic copper plating film having a thickness of 15 vm (see Fig. 23 (c)). [Aqueous solution for electrolytic plating] Sulfuric acid 180 g / 1 Copper sulfate 80 g / 1 147 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) X--------- Order --- ------ line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 Λ „A / B7 V. Invention Description (w) Additives (Yate Tick Japan Co., Ltd. 'Trade name: Capalaseide GL) 1 ml / 1 [Electrolytic plating conditions] Current density 1 A / dm2 Time 30 minutes Temperature Room temperature (2) An inner layer copper pattern (including The substrate of the through-hole 3a) was washed with water and dried. In terms of an oxidation bath (blackening bath), an aqueous solution containing NaOH (20 g / 1), NaCKM50 g / 1), and Na3PCM 15.0 g / 1 was used. '' As for the reduction bath, an aqueous solution containing NaOH (2.7 g / 1) and NaBH4 (1.0 g / 1) is used as a redox treatment, and the entire surface of the inner conductor circuit 2 and the through hole 3 is supplied. The roughening layer 4 is provided (refer to FIG. 23 (d)). (3) Next, a conductive paste containing copper particles is filled into the through hole 3 by screen printing, and then dried and hardened. The roughened layer 4 on the inner layer of the conductor circuit 2 and the conductive paste 5 overflowing from the through hole 3 were rubbed with a tape honing machine using # 400 tape honing paper (manufactured by Sankyo Ricoh Chemical Co., Ltd.). Grinding removal, and in order to remove the abrasion caused by this belt honing machine, polishing honing is performed to flatten the surface of the substrate (refer to Figure 23 (e)). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs- — — — — — I — It i ^ II 1? ^ * II I &lt; Please read the precautions on the back before filling this page) —Line_ (4) On the substrate surface flattened in (3) above, follow A palladium colloidal catalyst is provided by a general method, and electroless plating is performed to form an electroless copper plating film 6 having a thickness of 0.6 μm (see FIG. 23 (f)). (5) Next, apply the following conditions. Copper was electroplated to form a copper shovel film 7 with a thickness of 15 # m, and then thickened as a part of the conductor circuit 9 and a conductive layer covered with the conductive paste 5 filled in the through hole 3 (covered with 148 sheets of paper) Applicable Standards_China National Standard (CNS) A4 Specification (210 X 297 mm) Consumption Cooperation of Employees of Intellectual Property Bureau, Ministry of Economy Du Yin 453 1 4 1 A7 ____ B7 V. described invention (called) forming part of the plating 1〇) (see FIG. 24 (b)). [Electroplating Solution]

硫酸 180 gA 硫酸銅 80 g/1 添加劑(亞特提克曰本公司製造，商品名：卡帕拉鍚德GL) [電解電鍍條件] 1 ml/1 電流密度 1 A/dm2 時間 30分鐘 溫度 室溫 (6) 於形成導體電路9及導體層10部分之基板的兩面 處，貼上市售之感光性乾式薄膜，進而裝設光罩，再以 100 nJ/cm2進行曝光、0.8%碳酸氫鈉進行顯像處理，從而 形成厚度15//m之抗蝕層8 (參照圖24(a))。 (7) 接著，將未形成抗蝕層8之部分的鍍膜，使用硫酸 及過氧化氫的混合液採蝕刻方式溶解去除之，又，將抗倉虫 層8以5%KOH剝離去除，乃形成獨立之導體電路9以及 覆有導電糊劑5之導體層（以下，簡稱此導體層爲覆鑛層) 10 (參照圖 24(b))。 (8) 其次，於包含導體電路9及覆鍍層10側面的全表 面形成由Cu-Ni-P合金構成之厚度爲2‘5ym的粗化層( 凹凸層）Π，再於此粗化層11的表面設置厚度0.3em的Sn 層(參照圖24(〇，311層未予圖示）。 其形成方法係如下所述。亦即，對基板予以酸性脫;脂 149 本紙張尺度適用中固國家標準（CNS)A4規格（210 X 297公釐） -------------1--------訂---------線 《請先閱讀背面之注意事項再填寫本頁) 4 經濟部智慧財產局員工消費合作社印製 53141 A7 ____B7______ 五、發明說明（) 而進行軟蝕刻，其次，以由氯化鈀及有機酸構成之觸媒溶 液進行處理以賦予Pd觸媒，將此觸媒活性化之後，藉由硫 酸銅8 g/Ι、硫酸鎳0.6 g/Ι、檸檬酸15 g/i、次亞磷酸鈉29 g/Ι、硼酸31 g/Ι、界面活性劑（日信化學工業製造之沙費諾 魯465)0.1 g/Ι之水溶液構成的pH二9的無電解鍍敷浴來實 施電鍍，而於導體電路9以及覆鍍層10的全表面形成由 Cu-Ni-Ρ合金所構成之粗化層11。接著’使用氟硼化錫 0.1 mol/丨以及硫脲l,0mol/l之水溶液，以溫度50°C、pH = 1.2的條件進行Cu-Sn置換反應，而於粗化層11的表面設 置厚度〇.3#m的Sn層(Sn層未予圖示）。 (9) 於基板的兩面，將厚度50/zm的熱硬化型聚烯烴樹 脂層(住友3M製造，商品名：1592)，在進行溫度5(M80t 昇溫的同時以壓力10 kg/cm2予以熱壓積層，而設置由聚 烯烴系樹脂構成之層間樹脂絕緣層12(參照圖24(d))。 (10) 其次，以波長10.4/zm的C〇2氣體雷射於聚烯烴系 樹脂所構成之樹脂絕緣層12設置直徑80μm的通孔用開口 13 »再者，藉由CR及氧混合氣體的電漿處理，以進行去 污及聚烯烴系樹脂絕緣層表面的改良。依此改良之表面當 中，確認具有OH基、羰基或COOH基等親水性基。 又，氧電漿處理條件，係電力800W、氣壓500mTorr ，時間20分鐘。 (11) 其次，採用Ni濺鍍靶，在氣壓〇.6Pa、溫度80°C 、電力200W，以及時間5分鐘的條件下進行濺鍍，則Ni 薄膜將於上述聚烯烴系樹脂絕緣層12的表面形成。此時， 150 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I ------農--------訂 ---1--ί 線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 53 141 a7 _B7_ 五、發明說明（即1) 所形成之Ni金屬層之厚度爲0.1/zm。 又，如圖(25)所示般，於最下層之Ni金屬層上，再以 同樣的條件而利用濺鍍方式彤成厚度〇.l#m的銅層。又， 用以濺鍍之裝置，係使用日本真空技術股份有限公司製造 之 SV —4540。 (12) 接著，對結束前述（11)處理之基板，再施以前述⑴ 之無電解鍍敷，而形成厚度〇.7#m的無電解鍍敷膜14(參 照圖 25(a))。 (13) 以前述（12)形成之無電解鍍敷膜14之基板兩面， 貼上市售之感光性乾式薄膜，進而裝設光罩，再以100 mJ/cm2進行曝光、0.8%碳酸鈉進行顯像處理，從而設置厚 度15#m之防鍍膜16 (參照圖25(b))。 (14) 實施前述(1)之電解電鍍，以形成厚度15/zrn之電 解電鍍膜15，藉此增厚導體電路9之部分，並對通孔17 之部分進行電鍍塡充(參照圖25(c))。 又，浸漬於氯化鎳30 g/Ι、次亞磷酸鈉10 g/Ι、檸檬酸 鈉10 gA之水溶液構成之pH = 5之無電解鍍鎳浴中1分鐘 ，形成厚度〇.l#m之鍍鎳層19。 (15) 又，將防鍍膜16以5%之KOH剝離去除之後，再 將位於該防鍍膜16下方之Ni膜以及無電解鍍敷膜14，以 硝酸以及硫酸/過氧化氫之混合液藉由蝕刻溶解去除之，而 形成由Ni膜、無電解鍍銅膜14及電解鍍銅膜15所構成之 厚度16/zm之導體電路(包含通孔17)(參照圖25(d))。 (16) 再者，藉由重複前述(8)〜(15)過程而得到多層電路 151 本紙張尺度適用中國國家標準（CNS)A4規格（2!0 X 297公釐） ----------士^------- - 訂---------線！ (請先閱讀背面之注意事項再填寫本頁) 453141 經濟部智慧財產局員工消費合作杜印製 A7 ____B7_ 五、發明說明（β) 板(參照圖26(a))。又’與實施例12的（14)相同般得到抗蝕 劑組成物。 (17) 其次’將在前述（16)得到之多層電路基板於垂直的 直立狀態下使其夾在一對塗佈用輥軋機的中間，以塗佈厚 度20 之抗蝕劑組成物。 (18) 其次’於70°C進行30分鐘的乾燥處理之後，以 1000 m〗/cm2的紫外線進行曝光，再進行DMTG顯像處理。 再者’以80°C1小時' 100°C1小時、120°C1小時、15CTC3 小時的條件進行加熱處理，而於通孔、焊墊、格子狀電源 層上面的一部份形成具有開□(開口直徑200# m)之防焊層( 厚度 20/m)18。 (19) 其次，將該基板於氰化金鈣2 g/Ι、氯化銨75 g/Ι、 擰檬酸鈉50 g/1、次亞磷酸鈉10 g/1之水溶液構成之無電解 鍍金液中以93°C的條件浸漬23秒，而於鍍鎳層上形成厚度 0.03 /z m之鍍金層20。 (20) 之後，於防焊層18之開口部印刷焊接糊劑’於 20(TC藉由迴焊形成焊接凸塊21，而製造具有焊接凸塊21 之多層印刷電路板(參照圖26(b))。 [實施例29] 於本實施例，就聚烯烴系樹脂而言’係使用三井化學 製造之TPX(商品名），藉由與實施例28相同的氧電漿條件 進行去污，接著藉由低壓水銀燈照射30~60秒之紫外線來 進行表面改良，以導入ΟΗ基以及羰基° 於本實施例除了再將Pd以氣壓0.6Pa'溫度l〇〇°C、 152 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公f ) ϋ I —1 I I n Ϊ n - d I * n ϋ I n n ^ ϋ I n n ϋ ϋ n I (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B? 五、發明說明（6丨） 電力200W，以及時間2分鐘的條件附著厚度〇.l#m至聚 烯烴系樹脂絕緣層以外，其餘則係與實施例28相同之方法 製造多層印刷電路板。 [實施例30] 於本實施例，就聚烯烴系樹脂而言，除了使用出光石 油化學製造之SPS(商品名），而將Ti以氣壓〇.6Pa、溫度 100°C、電力200W，以及時間5分鐘的條件附著厚度 m至聚烯烴系樹脂絕緣層及導體電路上以外’其餘則係與 實施例28相同之方法製造多層印刷電路板。 [實施例31] 於本實施例，除了替代掉Ni而以Cr、Sn、Mo、W、 Fe進行濺鍍之外，其餘則係與實施例28相同之方法製造 多層印刷電路板。 又，濺鍍的進行係於氣壓〇.6Pa、溫度100°C、電力 200W，以及時間2分鐘的條件下於聚烯烴系樹脂絕緣層表 面及導體電路上附著厚度0.1 之物。 針對以此製造之有關實施例之多層印刷電路板，測定 其剝離強度。 又，將電路板以-55°C~125°C進行500循環之試驗。 另外，於組裝1C晶片之後，於相對溼度100%之周圜 氣氛下，於室溫驅動1000小時之後對遷移的有無進行評價 β遷移的有無，係依據層間導通的有無來判斷。又，對可 製造之最小L/S調查之，其結果示於表4。 153 本紙張尺度適用中國國家標準（CNS)A4規格（210 X Μ7公釐) — II---------農---II--訂-------11.^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 53 1 4 1 ΑΊ Β7 五、發明說明（A&gt;) 剝離強度 (kg/cm) 遷移 龜裂 L/S ( βΐΐΐ) 實施例28(Ni) 2.4 無 無 15/15 實施例29(Pd) 2.0 ,^τγΤ 無 Art 無 15/15 實施例30(Ti) 1.5 Μ 15/15 ^ 施例 31-l(Cr) 2.0 赫 /Μ、 無 15/15 實施例31-2(Sn) 2.0 Μ te yi «、 15/15 實施例3Ι·3(Μο) 2.0 Μ 姐 小N 15/15 實施例31-4(W) 1.5 Μ JrrT 热 15/15 由表4所示之結果可明顯地看出’有關實施例之電路 板，不管其是否於層間樹脂絕緣層設置粗化面’皆可確保 充分之剝離強度。 又，有關實施例之電路板’不管其放熱性是否不佳’ 由於藉由Ni、Pd等金屬來抑制銅的擴散’故不會發生遷移 而可確保層間絕緣性。 亦即，於樹脂基板的兩面形成增厚層’又’透過直接 設置於樹脂絕緣層表面之擇自週期表4A族到4B族之第1B 族中第4〜第7週期的金屬(除了 Cu之外)之中至少1種的金 屬所構成之金屬層，而形成有導體層’藉此乃使本發明得 以奏效。 又，於本發明，可形成L/S = 15/15之細密的電路。 [實施例32] (1)於BT(雙順丁烯二胺三氮雜苯）樹脂構成之厚度 0.8mm之基板1的兩面積層厚度18/zm之銅箔2，而以此 BT樹脂銅面積層板(三菱氣體化學製造’商品名：HL830-0.8T12D)做爲起始材料(參照圖29(a))。首先’將此銅面積 154 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ! I-----1— R i 1---------1---^ &lt;請先W讀背面之注意事項再填寫本頁) A7 4 53 1 41 _B7_ 五、發明說明（ 層板鑽孔形成貫通孔(參照圖29(b))，其次，將Pd—Sn膠體 附著於表面，以下述組成之無電解鍍敷水溶液、下述條件 實施無電解鍍敷，於基板全面形成〇.7/im之無電解鍍敷膜 〇 [無電解鍍敷水溶液] EDTA 150 g/1 硫酸銅 20 g/1 HCHO 30 ml/1 NaOH 40 g/1 a ,α'— 聯二 〇t[；n定 80 mg/1 聚乙二醇(PEG) 0.1 g/1 [無電解鍍敷條件] 70°C之液溫，30分鐘。 再者，以下述組成之電解電鍍水溶液、下述條件實施 電解鍍銅，形成厚度15 μ m之電鍍銅膜。 [電鍍水溶液] 硫酸 180 g/1 硫酸銅 80 g/1 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 1 ml/1 [電鍍條件] 電流密度 1 A/dm2 時間 30分鐘 溫度 室溫 155 本紙張尺度適用中國國家標準（CNS)A4規格（2〗0 X 297公爱） --------I ------- - 訂--------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 4 經濟部智慧財產局員工消費合作社印製 53141 a? _____B7__ 五、發明說明（W) (2) 將藉由上述過程於基板全面形成導體層3(包含通孔 3a)之基板(參照圖29(c))進行水洗，而乾燥之後，乃對該基 板使用含有 NaOH(20 g/1)、NaClCb(50 g/1) ' Na3P〇4(15_0 g/1) 之水溶液構成之氧化浴(黑化浴），以及含有NaOH(2.7 g/1) 、NaBH^l.O g/1)之水溶液構成之還原浴，以供給做爲氧化 還原處理，而於包含通孔3a之導體層3的全表面設置粗化 層4(參照圖29(d))。 (3) 其次，將含有平均粒徑15μπι之銅粒子的金屬粒子 糊劑(達自達電線公司製造，DD糊劑：非導電性塡孔銅糊 劑)藉由網板印刷塡充至通孔3a內，於10CTC30分鐘、180 °C2小時的條件下使之乾燥、硬化。接著，將導體層3表 面形成之粗化層4及自通孔3a溢出之金屬粒子糊劑5，利 用#400的帶式硏磨紙(三共理化學製造)而藉由帶式硏磨機 將該等之物硏磨去.除之，又爲了將由於此帶式硏磨機造成 的磨損去除，乃藉由AhCh硏磨或SiC硏磨顆粒進行拋光硏 磨，將基板表面平坦化(參照圖29(e))。 (4) 在上述(3)平坦化之基板表面，依一般方法賦予鈀膠 體觸媒，而藉由實施無電解鍍敷以形成厚度0.6mm之無電 解鍍銅膜6(參照圖29(f))。 (5) 接下來，以下面之條件施以電鍍銅，形成厚度15μ m的電鍍銅膜7，於後述圖(30)之過程中，乃增厚成爲下層 導體電路9之部分，以及進行將塡充於通孔3a之金屬粒子 糊劑5覆蓋的成爲導體層10之部分的形成。 [電鍍水溶液] 156 本紙張尺度適用中國园家標準（CNS)A4規格（2】0 X 297公釐） ----------I---定.__ (請先閱讀背面之注意事項再填寫本頁) 線' 453 1 4 1 A7 B7 五、發明說明（π) 硫酸 180 g/1 硫酸銅 80g/l 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 1 ml/1 [電鍍條件]1 電流密度 1 A/dm2 時間 30分鐘 溫度 室溫 (6) 於形成導體電路9及導體層10之部分的基板兩面 處，貼上市售之感光性乾式薄膜，進而裝設光罩，再以 100 m〗/cm2進行曝光' 0.8%碳酸氫鈉進行顯像處理，從而 形成厚度15#m之抗蝕層8 (參照圖30(a))。 (7) 接著，將未形成抗蝕層8之部分的鍍膜，使用硫酸 及過氧化氫的水溶液採蝕刻方式涪解去除之，又，將抗蝕 層8以5%KOH剝離去除，乃形成獨立之導體電路9以及 覆有金屬粒子糊劑5之導體層10 (參照圖30(b))。 (8) 其次，於下層導體電路9及覆有金屬粒子糊劑5之 導體層10的表面形成由Cu-Ni — P合金構成之厚度爲2,5 μιη的粗化層(凹凸層）1丨，再於此粗化層11的表面設置厚 度0.3 的Sn層(參照圖30(c))。該等層之形成方法係如 下所述。又，於圖30(c)中Sn層未予圖示。 亦即，對基板予以酸性脫脂而進行軟蝕刻，其次，以 由氯化鈀及有機酸構成之觸媒溶液進行處理使Pd觸媒附著 其上，將此觸媒活性化之後’藉由包含硫酸銅(8 g/Ι)、硫酸 157 本紙張尺度適用中國國家標準（CNS)A4規格（2〗〇 X 297公釐） (請先M讀背面之注意事項再填寫本頁) L§J· 線. 經濟部智慧財產局員工消費合作社印製 五、發明說明（4) 鎳(0_6 g/Ι)、檸檬酸（15 g/I)、次亞磷酸鈉(29 g/丨）、硼酸(31 g/Ι)、界面活性劑（日信化學工業製造之沙費諾魯465)(0.1 g/Ι)之pH = 9的無電解鍍敷浴來實施無電解鍍敷，而於導 體電路的全表面形成由Cu- Νι-Ρ合金所構成之粗化層 11(凹凸層）。接著，將其浸漬於包含氟硼化錫(0.1 mol/1)以 及硫脲（l.〇mol/l)之pH = 1.2、溫度50°C的無電解錫置換鍍 浴中，而於上述粗化層的表面設置厚度〇.3#m的Sn層。 (9)其次，於經過上述過程之基板的兩面，將厚度50 的熱硬化型聚烯烴樹脂層(住友3M製造，1592)，在進 行溫度50〜180°C昇溫的同時以壓力10 kg/cm2予以熱壓積層 ，而設置由聚烯烴系樹脂構成之層間樹脂絕緣層12(參照圖 30(d)” (10) 其次，以波長10.4/zm的CCh氣體雷射於聚烯烴系 樹脂所構成之層間樹脂絕緣層12設置直徑80//m的通孔用 開口 13。之後，使用氧電漿進行去污處理(參照圖30(e))。 (11) 其次，爲達成對層間樹脂絕緣層的表面洗淨以及 表面改良之目的，乃對藉由濺鍍形成之薄膜進行蝕刻。此 蝕刻係使用德田製造公司的CFS- 12Ρ- 100，對內部以氬 氣進行置換之後，於氣壓0.6Pa、基板溫度70°C、電力(RF) 200W，以及時間2分鐘的條件下進行之。 (12) 其次，使用相同之裝置，於氬氣周圍氣氛之下， 採用Ni濺鍍靶，而於氣壓〇.6Pa、基板溫度70°C、電力 (DC)400W，以及時間1分鐘的條件下進行濺鍍，而於聚烯 烴系層間樹脂絕緣層12之表面形成由Ni層構成之第1導 158 本紙張尺度適用中囷國家標準（CNS)A4規格〇?10 X 297公釐） ----------------- (請先閱讀背面之注意事項再填寫本頁) 訂_ •線- 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 453 1 4 1 a? _ B7 五、發明說明（β) 體層14a。此時形成之第1導體層14a的厚度係0.05#m。 (13) 其次，於第1導體層14a的上面藉由濺鍍形成由 Cu層構成之第2導體層14b(圖31(a))。又濺鍍之條件除了 電力(DC)4500W、時間2分鐘以外，其餘皆與第1導體層 14a的形成條件相同。此時所形成之Cu層的厚度係0.15 y m ° 又，自圖31(b)以後，係將第1導體層14a與第2導體 層14b合倂稱之爲14。 (14) 於結束上述處理之基板的兩面，貼上市售之感光 性乾式薄膜(尼季構摩頓公司製造，NIT- 215)，進而裝設 光罩，再以40 mJ/cm2進行曝光、0.8%碳酸氫鈉進行顯像處 理，從而形成厚度15 μm之防鍍膜16的圖案(參照圖31(b)) 〇 (15) 其次，以與記載於前述（1)之條件幾乎相同的條件 實施之電鍍，以形成厚度l〇#m之電鍍膜15。又，藉由此 電鍍膜15，則可增厚導體電路9之部分，且可對通孔17 部分進行電鍍塡充(參照圖31(c))。 (16) 再者，將防鑛膜16以5%之KOH剝離去除之後， 再將位於該防鍍膜16下方之第1導體層(Ni層）14a以及第 2導體層(Cu層)14b以硫酸-過氧化氫之混合水溶液藉由蝕 刻溶解去除之，而形成由第1導體層(Ni層）、第2導體層 (Cu層)以及電鍍銅膜15所構成之厚度10//m之導體電路 19(包含通孔17)(參照圖31(d))。 (17) 之後，於導體電路19(包含通孔17)上形成鍍鎳層 159 本紙張尺度適用中0國家標準（CNS)A4規格（2〗0 X 297公釐) ί 发--------訂·！------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 53 14 1 A7 B7 五、發明說明（θ) 20(圖32(a))，藉由重複(9Μ16)之過程，而進行多層化。又 ，於圖示中，在圖32(b)以後’係省略多層化之過程，而於 1層之層間樹脂絕緣層12及上層導體電路19上形成防焊 層(參照圖32(b)〜(c))。防焊層之形成方法係如下所述。 (18) 亦即，首先，與實施例12之（14)相同的方法調製 阻焊劑袓成物。其次，於多層電路基板的兩面，將上述阻 焊劑組成物塗佈20//m之厚度，而進行乾燥處理之後，將 成爲防焊層開口部部分之描繪有圖案的光罩使其密接於防 焊層，而以1000 m〗/cm2的紫外線進行曝光，再以DMTG溶 液予以顯像處理，從而形成開口。再者，以80°C1小時' 100°C1小時、120°C1小時、150°C3小時的條件進行加熱處 理使防焊層硬化，而形成具有開孔21、厚度20#m之阻焊 圖案層18(參照圖32(b))。 (19) 其次，將形成有阻焊圖案層18之基板’於氯化鎳 (30 gA)、次亞磷酸鈉(10 g /1)、檸檬酸鈉2 /1)構成之PH =5的無電解鍍鎳液中浸漬20分鐘，而於開孔21之底部形 成厚度之鍍鎳層。 再者，將該基板於氰化金鈣(2 g/Ι)、氯化錢(75 g/Ι)、 檸檬酸鈉(50 g/1)、次亞磷酸鈉（10 g/1)構成之無電解鍍敷液 中以93°C的條件浸漬23秒，而於鍍鎳層上形成厚度〇·〇3 # m之鍍金層22。又，於圖32(c)中’將形成之鍍鎳層及鍵金 層合倂而賦予符號22。 (20) 之後，於阻焊圖案層18之開孔21印刷焊接糊劑 ，於200°C藉由迴焊形成焊接凸塊(焊接體)23 ’而製造具有 160 本紙張尺度適用尹國國家標準（CNS)A4規格（2]0 X 297公釐） -------&quot;·------—訂--------線 (請先閱讀背面之注意事項再填寫本頁) 453 1 4 1 A7 B7 五、發明說明（d) 焊接凸塊23之多層印刷電路板(參照圖32(c))。 --------------ta--- {請先閱讀背面之注意事項再填寫本頁) 如此般製造多層印刷電路板之後，對蝕刻殘留之有無 進行觀察，其結果發現並無蝕刻殘留的情況。 [實施例33〜43] 除了使用下述表5之金屬來形成第1導體層14a及第 2導體層14b之外，其餘皆與實施例1相同方式製造多層 印刷電路板。 又，針對製造之多層印刷電路板，乃對蝕刻殘留之有 無進行觀察。其結果係示於表5。 表5 第1導體層之金屬 第2導體層之金屬 蝕刻之殘留 實施例33 Ni Sn Μ 實施例34 Ni Pb 無 實施例35 A1 Cu Μ 實施例36 A1 Pb 無 實施例37 A1 Sn ίΕ JSW 實施例38 A1 Fe Μ 實施例39 Ti Cu ίΕ j\w 實施例40 Ta Sn dnL m 實施例41 Co Cu Τ11Γ 實施例42 Nb Sn 實施例43 Cr Cu 4vrf 比較例6 Ni — 有 -線 經濟部智慧財產局員工消費合作社印製 如表5所示，所製造之多層印刷電路板皆無蝕刻殘留 的現象。 [比較例6] 與實施例32相同進行（1)〜(12)之過程，形成由Ni層所 161 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 五、發明說明（π ) 成之第1導體層14a之後’並不形成第2導體層14b，之後 ，與實施例丨相同般’乃進行使用感光性乾式薄膜之阻蝕 層的形成（14)以及電鍍(15)。 [實施例44] A. 無電解鍍敷用黏著劑之調製 係與實施例14相同之方法獲致無電解鍍敷用黏著劑。 B. 多層印刷電路板之製造方法 (1) 於厚度1mm之玻璃環氧樹脂或是BT(聚對苯二甲酸 乙酯)樹脂構成之基板101的兩面積層有銅箔1〇8， 而以此銅面積層板做爲起始材料(參照圖33(a))。首先，對 此銅面積層板進行鑽削孔，接著於形成防鍍膜之後，於此 基板施以無電解鍍敷處理以形成通孔109，再者，將銅范 藉由一般方法進行圖案狀的蝕刻，而於基板兩面形成內層 銅圖案(內層導體電路)ΚΗ。 將形成內層導體電路104之基板予以水洗、乾燥之後 ，以含有 Na〇H(10 g/1)、NaCl〇2(40 g/1)、Na3PCK6 g/Ι)之水 溶液爲氧化浴(黑化浴)進行氧化浴處理，而於包含通孔l〇9 之內層導體電路104的全表面形成粗化面104a、l〇9a(參照 圖 33(b))。 (2) 將以環氧樹脂做爲主成分之樹脂塡充劑，藉由 使用印刷機而塗佈至基板的兩面，使得內層導體電路1〇4 間或是通孔109內塡充該物，再進行加熱乾燥。亦即，藉 由此過程，樹脂塡充劑係塡充於內層導體電路1〇4間或是 通孔109之內(參照圖33(c))。 162 本紙張尺度適用中國國家標準（CNS)A4規格（2】〇 X 297公笼） — — — — — —--11 I I I Λ ----!| 訂--------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 53 14 1 A7 B7 五、發明說明（4/) (3) 將結束上述(2)處理之基板的單面，藉由使用帶式硏 磨機(三共理化學公司製造）進行帶式硏磨，使得內層導體 電路104表面或通孔109之焊墊表面以不留下樹脂塡充劑 110的方式予以硏磨，接著，爲去除因上述帶式硏磨所造 成之磨損乃進行拋光硏磨。此一連串的硏磨亦於基板的另 一面進行。然後，將塡充之樹脂塡充劑110加熱硬化之(參 照圖 33(d))。 藉此，將塡充於通孔109等之樹脂塡充劑110之表層 部以及內層導體電路104上面之粗化層l〇4a去除使得基板 的兩面平滑化，樹脂塡充劑110與內層導體電路104側面 透過粗化層104a而強固的密接，又通孔1〇9的內壁面與樹 脂塡充劑110則透過粗化面l〇9a強固地密接而得到此電路 基板。 (4) 再者，於外露之內層導體電路1〇4以及通孔109的 焊墊上面，形成厚度2/zm之由Cu —Ni —P構成的多孔質 合金粗化層111，再於此粗化層111的表面設置厚度0.3# m之Sn層(參照圖34(a))。然而，對於Sn層並未予圖示。 該粗化層111的形成方法係如下所述。亦即，對基板 予以鹼性脫脂而進行軟蝕刻，其次，以氯化鈀及有機酸構 成之觸媒溶液進行處理，而賦予Pd觸媒，以將此觸媒活性 化。 之後’於硫酸銅（3.2 Xl0_2mol/1)、硫酸鎳(2·4 Xl〇-3 mol/1)、檸檬酸（5‘2 Xl〇_2mol/1)、次亞磷酸鈉（2_7 χιό1 mol/1)、硼酸(5.0 Χ10·1 mol/1)、界面活性劑（日信化學工業 163 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -----&gt; -----— i 訂--------1 (請先閱讀背面之注意事項再填寫本頁) 4 經濟部智慧財產局員工消費合作社印製 53 1 4 1 A7 _____B7___ 五、發明說明（，Α) 製造之沙費諾魯465)(1.0 g/丨)之水溶液構成之pH = 9的無電 解鍍敷浴中實施無電解鏟敷，而於導體電路之全表面形成 由Cu—Ni —P構成之粗化層111。 再者，浸漬於含有氟硼化錫（0.1 mol/1)、硫脲（1.0 m〇m)之pH = 1.2、溫度50°C的無電解錫置換鍍浴中，而 於上述粗化層的表面設置厚度〇.3/zm的Sn層。 (5) 於基板的兩面，將上述A記載之組成的無電解鍍敷 用黏著劑使用輥軋機塗佈其上2次，而於水平狀態下放置 20分鐘之後，於6(TC乾燥300分鐘(參照圖34(b))。 (6) 於上述(5)形成之無電解鍍敷用黏著劑層之基板的兩 面，將印刷有直徑85μιη黑圓的光罩薄膜黏著其上，藉由 超高壓水銀燈產生的500 mJ/cm2強度來進行曝光。將此藉 由甘醇二甲醚(DMDG)溶液進行噴塗顯影，以使該黏著劑層 形成直徑85vm之通孔用開孔106。又，將該基板以超高 壓水銀燈產生的3000 m〗/cm2強度來進行曝光，之後藉由 100°C1小時、150°C5小時的加熱處理，乃形成具有開孔(通 孔形成用開孔106)之厚度18/im的層間樹脂絕緣層 102(102a' 102b)(參照圖34(c))。其中，該開孔之尺寸精度 的優異性係相當於光罩薄膜。 (7) 將形成有通孔形成用開孔106的基板浸漬於73°C之 鉻酸水溶液(700g)中20分鐘，以溶解去除存在於層間樹脂 絕緣層102表面之環氧樹脂粒子，而將其表面粗化，以得 到粗化面。之後，浸漬於中和溶液(西普雷公司製造）中並 水洗之(參照圖34(d))。 164 C請先閲讀背面之注意事項再填寫本頁) 訂- —線 本紙張尺度適用中0國家標準（CNS)A4規格（210 X 297公釐） 4 53141 a7 _ B7__ 五、發明說明（；1Λ) 再者，於經過粗化面處理之該基板的表面，藉由賦予 鈀觸媒(亞特提克公司製造），而於層間絕緣材質層102表 面及通孔用開孔106的內壁面附著觸媒核。 (8)其次，將基板浸漬於以下組成之無電解鍍銅水溶液 中，而於粗化面全體形成厚度之無電解鍍銅膜112( 參照圖35(a))。 [無電解鍍敷水溶液] EDTA 60 g/i 硫酸銅 10 g/1 HCHO 6 ml/1Sulfuric acid 180 gA Copper sulfate 80 g / 1 Additive (made by Attik, our product name: Kapallad GL) [Electrolytic plating conditions] 1 ml / 1 Current density 1 A / dm2 Time 30 minutes Temperature chamber Temperature (6) On both sides of the substrate forming the conductor circuit 9 and the conductor layer 10, a commercially available photosensitive dry film is pasted, a photomask is installed, and exposure is performed at 100 nJ / cm2 and 0.8% sodium bicarbonate. The developing process is performed to form a resist layer 8 having a thickness of 15 // m (see FIG. 24 (a)). (7) Next, the plating film of the portion where the resist layer 8 is not formed is dissolved and removed by using a mixed solution of sulfuric acid and hydrogen peroxide by etching, and the anti-cangworm layer 8 is peeled and removed at 5% KOH to form An independent conductor circuit 9 and a conductor layer (hereinafter, this conductor layer is referred to as an ore-covered layer) 10 covered with a conductive paste 5 (refer to FIG. 24 (b)). (8) Next, a roughened layer (concavo-convex layer) made of Cu-Ni-P alloy and having a thickness of 2'5ym is formed on the entire surface including the side surfaces of the conductor circuit 9 and the plating layer 10, and then the roughened layer 11 is formed there. An Sn layer with a thickness of 0.3em is provided on the surface (refer to FIG. 24 (0,311 layer is not shown). The formation method is as follows. That is, the substrate is subjected to acid degreasing. Standard (CNS) A4 specification (210 X 297 mm) ------------- 1 -------- Order --------- line "Please read first Note on the back, please fill in this page again) 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 53141 A7 ____B7______ 5. Description of the invention () and soft etching, followed by a catalyst solution composed of palladium chloride and organic acid After processing to give a Pd catalyst, the catalyst was activated by copper sulfate 8 g / 1, nickel sulfate 0.6 g / 1, citric acid 15 g / i, sodium hypophosphite 29 g / 1, and boric acid 31 g. / I. Surfactant (Shafenuru 465 manufactured by Nissin Chemical Industry) 0.1 g / 1 aqueous solution with an electroless plating bath of pH 2.9 for electroplating, and plating on conductor circuits 9 and plating Full-surface 10 forming a roughened layer 11 of Cu-Ni-Ρ alloy composed of. Next, a Cu-Sn substitution reaction was performed using an aqueous solution of tin fluoroboride 0.1 mol / 丨 and thiourea 1.0 mol / l at a temperature of 50 ° C and a pH of 1.2, and a thickness was set on the surface of the roughened layer 11 0.3 # m Sn layer (Sn layer is not shown). (9) On both sides of the substrate, a thermosetting polyolefin resin layer (manufactured by Sumitomo 3M, trade name: 1592) with a thickness of 50 / zm was hot-pressed at a pressure of 10 kg / cm2 while heating up at a temperature of M80t It is laminated to provide an interlayer resin insulating layer 12 made of a polyolefin resin (see Fig. 24 (d)). (10) Next, a CO 2 gas with a wavelength of 10.4 / zm is irradiated onto the polyolefin resin. The resin insulating layer 12 is provided with an opening 13 for a through hole having a diameter of 80 μm. Furthermore, the surface of the polyolefin-based resin insulating layer is decontaminated and treated with a plasma treatment of a mixed gas of CR and oxygen. Among the improved surfaces, It is confirmed that it has hydrophilic groups such as OH group, carbonyl group, and COOH group. In addition, the oxygen plasma treatment conditions are 800 W of electric power and 500 mTorr of air pressure for 20 minutes. (11) Next, a Ni sputtering target is used at a pressure of 0.6 Pa. , The temperature is 80 ° C, the power is 200W, and the sputtering is performed under the conditions of 5 minutes, the Ni film will be formed on the surface of the above-mentioned polyolefin-based resin insulating layer 12. At this time, the 150 paper size applies to the Chinese national standard (CNS ) A4 size (210 X 297 mm) I ------ Agriculture ---- ---- Order --- 1--ί line (please read the notes on the back before filling this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 53 141 a7 _B7_ V. Description of the invention (ie 1) The thickness of the Ni metal layer is 0.1 / zm. As shown in (25), on the lower Ni metal layer, the same conditions are used to form a thickness of 0.1 mm by sputtering. Copper layer. The device used for sputtering is SV-4540 manufactured by Japan Vacuum Technology Co., Ltd. (12) Next, the substrate of which (11) is finished is subjected to the aforementioned electroless plating. To form an electroless plated film 14 having a thickness of 0.7 # m (see FIG. 25 (a)). (13) The two surfaces of the substrate of the electroless plated film 14 formed by the above (12) are affixed to the market. A photosensitive dry film was further equipped with a photomask, and then exposed at 100 mJ / cm2 and developed with 0.8% sodium carbonate to provide a 15 #m thick resist coating 16 (see Fig. 25 (b)). (14) ) The electrolytic plating of the above (1) is performed to form an electrolytic plating film 15 having a thickness of 15 / zrn, thereby thickening the portion of the conductor circuit 9 and the portion of the through-hole 17 Electroplating was performed (see FIG. 25 (c)). Electroless plating was performed by dipping in an aqueous solution of nickel chloride 30 g / 1, sodium hypophosphite 10 g / 1, and sodium citrate 10 gA at pH = 5. In a nickel bath for 1 minute, a nickel plating layer 19 having a thickness of 0.1 #m was formed. (15) After the anti-plating film 16 was stripped and removed with 5% KOH, the Ni film and the non- The electrolytic plating film 14 is removed by etching and dissolving with a mixed solution of nitric acid and sulfuric acid / hydrogen peroxide to form a film having a thickness of 16 / zm composed of a Ni film, an electroless copper plating film 14, and an electrolytic copper plating film 15. Conductor circuit (including through hole 17) (see FIG. 25 (d)). (16) Furthermore, by repeating the above procedures (8) to (15), 151 multilayer circuits are obtained. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2! 0 X 297 mm) ------ ---- Shi ^ --------Order --------- Line! (Please read the precautions on the back before filling this page) 453141 Consumption Cooperation by Employees of Intellectual Property Bureau, Ministry of Economic Affairs, printed A7 ____B7_ V. Invention Description (β) Board (refer to Figure 26 (a)). Further, in the same manner as in (14) of Example 12, a resist composition was obtained. (17) Secondly, the multilayer circuit board obtained in the above (16) is sandwiched between a pair of coating rollers in a vertical upright state to apply a resist composition having a thickness of 20 mm. (18) Next, a drying process is performed at 70 ° C for 30 minutes, and then exposed to ultraviolet light of 1000 m / cm2, followed by DMTG development. Furthermore, heat treatment was performed under the conditions of 1 hour at 80 ° C, 1 hour at 100 ° C, 1 hour at 120 ° C, and 3 hours at 15CTC, and a part of the upper surface of the through hole, the pad, and the grid-shaped power supply layer was formed with an opening (opening) 200 # m) solder mask (thickness 20 / m) 18. (19) Next, the substrate is electrolessly plated with an aqueous solution of 2 g / 1 gold calcium cyanide, 75 g / 1 ammonium chloride, 50 g / 1 sodium citrate, and 10 g / 1 sodium hypophosphite. The solution was immersed in the liquid at 93 ° C for 23 seconds to form a gold plating layer 20 having a thickness of 0.03 / zm on the nickel plating layer. (20) Thereafter, a solder paste is printed on the opening of the solder resist layer 18 at 20 (TC to form a solder bump 21 by reflow, and a multilayer printed circuit board having the solder bump 21 is manufactured (see FIG. 26 (b). )). [Example 29] In this example, the polyolefin resin is TPX (trade name) manufactured by Mitsui Chemicals, and is decontaminated under the same oxygen plasma conditions as in Example 28. Then, The surface improvement was performed by irradiating ultraviolet rays for 30 to 60 seconds with a low-pressure mercury lamp to introduce a carbonyl group and a carbonyl group. In this example, in addition to Pd, the pressure was 0.6 Pa 'and the temperature was 100 ° C. 152 This paper is applicable to China Standard (CNS) A4 specification (210 X 297 male f) ϋ I —1 II n Ϊ n-d I * n ϋ I nn ^ ϋ I nn ϋ ϋ n I (Please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 A7 B? V. Description of the invention (6 丨) Power 200W and the thickness of 2 minutes under the condition of 0.1 # m outside the polyolefin resin insulation layer, The rest is a multilayer printed circuit board manufactured in the same manner as in Example 28. [Example 30] In this example, in addition to the polyolefin resin, in addition to using SPS (trade name) manufactured by Idemitsu Petrochemical, Ti was deposited under the conditions of a pressure of 0.6 Pa, a temperature of 100 ° C, a power of 200 W, and a time of 5 minutes. m to the polyolefin resin insulating layer and the conductor circuit, and the rest are manufactured in the same manner as in Example 28. [Example 31] In this example, Cr, Sn, and Cr were used instead of Ni. Except that Mo, W, and Fe were sputtered, the rest were manufactured in the same manner as in Example 28. The sputtering was performed at a pressure of 0.6 Pa, a temperature of 100 ° C, a power of 200 W, and time. A substance having a thickness of 0.1 was adhered to the surface of the polyolefin-based resin insulating layer and the conductor circuit under the condition of 2 minutes. The multilayer printed circuit board of the example manufactured in this manner was measured for its peel strength. The circuit board was set at -55. A 500-cycle test was performed at ° C to 125 ° C. In addition, after the 1C wafer was assembled, the presence or absence of migration was evaluated after being driven at room temperature for 1,000 hours under ambient ambient humidity of 100% relative humidity. Judgment is based on the presence of interlayer continuity. In addition, the minimum L / S that can be manufactured is investigated. The results are shown in Table 4. 153 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X M7 mm)-II --------- Agriculture --- II--Order ------- 11. ^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 1 4 1 ΑΊ B7 5. Description of the invention (A &gt;) Peel strength (kg / cm) Migration crack L / S (βΐΐΐ) Example 28 (Ni) 2.4 None None 15/15 Example 29 (Pd) 2.0 ^ τγΤ No Art No 15/15 Example 30 (Ti) 1.5 Μ 15/15 ^ Example 31-1 (Cr) 2.0 Hz / M, No 15/15 Example 31-2 (Sn) 2.0 Μ te yi «, 15/15 Example 3 1 · 3 (Μο) 2.0 Μ elder N 15/15 Example 31-4 (W) 1.5 Μ JrrT heat 15/15 It can be clearly seen from the results shown in Table 4 that the The circuit board of the embodiment can ensure sufficient peel strength regardless of whether or not a roughened surface is provided on the interlayer resin insulating layer. In addition, the circuit board of the embodiment is "irrespective of whether or not its heat release property is not good". Since the diffusion of copper is suppressed by metals such as Ni and Pd, migration does not occur and interlayer insulation can be ensured. That is, the thickened layers are formed on both sides of the resin substrate, and the metals selected from the 4th to 7th periods in Group 1B of the Periodic Table 4A to 4B Group (except Cu The conductor layer is formed of a metal layer composed of at least one of the metals, and thereby the present invention is effective. In addition, in the present invention, a fine circuit with L / S = 15/15 can be formed. [Example 32] (1) A copper foil 2 having a thickness of 18 / zm on both surfaces of a substrate 1 having a thickness of 0.8 mm and a thickness of 0.8 mm on a substrate 1 made of BT (biscis butadiene diamine triazabenzene) resin. As a starting material, a laminated board (trade name: HL830-0.8T12D manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used (see FIG. 29 (a)). First of all, this copper area of 154 paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm)! I ----- 1— R i 1 --------- 1-- -^ &lt; Please read the precautions on the back before filling in this page) A7 4 53 1 41 _B7_ V. Description of the invention (Laminated holes are drilled to form through holes (refer to Figure 29 (b)). Second, Pd—Sn The colloid was adhered to the surface, and electroless plating was performed under the following composition of an electroless plating solution and the following conditions to form an electroless plating film of 0.7 / im on the entire substrate. [Electrolytic plating solution] EDTA 150 g / 1 copper sulfate 20 g / 1 HCHO 30 ml / 1 NaOH 40 g / 1 a, α′- dioxin 20t [; n 80mg / 1 polyethylene glycol (PEG) 0.1 g / 1 [electroless plating Coating conditions] Liquid temperature of 70 ° C for 30 minutes. Furthermore, electrolytic copper plating was performed under an electrolytic plating aqueous solution with the following composition and the following conditions to form a copper plating film with a thickness of 15 μm. [Plating solution] sulfuric acid 180 g / 1 Copper sulfate 80 g / 1 additive (made by Attic Japan, trade name: Capalaseide GL) 1 ml / 1 [Plating conditions] Current density 1 A / dm2 Time 30 minutes Temperature Room temperature 155 sheets scale Use Chinese National Standard (CNS) A4 specification (2〗 0 X 297 public love) -------- I --------Order -------- line (please read the back first Please note that this page is to be filled out again) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 53141 a? The substrate (see FIG. 29 (c)) with the conductor layer 3 (including the through hole 3a) formed on the entire substrate is washed with water, and after drying, the substrate contains NaOH (20 g / 1) and NaClCb (50 g / 1). 'Oxidation bath (blackening bath) consisting of aqueous solution of Na3P〇4 (15_0 g / 1), and reduction bath consisting of aqueous solution containing NaOH (2.7 g / 1), NaBH ^ 10 g / 1). In the redox process, a roughened layer 4 is provided on the entire surface of the conductor layer 3 including the through hole 3a (see FIG. 29 (d)). (3) Next, a metal particle paste (manufactured by Dazda Electric Wire Co., Ltd., DD paste: non-conductive copper perforated copper paste) containing copper particles having an average particle diameter of 15 μm was filled into the through holes by screen printing. Within 3a, dry and harden at 10CTC for 30 minutes and 180 ° C for 2 hours. Next, the roughened layer 4 formed on the surface of the conductor layer 3 and the metal particle paste 5 overflowing from the through-hole 3a were passed through a belt honing paper (manufactured by Sankyo Ricoh Chemical Co., Ltd.) using a # 400 belt honing machine In addition, in order to remove the abrasion caused by this belt honing machine, polishing and honing are performed by AhCh honing or SiC honing particles to flatten the substrate surface (refer to the figure) 29 (e)). (4) A palladium colloid catalyst is applied to the flattened substrate surface as described in (3) above, and electroless plating is performed to form an electroless copper-plated film 6 having a thickness of 0.6 mm (see FIG. 29 (f)). ). (5) Next, copper plating is applied under the following conditions to form a copper plating film 7 with a thickness of 15 μm. In the process shown in Figure (30) described later, the portion that becomes the lower-layer conductor circuit 9 is thickened, and Formation of the portion to be the conductor layer 10 covered by the metal particle paste 5 filled in the through hole 3a. [Electroplating solution] 156 This paper size is applicable to China Gardener's Standard (CNS) A4 specification (2) 0 X 297 mm) ---------- I --- fixed .__ (Please read the Note: Please fill in this page again) Line '453 1 4 1 A7 B7 V. Description of the invention (π) Sulfuric acid 180 g / 1 Copper sulfate 80 g / l Additive (made by Attic Japan Co., Ltd., trade name: Capalaseide GL) 1 ml / 1 [Plating conditions] 1 Current density 1 A / dm2 Time 30 minutes Temperature Room temperature (6) On both sides of the substrate where the conductor circuit 9 and the conductor layer 10 are formed, a commercially available photosensitive dry film is affixed Then, a photomask was installed, and exposure was performed at 100 m / cm2 '0.8% sodium bicarbonate for development processing to form a resist layer 8 having a thickness of 15 # m (see FIG. 30 (a)). (7) Next, the plating film of the portion where the resist layer 8 is not formed is decomposed and removed using an aqueous solution of sulfuric acid and hydrogen peroxide, and the resist layer 8 is peeled off at 5% KOH to form an independent layer. The conductor circuit 9 and the conductor layer 10 covered with the metal particle paste 5 (see FIG. 30 (b)). (8) Next, a roughened layer (concavo-convex layer) made of Cu-Ni-P alloy and having a thickness of 2,5 μm is formed on the surface of the lower-layer conductor circuit 9 and the conductor layer 10 covered with the metal particle paste 5 丨Then, an Sn layer having a thickness of 0.3 is provided on the surface of the roughened layer 11 (see FIG. 30 (c)). The layers are formed as described below. Note that the Sn layer is not shown in FIG. 30 (c). That is, the substrate is subjected to acid degreasing and soft etching is performed. Next, a catalyst solution composed of palladium chloride and an organic acid is processed to attach a Pd catalyst thereon, and the catalyst is activated by including sulfuric acid. Copper (8 g / Ι), sulfuric acid 157 This paper is sized for the Chinese National Standard (CNS) A4 (2) 0 × 297 mm (please read the precautions on the back before filling this page) L§J · Line Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (4) Nickel (0_6 g / Ι), citric acid (15 g / I), sodium hypophosphite (29 g / 丨), boric acid (31 g / Ι), a surfactant (Safonolu 465 manufactured by Nissin Chemical Industry) (0.1 g / Ι), an electroless plating bath with a pH of 9 to perform electroless plating, and the entire surface of the conductor circuit A roughened layer 11 (concavo-convex layer) made of a Cu-Nm-P alloy is formed. Next, it was immersed in an electroless tin replacement plating bath containing tin borofluoride (0.1 mol / 1) and thiourea (1.0 mol / l) at a pH of 1.2 and a temperature of 50 ° C. An Sn layer having a thickness of 0.3 # m was provided on the surface of the chemical layer. (9) Next, on both sides of the substrate after the above process, a thermosetting polyolefin resin layer (manufactured by Sumitomo 3M, 1592) with a thickness of 50 was heated at a temperature of 50 to 180 ° C and a pressure of 10 kg / cm2 An interlayer resin insulating layer 12 made of a polyolefin resin is provided by thermocompression lamination (refer to FIG. 30 (d) "(10). Next, a CCh gas with a wavelength of 10.4 / zm is irradiated onto the polyolefin resin. The interlayer resin insulating layer 12 is provided with a through hole opening 13 having a diameter of 80 // m. After that, an oxygen plasma is used for decontamination treatment (see FIG. 30 (e)). (11) Next, in order to achieve the The purpose of surface cleaning and surface improvement is to etch the thin film formed by sputtering. This etching uses CFS-12P-100 of Tokuta Manufacturing Co., and replaces the inside with argon. The pressure is 0.6Pa, The substrate temperature was 70 ° C, the power (RF) was 200W, and the time was 2 minutes. (12) Secondly, using the same device, under a surrounding atmosphere of argon, a Ni sputtering target was used, and the gas pressure was 0. .6Pa, substrate temperature 70 ° C, power (DC) 400W, and time 1 minute Sputtering is performed under the conditions of a clock, and a first guide made of a Ni layer is formed on the surface of the polyolefin-based interlayer resin insulation layer 158. This paper size is applicable to the Chinese National Standard (CNS) A4 specification 〇 10 X 297 mm ) ----------------- (Please read the notes on the back before filling out this page) Order _ • Line-Printed by Intellectual Property of the Ministry of Economy Printed by the Bureau ’s Consumer Cooperative 453 1 4 1 a? _ B7 V. Description of the Invention (β) The body layer 14a. The thickness of the first conductor layer 14a formed at this time is 0.05 # m. (13) Next, on the first conductor layer The second conductor layer 14b (Fig. 31 (a)) composed of a Cu layer is formed on the upper surface of 14a by sputtering. The conditions of the sputtering are the same as those of the first conductor layer except for the power (DC) 4500W and the time 2 minutes. The formation conditions of 14a are the same. The thickness of the Cu layer formed at this time is 0.15 μm, and since FIG. 31 (b), the first conductor layer 14a and the second conductor layer 14b are combined to be called 14. 14) On both sides of the substrate on which the above-mentioned processing has been completed, a commercially-available photosensitive dry film (manufactured by Nikita Morton Co., Ltd., NIT-215) is attached, and then a photomask is installed, and then 40 mJ / cm2 was exposed, and 0.8% sodium bicarbonate was subjected to development processing to form a pattern of the plating resist 16 having a thickness of 15 μm (refer to FIG. 31 (b)). 〇 (15) Next, it is the same as described in (1) above. The plating is performed under almost the same conditions to form a plating film 15 having a thickness of 10 # m. Furthermore, by this plating film 15, the portion of the conductor circuit 9 can be thickened, and the portion of the through-hole 17 can be plated. Recharge (see Figure 31 (c)). (16) After removing the anti-mineral film 16 with 5% KOH, the first conductor layer (Ni layer) 14a and the second conductor layer (Cu layer) 14b located below the anti-plating film 16 are sulfuric acid. -A mixed aqueous solution of hydrogen peroxide is removed by etching to form a conductor circuit having a thickness of 10 // m composed of a first conductor layer (Ni layer), a second conductor layer (Cu layer), and a copper plating film 15 19 (including through hole 17) (see FIG. 31 (d)). (17) After that, a nickel-plated layer 159 is formed on the conductor circuit 19 (including the through hole 17). The paper size is applicable to the 0 National Standard (CNS) A4 specification (2〗 0 X 297 mm). --- Ordered! ------ line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 14 1 A7 B7 V. Description of the invention (θ) 20 (Figure 32 (a) ), By repeating the process of (9M16), multilayering is performed. In the illustration, after FIG. 32 (b), the process of multilayering is omitted, and a solder resist layer is formed on the interlayer resin insulating layer 12 and the upper conductor circuit 19 (see FIG. 32 (b) to (c)). The formation method of the solder resist is as follows. (18) That is, first, a solder resist formed product was prepared in the same manner as in (14) of Example 12. Next, the two sides of the multilayer circuit board were coated with the solder resist composition to a thickness of 20 // m, and after the drying process, a patterned photomask, which became the opening portion of the solder resist layer, was tightly attached to the solder resist. The solder layer is exposed with ultraviolet light of 1000 m / cm2, and then developed with a DMTG solution to form an opening. Furthermore, heat treatment was performed under conditions of 80 ° C for 1 hour, 100 ° C for 1 hour, 120 ° C for 1 hour, and 150 ° C for 3 hours to harden the solder resist layer to form a solder resist pattern layer having openings 21 and a thickness of 20 # m. 18 (refer to FIG. 32 (b)). (19) Next, the substrate on which the solder resist pattern layer 18 is formed is formed of nickel chloride (30 gA), sodium hypophosphite (10 g / 1), and sodium citrate 2/1). After being immersed in the electrolytic nickel plating solution for 20 minutes, a nickel plating layer having a thickness is formed on the bottom of the opening 21. Furthermore, the substrate was composed of gold calcium cyanide (2 g / 1), sodium chloride (75 g / 1), sodium citrate (50 g / 1), and sodium hypophosphite (10 g / 1). The electroless plating solution was immersed at 93 ° C. for 23 seconds to form a gold plating layer 22 having a thickness of 0.03 # m on the nickel plating layer. In Fig. 32 (c), the formed nickel plating layer and the bonding gold layer are combined with each other to designate a reference numeral 22. (20) After that, a solder paste is printed on the openings 21 of the solder resist pattern layer 18, and a solder bump (welded body) 23 'is formed by reflow soldering at 200 ° C. The paper size is 160 and the national standard of Yin State is applied. (CNS) A4 specification (2) 0 X 297 mm) ------- &quot; · ------- order -------- line (please read the precautions on the back before (Fill in this page) 453 1 4 1 A7 B7 V. Description of the invention (d) Multilayer printed circuit board with solder bump 23 (refer to Figure 32 (c)). -------------- ta --- {Please read the precautions on the back before filling this page) After manufacturing the multilayer printed circuit board in this way, observe the presence or absence of etching residues, and the results No etching residue was found. [Examples 33 to 43] A multilayer printed wiring board was manufactured in the same manner as in Example 1 except that the first conductive layer 14a and the second conductive layer 14b were formed using the metals in Table 5 below. The multilayer printed circuit board manufactured was examined for the presence or absence of etching residue. The results are shown in Table 5. Table 5 Residues of metal etching of the first conductor layer and metal etching of the second conductor layer Example 33 Ni Sn Μ Example 34 Ni Pb No Example 35 A1 Cu Μ Example 36 A1 Pb No Example 37 A1 Sn ΕΕ JSW Example 38 A1 Fe Μ Example 39 Ti Cu ίΕ j \ w Example 40 Ta Sn dnL m Example 41 Co Cu Τ11Γ Example 42 Nb Sn Example 43 Cr Cu 4vrf Comparative Example 6 Ni — Yes-Bureau of Intellectual Property, Ministry of Economics Printed by the employee consumer cooperative as shown in Table 5, the multilayer printed circuit boards manufactured have no etching residue. [Comparative Example 6] The process of (1) to (12) was performed in the same manner as in Example 32, and the paper layer formed by the Ni layer was 161. The paper size was applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Intellectual property of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau 453 1 4 1 V. Description of the invention (π) After the first conductive layer 14a is formed, the second conductive layer 14b is not formed. After that, the same as in the embodiment 丨 is performed using a photosensitive dry type Formation of a thin film resist layer (14) and electroplating (15). [Example 44] A. Preparation of Adhesive for Electroless Plating An adhesive for electroless plating was obtained in the same manner as in Example 14. B. Manufacturing method of multilayer printed circuit board (1) Copper foil 10 is applied to two areas of substrate 101 made of glass epoxy resin or BT (polyethylene terephthalate) resin with a thickness of 1 mm. A copper area laminate is used as a starting material (see FIG. 33 (a)). First, drill holes in this copper area laminate, and then, after forming an anti-plating film, apply electroless plating to this substrate to form through-holes 109, and then pattern the copper pattern by a general method. By etching, an inner-layer copper pattern (inner-layer conductor circuit) KK is formed on both sides of the substrate. The substrate on which the inner-layer conductor circuit 104 was formed was washed with water and dried, and then an aqueous solution containing NaOH (10 g / 1), NaClO2 (40 g / 1), and Na3PCK6 g / 1 was used as an oxidation bath (blackening) Bath), an oxidation bath treatment is performed, and roughened surfaces 104a, 10a are formed on the entire surface of the inner-layer conductor circuit 104 including the through-holes 10 (see FIG. 33 (b)). (2) A resin filler containing epoxy resin as the main component is applied to both sides of the substrate by using a printing machine, so that the inner conductor circuit 104 or the through hole 109 is filled with the object. , And then heat drying. That is, by this process, the resin filler is filled between the inner-layer conductor circuits 104 or the through-holes 109 (see Fig. 33 (c)). 162 This paper size applies to China National Standard (CNS) A4 specifications (2) 0X 297 male cage — — — — — — —-11 III Λ ----! | Order -------- line ( Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 14 1 A7 B7 V. Description of the invention (4 /) (3) The list of substrates processed in (2) above Surface, by using a belt honing machine (manufactured by Sankyo Ricoh Chemical Co., Ltd.) to perform belt honing, so that the surface of the inner layer conductor circuit 104 or the pad surface of the through-hole 109 is left without leaving the resin honing agent 110. Honing is followed by polishing honing to remove the wear caused by the belt honing described above. This series of honing is also performed on the other side of the substrate. Then, the resin-filled resin filler 110 is heat-hardened (see Fig. 33 (d)). With this, the surface layer portion of the resin filler 110 filled in the through hole 109 and the roughened layer 104a on the inner conductor circuit 104 is removed to smooth both sides of the substrate, and the resin filler 110 and the inner layer are smoothed. The side surface of the conductor circuit 104 is firmly adhered through the roughened layer 104a, and the inner wall surface of the through hole 109 and the resin filler 110 are firmly adhered through the roughened surface 10a to obtain the circuit substrate. (4) Furthermore, on the exposed inner layer conductor circuit 104 and the pads of the through-hole 109, a porous alloy roughened layer 111 made of Cu—Ni—P with a thickness of 2 / zm is formed, and then here An Sn layer having a thickness of 0.3 # m is provided on the surface of the roughened layer 111 (see FIG. 34 (a)). However, the Sn layer is not shown. The method for forming the roughened layer 111 is as follows. That is, the substrate is subjected to alkaline degreasing to perform soft etching, and then treated with a catalyst solution composed of palladium chloride and an organic acid to give a Pd catalyst to activate the catalyst. Afterwards, in copper sulfate (3.2 Xl0_2mol / 1), nickel sulfate (2.4 Xl0-3 mol / 1), citric acid (5'2 Xl0_2mol / 1), sodium hypophosphite (2_7 χιό1 mol / 1) Boric acid (5.0 × 10 · 1 mol / 1), surfactant (Nissin Chemical Industry Co., Ltd. 163 This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) ----- &gt;- ----— I Order -------- 1 (Please read the notes on the back before filling this page) 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 53 1 4 1 A7 _____B7___ V. Description of Invention (, Α) Safanoru 465) (1.0 g / 丨) produced by an aqueous solution of pH = 9 in an electroless plating bath, and electroless spatula was formed on the entire surface of the conductor circuit. —P is a roughened layer 111. Furthermore, it was immersed in an electroless tin replacement plating bath containing tin borofluoride (0.1 mol / 1) and thiourea (1.0 mm) at a pH of 1.2 and a temperature of 50 ° C. A Sn layer having a thickness of 0.3 / zm was provided on the surface. (5) On both sides of the substrate, apply the adhesive for electroless plating of the composition described in A above with a roll mill twice, and leave it for 20 minutes in a horizontal state, and then dry it at 6 (TC for 300 minutes ( (Refer to Fig. 34 (b)). (6) On both sides of the substrate of the adhesive layer for electroless plating formed in the above (5), a photomask film printed with a black circle having a diameter of 85 μm was adhered thereto, and the ultrahigh pressure was applied thereto. Exposure was performed at an intensity of 500 mJ / cm2 generated by a mercury lamp. This was spray-developed with a dimethyl ether (DMDG) solution to make the adhesive layer form a through-hole opening 106 with a diameter of 85 vm. The substrate was exposed at an intensity of 3000 m / cm2 generated by an ultra-high pressure mercury lamp, and then heated to 100 ° C for 1 hour and 150 ° C for 5 hours to form a thickness of 18 with openings (openings 106 for through-hole formation). / im The interlayer resin insulating layer 102 (102a '102b) (see FIG. 34 (c)). Among them, the excellent dimensional accuracy of the opening is equivalent to a photomask film. (7) A through-hole formation will be formed The substrate with the opening 106 was immersed in a chromic acid aqueous solution (700g) at 73 ° C for 20 minutes to dissolve and remove the The epoxy resin particles on the surface of the inter-resin insulating layer 102 are roughened to obtain a roughened surface. Then, they are immersed in a neutralization solution (manufactured by Shipley Corporation) and washed with water (see FIG. 34 (d)). ) 164 C Please read the precautions on the back before filling out this page.) Order-— The paper size of the thread is applicable in the national standard (CNS) A4 specification (210 X 297 mm) 4 53141 a7 _ B7__ 5. Description of the invention ( 1Λ) Furthermore, on the surface of the substrate subjected to the roughened surface treatment, a palladium catalyst (made by Attic) is provided on the surface of the interlayer insulating material layer 102 and the inside of the through-hole opening 106. A catalyst core is attached to the wall. (8) Next, the substrate is immersed in an electroless copper plating aqueous solution having the following composition, and an electroless copper plating film 112 is formed on the entire roughened surface to a thickness (see FIG. 35 (a)). [Aqueous electroless plating solution] EDTA 60 g / i Copper sulfate 10 g / 1 HCHO 6 ml / 1

NaOH 10 g/1 α,α’—聯二姬13定 80mg/l 聚乙二醇(PEG) 0.1 g/1 [無電解鍍敷條件] 60°C之液體溫度，20分鐘。 (9) 將市售之感光性乾式薄膜張貼於無電解鍍銅膜112 上，進而裝設光罩，再以UK) m〗/cm2進行曝光、0.8%碳酸 氫鈉進行顯像處理，從而設置防鍍膜103 (參照圖35(b))。 (10) 再者，以下述條件實施電鍍銅，形成厚度13#m 之電鍍銅膜113。 [電鍍水溶液] 硫酸 180 g/1 硫酸銅 80 g/1 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 165 本紙張尺度適用1f1國國家標準（CNS)A4規格（210 X 297公釐） --------------义___ (請先閱讀背面之注意事項再填乾本頁&gt; 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B7 五、發明說明（ 1 ml/1 [電鍍條件] 電流密度 1 A/dm2 時間 30.分鐘 溫度 室溫 (11) 再者，於氯化鎳(30 g/1)、次亞磷酸鈉（10 g/ι)、檸 檬酸鈉（10 g/ι )之水溶液(90°c)的無電解鍍鎳液中浸漬’而 於電鍍銅膜113上形成厚度1.2//m的鎳膜114(參照圖 35(c))。 (12) 將防鍍膜103以5%之KOH水溶液剝離去除之後， 再將位於該防鍍膜103下方之無電解鍍敷膜112以硫酸與 過氧化氫之混合液藉由蝕刻處理溶解去除之，而形成由無 電解鍍銅膜112及電鍍銅膜113及鎳膜114所構成之L/S = 28/28之厚度11/zm之上層導體電路105(包含通孔107)(參 照圖 35(d)) »NaOH 10 g / 1 α, α'-Linjiji 13mg 80mg / l Polyethylene glycol (PEG) 0.1 g / 1 [Electroless plating conditions] Liquid temperature at 60 ° C for 20 minutes. (9) Put a commercially available photosensitive dry film on the electroless copper-plated film 112, and then install a photomask, and then expose it at UK m / cm2, and perform development processing with 0.8% sodium bicarbonate. Anti-plating film 103 (see FIG. 35 (b)). (10) Furthermore, copper plating was performed under the following conditions to form a copper plating film 113 having a thickness of 13 #m. [Aqueous plating solution] Sulfuric acid 180 g / 1 Copper sulfate 80 g / 1 Additive (manufactured by Attic Japan Co., Ltd., trade name: Capalaseide GL) 165 This paper size is applicable to 1f1 National Standard (CNS) A4 specifications ( 210 X 297 mm) -------------- Yi ___ (Please read the precautions on the back before filling out this page &gt; Printed by the Ministry of Economic Affairs Intellectual Property Bureau Employee Consumer Cooperatives Printed by the Ministry of Economic Affairs Printed by the Intellectual Property Bureau Staff Consumer Cooperative 453 1 4 1 A7 B7 V. Description of the Invention (1 ml / 1 [Plating Conditions] Current Density 1 A / dm2 Time 30. Min. Temperature Room Temperature (11) Furthermore, on nickel chloride (30 g / 1), sodium hypophosphite (10 g / ι), sodium citrate (10 g / ι) aqueous solution (90 ° c), immersed in an electroless nickel plating solution, and deposited on the copper plating film 113 A nickel film 114 having a thickness of 1.2 // m is formed (see FIG. 35 (c)). (12) After the anti-plating film 103 is stripped and removed with a 5% KOH aqueous solution, the electroless plating film located below the anti-plating film 103 is removed. 112 is formed by dissolving and removing the mixed solution of sulfuric acid and hydrogen peroxide by etching to form an electroless copper plating film 112, an electroplated copper film 113, and a nickel film 114. L / S = 28/28 The thickness of 11 / zm of the upper layer conductor circuits 105 (including via holes 107) (see Fig. 35 (d)) »

(13) 其次，將結束上述(12)過程之基板浸漬於液溫25°C 、濃度6.0 mol/1鹽酸中3分鐘，以去除形成於表面之氧化 膜，之後，再進行相同於上述(4)的處理，而於上層導體電 路105的表面形成厚度2ίΐπι之Cu—Ni-P合金粗化層111 〇 (14) 接著，藉由重複上述(5H13)的過程，再形成上層 之上層導體電路105、通孔107，以及粗化層111，最後形 成具有開孔之防焊層115，而在進行鍍鎳膜116及鍍金膜 117形成之後，形成焊接凸塊118，而得到具有焊接凸塊 166 本紙張尺度適用中國國家標準（CNS&gt;A4規格（210 X 297公爱） I ------------又---- {請先閲讀背面之注意事項再填寫本頁) 幻· 線- 經濟部智慧財產局員工消費合作社印制衣 453 1 4 1 A7 B7 五、發明說明（β) 118之多層印刷電路板(參照圖36(a)〜圖37(c)) ° 又，於上述過程之中，亦於鍍鎳膜116形成之後，將 此基板浸漬於液溫25°c、濃度6·0 mol/i鹽酸中3分鐘’以 去除於表面形成之氧化膜。 [實施例45] 係於上述實施例44(11)之過程中，使用由硫酸鎳240 g/Ι、氯化鎳45 g/Ι、硼酸30 g/Ι構成之電鍍鎳浴’而於銅電 鍍膜上形成厚度〇·6 Am之電鍍鎳膜。 係於上述實施例44(13)之過程中，除了將經過上述(12) 過程之基板浸漬於液溫4〇°C、濃度4.0 mol/1鹽酸溶液中5 分鐘，以去除形成於表面之氧化膜之外’其餘皆與實施例 44相同來製造多層印刷電路板。 [實施例46] 係於上述實施例44(13)之過程中，除了將經過上述(12) 過程之基板浸漬於液溫2〇°C、濃度10.0 mol/1鹽酸溶液中1 分鐘，以去除形成於表面之氧化膜之外’其餘皆與實施例 44相同來製造多層印刷電路板。 [比較例7] 除了不實施上述實施例44(13)的過程以外’其餘皆與 實施例44相同來製造多層印刷電路板° [比較例8] 係於上述實施例44(13)之過程中’除了將經過上述(12) 過程之基板浸漬於液溫25°C、濃度4.0 mol/1硫酸水溶液中 5分鐘之外，其餘皆與實施例44相同來製造多層印刷電路 167 本紙張尺度適用中國國家標準（CNS)A4規格（2〗0 X 297公釐） -mill — — — —— — — --------^ . ---I I ----- (請先閱讀背面之注意事項再填寫本頁) 4 5314】 A7 _ B7 五、發明說明（#) 板。 [比較例9] 係於上述實施例44(13)之過程中，除了將經過上述(12) 過程之基板浸漬於液溫25°C、濃度6.0 mol/Ι磷酸水溶液中 5分鐘之外，其餘皆與實施例44相同來製造多層印刷電路 板。 [比較例10] 係於上述實施例44(13)之過程中，除了將經過上述（12) 過程之基板浸漬於液溫25t、濃度3.0 mol/1硝酸水溶液中 5分鐘之外，其餘皆與實施例44相同來製造多層印刷電路 板。 針對自以上實施例44~46及比較例7〜10所得之多層印 刷電路板，乃於Cu_Ni-P合金粗化層貼上黏著膠帶，再 加以剝除，以就粗化層是否有剝落的發生確認之。 又，於-55°C~125°C進行1000次之熱循環試驗，而藉由 光學顯微鏡來觀察Ni膜與Cu-Ni-P合金粗化層間有無剝 離的發生。其結果係示於下面之表6。 表6 _ _ 經濟部智慧財產局員工消費合作社印製 剝落的有無 剝離的有無 實施例44 jfnt 無 jfrrr. Ν1Γ VI、、 實施例45 並 Ate ΤΤΠΓ i 1 實施例46 Μ *E t 1 比較例7 有 有 比較例8 有 有 比較例9 有 有 比較例10 有 有 168 -1 ----------丄--------訂----------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國囷家標準（CNS)A4規格（210^ 297公釐） 4531 4 1 A7 經濟部智慧財產局員工消費合作杜印製 B7 五、發明說明（似） 由上述表6之結果可明顯地看出’實施例之多層印刷 電路板具有大的剝離強度，將構成導體電路5或通孔焊墊 7之鎳膜14上的氧化膜藉由具有濃度2.(M〇.〇 mol/1之還原 性酸之水溶液去除，則於實證上發現可確保導體電路等與 其上彤成之Cu- Ni-P合金粗化層間的密接性’另外亦可 防止由於在上述鎳膜上形成有氧化膜而造成導體電路的剝 離。 另一方面，發現於比較例：M0製造之多層印刷電路板 ，其由於上述鍍鎳膜上形成有氧化膜而造成其剝離強度小 ，使得Cu-Ni —P粗化層易於剝離。 [實施例47] A. 無電解鍍敷用黏著劑之調製 係與實施例14相同之方法獲致無電解鍍敷用黏著劑。 B. 多層印刷電路板之製造方法 (1)於厚度1mm之玻璃環氧樹脂或是BT(聚對苯二甲 酸乙酯)樹脂構成之基板101的兩面積層有18/zm銅箔1〇8 ’而以此銅面積層板做爲起始材料(參照圖38(a))。首先， 對此銅面積層板進行鑽削孔’接著於形成防鍍膜之後，於 此基板施以無電解鏡敷處理以形成通孔1〇9，再者，將銅 范藉由一般方法進行圖案狀的蝕刻，而於基板兩面形成內 層銅圖案(下層導體電路）104。 將形成下層導體電路104之基板予以水洗、乾燥之後 ，以含有 NaOH(10 g/1)、NaCl〇2(4〇 g/i)、Na3p〇4(6 g/1)之水 169 L紙張尺度適用中國國家標準（CNS)A4規格（2】0 x 297公餐 —t-Λ---—----訂·--I---— 線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 53 1 41 a? B7 五、發明說明（iti ) 溶液爲氧化浴(黑化浴)進行氧化浴處理，而於包含通孔109 之下層導體電路104的全表面形成粗化面104a、109a(參照 圖 38(b))。 (2) 將以環氧樹脂做爲主成分之樹脂塡充劑110,藉由 使用印刷機而塗佈至基板的兩面，使得下層導體電路104 間或是通孔109內塡充該物，再進行加熱乾燥。亦即，藉 由此過程，樹脂塡充劑係塡充於下層導體電路104間或是 通孔109之內(參照圖38(c))。 (3) 將結束上述(2)處理之基板的單面，藉由使用帶式硏 磨機（三共理化學公司製造)進行帶式硏磨，使得下層導體 電路104表面或通孔109之焊墊表面以不留下樹脂塡充劑 110的方式予以硏磨，接著，爲去除因上述帶式硏磨所造 成之磨損乃進行拋光硏磨。此一連串的硏磨亦於基板的另 一面進行。然後，將塡充之樹脂塡充劑110加熱硬化之(參 照圖 38(d))。 藉此，將塡充於通孔109等之樹脂塡充劑110之表層 部以及下層導體電路104上面之粗化層104a去除使得基板 的兩面平滑化，樹脂塡充劑110與下層導體電路104側面 透過粗化層l〇4a而強固的密接著，又通孔109的內壁面與 樹脂塡充劑110則透過粗化面109a強固地密接而得到此電 路基板。 (4) 將經過上述(3)過程之基板，浸漬於包含氯化鎳(30 gA)、次亞磷酸鈉（10 g/Ι)、檸檬酸鈉（10 g/丨）之水溶液(90°C) 的無電解鍍鎳液中，而於下層導體電路104的上面及通孔 170 本紙張尺度適用中國國家標準（CNS)A4規格（210 497公釐） ( I--*《.11-----訂.！--1線 (請先閱讀背面之注音Ϊ事項再填寫本頁) A7 453 1 4 1 ____B7___ 五、發明說明（Μ) 109的焊墊上面形成厚度i.2#m之鎳被覆層Ilia。 (5) 再者，於外露之導體電路104以及通孔109的焊墊 上面的鎳層上，形成厚度之由Cu-Ni-P構成的針 狀或多孔質合金粗化層111b，再於此粗化層111b的表面設 置厚度〇.3#m之Sn層(參照圖39(a))。然而，對於Sn層並 未予圖示。 該粗化層111b的形成方法係如下所述。亦即，對基板 予以鹼性脫脂而進行軟蝕刻，其次，以由氯化鈀及有機酸 構成之觸媒溶液進行處理，而賦予Pd觸媒，將此觸媒活性 化之後’於硫酸銅（3.2 X10_2mol/1)、硫酸鎳（2.4 X10·3 mol/1)、檸檬酸(5.2 X 10_2 mol/1)、次亞磷酸鈉(2.7 X 101 mol/1)、硼酸(5.〇 xi〇_l m〇l/l)、界面活性劑（日信化學工業 製造之沙費諾魯465)(1.0 g/Ι)之水溶液構成之pH = 9的無電 解鍍敷銅浴中置入基板，於浸漬2分鐘後開始以1秒1次 的速率於縱方向使其振動，而於銅導體電路104及通孔 109的焊墊表面的鎳層上設置厚度的由Cu-Ni —P構 成之針狀或多孔質狀的合金粗化層111b。再者，於含有氟 硼化錫 0.1 m〇l/l、硫脲 1.0 m〇l/l，溫度 35°C，pH = 1.2 的條 件下進行Cii-Sn置換反應，而於粗化層的表面設置厚度 0.3/zm的Sn層(未圖示）。 (6) 於基板的兩面，將上述a記載之組成的無電解鍍敷 用黏著劑使用輥軋機塗佈其上2次，而於水平狀態下放置 20分鐘之後，於60°C乾燥3〇〇分鐘(參照圖39(b))。 (7) 於上述(6)形成之無電解鍍敷用黏著劑層之基板的兩 __ 171 ί張尺度適用中國國家標準（CNs)/vi規格（2〗〇χ 297公釐) ---^ i — — — — — — ^111 11^. (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 53141 a? B7 五、發明說明（ 面，將印刷有直徑85ym黑圓的光罩薄膜黏著其上，藉由 超高壓水銀燈產生的500 m〗/cm2強度來進行曝光。將此藉 由甘醇二甲醚(DMDG)溶液進行噴塗顯影，以使該黏著劑層 形成直徑85/zm之通孔所成之開口。又，將該基板以超高 壓水銀燈產生的3000 mJ/cm2強度來進行曝光，再藉由1〇〇 °C ' 1小時，以及之後150°C、5小時的加熱處理，乃形成 具有開孔(通孔用開口 106)之厚度18/zm的層間樹脂絕緣層 102(102a、102b)(參照圖39(c))。其中，該開孔的尺寸精度 係相當於光罩薄膜般優異。 (8) 將形成有通孔用開口 106的基板浸漬於73°C之鉻酸 水溶液(7500 g/Ι)中20分鐘，以溶解去除存在於層間樹脂絕 緣層102表面之環氧樹脂粒子，而將其表面粗化，以得到 粗化面。之後，浸漬於中和溶液(西普雷公司製造）中再水 洗之(參照圖39(d))。 再者，於經過粗化面處理之該基板的表面，藉由賦予 鈀觸媒(亞特提克公司製造），而於層間樹脂絕緣層102表 面及通孔用開口 106的內壁面附著觸媒核。 (9) 其次，將基板浸漬於以下組成之無電解鍍銅水溶液 中，而於粗化面全體形成厚度〇.8^m之無電解鍍銅膜112( 參照圖40(a))。 [無電解鍍敷水溶液] EDTA 50 g/1 硫酸銅 10 g/1 HCHO 10 ml/1 172 本紙張尺度適用中國國家標準（CMS)A4規格（210 X 297公釐） --------------X 1 I (請先閲讀背面之注意事項再填寫本頁) *·δΊ. 線- 經濟部智慧財產局負工消費合作社印製 經濟部智慧財產局員工消費合作杜印製 53141 a? __B7 ___ 五、發明說明（iV)(13) Secondly, immerse the substrate after the above (12) process in a liquid temperature of 25 ° C and a concentration of 6.0 mol / 1 hydrochloric acid for 3 minutes to remove the oxide film formed on the surface, and then perform the same as the above (4) ) To form a Cu-Ni-P alloy roughened layer with a thickness of 2 ΐ 2 μm on the surface of the upper-layer conductor circuit 105. Next, by repeating the process of (5H13) above, an upper-layer conductor circuit 105 is formed. , Through hole 107, and roughened layer 111, a solder resist layer 115 having openings is finally formed, and after forming nickel plating film 116 and gold plating film 117, solder bumps 118 are formed to obtain 166 solder bumps. Paper size applies to Chinese national standard (CNS &gt; A4 specification (210 X 297 public love) I ------------ Again ---- {Please read the precautions on the back before filling this page) Magic · Line-Printed clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 A7 B7 V. Description of the invention (β) 118 multilayer printed circuit board (refer to Figure 36 (a) ~ Figure 37 (c)) ° Also, In the above process, after the nickel plating film 116 was formed, the substrate was immersed at a liquid temperature of 25 ° c and a concentration of 6.0 mol / i. Acid 3 minutes' to remove the oxide film on the surface. [Example 45] In the process of the above Example 44 (11), a copper electroplating nickel bath composed of 240 g / l of nickel sulfate, 45 g / l of nickel chloride, and 30 g / l of boric acid was used for copper electrolysis. An electroplated nickel film having a thickness of 0.6 Am was formed on the plating film. In the process of the above Example 44 (13), in addition to immersing the substrate after the above (12) process in a liquid temperature of 40 ° C and a concentration of 4.0 mol / 1 hydrochloric acid solution for 5 minutes, in order to remove the oxidation formed on the surface Except for the film, the rest were the same as in Example 44 to manufacture a multilayer printed circuit board. [Example 46] In the process of the above Example 44 (13), except that the substrate subjected to the above (12) process was immersed in a liquid temperature of 20 ° C and a concentration of 10.0 mol / 1 hydrochloric acid solution for 1 minute to remove The rest of the oxide film formed on the surface was the same as in Example 44 to manufacture a multilayer printed circuit board. [Comparative Example 7] A multilayer printed circuit board was manufactured in the same manner as in Example 44 except that the process of Example 44 (13) was not carried out. [Comparative Example 8] In the process of Example 44 (13) above 'Except that the substrate subjected to the above (12) process was immersed in a liquid temperature of 25 ° C and a concentration of 4.0 mol / 1 aqueous sulfuric acid solution for 5 minutes, the rest were the same as in Example 44 to manufacture a multilayer printed circuit. 167 This paper is applicable to China National Standard (CNS) A4 Specification (2〗 0 X 297 mm) -mill — — — — — — — -------- ^. --- II ----- (Please read the Please fill in this page again for attention) 4 5314] A7 _ B7 V. Invention Description (#) board. [Comparative Example 9] In the process of the above Example 44 (13), except that the substrate subjected to the above (12) process was immersed in a liquid temperature of 25 ° C and a 6.0 mol / I phosphoric acid aqueous solution for 5 minutes, the rest A multilayer printed circuit board was manufactured in the same manner as in Example 44. [Comparative Example 10] In the process of Example 44 (13), except that the substrate subjected to the process (12) was immersed in a liquid temperature of 25t and a concentration of 3.0 mol / 1 nitric acid solution for 5 minutes, the rest were Example 44 was the same to manufacture a multilayer printed circuit board. For the multilayer printed circuit boards obtained from the above Examples 44 to 46 and Comparative Examples 7 to 10, an adhesive tape was attached to the roughened layer of the Cu_Ni-P alloy, and then stripped to determine whether the roughened layer was peeling. Confirm it. In addition, a thermal cycle test was performed at -55 ° C to 125 ° C for 1,000 times, and the occurrence of peeling between the Ni film and the roughened layer of the Cu-Ni-P alloy was observed with an optical microscope. The results are shown in Table 6 below. Table 6 _ _ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives with or without peeling. Example 44 jfnt No jfrrr. Yes Comparative Example 8 Yes Comparative Example 9 Yes Comparative Example 10 Yes 168 -1 ---------- 丄 -------- Order ---------- Line (please read the notes on the back before filling this page) This paper size is applicable to the Chinese family standard (CNS) A4 specification (210 ^ 297 mm) 4531 4 1 A7 Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Du printed B7 V. Description of the invention (It seems) From the results in Table 6 above, it is obvious that the multilayer printed circuit board of the embodiment has a large peeling strength and will oxidize the nickel film 14 constituting the conductor circuit 5 or the through-hole pad 7. The film was removed by an aqueous solution of a reducing acid having a concentration of 2.0 (mol. Mol / 1), and it was found empirically that the adhesion between the conductor circuit and the roughened layer of the Cu-Ni-P alloy formed thereon can be ensured. 'It also prevents peeling of the conductor circuit caused by the oxide film formed on the nickel film. On the other hand, Comparative Example: A multilayer printed circuit board manufactured by M0, which has a small peel strength due to the formation of an oxide film on the nickel-plated film, makes the Cu-Ni-P roughened layer easy to peel. [Example 47] A. The preparation of the adhesive for electroless plating was obtained in the same manner as in Example 14. B. The method for producing an electroless plating adhesive. (1) Manufacturing method of a multilayer printed circuit board (1) Glass epoxy resin with a thickness of 1 mm or BT ( Polyethylene terephthalate) resin-based substrate 101 has two areas of 18 / zm copper foil 108 'and this copper area laminate is used as a starting material (see FIG. 38 (a)). First, This copper area laminate is drilled with holes. Then, after the anti-plating film is formed, the substrate is subjected to an electroless mirror coating process to form a through hole 109. Furthermore, the copper pattern is etched in a pattern by a general method. An inner layer copper pattern (lower conductor circuit) 104 is formed on both sides of the substrate. The substrate forming the lower conductor circuit 104 is washed with water and dried, and then contains NaOH (10 g / 1), NaClO2 (40 g / i). ), Na3p〇4 (6 g / 1) water 169 L paper size applies Chinese National Standard (CNS) A4 regulations (2) 0 x 297 public meals—t-Λ --------- Order · --I ---— line (please read the precautions on the back before filling this page) Staff Consumption of Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative 4 53 1 41 a? B7 V. Description of the invention (iti) The solution is an oxidation bath (blackening bath) for an oxidation bath treatment, and a roughened surface 104a is formed on the entire surface of the conductor circuit 104 below the through hole 109 And 109a (see FIG. 38 (b)). (2) A resin filler 110 containing epoxy resin as a main component is applied to both sides of the substrate by using a printing machine, so that the lower conductor circuit 104 or the through hole 109 is filled with the object, and then Heat-dried. That is, by this process, the resin filler is filled between the lower-layer conductor circuits 104 or the through-holes 109 (see Fig. 38 (c)). (3) The single side of the substrate on which the above (2) processing is finished is subjected to a belt honing by using a belt honing machine (manufactured by Sankyo Ricoh Chemical Co., Ltd.) so that the pads on the surface of the lower conductor circuit 104 or the through-hole 109 The surface is honed in such a manner that the resin honing filler 110 is not left. Next, polishing honing is performed to remove the wear caused by the belt honing described above. This series of honing is also performed on the other side of the substrate. Then, the resin-filled resin filler 110 is heat-hardened (see FIG. 38 (d)). Thereby, the surface layer of the resin filler 110 filled in the through hole 109 and the roughened layer 104a on the lower conductor circuit 104 are removed to smooth both sides of the substrate, and the resin filler 110 and the side of the lower conductor circuit 104 are smoothed. The circuit board is obtained by the strong adhesion through the roughened layer 104a, and the inner wall surface of the through hole 109 and the resin filler 110 are firmly adhered through the roughened surface 109a. (4) The substrate subjected to the above (3) process is immersed in an aqueous solution (90 ° C) containing nickel chloride (30 gA), sodium hypophosphite (10 g / 1), and sodium citrate (10 g / 丨). ) In the electroless nickel plating solution, and on the upper conductor circuit 104 and the through hole 170 of this paper, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 497 mm) (I-* 《. 11 --- --Order.!-1 line (please read the phonetic notes on the back before filling this page) A7 453 1 4 1 ____B7___ V. Description of the invention (Μ) 109 The thickness of nickel on the pad is i.2 # m Coating layer Ilia. (5) Furthermore, a needle-like or porous alloy roughened layer 111b made of Cu-Ni-P is formed on the nickel layer on the exposed conductive circuit 104 and the pads of the through-hole 109. Then, an Sn layer with a thickness of 0.3 # m is provided on the surface of the roughened layer 111b (see FIG. 39 (a)). However, the Sn layer is not shown. The method for forming the roughened layer 111b is as follows. That is, the substrate is subjected to alkaline degreasing and then subjected to soft etching, followed by treatment with a catalyst solution composed of palladium chloride and an organic acid to give a Pd catalyst and activate the catalyst. In copper sulfate (3.2 X10_2 mol / 1), nickel sulfate (2.4 X10 · 3 mol / 1), citric acid (5.2 X 10_2 mol / 1), sodium hypophosphite (2.7 X 101 mol / 1), boric acid (5. 〇xi〇_lm〇l / l), an electroless copper plating bath having a pH value of 9 composed of an aqueous solution of a surfactant (safenurol 465 manufactured by Nissin Chemical Industry Co., Ltd. (1.0 g / l)) The substrate was vibrated in the longitudinal direction at a rate of 1 second after immersion for 2 minutes, and a thickness of Cu-Ni-P was formed on the nickel layer on the surface of the pad of the copper conductor circuit 104 and the through-hole 109. Needle-like or porous alloy roughened layer 111b. Furthermore, under conditions containing 0.1 mol / l tin borohydride, 1.0 mol / l thiourea, temperature 35 ° C, pH = 1.2 A Cii-Sn substitution reaction is performed, and a Sn layer (not shown) having a thickness of 0.3 / zm is provided on the surface of the roughened layer. (6) On both sides of the substrate, an electroless plating adhesive having the composition described in a above is used. It was applied twice with a roll mill, and after being left in a horizontal state for 20 minutes, it was dried at 60 ° C. for 3,000 minutes (see FIG. 39 (b)). (7) The electroless solution formed in the above (6) Substrate for plating adhesive layer __ 171 The scale is applicable to Chinese National Standards (CNs) / vi specifications (2 〖〇χ 297mm) --- ^ i — — — — — — ^ 111 11 ^. (Please read the notes on the back before filling This page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53141 a? B7 V. Description of the invention (the surface, a mask film printed with a black circle with a diameter of 85ym is adhered to it, and 500 m produced by an ultra-high-pressure mercury lamp} / cm2 intensity for exposure. This was spray-developed by a solution of glycol dimethyl ether (DMDG), so that the adhesive layer formed an opening formed by a through hole having a diameter of 85 / zm. In addition, the substrate was exposed at an intensity of 3000 mJ / cm2 generated by an ultra-high pressure mercury lamp, and then subjected to a heat treatment at 100 ° C 'for 1 hour, and then 150 ° C and 5 hours to form an open hole ( The interlayer resin insulating layer 102 (102a, 102b) having a thickness of 18 / zm for the through-hole opening 106) (see FIG. 39 (c)). Among them, the dimensional accuracy of the opening is as excellent as that of a mask film. (8) The substrate having the through-hole opening 106 formed therein was immersed in a chromic acid aqueous solution (7500 g / 1) at 73 ° C for 20 minutes to dissolve and remove epoxy particles existing on the surface of the interlayer resin insulating layer 102, and The surface is roughened to obtain a roughened surface. After that, it was immersed in a neutralization solution (manufactured by Shipley Corporation) and washed with water (see Fig. 39 (d)). Furthermore, on the surface of the substrate subjected to the roughened surface treatment, a catalyst was attached to the surface of the interlayer resin insulating layer 102 and the inner wall surface of the through-hole opening 106 by applying a palladium catalyst (manufactured by Attic). nuclear. (9) Next, the substrate was immersed in an electroless copper plating aqueous solution having the following composition, and an electroless copper plating film 112 having a thickness of 0.8 m was formed on the entire roughened surface (see FIG. 40 (a)). [Aqueous solution without electroplating] EDTA 50 g / 1 copper sulfate 10 g / 1 HCHO 10 ml / 1 172 The paper size is applicable to Chinese National Standard (CMS) A4 (210 X 297 mm) ------- ------- X 1 I (Please read the notes on the back before filling out this page) * · δΊ. Line-Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, and printed by the Intellectual Property Bureau of the Ministry of Economic Affairs. 53141 a? __B7 ___ V. Description of the Invention (iV)

NaOH 6 g/1 α，α’—聯二Ith陡 80mg] 聚乙二醇(PEG) 0.1 g/1 [無電解鍍敷條件] 70°C之液溫，15分鐘。 (10) 將市售之感光性乾式薄膜U2張貼上去’進而裝 設光罩，再以100 ml/cm2進行曝光、〇.8%碳酸氳鈉進行顯 像處理，從而設置防鍍膜103 (參照圖40(b))。 (11) 再者，以下述條件實施電解鍍銅，形成厚度 m之電解鍍銅膜1Π(參照圖40(c)) ° [電解電鍍水溶液] 硫酸 180 g/1 硫酸銅 80 g/1 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 1 ml/1 [電解電鍍條件] 電流密度 1 A/dm2 時間 30分鐘 溫度 室溫 (12) 將防鍍膜103以5%之K0H水溶液剝離去除之後’ 再將位於該防鍍膜103下方之無電解鍍敷膜112以硫酸與 過氧化氫之混合液藉由蝕刻處理溶解去除之，而形成由無 電解鍍銅膜112及電解鑛銅膜113所構成之L/s = 28/28之 厚度之上層導體電路1〇5(包含通孔107) ° 173 _____ (請先閱讀背面之注意事項再填寫本頁) 訂· --線. 本紙張尺度適用中國囷家標準（CNS)A4規格（2〗0 X 297公釐） 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B7 五、發明說明（\Ί〇 再者，浸漬於氯化鎳(30 g/1)、次亞磷酸鈉（10 g/1)、檸 檬酸鈉（1〇 g/Ι )之水溶液(90°c)的無電解鍍鎳液中，而於導 體電路全面以及通孔焊墊全面形成厚度1.2/zm的鎳被覆層 llla(參照圖 40(d))。 (13) 對形成有上層導體電路105及鎳被覆層Ilia的基 板進行相同於上述(5)的處理，而於上層導體電路105的表 面形成厚度之由Cu —Ni-P構成之合金粗化層111M 參照圖41(a))。又，於含有氟硼化錫〇·1 mol/Ι、硫腺1_〇 mol/1，溫度35°C，pH = 1.2的條件下進行Cu—Sn置換反應 ，而於粗化層的表面設置厚度0.3 Am的Sn層(未圖示” (14) 藉由重複上述(6H13)的過程，再形成上層導體電 路(參照圖41(b)〜圖42(d))，此處雖未予圖示，最後係形成 具有開孔之防焊層，而在進行鍍金處理之後’形成焊接凸 塊，而得到具有焊接凸塊之多層印刷電路板。 [實施例48] 除了將過程（12)以下述方式取代之外’其餘皆與實施 例47相同來製造多層印刷電路板° (12)在實施電解鍍銅之後，再進—步，將基板浸漬於 硫酸鎳(240 g/Ι)、氯化鎳(45 g/Ι)、硼酸〇〇 g/Ι)之水溶液所構 成之pH = 4.5的鍍浴，而於溫度55土5°c、電流密度 4A/dm2的條件下，對做爲陽極的Ni板施以電鍍鎳，而形成 厚度0.8vm的鎳被覆層。 再者，將防鍍膜1〇3以5%之KOH水溶液剝離去除之 後，再將位於該防鑛膜103下方之無電解鍍敷膜丨12以硫 174 本紙張尺度適用中國國家標準（CNS&gt;A4規格（210 X 297公釐） ----I-----------------訂---------* 線 &lt;請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 453141 五、發明說明（η)) 酸與過氧化氫之混合液藉由餓刻處理溶解去除之’而形成 由無電解鑛銅膜112及電解鑛銅膜113所構成之L/S = 28/28之厚度之上層導體電路105(包含通孔107)(參 照圖43(a)” 又，於圖43(a)所示之基板上再形成新的上層導體電路 時，其情形係如圖43(b)。 [比較例11] 除了未形成鎳被覆層以外，其餘皆與實施例47相同之 方法來製造多層印刷電路板。 [實施例49] 除了取代掉鎳層而改以無電解鍍敷來形成厚度l.lvm 之錫層以外，其餘皆與實施例47相同之方法來製造多層印 刷電路板。電鑛液具有以下之組成及溫度° 檸檬酸鈉 0J4 mol/i EDTA 0.04 mol/1 氯化錫 0.04 mol/1 醋酸鈉 0.12 mol/1 氯化鈦 0.029 mol/1NaOH 6 g / 1 α, α'-biphenyl Ith steep 80mg] polyethylene glycol (PEG) 0.1 g / 1 [electroless plating conditions] at a liquid temperature of 70 ° C for 15 minutes. (10) Put a commercially available photosensitive dry film U2 on it, install a photomask, and then expose it at 100 ml / cm2, and develop the 0.8% sodium carbonate to develop a resist film 103 (see figure 40 (b)). (11) Furthermore, electrolytic copper plating was performed under the following conditions to form an electrolytic copper plating film 1Π with a thickness of m (see FIG. 40 (c)) ° [Electrolytic plating aqueous solution] sulfuric acid 180 g / 1 copper sulfate 80 g / 1 additive ( Manufactured by Attic Japan, trade name: Capalaseide GL) 1 ml / 1 [Electrolytic plating conditions] Current density 1 A / dm2 Time 30 minutes Temperature Room temperature (12) Set the anti-plating film 103 to 5% After the K0H aqueous solution is stripped and removed, the electroless plating film 112 located below the anti-plating film 103 is dissolved and removed by etching with a mixed solution of sulfuric acid and hydrogen peroxide to form an electroless copper plating film 112 and electrolytic ore. The upper layer conductor circuit composed of copper film 113 with a thickness of L / s = 28/28 (including through hole 107) ° 173 _____ (Please read the precautions on the back before filling this page) This paper size is in accordance with the Chinese Family Standard (CNS) A4 specification (2〗 0 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 A7 B7 V. Description of the invention In an aqueous solution of nickel chloride (30 g / 1), sodium hypophosphite (10 g / 1), sodium citrate (10 g / 1) (90 ° c In the electroless nickel plating solution, a 1.2 / zm thickness nickel coating layer 11a is formed on the entire conductor circuit and through-hole pads (see Figure 40 (d)). (13) For the upper conductor circuit 105 and The substrate of the nickel coating layer Ilia is subjected to the same treatment as in the above (5), and a roughened layer 111M of Cu—Ni-P is formed on the surface of the upper conductor circuit 105 with a thickness (see FIG. 41 (a)). In addition, Cu—Sn substitution reaction was performed under the conditions of tin borohydride 0.1 mol / 1, sulfur gland 1 〇mol / 1, temperature 35 ° C, and pH = 1.2, and the surface of the roughened layer was provided. Sn layer (not shown) with a thickness of 0.3 Am (14) By repeating the process of (6H13) above, an upper-layer conductor circuit is formed (see Fig. 41 (b) ~ 42 (d)). Although not shown here In the end, a solder resist layer with openings is formed, and after the gold plating process is performed, a solder bump is formed to obtain a multilayer printed circuit board with solder bumps. [Example 48] In addition to the process (12), the following Except for the method substitution, the rest are the same as in Example 47 to manufacture a multilayer printed circuit board. (12) After electrolytic copper plating is performed, the substrate is further immersed in nickel sulfate (240 g / 1) and nickel chloride. (45 g / l), boric acid (00 g / l) aqueous solution with a pH of 4.5, and at a temperature of 55 to 5 ° c and a current density of 4 A / dm2, Ni was used as the anode. The plate was plated with nickel to form a nickel coating layer with a thickness of 0.8 vm. Furthermore, the anti-plating film 10 was peeled and removed with a 5% aqueous KOH solution, and then the anti-mineral film 1 was placed thereon. The electroless plating film below 03 丨 12 Sulfur 174 This paper size applies to Chinese national standards (CNS &gt; A4 specification (210 X 297 mm) ---- I ------------- ---- Order --------- * Thread &lt; Please read the notes on the back before filling this page) Consumption Cooperation by Employees of Intellectual Property Bureau, Ministry of Economic Affairs Du printed 453141 V. Invention Description (η)) The mixed solution of the acid and hydrogen peroxide is dissolved and removed by starving treatment to form an upper-layer conductor circuit 105 having a thickness of L / S = 28/28 composed of the electroless copper film 112 and the electrolytic copper film 113 ( Including through hole 107) (refer to Fig. 43 (a) "When a new upper conductor circuit is formed on the substrate shown in Fig. 43 (a), the situation is as shown in Fig. 43 (b). [Comparative Example 11] Except that no nickel coating layer was formed, a multilayer printed circuit board was manufactured in the same manner as in Example 47. [Example 49] A tin layer having a thickness of l.lvm was formed by replacing the nickel layer with electroless plating. Except for the rest, the same method as in Example 47 was used to manufacture the multilayer printed circuit board. The electric mineral liquid has the following composition and temperature ° Sodium citrate 0J4 mol / i EDTA 0.04 mol / 1 chlorination 0.04 mol / 1 sodium acetate 0.12 mol / 1 of titanium chloride 0.029 mol / 1

液溫 70〜90°CLiquid temperature 70 ~ 90 ° C

[實施例50] 除了不形成鎳層而改以無電解鍍敷形成姑層外’其餘 皆與實施例47的方法相同來製造多層印刷電路板。無電解 鍍敷之條件如下= [無電解鍍敷液] 175 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) V &gt; -----ιί·訂- ------！線 (請先閱讀背面之沒意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 53 1 4 1 A7 _B7 五、發明說明（ 氯化鈷 0.60 mol/1 次亞磷酸鈉 0.26 mol/1 酒石酸鈉 0.90 mol/1 氯化銨 1.30 mol/1 pH 8~10 液溫 90〜100°C [實施例51] 除了不形成鎳層而改以無電解鍍敷形成鈀層外，其餘 皆與實施例47的方法相同來製造多層印刷電路板。無電解 鍍敷之條件如下： [無電解鍍敷液] 四鈀膠體 5.4 g/1 EDTA 鈉鹽 33.6 gd 氨 350 g/1 聯氨 0.3 g/1[Example 50] A multilayer printed wiring board was manufactured in the same manner as in Example 47 except that a nickel layer was formed instead of the nickel layer. The conditions of electroless plating are as follows: [Electroless plating solution] 175 This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) V &gt; ----- ιί · Order- ----- ---! (Please read the unintentional matter on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 53 1 4 1 A7 _B7 V. Description of the invention (Cobalt chloride 0.60 mol / 1 sodium hypophosphite 0.26 mol / 1 Sodium tartrate 0.90 mol / 1 ammonium chloride 1.30 mol / 1 pH 8 ~ 10 Liquid temperature 90 ~ 100 ° C [Example 51] Except that instead of forming a nickel layer, electroless plating was used to form a palladium layer. The method of Example 47 was the same to manufacture a multilayer printed circuit board. The conditions for electroless plating were as follows: [Electroless plating solution] Tetrapalladium colloid 5.4 g / 1 EDTA Sodium salt 33.6 gd Ammonia 350 g / 1 Hydrazine 0.3 g / 1

液溫 90°CLiquid temperature 90 ° C

[實施例52] 除了不形成鎳層而改以電解電鍍形成鉻層外，其餘皆 與實施例48的方法相同來製造多層印刷電路板。電解電鍍 之條件如下： [電解電鍍液] 無水鉻酸 300 g/1 氟矽化鈉 15g/l 硫酸 0.5 g/1 176 本紙張尺度適用中國國家標準（CNS)A4規格（2]0 X 297公釐） ------νΛ--------訂 ---------線 (諝先閱讀背面之注意事項再填寫本頁) 經濟部智铥財產局員工消費合作社印製 20 g/1 150 g/1 200 g/1 8 g/1 2 g/1 15 g/1 453 1 4 1 at ____B7_ 五、發明說明（ΓΤ；)[Example 52] A multilayer printed circuit board was manufactured in the same manner as in Example 48 except that a chromium layer was formed by electrolytic plating instead of forming a nickel layer. The conditions for electrolytic plating are as follows: [Electrolytic plating solution] Anhydrous chromic acid 300 g / 1 Sodium fluorosilicone 15g / l Sulfuric acid 0.5 g / 1 176 This paper size applies to Chinese National Standard (CNS) A4 specifications (2) 0 X 297 mm ) ------ νΛ -------- Order --------- line (谞 Please read the notes on the back before filling this page) 20 g / 1 150 g / 1 200 g / 1 8 g / 1 2 g / 1 15 g / 1 453 1 4 1 at ____B7_ V. Description of the invention (ΓΤ;)

液溫 45 °CLiquid temperature 45 ° C

[電解電鍍條件] 電流密度 20 A/dm2 [實施例53] 除了不以電解鍍鎳形成鎳層而改以濺鍍形成鋁層，又 不形成Cu-Ni-P合金之粗化層而改以藉由電鍍銅塊來形 成粗化層之外，其餘皆與實施例48的方法相同來製造多層 印刷電路板。電解電鍍之條件如下： [鋁濺鍍之條件] 濺鍍裝置 日本真空股份有限公司製造，SV —4540 氣壓 0.7Pa[Electrolytic plating conditions] Current density 20 A / dm2 [Example 53] In addition to not forming a nickel layer by electrolytic nickel plating and forming an aluminum layer by sputtering instead of a roughened layer of Cu-Ni-P alloy, Except that the roughened layer is formed by electroplating a copper block, the rest are the same as the method of Example 48 to manufacture a multilayer printed circuit board. The conditions of electrolytic plating are as follows: [Conditions of aluminum sputtering] Sputtering device Manufactured by Japan Vacuum Co., Ltd., SV —4540 pressure 0.7Pa

電力 200W 時間 15分鐘 錦層厚度 0.4//m [電鍍銅塊之電鍍浴] 硫酸銅 EDTA 焦磷酸鈉 硝酸鈉 氨 正磷酸鈉 [實施例54] 除了不形成鎳層而改以無電解鍍鋅形成鋅層外，其餘 皆與實施例48的方法相同來製造多層印刷電路板。無電解 177 ---I I — ί^. I — — — — — — 訂.--— ！_ 線 (請先閲讀背面之注咅？事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（2]0 X 297公釐） 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 B7 五、發明說明（小） 鍍敷之條件如下： [無電解鍍敷液] 氫氧化鈉 100〜800 g/l 氧化鋅 50〜200 g/1 液溫 常溫 [實施例55] 除了不形成鎳層而改以電解鍍鐵形成鐵層外，其餘皆 與實施例48的方法相同來製造多層印刷電路板。電解電鍍 之條件如下： [電解電鍍液] 硫酸亞鐵 1⑻〜400 g/1 硫酸銨 50〜200g/l [電解電鍍條件] 電流密度 6〜10A/dm2 [實施例56] 除了不以電解鍍鎳形成鎳層而改以無電解鍍鎳形成鎳 層外，其餘皆與實施例48的方法相同來製造多層印刷電路 板。無電解鍍敷之條件如下： [無電解鍍敷液] 氯化鎳 30 g/1 次亞磷酸鈉 10 g/1 檸檬酸鈉 10 g/1Power 200W time 15 minutes brocade thickness 0.4 // m [plating bath of electroplated copper block] copper sulfate EDTA sodium pyrophosphate sodium nitrate ammonia orthophosphate [Example 54] Instead of forming a nickel layer, it is formed by electroless zinc plating Except for the zinc layer, the rest were the same as the method of Example 48 to fabricate a multilayer printed circuit board. No electrolysis 177 --- I I — ί ^. I — — — — — — Order .----! _ Line (Please read the note on the back? Matters before filling out this page) This paper size applies to China National Standard (CNS) A4 specifications (2) 0 X 297 mm) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 453 1 4 1 A7 B7 5. Description of the invention (small) The plating conditions are as follows: [Electroless plating solution] Sodium hydroxide 100 ~ 800 g / l Zinc oxide 50 ~ 200 g / 1 Liquid temperature normal temperature [Example 55] Except Instead of forming a nickel layer and forming an iron layer by electrolytic iron plating, the rest are the same as the method of Example 48 to manufacture a multilayer printed circuit board. The conditions for electrolytic plating are as follows: [Electrolytic plating solution] Ferrous sulfate 1⑻ ~ 400 g / 1 ammonium sulfate 50 ~ 200g / l [Electrolytic plating conditions] Current density 6 ~ 10A / dm2 [Example 56] Except not using electrolytic nickel plating The nickel layer was formed and the electroless nickel plating was used to form the nickel layer, and the rest were the same as the method of Example 48 to manufacture a multilayer printed circuit board. The conditions for electroless plating are as follows: [Electroless plating solution] Nickel chloride 30 g / 1 sodium phosphite 10 g / 1 sodium citrate 10 g / 1

液溫 90°C 關於上述實施例與比較例所得之電路板，其截面係藉 178 本紙張尺度適用中國國家標準（CNS)A4規格（2]0 X 297公釐） ------I------------訂·-------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 453 1 4 1 A7 _ B7 五、發明說明) 由光學顯微鏡觀察，以觀察導體電路的溶解以及Cu — Ni-P粗化層的未析出。 在實施例47〜56，未見到導體電路的溶解，但於比較 例15 ’則在電源層(平面層)的一部份見到溶解的現象。 又’在實施例47〜52以及54〜56，於進行Cu—Ni—P 構成之針狀或多孔質狀合金的電鍍處理時，即使經過1〇次 轉動亦未事電鑛未析出的發生，但在比較例丨5，則於3次 轉動時便發生電鍍未析出的現象。又，在實施例54之電鍍 銅塊亦未見到電鍍未析出的發生 再者’關於可形成之圖案寬度(L/S)，在實施例48以 及52〜56 ’可形成5/15/zm之窄的圖案寬度，但在比較例 ，只能形成30/30之寬的圖案寬度。 [實施例57] A.上層粗化面形成用樹脂組成物的調製 (a) 甲酚酚醛型環氧樹脂（日本化藥公司製造，分子量： 2500)之25%丙烯化物以80重量％的濃度溶解於甘醇二甲醚 (DMDG)之樹脂液400重量份、感光性單體(東亞合成公司 製造，阿羅尼克斯M325)60重量份、消泡劑(三能普克公司 製造，S-65)5重量份，以及N—甲基毗咯烷酮(NMP)35重 量份裝入容器中，進行攪拌、混合以調製混合組成物。 (b) 將聚醚磺(PES)80重量份，環氧樹脂粒子(三洋化成 公司製造，聚合物保羅)平均粒徑之物72重量份與 平均粒徑0.5/zm之物31重量份裝入別的容器中’進行攪 拌、混合之後，再添加NMP257重量份’以粒子硏磨機攪 179 本紙張尺度適用中國®家標準（CNS)A4規格（210 X 297公釐) ----------t,i--------訂----1-----線 (請先間讀背面之注意事項再填寫本頁) 453 1 4 1 A7 B7 五、發明說明（) 拌混合，以調製另外之混合組成物。 (c)將咪唑硬化劑（四國化成公司製造，2E4MZ — CN)20 重量份、光重合起始劑(苯酚)20重量份、光增感劑(吉巴蓋 及公司製造，EBA)4重量份以及NMP16重量份再裝入別的 容器中，進行攪拌、混合，以調製混合組成物。 接著，將於(a)、（b)及(c)所調製之混合組成物藉混合而 得到粗化面形成用樹脂組成物》 B.下層之粗化面形成用樹脂組成物的調製 (a) 甲酚酚醛型環氧樹脂（日本化藥公司製造，分子量： 2500)之25%丙烯化物以80重量％的濃度溶解於甘醇二甲醚 (DMDG)之樹脂液400重量份、感光性單體(東亞合成公司 製造，阿羅尼克斯M325)60重量份、消泡劑(三能普克公司 製造，S-65)5重量份，以及N—甲基毗咯烷酮(NMP)35重 量份裝入容器中，進行攪拌、混合以調製混合組成物。 (b) 將聚醚磺(PES)80重量份以及環氧樹脂粒子(三洋化 成公司製造，聚合物保羅)平均粒徑0.5^m之物145重量 份裝入別的容器中，進行攪拌、混合之後，再添加 NMP285重量份，以粒子硏磨機攪拌混合，以調製另外之 混合組成物。 (c) 將咪唑硬化劑（四國化成公司製造，2E4MZ-CN)20 重量份、光重合起始劑(苯酚)20重量份、光增感劑(吉巴蓋 及公司製造，EBA)4重量份以及NMP16重量份再裝入別的 容器中，進行攪拌、混合，以調製混合組成物。 接著’將於(a)、（b)及(c)所調製之混合組成物藉混合而 180 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚） --------------A___ (請先閱讀背面之注意事項再填寫本頁) 訂· -·線- 經濟部智慧財產局員工消費合作钍印製 A7 4 53 1 4 1 ___B7_ 五、發明說明（ 得到無電解鍍敷用黏著劑。 C. 樹脂塡充劑之調製 將雙酚醛F型環氧單體(油化謝魯公司製造，分子量： 310，YL983U)100重量份、表面鍍有矽烷偶合劑之平均粒 徑1.6#m、且最大粒子直徑15#m以下之Si02球狀粒子( 亞特提克公司製造，CRS 1101 —CE)170重量份以及均勻劑( 三能普克公司製造，培雷諾魯S4)170重量份裝入容器中， 藉由進行攪拌混合，乃調製黏度在23土PC時爲45〜49Pa · s 之樹脂塡充劑。 又，以硬化劑而言，係使用咪唑硬化劑（四國化成公司 製造，2E4MZ— CN)6.5重量份。 D. 多層印刷電路板之製造方法 (1) 於厚度0.6mm之玻璃環氧樹脂或是BT(聚對苯二甲 酸乙酯)樹脂構成之基板101的兩面積層有18//m的銅箔 108，而以此銅面積層板做爲起始材料(參照圖44(a))。首先 ，對此銅面積層板進行鑽削孔，再施以無電解鍍敷處理， 藉由進行圖案狀的蝕刻，而於基板101兩面形成下層導體 電路丨04及通孔109。 (2) 將形成通孔109及下層導體電路104之基板予以水 洗、乾燥之後，以含有NaOH(10 g/丨）、NaClCh(40 g/Ι)、 Na3P(M16 g/1)之水溶液爲黑化浴(氧化浴)進行黑化浴處理， 以及，以含有NaOH(19 g/1)、NaBH&lt;(5 g/Ι)的水溶液爲還原 浴進行還原處理，而於包含通孔109之下層導體電路104 的全表面形成粗化面104a、109a(參照圖44(b))。 181 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 11 iA.----1---β —-------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作杜印製 4 53 14 1 A7 B7 五、發明說明（π ) (3) 於基板之一面藉由使用輥軋機塗佈而將樹脂塡充劑 110塡充至下層導體電路1〇4間或是通孔丨09內，而進行加 熱乾燥之後，對另外一面亦同樣將樹脂塡充劑丨1〇塡充至 導體電路104間或是通孔109內’再進行加熱乾燥(參照圖 44(c)) 0 (4) 將結束上述(3)處理之基板的單面’藉由使用#600帶 式硏磨紙（三共理化學公司製造）進行帶式硏磨’使得內層 銅圖案104表面或通孔109之焊墊表面以不留下樹脂塡充 劑110的方式予以硏磨，接著’爲去除因上述帶式硏磨所 造成之磨損乃進行拋光硏磨。此一連串的硏磨亦於基板的 另一面進行。接著，以100°C1小時、120°C3小時、150°C1 小時、180°C7小時的條件進行加熱處理使樹脂塡充劑110 硬化。 藉此，將形成於通孔109或導體電路非形成部之樹脂 塡充劑110之表層部以及下層導體電路104的表面平坦化 ，樹脂塡充劑110與下層導體電路104側面透過粗化層 104a而強固的密接，又逋孔109的內壁面109a與樹脂塡充 劑110亦透過粗化面強固地密接而得到此電路基板(參照圖 44(d))。依此過程，樹脂塡充劑11〇的表面及下層導體電路 104的表面成爲同一平面。此處，所充塡之硬化樹脂其Tg 點係155.6°C，線熱膨脹係數係44.5X10_6/°C。 (5) 於上述(4)處理之外露的下層導體電路104以及通孔 109的焊墊上面，形成厚度2.5//m之由Cu—Ni - P構成的 粗化層(凹凸層)111(參照圖45(d))。 182 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公釐) I In----1 — — — — — 1^· — — — —----^ (請先閱讀背面之;i意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（id) 其形成方法係如下所述。亦即，將基板置入硫酸銅(8 g/Ι)、硫酸鎳(0.6 g/Ι)、檸檬酸(15 g/Ι)、次亞磷酸鈉(29 g/1) 、硼酸(31 g/1)、界面活性劑（日信化學工業製造，沙費諾魯 465)(0.1 g/Ι)之水溶液構成之pH = 9的無電解鍍銅浴中’在 浸漬1分鐘後開始以4秒1次的速率於縱方向及橫方向使 其振動，而於下層導體電路及通孔的焊墊表面設置由Cu-Ni-P構成之針狀合金粗化層111。 (6) 將設有此粗化層111之基板置入加熱裝置中，於大 氣周圍氣氛下，以150°C之溫度加熱1小時’藉此’於其表 面形成O.l/zm之氧化膜。此氧化膜的形成可藉由粗化層的 顏色來判斷，亦可藉由螢光X射線分析裝置(Rigaku公司製 造RIX 2100)來確認其存在。然而，此處未對所形成之膜 加以圖示。 再者，於含有氟硼化錫0.1 mol/卜硫脲1·〇 mol/ι，溫 度35°C，pH = 1.2的條件下進行Cu—Sn置換反應，而於粗 化層的表面設置厚度0.3的Sn層(未圖不）° (7) 其次，於基板的兩面，將上述B之無電解鍍敷用黏 著劑(黏度：1.5Pa · s)使用輥軋機塗佈之，而於水平狀態下 放置20分鐘之後，於60°C乾燥300分鐘，以形成無電解鍍 敷用黏著劑層102。 再於此無電解鍍敷用黏著劑層102上將上述A之無電 解鍍敷用黏著劑(黏度：7Pa · s)使用輥軋機塗佈之’而於水 平狀態下放置20分鐘之後，於60°C乾燥30分鐘’以形成 黏著劑層l〇2b，從而彤成厚度35/zm的無電解鍍敷用黏著 183 I--------1---UVA--------訂------I — (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Liquid temperature 90 ° C. For the circuit boards obtained in the above examples and comparative examples, the cross-section is based on 178 paper sizes. Applicable to China National Standard (CNS) A4 specifications (2) 0 X 297 mm. ------ I ------------ Order · ------- line (please read the notes on the back before filling out this page) Printed by the Employee Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 453 1 4 1 A7 _ B7 V. Description of the invention) Observe with an optical microscope to observe the dissolution of the conductor circuit and the absence of the Cu—Ni-P roughened layer. In Examples 47 to 56, no dissolution of the conductor circuit was observed, but in Comparative Example 15 ', a dissolution phenomenon was seen in a part of the power supply layer (planar layer). In addition, in Examples 47 to 52 and 54 to 56, when electroplating of needle-like or porous alloys composed of Cu—Ni—P was performed, no precipitation of electricity ore occurred even after 10 rotations. However, in Comparative Example 1-5, the phenomenon that plating did not precipitate occurred at three rotations. In addition, no plating precipitation occurred in the electroplated copper block of Example 54. Further, regarding the pattern width (L / S) that can be formed, in Examples 48 and 52 to 56, 5/15 / zm can be formed. The narrow pattern width, but in the comparative example, only a pattern width of 30/30 can be formed. [Example 57] A. Preparation of resin composition for forming roughened surface of upper layer (a) 25% acryl compound of cresol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 2500) at a concentration of 80% by weight 400 parts by weight of a resin solution dissolved in glycol dimethyl ether (DMDG), 60 parts by weight of a photosensitive monomer (manufactured by Toa Kosei Co., Ltd., Aronix M325), an antifoaming agent (manufactured by Sannenkeke Corporation, 65) 5 parts by weight and 35 parts by weight of N-methylpyrrolidone (NMP) were put into a container, and stirred and mixed to prepare a mixed composition. (b) Charge 80 parts by weight of polyethersulfonate (PES), 72 parts by weight of epoxy resin particles (manufactured by Sanyo Chemical Co., Ltd., polymer Paul) and 31 parts by weight of average particle diameter 0.5 / zm. In another container, 'After stirring and mixing, add NMP257 parts by weight' and use a particle honing machine to stir 179. This paper size applies to China® Home Standard (CNS) A4 (210 X 297 mm) ------ ---- t, i -------- Order ---- 1 ----- line (please read the precautions on the back before filling this page) 453 1 4 1 A7 B7 V. Invention Explanation () Mix and mix to prepare another mixed composition. (c) 20 parts by weight of an imidazole hardener (manufactured by Shikoku Chemical Co., Ltd., 2E4MZ — CN), 20 parts by weight of a photoregeneration initiator (phenol), and 4 parts by weight of a photosensitizer (made by Gibbaga & Co., EBA) Parts and 16 parts by weight of NMP were put into another container, and stirred and mixed to prepare a mixed composition. Next, the mixed composition prepared in (a), (b), and (c) is mixed to obtain a resin composition for forming a roughened surface "B. Preparation of a resin composition for forming a roughened surface in the lower layer (a ) 25% acryl of cresol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 2500) is dissolved in 400 parts by weight of a resin solution of glycerol dimethyl ether (DMDG) at a concentration of 80% by weight, and is photosensitive. Body (manufactured by Toa Kosei Co., Ltd., Aronix M325), 60 parts by weight, 5 parts by weight of an antifoaming agent (manufactured by Sannenkeke Corporation, S-65), and 35 parts by weight of N-methylpyrrolidone (NMP) The portion is put into a container, and the mixture is stirred and mixed to prepare a mixed composition. (b) Put 80 parts by weight of polyethersulfonate (PES) and 145 parts by weight of epoxy resin particles (manufactured by Sanyo Chemical Co., Ltd., polymer) with an average particle diameter of 0.5 ^ m into another container, and stir and mix After that, 285 parts by weight of NMP was further added, and the mixture was stirred and mixed with a particle honing machine to prepare another mixed composition. (c) 20 parts by weight of an imidazole hardener (manufactured by Shikoku Chemical Co., Ltd., 2E4MZ-CN), 20 parts by weight of a photo-recombination initiator (phenol), and 4 parts by weight of a photosensitizer (made by Gibbaga & Co., EBA) Parts and 16 parts by weight of NMP were put into another container, and stirred and mixed to prepare a mixed composition. Then '180 paper sizes will be adapted to the Chinese National Standard (CNS) A4 specification (210 X 297 cm) by mixing the mixed composition prepared by (a), (b) and (c) ------ -------- A___ (Please read the precautions on the back before filling this page) Order--· Line-Consumption Cooperation of Employees of Intellectual Property Bureau of the Ministry of Economic Affairs 钍 Printed A7 4 53 1 4 1 ___B7_ V. Description of Invention (The adhesive for electroless plating was obtained. C. Preparation of the resin filler) 100 parts by weight of bisphenol F-type epoxy monomer (manufactured by Xielu Company, molecular weight: 310, YL983U), and the surface was coated with silane coupling 170 parts by weight of Si02 spherical particles (manufactured by Attic, Inc., CRS 1101-CE) with an average particle diameter of 1.6 # m and a maximum particle diameter of 15 # m or less, and a leveling agent (manufactured by Sannenkeke, Inc. 170 parts by weight of Reynolds S4) is put into a container, and is stirred and mixed to prepare a resin filler with a viscosity of 45 to 49 Pa · s at 23 clay PC. In addition, as the hardener, it is hardened with imidazole. 6.5 parts by weight (manufactured by Shikoku Chemical Co., Ltd., 2E4MZ-CN). D. Manufacturing method of multilayer printed circuit board (1) at a thickness of 0. 6 mm glass epoxy or BT (polyethylene terephthalate) resin substrate 101 has two areas of 18 // m copper foil 108 on the two areas, and the copper area laminate is used as the starting material (see (Fig. 44 (a)). First, the copper area laminate is drilled with holes, and then electroless plating is applied, and patterned etching is performed to form lower-layer conductor circuits on both sides of the substrate 101. Hole 109. (2) The substrate forming the through hole 109 and the lower-layer conductor circuit 104 is washed with water, and then dried with NaOH (10 g / 丨), NaClCh (40 g / 1), Na3P (M16 g / 1) The aqueous solution is a blackening bath (oxidation bath) for a blackening bath treatment, and the aqueous solution containing NaOH (19 g / 1), NaBH &lt; (5 g / 1) is used as a reducing bath for reduction treatment, and the through hole 109 is included. The entire surface of the lower layer conductor circuit 104 forms roughened surfaces 104a, 109a (refer to Figure 44 (b)). 181 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 11 iA .--- -1 --- β —------- ^ (Please read the notes on the back before filling out this page) The Intellectual Property Bureau of the Ministry of Economic Affairs Prints the wisdom of the Ministry of Economy Production cooperation between employees of the Bureau of Production and Du Printing 4 53 14 1 A7 B7 V. Description of the invention (π) (3) On one side of the substrate, the resin filler 110 is charged to the lower conductor circuit 1 by coating with a roll mill. 4 or through holes 丨 09, and after heating and drying, the other side is also filled with resin 塡 filler 丨 10 塡 into the conductor circuit 104 or through holes 109 ′ and then heat-dried (refer to the figure) 44 (c)) 0 (4) One side of the substrate on which the above-mentioned (3) processing is to be carried out is “belt honing by using # 600 tape honing paper (manufactured by Sankyo Rika Co., Ltd.) so that the inner copper pattern is formed. The surface of the pad 104 or the pad 109 of the through hole 109 is honed in such a manner that the resin honing agent 110 is not left, and then the polishing honing is performed to remove the wear caused by the belt honing described above. This series of honing is also performed on the other side of the substrate. Next, the resin filler 110 was cured by heat treatment under the conditions of 100 ° C for 1 hour, 120 ° C for 3 hours, 150 ° C for 1 hour, and 180 ° C for 7 hours. Thereby, the surface portion of the resin filler 110 formed in the through hole 109 or the non-formed conductor circuit portion and the surface of the lower conductor circuit 104 are planarized, and the sides of the resin filler 110 and the lower conductor circuit 104 penetrate the roughened layer 104a. The circuit board is obtained by a strong tight contact, and the inner wall surface 109a of the countersink 109 and the resin filler 110 are firmly adhered through the roughened surface (see FIG. 44 (d)). According to this process, the surface of the resin filler 11 and the surface of the lower-layer conductor circuit 104 become the same plane. Here, the Tg point of the filled hardened resin is 155.6 ° C, and the linear thermal expansion coefficient is 44.5X10_6 / ° C. (5) A roughened layer (concave-convex layer) made of Cu-Ni-P with a thickness of 2.5 // m is formed on the pads of the lower-layer conductor circuit 104 and the through-hole 109 exposed in the above-mentioned (4) treatment (refer to FIG. Figure 45 (d)). 182 This paper size applies to China National Standard (CNS) A4 specifications (2) 0 X 297 mm) I In ---- 1 — — — — — 1 ^ · — — — —---- ^ (Read first (I will fill in this page on the back of the page; I will fill in this page) A7 printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (id) The method of formation is as follows. That is, the substrate was placed in copper sulfate (8 g / 1), nickel sulfate (0.6 g / 1), citric acid (15 g / 1), sodium hypophosphite (29 g / 1), and boric acid (31 g / 1). Surfactant (manufactured by Nissin Chemical Industry Co., Ltd., Safanoru 465) (0.1 g / 1) in an electroless copper plating bath with a pH of 9 consisting of an aqueous solution ', immersed for 1 minute in 4 seconds 1 The secondary velocity makes it vibrate in the vertical and horizontal directions, and a needle-like alloy roughened layer 111 made of Cu-Ni-P is provided on the surface of the lower-layer conductor circuit and the pad of the through hole. (6) The substrate provided with the roughened layer 111 is placed in a heating device, and is heated at 150 ° C for 1 hour under the atmosphere of the atmosphere ', thereby forming an oxide film of 0.1 / zm on its surface. The formation of this oxide film can be judged by the color of the roughened layer, and its existence can also be confirmed by a fluorescent X-ray analyzer (RIX 2100 manufactured by Rigaku Corporation). However, the formed film is not illustrated here. Furthermore, Cu—Sn substitution reaction was performed under the conditions containing 0.1 mol of tin borohydride / thiothiourea 1.0 mol / m, temperature of 35 ° C, and pH = 1.2, and a thickness of 0.3 was set on the surface of the roughened layer. Sn layer (not shown) ° (7) Next, on both sides of the substrate, apply the above-mentioned adhesive for electroless plating of B (viscosity: 1.5Pa · s) using a rolling mill, and in a horizontal state After standing for 20 minutes, it was dried at 60 ° C. for 300 minutes to form an adhesive layer 102 for electroless plating. Then, on the adhesive layer 102 for electroless plating, the adhesive for electroless plating (viscosity: 7Pa · s) of A described above was applied using a roll mill, and left to stand for 20 minutes in a horizontal state, and then at 60 Drying at ° C for 30 minutes' to form an adhesive layer 102b, thereby forming an adhesive for electroless plating with a thickness of 35 / zm 183 I -------- 1 --- UVA ------ --Order ------ I — (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

4531 ^_ I 五、發明說明（ 劑層102 (參照圖45(b))。 (8) 於上述(7)形成之無電解鍍敷用黏著劑層1〇2之基板 101的雨面，將印刷有直徑85#m黑圓的光罩薄膜黏著其 上，藉由超高壓水銀燈產生的500 m〗/cm2強度進行曝光之 後，以DMDG溶液進行噴塗顯影。之後，再將該基板以超 高壓水銀燈產生的3000 mJ/cm2強度來進行曝光，之後，實 施10CTC1小時、150°C5小時的加熱處理，乃形成具有通孔 用開口 106之厚度35/zm的層間樹脂絕緣層102 (參照圖 45(c))。其中，該開口的尺寸精度係相當於光罩薄膜般優異 〇 (9) 將形成有通孔形成用開孔106的基板浸漬於包含 800 g/Ι鉻酸之70°C的水溶液中19分鐘，以溶解去除存在 於層間樹脂絕緣層102表面之環氧樹脂粒子，藉此，以將 層間樹脂絕緣層102表面粗化(深度3/zm)(參照圖45(d))。 此時，於下層導體電路104上粗化層111的表面所形 成的氧化膜並未受到蝕刻，亦無發生空孔現象。 (10) 其次，將結束上述處理之基板浸瀆於中和溶液(西 普雷公司製造)再水洗之。再者，於經過粗化面處理之該基 板的表面，藉由賦予鈀觸媒(亞特提克公司製造），以使觸 媒核得以附著於層間樹脂絕緣層102表面及通孔用開口 106之內壁面。 (11) 其次，將基板浸漬於以下組成之無電解鍍銅水溶 液中，而於粗化面全體形成厚度〇.8#m之無電解鍍銅膜 112 (參照圖46(a))。此時，由於鍍膜甚薄乃可觀察無電解 184 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------A___ (請先閱讀背面之注意事項再填寫本頁) 訂_ -線. 經濟部智慧財產局員工消費合作社印製 4 53 了 41 A7 B7 經濟部智慧財產局員工消費合作杜印製 五、發明說明（πυ 鍍膜表面之凹凸情形^ [無電解鍍敷水溶液] EDTA 50 g/1 硫酸銅 10 g/1 HCHO 8 ml/1 NaOH 10 g/1 α，α’—聯二Dt[;D定 80mg/l 聚乙二醇(PEG) 0.1 g/1 [無電解鍍敷條件] 70°C之液體溫度，30分鐘。 (12) 將市售之感光性乾式薄膜貼於無電解鍍銅膜112 上，進而裝設光罩，再以100 rruf/cm2進行曝光、0.8%碳酸 氫鈉水溶液進行顯像處理，從而設置防鍍膜103 (參照圖 46(b))。 (13) 接著，將基板以50°C水洗淨脫脂，再以25°C水洗 淨之後，以硫酸加以洗淨，而就以下之條件實施電解鍍銅 ，形成厚度15#m之電解鍍銅膜113(參照圖46(c))。 [電解電鍍水溶液] 硫酸 180 g/1 硫酸銅 80 g/1 添加劑(亞特提克日本公司製造，商品名：卡帕拉錫德GL) 1 ml/1 [電解電鍍條件] 電流密度 1 A/dm2 185 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ,--------I----- — ί (請先閱讀背面之注意事項再填寫本頁) -j=OJ· -線- 453141 A7 B7__ 五、發明說明（唞） 時間 30分鐘 溫度 室溫 (14) 將防鍍膜103以5%之KOH水溶液剝離去除之後’ 再將位於該防鍍膜103下方之無電解鍍敷膜112以硫酸與 過氧化氫之混合液藉由蝕刻處理溶解去除之’而形成由無 電解鍍銅膜112及電解鍍銅膜113所構成之厚度18/zm之 導體電路(包含通孔107)105。再者，浸漬於包含800 g/Ι鉻 酸之70°C的水溶液中3分鐘’而將位於導體電路非形成部 分之導體電路間的層間樹脂絕緣層102表面進行的蝕 刻處理，以去除殘存於其表面之鈀觸媒(參照圖46(d)) ° (15) 將形成導體電路105之基板浸漬於硫酸銅(8 g/1)、 硫酸鎳(0.6 g/1)、檸檬酸(15 g/1)、次亞磷酸鈉(29 g/1) '硼酸 (31 g/Ι)、界面活性劑（日信化學工業製造’沙費諾魯 465)(0.1 g/Ι)之水溶液構成之PH = 9的無電解鍍銅浴中’在 浸漬1分鐘後開始以4秒1次的速率於縱方向及橫方向使 其振動，而於下層導體電路及通孔的焊墊表面設置由Cu_ Ni_P構成之針狀合金粗化層111(參照圖47(a))。此時’將 形成之粗化層111經由ΕΡΜΑ(螢光X射線分析裝置)分析的 結果，發現到組成比係Cu : 98莫爾％、Ni : 1.5莫爾％、Ρ :〇,5莫爾％。 (16) 藉由重複上述(6)〜(15)之過程，再形成上層導體電 路，以得到多層印刷電路板。然而’未進行Sn置換反應( 參照圖47(b)〜48(b))。 (17) 其次，藉由將甲酚酚醛型環氧樹脂（日本化藥公司 186 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I 11----· ^ ------11 -------— ^ (請先M讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 453 1 4 1 ___B7__ 五、發明說明（必） 製造）之環氧基50%丙烯化之感光性賦予的低聚物(分子量 :4000)46.67重量份以成爲濃度60重量％般的方式溶解於 甘醇二甲醚(DMDG)中、溶解於甲基乙基酮之80重量％的 雙酚醛A型環氧樹脂(油化謝魯公司製造，商品名：環氧樹 脂1001)6.67重量份、同樣爲雙酚醛A型環氧樹脂(油化謝 魯公司製造，商品名：環氧樹脂E—1001 —B80) 6.67重量 份、咪唑硬化劑（四國化成公司製造，商品名：2E4MZ-ClSi)l.6重量份、感光性單體之2官能丙烯單體（日本化藥公 司製造，商品名：R604)4.5重量份、同樣爲多價丙烯單體( 共榮化學公司製造，商品名：DPE6A)1.5重量份、由丙烯 酸酯聚合物構成之均勻劑(共榮化學公司製造，茼品名：寶 利弗洛N〇.75)0,36重量份裝入容器中，進行攪拌、混合以 調製混合組成物，對此混合組成物加入做爲光聚合起始劑 之伊魯喀克亞I- 907(吉巴蓋及公司製造）2.0重量份、做爲 光增感劑之DETX-S(日本化藥公司製造)0.2重量份、 DMDG 0.6重量份，而得到於25°C經調整之黏度爲1.4土 0.3Pa s之阻焊劑組成物。又，黏度測定係依據B型黏度計 (東京計量儀器公司製造，DVL-B型)於60rpm時採用迴轉 器編號4、而於6rpm時採用迴轉器編號3。 (18)其次，於多層電路基板的兩面，將上述阻焊劑組 成物塗佈20#m之厚度，以70°C20分鐘、70°C30分鐘的條 件進行乾燥處理之後，將描繪有防焊層開口部圖案的厚度 5mm之光罩使其密接於防焊層，而以1〇〇〇 m〗/Cm2的紫外線 進行曝光，再以DMTG溶液予以顯像處理，從而形成直徑 187 本紙張尺度適用中國國家標準（CNS)A4規格（2]0 X 297公爱） (請先閱讀背面之注意事項再填寫本頁) --δ _ 線· 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社扣 五、發明說明（冰） 200 // m 的開口。 再者，以80°C1小時、10〇°Cl小時、120tl小時、150 t：3小時的條件分別進行加熱處理使防焊層硬化’形成具 有開口之厚度20 μ m之阻焊圖案層1H ° (19) 其次，將形成有防焊層114之基板’於包含氣化 鎳(30 g/U、次亞磷酸鈉Μ)、檸檬酸鈉（10运⑴之阳=5 的無電解鍍鎳液中浸漬2〇分鐘’而於開口部形成厚度5 # m之鍍鎳層115。再者’將該基板於包含氰化金鈣(2 g/Ι)、 氯化銨(75 g/1)、檸檬酸鈉(50 g/1)、次亞磷酸鈉(1〇 g/丨)之無 電解鍍敷液中以93°C的條件浸漬23秒’而於鍍鎳層115上 形成厚度0.03 A m之鍍金層116 ° (20) 之後，於防焊層1U之開口印刷焊接糊劑’於200 °C藉由迴焊形成焊接凸塊(焊接體）117 ’而製造具有焊接凸 塊117之多層印刷電路板(參照圖48(c))。 [實施例58] 除了於上述(5)及（16)之過程中’將結束⑷或是（15)過 程之基板進行水洗、酸性脫脂之後’再予以軟蝕刻’其次 ，將蝕刻液藉由噴塗機噴灑至基板的兩面上’使得下層導 體電路表面及通孔之焊墊表面'內壁藉由蝕刻的進行’而 於下層導體電路之全表面形成粗化面之外’其餘皆與實施 例57相同來製造多層印刷電路板。 又，就蝕刻液而言，係使用咪唑銅（Π)錯合物10重量 份、乙二酸7重量份、氯化鈣5重量份、以及離子交換水 78重量份混合之物。 188 ·.度適用ΐ國國家標準（CNS)A4規格（210 X 297公楚Γ f---------訂--I------線 (請先閱讀背面之注意事項再填寫本頁&gt; Α7 Β7 4 53141 五、發明說明（α) [比較例12] 除了於上述(6)以及與上述(6)相同之過程中不形成氧化 膜，而再將形成有粗化層之基板浸漬於包含氟硼化錫(0.1 mol/丨)以及硫胨(1.0 m〇l/l)之溫度50°C、pH = 1.2的鍍浴中進 行Cu — Sn置換反應，以於粗化層之表面形成厚度0.3#m 的Sn層以外，其餘皆與實施例57相同來製造多層印刷電 路板。 [比較例13] 除了於上述(6)以及與上述(6)相同之過程中不形成氧化 膜’而再將形成有粗化層之基板浸漬於包含氟硼化錫(0.1 mol/1)以及硫脲(1.0 mol/1)之溫度50t、pH = 1.2的鍍浴中進 行Cu-Sn置換反應，以於形成粗化層之表面形成厚度〇.3 //m的Sn層以外，其餘皆與實施例58相同來製造多層印 刷電路板。 針對以此製造之實施例57〜58以及比較例12、13之多 層印刷電路板，所實施之熱循環試驗係將其保持在-55°C30 分鐘後，再保持於125°C30分鐘之此種熱循環重複1〇〇◦次 ’最後將通孔部份之連接加以剖面而藉由顯微鏡觀察來得 之結果。 其結果，於實施例57〜58的多層印刷電路板，就以相 同的條件製造之所有之物而言，其通孔與下面之導體電路 強固地連接著’而完全沒有見到任何剝離的現象；關於比 較例12、13之多層印刷電路板，則可於一部份之物當中觀 察到通孔及下面之導體電路的連接部分有剝離現象 189 ---------------- t請先閱讀背面之注意事項再填寫本頁) 訂· -線· 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規袼（2】〇χ 297公釐） 453 1 4 1 A7 B7 五、發明說明（w) [產業上之可利用性] 如以上所說明般，依據本發明之第一群之多層印刷電 路板，則所提供之多層印刷電路板其導體電路不會有密接 強度降低的情況、且其具有優良之耐熱循環特性、高頻率 區域之訊號傳送性、焊接耐熱性等》 又，依據本發明之第二群之第一發明的多層印刷電路 板，由於在層間樹脂絕緣層上係使用環烯烴系樹脂之故， 故其具有小的介電常數及介電耗損因數，即使使用GHz區 域之高頻率訊號的情況，亦將不易發生訊號延遲或訊號錯 誤的現象，又，由於其具有優異之剛性等機械特性，乃可 提高導體電路彼此間連接的可靠度，而在導體電路與層間 樹脂絕緣層間的密接性上亦優。 又，依據本發明之第二群之第二發明之多層印刷電路 板的製造方法，由於藉由於導體電路上積層環烯烴系樹脂 層而形成層間樹脂絕緣層之故，故不需使用溶劑等之物， 使得製造過程簡易化，而可輕易地製造多層印刷電路板。 又，依據本發明之第三群之多層印刷電路板’在藉由 酸等對基板進行處理之時，可完全阻止因導體電路之局部 電池反應使得導體電路溶解，又，於導體電路實施Cu-Ni -P構成之針狀合金的電鍍處理時，可充分地進行電鍍析 出反應，而確實地形成粗化層》 又，依據本發明之第四群之多層印刷電路板的製造方 法，於樹脂絕緣層上形成金屬層之後，藉由進行酸洗淨來 去除金屬層表面之氧化膜，乃可防止電解鍍銅膜自金屬層 190 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -1° 丨線· 經濟部智慧財產局員工消費合作社印制^ 經濟部智慧財產局員工消費合作社印製 4 53 1 4 1 A7 B7 五、發明說明（ 剝離，其結果，將可提升導體電路之可靠度。又’藉由將 導體電路之表面平坦化，乃可防止訊號傳送延遲的發生。 又，依據本發明之第五群之多層印刷電路板，則所提 供之多層印刷電路板其導體電路的密接強度不會降低’又 由於將樹脂絕緣層平坦化之故乃於高頻率區域具有優異之 訊號傳送性。 又，依據本發明之第六群之多層印刷電路板’則所*提 供之多層印刷電路板其導體電路的密接強度不會降低’又 由於將樹脂絕緣層平坦化之故乃於高頻率區域具有優異之 訊號傳送性。又’可抑制龜裂的發生而提昇電路的可靠度 。再者，可實現電路之精密化。 又，依據本發明之第七群第一發明之多層印刷電路板 的形成方法，於絕緣基板上先形成由Ni或Α1等於表面形 成鈍態之金屬構成的第1導體層後，由於在上述第1導體 層上再形成第2導體層(其離子化傾向較形成上述鈍態之金 屬爲小），乃可使用管理容易之酸性蝕刻液來對第1導體層 及第2導體層同時進行選擇性之蝕刻，而藉由上述之蝕刻 以形成導體電路6 又，所形成之導體電路其不僅與樹脂基板等絕緣基板 有優異之密接性’且由於導體電路之表面平坦化之故’於 使用高頻率區域之訊號時，可防止雜訊的產生。 又，依據本發明之第七群第二發明之多層印刷電路板 的製造方法，由於在絕緣基板上依序形成有由Ni或A1等 於表面形成鈍性膜之金屬所構成之第1金屬層以及由較形 191 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) ------1·、-!!1---訂--------- (請先閱讀背面之注意事項再填寫本頁) A7 B7 4 53 1 4 1 五、發明說明（ 成上述鈍態之金屬有更小的離子化傾向金屬所構成之第2 金屬層之故’在接下來的防鍍膜的形成、電鍍、進行防鍍 膜的剝離後’可使用易於管理之蝕刻液對存在於防鍍膜之 下的第1導體層與第2導體層同時進行f虫刻，而藉由此餘 刻可形成導體電路。 又’所形成之導體電路其不僅與層間樹脂絕緣層有優 異之密接性，且由於導體電路之表面平坦化之故，於使用 高頻率區域之訊號時，可防止雜訊的產生。 又，依據本發明之第八群之第一發明的金屬膜形成方 法，可形成之導體電路其於基板上形成之鎳膜與於鎳膜上 形成之其他金屬之間的密接性大，乃可防止由於前述鎳膜 上之氧化膜而造成金屬層間的剝離現象。 又，依據本發明之第八群之第二發明之多層印刷電路 板之製造方法，可防止在導體電路中形成之鍍鎳膜及於鎳 膜上形成之Cu-Ni-P合金粗化層間的剝離現象。 又，依據本發明之第九群之多層印刷電路板，.在藉* 酸等對基板進行處理之時，可完全阻止因導體電路之局部 電池反應使得導體電路溶解，又，於導體電路實施Cu-Ni 構成之針狀合金的電鍍處理時，可充分地進行電鍍析 出反應，而確實地形成粗化層。 又，依據本發明之第十群之多層印刷電路板的製造方 法，藉由較爲簡略化的方法，可於形成有粗化面或粗化層 之導體電路上形成保護膜，而可確保通孔之連接可靠度以 製造多層印刷電路板。 192 (請先閱讀背面之注意事項再填寫本頁)4531 ^ _ I V. Description of the invention (agent layer 102 (refer to FIG. 45 (b)). (8) The rain surface of the substrate 101 of the electroless plating adhesive layer 10 formed in (7) above will be A mask film printed with a black circle with a diameter of 85 # m was adhered to it, and exposed to an intensity of 500 m / cm2 generated by an ultra-high pressure mercury lamp, and then spray-developed with a DMDG solution. Then, the substrate was subjected to an ultra-high pressure mercury lamp. The generated 3000 mJ / cm2 intensity was used for exposure, and then heat treatment was performed at 10 CTC for 1 hour and 150 ° C for 5 hours to form an interlayer resin insulation layer 102 having a thickness of 35 / zm with a through hole opening 106 (refer to FIG. 45 (c )) Among them, the dimensional accuracy of the opening is as good as that of a mask film. (9) The substrate on which the through-hole opening 106 is formed is immersed in an aqueous solution containing 800 g / 1 chromic acid at 70 ° C. 19 minutes, the epoxy resin particles existing on the surface of the interlayer resin insulating layer 102 were removed by dissolution, thereby roughening the surface of the interlayer resin insulating layer 102 (depth 3 / zm) (see FIG. 45 (d)). The oxide film formed on the surface of the roughened layer 111 on the lower conductor circuit 104 is not affected. Etching did not occur. (10) Next, the substrate on which the above-mentioned treatment was completed was immersed in a neutralizing solution (manufactured by Siple Corporation) and then washed. Furthermore, the substrate on the roughened surface was treated with water. The surface is provided with a palladium catalyst (manufactured by Attic), so that the catalyst core is adhered to the surface of the interlayer resin insulating layer 102 and the inner wall surface of the through-hole opening 106. (11) Next, the substrate is immersed in In the electroless copper plating aqueous solution of the following composition, an electroless copper plating film 112 having a thickness of 0.8 # m is formed on the entire roughened surface (see FIG. 46 (a)). At this time, since the plating film is very thin, no Electrolysis 184 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------------- A___ (Please read the precautions on the back before filling this page) Order _ -Line. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 41 41 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. EDTA 50 g / 1 copper sulfate 10 g / 1 HCHO 8 ml / 1 NaOH 10 g / 1 α, α'—LiandiD t [; D fixed 80mg / l polyethylene glycol (PEG) 0.1 g / 1 [non-electrolytic plating conditions] liquid temperature of 70 ° C, 30 minutes. (12) paste a commercially available photosensitive dry film on On the electrolytic copper-plated film 112, a photomask was further installed, and exposure was performed at 100 rruf / cm2, and development processing was performed with a 0.8% sodium bicarbonate aqueous solution to provide a plating resist 103 (see FIG. 46 (b)). (13) Next, the substrate was washed and degreased with water at 50 ° C, and then washed with water at 25 ° C, and then washed with sulfuric acid, and electrolytic copper plating was performed under the following conditions to form an electrolytic plating with a thickness of 15 # m. The copper film 113 (see FIG. 46 (c)). [Aqueous solution for electrolytic plating] Sulfuric acid 180 g / 1 Copper sulfate 80 g / 1 Additive (manufactured by Attic Japan, trade name: Capalaseide GL) 1 ml / 1 [Electrolytic plating conditions] Current density 1 A / dm2 185 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm), -------- I ----- — ί (Please read the precautions on the back before filling this page ) -j = OJ · -line- 453141 A7 B7__ V. Description of the invention (唞) Time 30 minutes Temperature room temperature (14) After stripping and removing the anti-plating film 103 with 5% KOH aqueous solution, it will be located below the anti-plating film 103 The electroless plated film 112 is formed by a mixed solution of sulfuric acid and hydrogen peroxide and dissolved and removed by etching to form a conductor circuit having a thickness of 18 / zm composed of the electroless copper plated film 112 and the electrolytic copper plated film 113 ( Contains through holes 107) 105. Furthermore, the surface of the interlayer resin insulating layer 102 between the conductor circuits located in the non-formed part of the conductor circuit was immersed in an aqueous solution containing 800 g / 1 of chromic acid at 70 ° C for 3 minutes to remove the remaining in the The surface of the palladium catalyst (see Figure 46 (d)) ° (15) The substrate forming the conductor circuit 105 is immersed in copper sulfate (8 g / 1), nickel sulfate (0.6 g / 1), and citric acid (15 g / 1), PH composed of aqueous solution of sodium hypophosphite (29 g / 1) 'boric acid (31 g / 1), surfactant (manufactured by Nissin Chemical Industry Co., Ltd.'s Safinolu 465) (0.1 g / 1) In the electroless copper plating bath of = 9 ', after immersing for 1 minute, it is vibrated in the vertical and horizontal directions at a rate of 4 seconds once, and the surface of the pads of the lower conductor circuit and the through hole is made of Cu_Ni_P. Needle-shaped alloy roughened layer 111 (see FIG. 47 (a)). At this time, as a result of analyzing the roughened layer 111 to be formed through EPMA (fluorescence X-ray analysis device), it was found that the composition ratios were Cu: 98 Molar%, Ni: 1.5 Molar%, and P: 0.5 Moore. %. (16) By repeating the above processes (6) to (15), an upper-layer conductor circuit is formed to obtain a multilayer printed circuit board. However, 'Sn substitution reaction was not performed (see Figs. 47 (b) to 48 (b)). (17) Secondly, by using cresol novolac epoxy resin (186 paper sizes of Nippon Kayaku Co., Ltd., the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied. I 11 ---- · ^- ----- 11 --------- ^ (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 453 1 4 1 ___B7__ V. Description of the invention ( (Required) 46.67 parts by weight of 50% propylene-based oligomerized epoxy group (molecular weight: 4000) dissolved in glycol dimethyl ether (DMDG) so as to have a concentration of 60% by weight 8067% by weight of methyl ethyl ketone bisphenol A type epoxy resin (manufactured by Xielu Company, trade name: epoxy resin 1001) 6.67 parts by weight, which is also a bisphenol A type epoxy resin (oiled Manufactured by Xielu Company, trade name: epoxy resin E-1001 —B80) 6.67 parts by weight, imidazole hardener (manufactured by Shikoku Chemical Co., Ltd., trade name: 2E4MZ-ClSi) 1.6 parts by weight, 2 of photosensitive monomer Functional propylene monomer (manufactured by Nippon Kayaku Co., Ltd., product name: R604) 4.5 parts by weight, also a polyvalent propylene monomer (Kyoei Chemical Co., Ltd.) (Product name: DPE6A) 1.5 parts by weight, a homogenizer composed of an acrylate polymer (manufactured by Kyoei Chemical Co., Ltd., product name: Polyflo No. 75), 0,36 parts by weight was put into a container, and Stirring and mixing to prepare a mixed composition. To this mixed composition, 2.0 parts by weight of Ilukakya I-907 (made by Gibbaga & Co., Ltd.) as a photopolymerization initiator and a photosensitizer are added. DETX-S (manufactured by Nippon Kayaku Co., Ltd.) was 0.2 parts by weight and DMDG was 0.6 parts by weight to obtain a solder resist composition having a viscosity adjusted to 1.4 to 0.3 Pa s at 25 ° C. The viscosity measurement is based on a B-type viscometer (manufactured by Tokyo Metrology Instruments Co., Ltd., DVL-B) using a gyrator number 4 at 60 rpm and a gyrator number 3 at 6 rpm. (18) Secondly, on both sides of the multilayer circuit board, the above solder resist composition was coated to a thickness of 20 # m, and dried at 70 ° C for 20 minutes and 70 ° C for 30 minutes, and then a solder resist opening was drawn. A mask with a thickness of 5mm is used to make the mask close to the solder mask, and it is exposed to ultraviolet light of 1000m / Cm2, and then processed with DMTG solution to form a diameter of 187. This paper size is applicable to the country of China Standard (CNS) A4 specification (2) 0 X 297 public love) (Please read the precautions on the back before filling out this page) --δ _ Line · Employees of Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Cooperatives, printed by employees of Intellectual Property Bureau, Ministry of Economic Affairs Consumption cooperative deduction V. Invention description (ice) 200 // m opening. Furthermore, heat treatment was performed under conditions of 80 ° C for 1 hour, 100 ° C, 120tl hours, and 150 t: 3 hours to harden the solder resist layer to form a solder resist pattern layer having an opening thickness of 20 μm at 1H °. (19) Next, the substrate on which the solder resist layer 114 is formed is used in an electroless nickel plating solution containing vaporized nickel (30 g / U, sodium hypophosphite M) and sodium citrate (10 yinyang = 5). It was immersed for 20 minutes' to form a nickel plating layer 115 with a thickness of 5 # m at the opening. Furthermore, the substrate was coated with calcium cyanide (2 g / 1), ammonium chloride (75 g / 1), An electroless plating solution of sodium citrate (50 g / 1) and sodium hypophosphite (10 g / 丨) was immersed at 93 ° C for 23 seconds to form a thickness of 0.03 A m on the nickel plating layer 115. After the gold-plated layer is 116 ° (20), a solder paste is printed on the opening of the solder resist 1U 'to form a solder bump (welded body) 117 by reflow at 200 ° C to manufacture a multi-layer printing with solder bump 117 Circuit board (refer to Figure 48 (c)). [Example 58] Except in the process of (5) and (16) above, 'the substrate after the process of (5) and (16) is washed with water and acid degreased', and then Soft etch ' Then, the etching solution is sprayed on both sides of the substrate by a spraying machine, so that the surface of the lower-layer conductor circuit and the pad surface of the through hole 'the inner wall is etched' to form a rough surface on the entire surface of the lower-layer conductor circuit. Except for the rest, a multilayer printed circuit board was produced in the same manner as in Example 57. In addition, as for the etching solution, 10 parts by weight of copper (II) complex, 7 parts by weight of oxalic acid, and 5 parts by weight of calcium chloride were used. And 78 parts by weight of ion-exchanged water. 188 Degrees: Applicable to National Standards (CNS) A4 (210 X 297 Gong Chu) f ------------ Order--I-- ---- Line (Please read the precautions on the back before filling this page> Α7 Β7 4 53141 V. Description of the invention (α) [Comparative Example 12] Except for the above (6) and the same process as the above (6) An oxide film is not formed in the substrate, and the substrate on which the roughened layer is formed is immersed in a solution containing tin fluoboride (0.1 mol / 丨) and thionium (1.0 mmol / l) at a temperature of 50 ° C and a pH of 1.2. A Cu-Sn substitution reaction was performed in the plating bath, except that a Sn layer having a thickness of 0.3 # m was formed on the surface of the roughened layer. [Comparative Example 13] Except that the oxide film was not formed in the above (6) and the same process as the above (6), the substrate on which the roughened layer was formed was immersed in a solution containing tin fluoroboride (0.1 mol). / 1) and thiourea (1.0 mol / 1) at a temperature of 50t and a pH of 1.2 in the plating bath, a Cu-Sn substitution reaction was performed to form a roughened layer with a thickness of 0.3 / m outside the Sn layer The rest are the same as in Example 58 to manufacture a multilayer printed circuit board. For the multilayer printed circuit boards of Examples 57 to 58 and Comparative Examples 12 and 13 manufactured in this way, the thermal cycle test was carried out after keeping them at -55 ° C for 30 minutes and then at 125 ° C for 30 minutes. The thermal cycle was repeated 100 times. Finally, the connection of the through-hole part was cross-sectioned, and the result was observed by a microscope. As a result, in the multilayer printed circuit boards of Examples 57 to 58, all the through-holes manufactured under the same conditions were strongly connected to the conductor circuits below, and no peeling was observed at all. ; As for the multilayer printed circuit boards of Comparative Examples 12 and 13, the peeling phenomenon of the connection part of the through-hole and the conductor circuit below was observed in a part of the object 189 ------------ ---- tPlease read the notes on the back before filling this page.) Order · -line · Printed on the paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is applicable to China National Standard (CNS) A4 Regulations (2) 〇χ 297 mm) 453 1 4 1 A7 B7 V. Description of the invention (w) [Industrial availability] As explained above, according to the multilayer printed circuit board of the first group of the present invention, the multilayer printing provided The circuit board does not have a decrease in the contact strength of the conductor circuit, and has excellent heat cycle characteristics, signal transmission properties in a high frequency region, soldering heat resistance, etc. "According to the first invention of the second group of the present invention, Multilayer printed circuit board due to Because of the use of cycloolefin resins on the interlayer resin insulation layer, it has a small dielectric constant and a dielectric loss factor. Even if high-frequency signals in the GHz region are used, signal delays or signal errors will not easily occur. Also, because it has excellent mechanical properties such as rigidity, it can improve the reliability of the connection between conductor circuits, and it is also excellent in the adhesion between the conductor circuit and the interlayer resin insulation layer. In addition, according to the manufacturing method of the multilayer printed circuit board according to the second invention of the second group of the present invention, since an interlayer resin insulating layer is formed by laminating a cycloolefin-based resin layer on a conductor circuit, a solvent or the like is not required. Materials, which simplifies the manufacturing process, and can easily manufacture multilayer printed circuit boards. In addition, the multilayer printed circuit board according to the third group of the present invention can completely prevent the dissolution of the conductor circuit due to the local battery reaction of the conductor circuit when the substrate is processed by an acid or the like, and Cu- In the electroplating process of a needle alloy made of Ni-P, a plating precipitation reaction can be sufficiently performed to form a roughened layer. Furthermore, according to the fourth group of the method for manufacturing a multilayer printed circuit board of the present invention, the resin is insulated. After the metal layer is formed on the layer, the oxide film on the surface of the metal layer is removed by acid cleaning, which can prevent the electrolytic copper plating film from the metal layer. 190 This paper applies the Chinese National Standard (CNS) A4 specification (2) 0 X 297 mm) (Please read the precautions on the back before filling out this page) -1 ° 丨 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ Printed by the Employee Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 53 1 4 1 A7 B7 V. Explanation of the invention (Stripping, as a result, the reliability of the conductor circuit can be improved. Also, by flattening the surface of the conductor circuit, the delay of signal transmission can be prevented. According to the multi-layer printed circuit board of the fifth group of the present invention, the provided multi-layer printed circuit board does not reduce the adhesion strength of the conductor circuit, and it is excellent in the high-frequency region due to the planarization of the resin insulating layer. Signal transmission. In addition, the multilayer printed circuit board according to the sixth group of the present invention 'provides that the multilayer printed circuit board does not reduce the adhesion strength of the conductor circuit', and because the resin insulating layer is flattened, The high-frequency region has excellent signal transmission. It also 'can suppress the occurrence of cracks and improve the reliability of the circuit. Furthermore, it can achieve the precision of the circuit. Moreover, the multilayer printing according to the seventh invention of the first group of the present invention In the method for forming a circuit board, a first conductor layer composed of a metal having a passive state of Ni or A1 is formed on an insulating substrate, and then a second conductor layer is formed on the first conductor layer (its ionization tendency). It is smaller than the metal forming the above passive state), and the acidic etching solution that is easy to manage can be used to selectively etch the first conductor layer and the second conductor layer simultaneously, and The conductor circuit 6 is formed by the above-mentioned etching. The formed conductor circuit has not only excellent adhesion with insulating substrates such as resin substrates, but also the surface of the conductor circuits is flattened. When a signal in a high frequency region is used, Noise can be prevented. In addition, according to the method for manufacturing a multilayer printed circuit board according to the seventh invention of the second group of the present invention, the metal substrate made of Ni or A1 equal to the surface forming a passive film is sequentially formed on the insulating substrate. The first metal layer is composed of 191 paper. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------ 1 ·,-!! 1 --- order --- ------ (Please read the precautions on the back before filling this page) A7 B7 4 53 1 4 1 V. Description of the invention (The metal that becomes the above passive state has a smaller ionization tendency. The reason for the metal layer is that after the formation of the plating film, plating, and peeling of the plating film, the first conductive layer and the second conductive layer existing under the plating film can be simultaneously performed using an easy-to-manage etching solution. Worm engraving, and through this the remaining moment can form a conductor circuit. The conductor circuit formed has not only excellent adhesion to the interlayer resin insulation layer, but also because the surface of the conductor circuit is flattened, noise can be prevented from occurring when using a signal in a high frequency region. In addition, according to the metal film forming method of the first invention of the eighth group of the present invention, a conductive circuit that can be formed has a large adhesion between the nickel film formed on the substrate and other metals formed on the nickel film. Prevents peeling between metal layers due to the oxide film on the nickel film. In addition, the method for manufacturing a multilayer printed circuit board according to the second invention of the eighth group of the present invention can prevent the nickel-plated film formed in the conductor circuit and the roughened layers of the Cu-Ni-P alloy formed on the nickel film. Peeling phenomenon. In addition, according to the multilayer printed circuit board of the ninth group of the present invention, when the substrate is processed by using * acid, etc., the conductor circuit can be completely prevented from dissolving due to the local battery reaction of the conductor circuit, and Cu can be implemented in the conductor circuit. In the electroplating treatment of a needle-shaped alloy made of -Ni, the plating precipitation reaction can be sufficiently performed to form a roughened layer reliably. In addition, according to the tenth group of the multilayer printed circuit board manufacturing method of the present invention, a protective film can be formed on a conductor circuit having a roughened surface or a roughened layer by a relatively simplified method, thereby ensuring the passivity. Reliability of hole connection to manufacture multilayer printed circuit boards. 192 (Please read the notes on the back before filling this page)

.—I J ί ---· - — — — ---I I 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公釐） A7 453141 B7 五、發明説明（丨A) [符號說明] 經濟部智慧財產局員工消費合作社印製 1 ' 101 基板 3、10 導體層 4 ' 11 ' 111 粗化層 9 ' 104 (下層)導體電路 12 、 102 層間樹脂絕緣層 13 、 106 通孔用開口 14a 、 32 第1導體層 14b 、 33 第2導體層 16 、 103 防鍍膜 17 、 107 通孔 18 ' 114 防焊層 19 、 105 (上層)導體電路 31 絕緣基板 118 氧化膜 193 (請先閲讀背面之注意事項再填寫本頁) I . ，1TJ. 1r.- I I—. . I-----I--- 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X 297公釐）. —IJ ί --- ·-— — — --- II Printed on paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy Standards for national papers (CNS) A4 (210 X 297 mm) A7 453141 B7 5 Description of the invention (丨 A) [Notation] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 '101 Substrate 3, 10 Conductor layer 4' 11 '111 Roughened layer 9' 104 (lower) Conductor circuit 12, 102 Interlayer Resin insulation layers 13, 106 through-hole openings 14a, 32 first conductor layer 14b, 33 second conductor layer 16, 103 anti-plating film 17, 107 through hole 18 '114 solder mask 19, 105 (upper) conductor circuit 31 insulation Substrate 118 Oxide film 193 (Please read the precautions on the back before filling this page) I., 1TJ. 1r.- II—.. ) A4 size (210X 297mm)

Claims (1)

年月 六 申請專利範圍 3 A8 B8 C8 D8 修煩 年請 爷委 ?貝 费明 f 7；Τ 多月 W 2 准i 早日 廢所 正提 之 經濟部智慧財產局員工消費合作杜印製 1·—種多層印刷電路板，係於基板上設有樹脂絕緣層 ’而在該樹脂絕緣層上形成有導體電路，其特徵爲，上述 樹脂絕緣層係由聚烯烴系樹脂所形成者。 2. 如申請專利範圍第1項之多層印刷電路板，其中上 述聚烯烴予樹脂係熱硬化型聚烯烴樹脂或是熱可塑型聚烯 烴樹脂。 3. 如申請專利範圍第2項之多層印刷電路板’其中上 述熱可塑型聚烯烴樹脂之熔點爲200°C以上。 4. 如申請專利範圍第1〜3項中任一項之多層印刷電路 板，其中上述聚烯烴系樹脂係由以下構造式（丨)所示之一種 重複單位所形成之樹脂’或者是由兩種以上相異之上述重 複單位相互共聚合所形成之樹脂； —^~CH—CH2~j— - · (ι &gt; 其中，n爲K10000，X爲氫 '烷基、苯基、羥基、 C2〜C3之不飽和碳氫化合物、氧基或者是內醋基。 5,如申請專利範圍第丨〜3項中任一項之多層印刷電路 板，其中上述聚烯烴系樹脂係具有以下構造式（丨)所示之重 複單位，且於其分子主鏈中，具有雙鍵、氧結構、內醋結 構、單環戊二烯結構或多環戊二烯結構； 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝--------訂---------線 (諳先閱讀背面之注意事項再填寫本頁) 申請專利範圍 Α8 B8 C8 D8 —(-CH—CH2^；--- (1 ) 修煩 单請 爷委 夸明 攀示 粟η f年if桑月 口 2准I 手R 修所 正提 之 其中，η爲！〜10000 X爲氫、烷基、苯基、羥基、C2~C3之不飽和碳氫化 合物、氧基或者是內酯基。 6.如申請專利範圍第1〜3項中任一項之多層印刷電路 板，其中，上述聚烯烴樹脂係： 擇自以下述構造式（1)所示之一種重複單位所形成之樹 脂、以及上述重複單位當中相異之兩種以上彼此共聚合之 樹脂中，相異之兩種以上之聚烯烴樹脂所得的混合樹脂； 擇自以下述構造式（1)所示之一種重複單位所形成之樹 脂以及上述重複單位當中相異之兩種以上彼此共聚合之樹 脂中，相異之兩種以上之聚烯烴樹脂相互交聯所得的樹脂 ;或是 擇自以下述構造式（1)所示之一種重複單位所形成之樹 脂以及上述重複單位當中相異之兩種以上彼此共聚合之樹 脂之聚烯烴樹脂，與熱硬化型樹脂所得之混合樹脂； ---------------------訂------(—線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 严―CH2ir. X f 1 其中，η爲1〜10000 X爲氫、烷基、苯基、羥基、C2〜C3之不飽和碳氫化 合物、氧基或者是內酯基。 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 2S7公釐）Application scope of patents on June 6 A8 B8 C8 D8 If you are troublesome, please ask the grandfather? Befemin f 7; TW more than W 2 quasi i Abandoned by the Institute of Intellectual Property Bureau of the Ministry of Economic Affairs, and consumer cooperation Du printed 1 · A multilayer printed circuit board is provided with a resin insulating layer on a substrate and a conductor circuit is formed on the resin insulating layer, wherein the resin insulating layer is formed of a polyolefin resin. 2. The multilayer printed circuit board according to item 1 of the patent application range, wherein the polyolefin pre-resin-based thermosetting polyolefin resin or thermoplastic polyolefin resin is used. 3. For the multilayer printed circuit board of item 2 of the patent application, wherein the melting point of the thermoplastic polyolefin resin is 200 ° C or more. 4. The multilayer printed circuit board according to any one of claims 1 to 3, wherein the above-mentioned polyolefin-based resin is a resin formed by a repeating unit represented by the following structural formula (丨) or two Resin formed by copolymerizing more than one of the above-mentioned repeating units with each other; — ^ ~ CH—CH2 ~ j—-(ι &gt; where n is K10000 and X is hydrogen 'alkyl, phenyl, hydroxyl, C2 Unsaturated hydrocarbons, oxy groups, or lactone groups of ~ C3. 5, such as the multilayer printed circuit board of any one of the scope of application for patents No. 1 to 3, wherein the above-mentioned polyolefin-based resin has the following structural formula (丨) The repeating unit shown in the figure has a double bond, an oxygen structure, an internal vinegar structure, a monocyclopentadiene structure or a polycyclopentadiene structure in the molecular main chain; This paper size applies to the Chinese National Standard (CNS ) A4 size (210 X 297 mm) installed -------- order --------- line (谙 read the precautions on the back before filling this page) patent application scope A8 B8 C8 D8 — (-CH—CH2 ^; --- (1) The troublesome list, please ask the grandfather to exaggerate, and show that the year η f year if Sang Yuekou 2 quasi I R is mentioned in it, η is! ~ 10000 X is hydrogen, alkyl, phenyl, hydroxyl, C2 ~ C3 unsaturated hydrocarbon, oxy group or lactone group. The multilayer printed wiring board according to any one of items 1 to 3, wherein the polyolefin resin is selected from a resin formed by a repeating unit represented by the following structural formula (1), and a difference among the repeating units. Among the two or more resins copolymerized with each other, a mixed resin obtained from two or more different polyolefin resins; selected from a resin formed by one repeating unit represented by the following structural formula (1) and a phase among the above repeating units Among the two or more resins copolymerized with each other, the resin obtained by cross-linking two or more different polyolefin resins with each other; or a resin formed by selecting a repeating unit represented by the following structural formula (1) And the polyolefin resins of two or more different resins copolymerized with each other among the above-mentioned repeating units, and the mixed resins obtained from thermosetting resins; ------------------- --Order ------ (-line (Please read the note on the back first Please fill in this page again) Printed strictly by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-CH2ir. X f 1 where η is 1 to 10000 X is hydrogen, alkyl, phenyl, hydroxyl, C2 to C3 unsaturated hydrocarbons Compound, oxygen or lactone group. This paper size is applicable to the national standard (CNS) A4 specification (210 X 2S7 mm) B8 C8 D8 六、申請專利範圍 經濟部智慧財產局員工消費合作社印製 修煩 正請 i委 f Μ 芎明 ¥示 更q % % !年 if II 予W 修所 正提 。之 7·如申請專利範圍第1〜3項中任一項之多層印刷電路 板，其中上述導體電路係透過擇自長週期型之週期表的第 4A族至第1B族之第4〜第7週期的金屬(但是Cu除外）、A1 以及Sn之中一種以上的金屬構成之金屬層而設於樹脂絕緣 層上。 8. 如申請專利範圍第1〜3項中任一項之多層印刷電路 板，其中上述金屬層係設於平坦的樹脂絕緣層上。 9. 如申請專利範圍第1~3項中任一項之多層印刷電路 板，其中上述樹脂絕緣層的表面係經由電漿處理或是輝光 放電處理所形成者。 10. 如申請專利範圍第1~3項中任一項之多層印刷電路 板，其中上述基板其內部或是表面形成有導體電路。 11. 一種多層印刷電路板，係於基板上依序形成導體電 路及樹脂絕緣層，又該等導體電路透過通孔連接而形成多 層印刷電路板，其特徵爲，上述樹脂絕緣層係由環烯烴系 樹脂所形成者。 12. 如申請專利範圍第11項之多層印刷電路板，其中 上述樹脂絕緣層於1GHz之介電常數在3.0以下，介電損耗 因數在0.01以下。 13. 如申請專利範圍第11或第12項之多層印刷電路板 ，其中上述環烯烴樹脂係2—原菠烷、5-亞乙基_2-原 菠烷或是其等的衍生物所形成之單體之均聚物或是共聚合 物。 14. 如申請專利範圍第11或第12項之多層印刷電路板 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 257公釐） -------I-----裝------II 訂-!1!! ·線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4年5 3入4傪正] i 9〇· 4. 3 ^補充丨__g_ 六、申請專利範圍 ’其中上述環烯烴樹脂係熱硬化性環烯烴樹脂。 15. —種多層印刷電路板之製造方法，係於基板上依序 形成導體電路及樹脂絕緣層，又將該等導體電路透過通孔 而連接’其特徵爲，於基板上形成之導體電路上面，將由 環烯烴樹脂所形成之薄膜於真空下或是減壓下進行壓合積 mf 堂|層以形成層間樹脂絕緣層。 16. 如申請專利範圍第15項之多層印刷電路板之製造 f方法’係於基板上形成之導體電路上面，由環烯烴樹脂形 If成層間樹脂絕緣層之後，對上述之層間樹脂絕緣層照射雷 平 内 奎奮 射光以形成通孔用開口。 是月 |j 17. —種多層印刷電路板，係於設有下層導體電路之基 |ff板上依序積層形成層間樹脂絕緣層及上層導體電路而多層 正描 β之化，其特徵爲，至少於上述之下層導體電路表面處，形成 有擇自Ni、Co、Sri以及貴金屬中至少1種的金屬所構成之 金屬層，又於該金屬層上彭成有由Cu-Ni-P所構成之粗 化層。 18. 如申請專利範圍第17項之多層印刷電路板，其中 上述層間樹脂絕緣層之中係設有通孔，而該通孔係透過上 述之擇自Ni、C〇、Sn以及貴金屬中至少1種的金屬所成之 金屬層以及上述粗化層，而與於基板上形成之上述下層導 體電路電連接之。 19. 如申請專利範圍第17項之多層印刷電路板’其中 上述粗化層上，被覆形成著含有離子化傾向較Cu爲高且 在Τι以下之至少1種金屬的金屬層或是貴金屬層。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） II-------- ---- I------^*ιιιιιί &lt;請先Μ讀背面之注意事項再填寫本頁) 奶3 1 4修正‘ ’補充— 申請專利範圍 Α8 Β8 C8 D8 修煩 年請 f委 無明 m 内7 ηil f 0 f所 三提 。之 經濟部智慧財產局員工消費合作社印製 20. 如申請專利範圍第17項之多層印刷電路板，其中 上述通孔係以鍍膜塡充所形成者。 21. —種多層印刷電路板之製造方法，係於樹脂基板上 形成有樹脂絕緣層及導體電路，其特徵爲，於上述樹脂絕 緣層的表^上，設置擇自屬於長週期型之週期表的第4A 族〜第1B族範圍之第4〜第7週期的金屬、A1以及Sn之中 至少一種以上的金屬構成金屬層後，將上述金屬層表面以 酸洗淨，接著於上述金屬層上形成導體電路。 22. 如申請專利範圍第21項之多層印刷電路板之製造 方法，其中上述擇自屬於長週期型之週期表的第4A族〜第 1B族範圍之第4〜第7週期的金屬、A1以及Sn之中至少一 種以上的金屬，係擇自Ni、Cr、M〇、Ti ' W、Cu、Al、Sn 、Pt、Pd以及Au之中至少一種以上的金屬。 23. 如申請專利範圍第21項之多層印刷電路板之製造 方法，其中上述樹脂絕緣層其表面爲平坦的。 24. 如申請專利範圍第21項之多層印刷電路板之製造 方法，其中上述之酸，係擇自鹽酸、硫酸、醋酸、磷酸之 中至少一種以上的酸或是混合酸。 25. —種多層印刷電路板，係於樹脂基板之兩面設有樹 脂絕緣層，於該樹脂絕緣層上形成導體電路，其特徵爲， 上述之導體電路係於上述樹脂絕緣層的表面透過擇自長週 期型之週期表的第4A族至第1B族之第4〜第7週期的金屬。 (但是Cu除外）、A1以及Sn中一種以上的金屬構成之金屬 層而形成者。 氣--------訂-----I---線 (諳先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 丨53 1 4 1修正 年月9+，補无 90. 4. ,1 A8 B8 C8 D8 申請專利範圍 修煩Cf 丰請 26. 如申請專利範圍第25項之多層印刷電路板 上述之金屬層係包含擇自Al、Fe、W、Mo ' Sn、Νι Τι以及貴金屬中至少一種的金屬之層。 27. 如申請專利範圍第25項之多層印刷電路板 I明上述樹脂絕緣層其表面爲平坦的。 變示 - 28.如申請專利範圍第25項之多層印刷電路板 其中 Co、 其中 其中 禹’上述樹脂絕緣層係熱硬化型聚烯烴樹脂或是熱可塑性聚嫌容士 丞4烴樹脂。 29.如申請專利範圍第25項之多層印刷電路板，其中 1提上述樹脂絕緣層之表面係被施以電漿處理或是輝光放電處 之 經濟部智慧財產局員工消費合作社印 理。 30. 如申請專利範圍第25項之多層印刷電路板，其中 上述導體電路之表面係設有擇自長週期型之週期表的第4A 族至第1B族之第4〜第7週期的金屬(但是Cu除外）、A1以 及Sn之中一種以上之金屬所構成的金屬層，而於該金屬層 上形成層間樹脂絕緣層或是防焊層。 31. 如申請專利範圍第25項之多層印刷電路板，係於 上述樹脂絕緣層之表面所形成之金屬層上再形成Cu層， 接著於該Cii層上形成導體電路。 32. 如申請專利範圍第25項之多層印刷電路板，其中 上述金屬層之厚度係0.01〜〇.2em。 33. —種多層印刷電路板，係於樹脂基板之兩面形成有 透過通孔而彼此連接之下層導體電路，又於該等下層導體 電路上分別設有層間樹脂絕緣層，並進一步於該等層間樹 **&quot;-------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用辛國國家標準（CNS)A4規格（210 X 297公釐） 4 5：!B8 C8 D8 VI. Scope of patent application Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. I am asking you to submit a copy of the report. I will show you q%%! Year II if I submit it to the institute. 7 · The multilayer printed circuit board according to any one of items 1 to 3 of the scope of patent application, in which the above-mentioned conductor circuit is selected from Groups 4A to 1B of the Long Period Periodic Table A metal layer composed of one or more of periodic metal (except Cu), A1, and Sn is provided on the resin insulating layer. 8. The multilayer printed circuit board according to any one of claims 1 to 3, wherein the metal layer is provided on a flat resin insulating layer. 9. The multilayer printed circuit board according to any one of claims 1 to 3, wherein the surface of the resin insulation layer is formed by plasma treatment or glow discharge treatment. 10. The multilayer printed circuit board according to any one of claims 1 to 3, wherein the above substrate has a conductor circuit formed on the inside or the surface thereof. 11. A multi-layer printed circuit board, which sequentially forms a conductor circuit and a resin insulation layer on a substrate, and the conductor circuits are connected through a through hole to form a multi-layer printed circuit board, characterized in that the resin insulation layer is made of cycloolefin Formed by resin. 12. For a multilayer printed circuit board with the scope of patent application No. 11, in which the dielectric constant of the above-mentioned resin insulating layer at 1 GHz is below 3.0, and the dielectric loss factor is below 0.01. 13. The multilayer printed circuit board according to item 11 or 12 of the scope of patent application, wherein the cycloolefin resin is formed from 2-ortho- spinane, 5-ethylidene-2--ortho- spinane or derivatives thereof. Homopolymers or copolymers of monomers. 14. If the multilayer printed circuit board with the scope of patent application No. 11 or No. 12 is applied, the paper size of this paper applies to China National Standard (CNS) A4 (210 X 257 mm) ------- I ----- pack ------ II Order-! 1 !! · Line (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for 4 years 5 3 into 4 years] i 9〇 · 4.3 ^ Supplement 丨 __g_ VI. The scope of patent application 'The above cycloolefin resin is a thermosetting cycloolefin resin. 15. —A method for manufacturing a multilayer printed circuit board, in which a conductor circuit and a resin insulation layer are sequentially formed on a substrate, and the conductor circuits are connected through a through hole. The feature is that the conductor circuit is formed on the substrate. , The thin film formed of the cycloolefin resin is laminated under a vacuum or a reduced pressure to form an mf layer | to form an interlayer resin insulating layer. 16. For example, the method for manufacturing a multilayer printed circuit board according to item 15 of the patent application method is based on a conductor circuit formed on a substrate, and the interlayer resin insulation layer is irradiated with a cycloolefin resin if If, then the above interlayer resin insulation layer is irradiated. Raypin Nei Khuen fires light to form openings for through holes. Is month | j 17. — A multilayer printed circuit board, which is based on a substrate provided with a lower-layer conductor circuit. The ff board is sequentially laminated to form an interlayer resin insulation layer and an upper-layer conductor circuit, and the multilayer positive drawing β is characterized by: A metal layer composed of at least one metal selected from Ni, Co, Sri, and noble metal is formed at least on the surface of the above-mentioned lower conductor circuit, and Cu-Ni-P is formed on the metal layer Roughening layer. 18. For a multilayer printed circuit board with a scope of 17 as claimed in the patent application, wherein the interlayer resin insulating layer is provided with a through hole, and the through hole is selected from at least 1 of Ni, Co, Sn and precious metals through the above selection. The metal layer made of a kind of metal and the roughened layer are electrically connected to the lower-layer conductor circuit formed on the substrate. 19. The multilayer printed circuit board according to item 17 of the scope of patent application, wherein the roughened layer is coated with a metal layer or a precious metal layer containing at least one metal having a higher ionization tendency than Cu and less than Ti. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) II -------- ---- I ------ ^ * ιιιιιί &lt; Please read the back Please fill out this page again) Milk 3 1 4 Amendment '' Supplement — Patent application scope Α8 Β8 C8 D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20. If the multilayer printed circuit board under the scope of patent application No. 17 is used, the above-mentioned through holes are formed by coating. 21. —A method for manufacturing a multilayer printed circuit board, comprising a resin insulating layer and a conductor circuit formed on a resin substrate, characterized in that a periodic table selected from the long-period type is set on the table of the resin insulating layer ^ After the metal layer is formed from at least one of the metals from the 4th to the 7th cycle of the Group 4A to 1B range, the surface of the metal layer is washed with acid, and then the metal layer is washed. Form a conductor circuit. 22. The method for manufacturing a multilayer printed circuit board according to item 21 of the patent application, wherein the above-mentioned metals are selected from Groups 4A to 1B of the Periodic Table of the Long Period Type, and A1 and At least one kind of metal among Sn is selected from at least one kind of metal among Ni, Cr, Mo, Ti'W, Cu, Al, Sn, Pt, Pd, and Au. 23. The method for manufacturing a multilayer printed circuit board according to claim 21, wherein the surface of the resin insulating layer is flat. 24. The method for manufacturing a multilayer printed circuit board according to item 21 of the patent application, wherein the above-mentioned acid is selected from at least one of hydrochloric acid, sulfuric acid, acetic acid, and phosphoric acid, or a mixed acid. 25. A multilayer printed circuit board having resin insulating layers on both sides of a resin substrate, and forming a conductor circuit on the resin insulating layer, characterized in that the above-mentioned conductor circuit is selected through the surface of the resin insulating layer. Metals from Groups 4A to 1B in the long-period periodic table. (Except Cu), a metal layer made of one or more metals of A1 and Sn. Gas -------- Order ----- I --- line (谙 Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297) (Centimeter) 丨 53 1 4 1 amended 9+, without 90. 4., 1 A8 B8 C8 D8 Patent application scope repair Cf please 26. Such as the application of the scope of the patent scope of the multilayer printed circuit board 25 metal mentioned above The layer system includes a layer of a metal selected from at least one of Al, Fe, W, Mo'Sn, Nom, and a noble metal. 27. The multilayer printed circuit board of item 25 of the scope of patent application shows that the surface of the above-mentioned resin insulating layer is flat. Variation-28. For example, the multilayer printed circuit board of the scope of application for the patent No. 25, where Co, where Wherein the above-mentioned resin insulation layer is a thermosetting polyolefin resin or a thermoplastic polymethylene hydrocarbon resin. 29. For multi-layer printed circuit boards under the scope of application for patent No. 25, the surface of the resin insulation layer mentioned above is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, which is treated with plasma treatment or glow discharge. 30. For example, a multilayer printed circuit board with a scope of application for item 25, wherein the surface of the conductor circuit is provided with metals selected from the 4A to 7B cycles of the long period periodic table ( However, Cu is excluded), A1, and Sn are metal layers made of one or more metals, and an interlayer resin insulating layer or a solder mask is formed on the metal layer. 31. For a multilayer printed circuit board with the scope of application for item 25, a Cu layer is formed on the metal layer formed on the surface of the resin insulation layer, and then a conductor circuit is formed on the Cii layer. 32. The multilayer printed circuit board according to item 25 of the application, wherein the thickness of the metal layer is 0.01 to 0.2em. 33. A multi-layer printed circuit board is formed on both sides of a resin substrate with through-holes connected to lower-layer conductor circuits, and interlayer resin insulation layers are respectively provided on the lower-layer conductor circuits, and further between the layers. Tree ** &quot; ------- Order --------- line (please read the precautions on the back before filling this page) This paper size is applicable to the National Standard of China (CNS) A4 ( 210 X 297 mm) 4 5 :! D8 經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 脂絕緣層上分別形成上層導體電路’其特徵爲’上述下層 導體電路其表面至少一部份，係透過擇自長週期型之週期 表的第4A族至第1B族之第4〜第7週期的金屬(但是Cu除 外）、A丨以及Sn之中一種以上的金屬構成之金屬層而形成 修煩 参善。 - Am 34·如申請專利範圍第33項之多層印刷電路板’其中 變示 眷加上述之金屬層係擇自Al ' Fe、w、Mo、Sn、Ni ' Co、Cr、 I念Ti以及貴金屬中至少一種以上的金屬所構成者。 || 35.如申請專利範圍第33項之多層印刷電路板’其中 否4 孝^上述之樹脂絕緣層係由熱硬化型聚烯烴樹脂或是熱可塑性 聚烯烴樹脂之其中一種所構成者。 ° ^ 36.如申請專利範圍第33項之多層印刷電路板’其中 上述之層間樹脂絕緣層其表面係爲平均粗度Ra在lem以 下之平坦面。 37_—種多層印刷電路板，係於樹脂基板的兩面分別形 成導體層，而於個別之導體層上，按照待配線之圖案而設 置防鍍膜後，於非防鍍膜部分形成鍍膜，之後’去除上述 之防鍍膜，並同時將該防鍍膜下的導體層以蝕刻處理去除 而形成下層導體電路，接著透過形成於該下層導體電路上 之層間樹脂層而形成上層導體電路，其特徵爲，在上述非 防鍍膜部分形成鍍膜之後，於該鍍膜表面之至少一部份形 成擇自長週期型之週期表的第4A族至第1B族之第4〜第7 週期的金屬(但是Cu除外）、A1以及Sn中一種以上的金屬 所構成之金屬層。 7 本紙張尺度適用中@國家標準（CNS)A4規格（210 X 297公釐） k--------訂---------線 (請先閱讀背面之注意事項再填寫本頁)D8 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. 6. Scope of patent application. Upper conductor circuits are formed on the fat insulation layer. It is characterized by at least a part of the surface of the above lower conductor circuit. Groups 4A to 1B in the 4th to 7th periods of the metal (except Cu), metal layers composed of one or more metals of A 丨 and Sn form troubles. -Am 34 · If the multi-layer printed circuit board No. 33 of the scope of patent application is used, the above-mentioned metal layer is selected from Al 'Fe, w, Mo, Sn, Ni' Co, Cr, I Ti and precious metals It is composed of at least one kind of metal. || 35. The multilayer printed circuit board according to item 33 of the patent application, where No. 4 The above-mentioned resin insulating layer is composed of one of a thermosetting polyolefin resin or a thermoplastic polyolefin resin. ° ^ 36. The multilayer printed circuit board according to item 33 of the application, wherein the surface of the above-mentioned interlayer resin insulating layer is a flat surface having an average thickness Ra below lem. 37_—A multilayer printed circuit board is formed with conductive layers on both sides of a resin substrate, and after an anti-plating film is provided on the individual conductor layer according to the pattern to be wired, a plating film is formed on the non-anti-plating film portion, and then the above is removed The anti-plating film is formed, and at the same time, the conductor layer under the anti-plating film is removed by etching to form a lower-layer conductor circuit, and then an upper-layer conductor circuit is formed through an interlayer resin layer formed on the lower-layer conductor circuit. After the anti-coating film is formed on the coating film, at least a part of the surface of the coating film is formed with a metal selected from Group 4A to Group 1B in the fourth to seventh periods (except Cu), A1, and A metal layer composed of one or more metals in Sn. 7 This paper size is applicable to the @National Standard (CNS) A4 specification (210 X 297 mm) k -------- Order --------- line (Please read the precautions on the back before (Fill in this page) 正充 修補 曰 | 4 0* Λ oq 8CP8 ABaD 經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 38.—種導體電路之形成方法，其特徵爲包含下述 (a)~(c)之過程，亦即： …(a)將表面形成鈍性膜之金屬構成之第丨導體層形成在 修g絕緣基板上的過程； 妾導 (t〇於上述第1導體層上，以較上述形成純性膜之金屬 有小的離子化傾向的金屬構成之第2導體餍的形成過程； P以及 h (c)藉由使用酸性蝕刻液進行選擇性的蝕刻，以將導體 電路非形成區域之第1導體層及第2導體層同時予以蝕刻 楽曰之過程。 4所 子| 39·如申請專利範圍第38項之導體電路之形成方法， 其中於上述表面形成鈍性膜之金屬係擇自Ni、Co、Cr、Ti 、Nb、Ta、A1中至少一種。 40. 如申請專利範圍第38項之導體電路之形成方法， 其中於上述表面形成鈍性膜之金屬係Ni，又較Νι有小離 子化傾向的金屬所構成之第2導體層係擇自Cu、Sn以及 Pb中至少一種的金屬所構成者。 41. 如申請專利範圍第38項之導體電路之形成方法， 其中於上述表面形成鈍性膜之金屬係A1，又較A1有小離 子化傾向的金屬所構成之第2導體層係擇自Cu、Sn以及 Pb中至少一種的金屬所構成者。 42. 如申請專利範圍第38、39、40或41項之導體電路 之形成方法，其中上述酸性蝕刻液係硫酸水溶液、鹽酸水 溶液或是硫酸-過氧化氫混合水溶液。 t紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） *k·-------訂--------- (請先閱讀背面之&gt;£意事項再填寫本頁) 5 4 1 年90.Positive charge repair | 4 0 * Λ oq 8CP8 ABaD Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Application for a patent scope 38. A method for forming a conductor circuit, which is characterized by including the following (a) ~ (c) Process, that is: (a) the process of forming a first conductive layer made of a metal with a passive film on its surface on a insulating substrate; and conducting (t0 on the first conductive layer to form Forming process of the second conductor 构成 made of a metal having a pure ionization tendency and having a small ionization tendency; P and h (c) The selective etching is performed by using an acidic etchant to form the first non-forming region of the conductor circuit. 1 The conductor layer and the second conductor layer are simultaneously etched. 4 Soko | 39. For the method for forming a conductor circuit in the 38th area of the patent application, the metal system forming the passive film on the surface is selected from Ni. At least one of Co, Cr, Ti, Nb, Ta, and A1. 40. For example, the method for forming a conductor circuit in the 38th area of the patent application, wherein the metallic Ni forming a passive film on the surface is smaller than Ni. Ionized metals The second conductive layer is composed of at least one metal selected from Cu, Sn, and Pb. 41. For example, the method for forming a conductive circuit in the 38th area of the patent application, wherein a metal system having a passive film is formed on the surface. A1, a second conductor layer made of a metal that has a smaller ionization tendency than A1 is made of a metal selected from at least one of Cu, Sn, and Pb. 42. If the scope of patent application is 38, 39, 40, or 41 The method for forming a conductor circuit according to the above item, wherein the acidic etching solution is a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution or a sulfuric acid-hydrogen peroxide mixed aqueous solution. T The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) * k · ------- Order --------- (Please read the &gt; £ Note on the back before filling out this page) 5 4 1 year 90. 正充修補 日* 站680808 經濟邹智慧財產局員工消費合作社印製 六、申請專利範圍 43. —種多層印刷電路板之製造方法，係於絕緣基板上 形成有樹脂絕緣層與導體電路’其特徵爲，包含下述 (a)〜(e)之過程，亦即： 修煩 （a)將表面形成鈍性膜之金屬所構成之第1導體層形成 主命 在樹脂絕緣層上的過程； if (b)於述第1導體層上以較上述形成鈍性膜之金屬有 •小的離子化傾向的金屬所構成之第2導體層的形成過程； 質在_ 1^： (c)於上述第2導體層上形成防鍍膜的過程； (d)於形成有防鍍膜之上述第2導體層上、以電鍍形成 拿^第3導體層之過程；以及 絛所 正样 (e)將防鍍膜剝離之後，使用酸性蝕刻液對存在於防鍍 ° &lt; 膜之下的第1導體層及第2導體層同時予以蝕刻的過程。 44. 如申請專利範圍第43項之多層印刷電路板之製造 方法，其中於上述表面形成鈍性膜之金屬係擇自Ni、Co、 Cr、Ti、Nb、Ta ' A1 之中至少一種。 45. 如申請專利範圍第43項之多層印刷電路板之製造 方法，其中於上述表面形成鈍性膜之金屬係Ni，又較犯 有小離子化傾向的金屬所構成之第2導體層係擇自Cu、Sn 、Pb以及Fe之中至少一種的金屬所構成者。 46. 如申請專利範圍第43項之多層印刷電路板之製造 方法’其中於上述表面形成鈍性膜之金屬係A1，又較A1 有小離子化傾向的金屬所構成之第2導體層係擇自Cu、Sn 、Pb以及Fe之中至少一種的金屬所構成者。 47. 如申請專利範圍第43、44 ' 45或46項之導體電路 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公发） d--------ti-------^ (請先閉讀背面之注意事項再填寫本頁) 4 5JT4 1 年月 修正 &gt;.4· 3肩充 A8 B8 C8 D8 經濟部智慧財產局員工消費八D作社印制衣 六、申請專利範圍 的形成方法，其中上述酸性蝕刻液係硫酸水溶液、鹽酸水 溶液或是硫酸-過氧化氫混合水溶液。 48. —種金屬膜之形成方法，係將Ni膜上存在之氧化 膜以濃度2.0〜10.0莫爾/升之還原性酸的水溶液去除之後， 修煩於上述之Ni膜的表面形成其他的金屬膜。 It 49.如申請專利範圍第48項之金屬膜的形成方法，其 中上述還原性酸的水溶液係鹽酸或氫氟酸。 50. 如申請專利範圍第48或49項之金屬膜的形成方法 |$，其中上述還原性酸的水溶液濃度係4.0〜8.0莫爾/升&quot; 51. —種多層印刷電路板之製造方法，係包含有： Ή (a)於形成有下層導體電路之基板上設置層間樹脂絕緣 脩所 層，而於該層間樹脂絕緣層設置通孔用開口之過程； (b) 於上述層間樹脂絕緣層上形成金屬膜之過程； (c) 於上述金屬膜上形成防鍍膜之過程； (d) 於實施電鍍之後，形成Ni膜而於上述防鍍膜之間 形成電鍍膜及Ni膜之過程； (e) 去除上述防鍍膜之後，將既存於上述防鍍膜下之上 述金屬膜以蝕刻去除之而形成上層導體電路及通孔的過程 :以及 ⑴於上述上層導體電路上形成由Cu-Ni-P合金構成 之粗化層的過程： 其特徵爲，於上述(e)之過程結束之後，將存在於上述 Ni膜之氧化膜以濃度2.0〜10.0莫爾/升的還原性酸的水溶液 予以去除* 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 4 4 A8 B8 C8 DS 啦年1 C正 90. 4. 3 &gt;甫充 六、申請專利範圍 52.如申請專利範圍第51項之多層印刷電路板的製造 修煩方法’其中上述還原性酸的水溶液係鹽酸或氫氟酸。 f| 53·如申請專利範圍第51或52項之多層印刷電路板的 ||製造方法，其中上述還原性酸的水溶液之濃度係4.0~8.0莫 If爾/升。 |年 54.—種多層印刷電路板，係於設有下層導體電路之基 板上依序形成層間樹脂絕緣層及上層導體電路而多層化， 其特徵爲，於上述之下層導體電路的表面，形成擇自離子 化傾向大於等於Sn且小於等於A1之金屬及貴金屬所構成 ° &lt;的群中至少1種的金屬所形成之金屬層，又於該金屬層上 形成粗化層5 55. 如申請專利範圍第54項之多層印刷電路板，其中 上述擇自離子化傾向大於等於Sn且小於等於A1之金屬及 貴金屬所構成群中至少1種的金屬，係擇自Al、Cr、Fe ' Zn、Ν!、Co、Sn及貴金屬所構成的群中至少1種的金屬。 56. 如申請專利範圍第54項之多層印刷電路板，其中 上述粗化層係Cu-Ni_P合金構成之物。 57. 如申請專利範圍第54項之多層印刷電路板，其中 上述層間樹脂絕緣層係設有通孔，而該通孔係透過擇自上 述之自離子化傾向大於等於Sn且小於等於A丨之金屬及貴 金屬所構成的群中至少1種的金屬形成之金屬層以及上述 粗化層，而與於基板上形成之上述下層導體電路電連接之 58.如申請專利範圍第54項之多層印刷電路板，其中 π 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 D8 14蜍正 年月日4士 9a 4, 3-補无 六、申請專利範圍 ^上述粗化層上係被覆著含有離子化傾向較Cl1爲闻且在丁1 ||以下之至少1種金屬之金屬層或是貴金屬層。 59.如申請專利範圔第54項之多層印刷電路板，其中 If上述通孔係以鍍膜塡充所成者。 60. 一種多層印刷電路板之製造方法，係於形成導體電 If路之後施ά粗化處理而於導體電路上形成粗化面，將具有 1._3上述粗化面之導體電路以層間樹脂絕緣層被覆之後再形成 ί所通孔用開口，藉由不斷重複如此般的過程’而於絕緣性基 正提 。之板上形成夾有層間樹脂絕緣層之複數層構成之導體電路’ 其特徵爲，於導體電路上形成粗化面後，藉由施以氧化處 理，以使得上述粗化面之表面全體形成氧化膜’之後’再 形成層間樹脂絕緣層° 61. 如申請專利範圍第60項之多層印刷電路板之製造 方法，係於上述導體電路上形成粗化面之後’在大氣周圍 氣氛下，以80~200°C加熱10分鐘〜3小時來施以氧化處理 ，而於上述粗化面之表面全體形成氧化膜。 62. —種多層印刷電路板，係於形成有以粗化面構成表 面之導體電路的基板上形成層間樹脂絕緣層，而於上述層 間樹脂絕緣層形成通孔用開口，接著，於上述通孔用開口 形成導電體以構成通孔，其特徵爲，於上述以粗化面構成 之導體電路表面全體，形成由氧化膜構成之被覆層。 63. 如申請專利範圍第62項之多層印刷電路板，其中 上述由氧化膜構成之被覆層的厚度係〇.〇l~〇.2Mm。 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） II I -----k^.· i I I [ I I I [ ------I 1 (請先閱讀背面之注意事項再填寫本頁) 經濟邹智慧財產局員工消費合作社印製Positive charge repair day * Station 680808 Economy Zou Intellectual Property Bureau employee consumer cooperative printed 6. Application for patent scope 43.-A method for manufacturing multilayer printed circuit boards, which is formed with a resin insulation layer and a conductor circuit on an insulating substrate. Its characteristics are , Including the following (a) ~ (e) processes, namely: repair (a) the process of forming the first conductor layer composed of a metal with a blunt film on the surface to form the main process on the resin insulation layer; if (b ) The formation process of the second conductor layer on the first conductor layer made of a metal with a smaller ionization tendency than the metal forming the passive film as described above; The quality is _ 1 ^: (c) in the second above A process of forming a plating resist on the conductor layer; (d) a process of forming a third conductor layer by electroplating on the above-mentioned second conductor layer on which the plating resist is formed; and (e) after peeling off the plating resist , Using an acidic etchant to simultaneously etch the first conductor layer and the second conductor layer existing under the anti-plating ° film. 44. The method for manufacturing a multilayer printed circuit board according to item 43 of the scope of patent application, wherein the metal forming the passive film on the surface is selected from at least one of Ni, Co, Cr, Ti, Nb, and Ta 'A1. 45. For example, a method for manufacturing a multilayer printed circuit board according to item 43 of the scope of patent application, in which the second conductive layer composed of a metal based Ni formed of a passive film on the surface and a metal with a tendency to ionize slightly is selected. It is composed of at least one metal of Cu, Sn, Pb, and Fe. 46. For example, a method for manufacturing a multilayer printed circuit board according to item 43 of the scope of the patent application, wherein the second conductor layer composed of a metal system A1 in which a passive film is formed on the above surface and a metal with a lower ionization tendency than A1 is selected. It is composed of at least one metal of Cu, Sn, Pb, and Fe. 47. If you apply for a conductor circuit with the scope of the patent No. 43, 44 '45 or 46, the paper size applies to the Chinese National Standard (CNS) A4 (210 x 297) d -------- ti --- ---- ^ (Please close the notes on the back before filling in this page) 4 5JT4 Revised in January &gt;. 4 · 3 Shoulder Charge A8 B8 C8 D8 Printed by the employee of the Intellectual Property Bureau of the Ministry of Economic Affairs Yi Liu. The method for forming a patent application, wherein the acidic etching solution is a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, or a sulfuric acid-hydrogen peroxide mixed aqueous solution. 48. A method for forming a metal film, after removing the oxide film existing on the Ni film with an aqueous solution of a reducing acid having a concentration of 2.0 to 10.0 mole / liter, repairing the surface of the above Ni film to form other metals membrane. It 49. The method for forming a metal film according to item 48 of the application, wherein the aqueous solution of the reducing acid is hydrochloric acid or hydrofluoric acid. 50. For example, a method for forming a metal film in the 48th or 49th of the scope of application for a patent | $, wherein the concentration of the above-mentioned aqueous solution of the reducing acid is 4.0 ~ 8.0 Moore / liter &quot; 51.-a method for manufacturing a multilayer printed circuit board, It includes: (a) the process of setting an interlayer resin insulation repair layer on a substrate on which a lower-layer conductor circuit is formed, and providing an opening for a through hole in the interlayer resin insulation layer; (b) on the above interlayer resin insulation layer The process of forming a metal film; (c) the process of forming an anti-plating film on the above metal film; (d) the process of forming a Ni film and forming an electroplated film and a Ni film between the above-mentioned anti-plating film after electroplating; (e) After removing the above-mentioned anti-plating film, the above-mentioned metal film existing under the above-mentioned anti-plating film is etched away to form an upper-layer conductor circuit and a through-hole: and forming a Cu-Ni-P alloy on the upper-layer conductor circuit The process of roughening the layer: It is characterized in that after the end of the process (e), the oxide film existing on the Ni film is removed with an aqueous solution of a reducing acid having a concentration of 2.0 to 10.0 mole / liter * Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ^ -------- Order --------- line (Please read the precautions on the back before filling this page) 4 4 A8 B8 C8 DS La Nien 1 C is 90. 4. 3 &gt; Fu Chong VI, the scope of patent application 52. Such as the application of the scope of the patent application No. 51 of the multilayer printed circuit board manufacturing and repair method 'where the above reducing acid The aqueous solution is hydrochloric acid or hydrofluoric acid. f | 53 · The manufacturing method of the multilayer printed circuit board according to item 51 or 52 of the patent application, wherein the concentration of the above-mentioned reducing acid aqueous solution is 4.0 to 8.0 mol / liter. Year 54. A multilayer printed circuit board is formed by sequentially forming an interlayer resin insulation layer and an upper conductor circuit on a substrate provided with a lower-layer conductor circuit, and multilayering it. It is characterized in that it is formed on the surface of the lower-layer conductor circuit. Select a metal layer formed by at least one metal in the group consisting of metals and precious metals with an ionization tendency of Sn or more and A1 or less, and a roughened layer 5 55. If applied The multilayer printed circuit board according to the 54th aspect of the patent, wherein the above-mentioned metal is selected from at least one metal in the group consisting of a metal and a precious metal having an ionization tendency of Sn or more and A1 or less, and is selected from Al, Cr, Fe 'Zn, At least one metal in the group consisting of Ν !, Co, Sn, and noble metal. 56. The multilayer printed circuit board according to item 54 of the application, wherein the roughened layer is made of Cu-Ni_P alloy. 57. For example, the multilayer printed circuit board of the scope of application for patent No. 54 in which the above-mentioned interlayer resin insulating layer is provided with through holes, and the through holes are selected from the above-mentioned self-ionization tendency greater than or equal to Sn and less than or equal to A 丨58. A multilayered printed circuit that is electrically connected to the above-mentioned lower-layer conductor circuit formed on the substrate, and a metal layer formed of at least one kind of metal in the group consisting of metals and precious metals, and the above-mentioned roughened layer. Board, of which π This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ^ -------- Order --------- line (please read the first Please fill in this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 14 Toad date 4 ± 9a 4, 3-Supplement No. 6 Scope of patent application ^ The above roughened layer is covered A metal layer or a noble metal layer containing at least one metal that has a higher ionization tendency than Cl1 and is less than 1 || 59. The multilayer printed circuit board according to item 54 of the patent application, wherein if the above-mentioned through-holes are formed by plating. 60. A method for manufacturing a multi-layer printed circuit board, which is formed by roughening a conductor circuit after forming a conductor circuit, and forming a roughened surface on the conductor circuit. The conductor circuit having the roughened surface of 1._3 is insulated by an interlayer resin. After the layer is covered, an opening for the through hole is formed, and the insulating substrate is raised by continuously repeating such a process. A conductor circuit composed of a plurality of layers with interlayer resin insulation layers formed on the board is characterized in that after a roughened surface is formed on the conductor circuit, an oxidation treatment is performed so that the entire surface of the roughened surface is oxidized. After the film, an interlayer resin insulation layer is formed. 61. For example, the manufacturing method of the multilayer printed circuit board under the scope of the patent application No. 60 is after the roughened surface is formed on the above conductor circuit. Oxidation is performed by heating at 200 ° C for 10 minutes to 3 hours, and an oxide film is formed on the entire surface of the roughened surface. 62. A multilayer printed circuit board formed by forming an interlayer resin insulating layer on a substrate on which a conductor circuit having a roughened surface is formed, and forming an opening for a through hole in the above interlayer resin insulating layer, and then forming a through hole in the through hole. A conductive body is formed by an opening to form a through hole, and a coating layer made of an oxide film is formed on the entire surface of the conductor circuit composed of the roughened surface. 63. The multilayer printed circuit board according to item 62 of the application, wherein the thickness of the coating layer composed of the oxide film is from 0.01 to 0.2 Mm. 12 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) II I ----- k ^. · I II [III [------ I 1 (Please read the Please fill in this page again for attention) Α8 Β8 C8 D8 六、申請專利範圍 64.如申請專利範圍第1〜3項中任一項之多層印刷電路 修煩板，其中，上述聚烯烴樹脂係： -r || 擇自具有以下述構造式（1)所示之重複單位且其分子主 鏈中具有雙鍵、氧結構、內酯結構、單環戊二烯結構或多 環戊二烯結構之樹脂中，相異之兩種以上之聚烯烴樹脂所 得的混合樹脂； 擇自具有以下述構造式（1)所示之重複單位且其分子主 鏈中具有雙鍵、氧結構、內酯結構、單環戊二烯結構或多 修所 夂學環戊二烯結構之樹脂中，相異之兩種以上之聚烯烴樹脂彼 。疋 此交聯所得的樹脂；或是 擇自具有以下述構造式（1)所示之重複單位且其分子主 鏈中具有雙鍵、氧結構、內酯結構、單環戊二烯結構或多 環戊二烯結構之樹脂所形成之聚烯烴樹脂，與熱硬化型樹 脂所得之混合樹脂： 一·^-CH—Cfl2-^— ⑴ X 其中，η爲1〜10000 X爲氫、烷基、苯基、羥基' C2〜C3之不飽和碳氫化 合物、氧基或者是內酯基。 I!含·-------訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作钍印*'ίί 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱）Α8 Β8 C8 D8 6. Application for patent scope 64. For the multilayer printed circuit repairing board according to any one of claims 1 to 3, in which the above-mentioned polyolefin resin is: -r || Among resins having a repeating unit represented by formula (1) and having a double bond, an oxygen structure, a lactone structure, a monocyclopentadiene structure, or a polycyclopentadiene structure in the main chain of the molecule, two or more different ones A mixed resin obtained from a polyolefin resin; selected from a compound having a repeating unit represented by the following structural formula (1) and having a double bond, an oxygen structure, a lactone structure, a monocyclopentadiene structure, or a polycyclic structure in its molecular main chain Among the resins having a cyclopentadiene structure, two or more polyolefin resins are different.树脂 The resin obtained by this cross-linking; or is selected from the group having a repeating unit represented by the following structural formula (1) and having a double bond, an oxygen structure, a lactone structure, a monocyclopentadiene structure, or a polycyclic ring in its molecular main chain Polyolefin resin formed from resin with pentadiene structure, and mixed resin obtained from thermosetting resin:-^ -CH-Cfl2-^-⑴ X where η is 1 ~ 10000 X is hydrogen, alkyl, benzene Unsaturated hydrocarbon, hydroxy 'C2 ~ C3, oxy or lactone group. I! Contains -------- Order --------- (Please read the precautions on the back before filling out this page) The stamp of consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs * 'ί This paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 public love)
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JP27279998 1998-09-28
JP27601098A JP2000114726A (en) 1998-09-29 1998-09-29 Printed wiring board
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JP29045098A JP2000124601A (en) 1998-10-13 1998-10-13 Method for manufacturing printed wiring board
JP31044598A JP2000138456A (en) 1998-10-30 1998-10-30 Multilayered printed wiring board and its manufacture

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