TW201124502A

TW201124502A - Adhesive film with copper foil

Info

Publication number: TW201124502A
Application number: TW099122977A
Authority: TW
Inventors: Hirohisa Narahashi; Tadahiko Yokota; Shigeo Nakamura
Original assignee: Ajinomoto Kk
Priority date: 2009-07-14
Filing date: 2010-07-13
Publication date: 2011-07-16
Also published as: JP5625566B2; TWI498408B; KR101682886B1; JP2011040727A; KR20110006626A

Abstract

To provide an adhesive film with a copper foil which enables a multilayer printed wiring board where a copper layer having high adhesive strength for an insulating layer is formed to be obtained although surface roughness of the insulating layer formed on a circuit board is extremely small. The copper foil having a copper alloy plating layer formed on a surface is stuck, by a specific method, on a curable resin composition layer formed on a base.

Description

201124502 六、發明說明：【發明所屬之技術領域】著薄膜及使用其之多層印刷本發明係關於附銅箔之黏配線板的製造方法。【先前技術】自過去已知於硬化性樹脂糙面，使硬化性樹脂組成物層凹凸上的錨效果，提高銅箔與脂組成物層）的密著力，可將。又，將銅箔貼合於硬化性樹經除去銅箔，將銅箔的粗糙面印製絕緣層的凹凸的錨效果，敷導體層之密著的技術爲已知凹凸變大時’雖鍍敷導體層的形成回路時，以蝕刻不要的導凸部分之導體層，在充分除去進行蝕刻時，會有回路配線之化的問題。另一方面’已知作爲等離止光反射，將表面以Ni合金利文獻1 )。組成物層表面貼合銅箔之粗硬化後藉由銅箔之粗糙面的絕緣層（硬化後的硬化性樹銅箔作爲導體層使用的技術脂組成物層並使其硬化後，凹凸轉印製絕緣層，藉由轉提高與形成於絕緣層上的鍍。但，一般若絕緣層表面的剝離強度會變大，於該反面體層方式除去時，難除去凹凹凸部分之導體層的條件下溶解顯著化，成爲微細配線子顯示面板用的銅箔，欲防等進行黑化處理的銅箱（專 [先行技術文獻] 201124502 [專利文獻] [專利文獻1]國際公開第2005/〇79 1 30號手冊【發明內容】本發明的課題係提供即使於回路基板所形成之絕緣層的表面粗度極小，在對於該絕緣層而言爲高密著強度下可得到形成銅層的多層印刷配線板之附銅箔之黏著薄膜。本發明者們經重複詳細硏究結果，發現藉由將特定銅合金鍍敷層形成於表面的銅箔，以特定方法貼合於形成於支持體上的硬化性樹脂組成物層，可解決上述課題而完成本發明。即，本發明含有以下內容。〔1〕一種附銅箔之黏著薄膜，其特徵爲將藉由電鍍於表面上形成銅合金鍍敷層的銅箔，於形成於支持體上的硬化性樹脂組成物層上，貼合成如銅合金鍍敷層與硬化性樹脂組成物層銜接。〔2〕如〔1〕記載的附銅箔之黏著薄膜，其特徵爲銅合金鍍敷層表面經防鏽處理》〔3〕如〔1〕或〔2〕記載的附銅箔之黏著薄膜，其特徵爲銅合金鍍敷層的表面粗度（Ra)爲300nm以下。〔4〕一種多層印刷配線板的製造方法，其特徵爲含有以下步驟（A )〜（D )； (A )剝離〔1〕〜〔3〕中任一所記載的附銅箱之黏著薄膜的支持體後，將硬化性樹脂組成物層層合於內胃 -6 - 201124502 回路基板的步驟、 (B )硬化硬化性樹脂組成物層後形成絕緣層之步驟、 (C )將銅箔以銅蝕刻液除去之步驟、 (D )於絕緣層表面藉由無電解鍍敷形成銅層之步驟。〔5〕如〔4〕記載的多層印刷配線板的製造方法，其特徵爲進一步含有（E)將銅合金鑛敷層以氧化劑溶液除去的步驟。〔6〕如〔4〕或〔5〕記載的多層印刷配線板的製造方法，其特徵爲絕緣層表面的表面粗度（Ra)爲300nm 以下。〔7〕如〔4〕〜〔6〕中任一項所記載的多層印刷配線板的製造方法，其特徵爲進一步含有（F)形成肓孔之步驟。〔8〕如〔4〕〜〔7〕中任一項所記載的多層印刷配線板的製造方法，其特徵爲進一步含有（G )去膠渣步驟〇〔9〕如〔4〕〜〔8〕中任一項所記載的多層印刷配線板的製造方法’其特徵爲進一步含有（H)藉由電鍍形成導體層的步驟。〔1 0〕如〔4〕〜〔9〕中任一項所記載的多層印刷配線板的製造方法’其特徵爲進一步含有（I )於導體層形成回路的回路形成步驟。 201124502 〔11〕一種多層印刷配線板的製造方法，其特徵爲數次重複進行上述步驟（A)〜步驟（I)止的一連串步驟而層合多段增層（build-up layer)。 [發明的效果] 本發明可提供藉由將於表面形成銅合金鍍敷層的銅箔 ’以特定方法貼合於支持體上所形成之硬化性樹脂組成物層’即使形成於回路基板的絕緣層表面粗度爲極小，以對於該絕緣層爲高的密著強度下可得到形成銅層的多層印刷配線板之附銅箔的黏著薄膜。 [實施發明的形態] 以下詳細說明。 <附銅箔之黏著薄膜> 本發明的附銅箔之黏著薄膜爲，將藉由電鍍於表面形成銅合金鍍敷層的銅箔，於支持體上所形成之硬化性樹脂組成物層上’貼合成如銅合金鍍敷層與硬化性樹脂組成物層銜接者。 [支持體] 支持體係爲具有自身支持性的薄膜至薄片狀物，可適用塑質薄膜。作爲塑質薄膜，可舉出聚對酞酸乙二酯、聚 2，6-萘二酸乙二醇酯、聚醯亞胺、聚醯胺醯亞胺、聚醯胺 -8 - 201124502 、聚四氟乙烯、聚碳酸酯等薄膜，以聚對酞酸乙二酯薄膜、聚2,6-萘二酸乙二醇酯薄膜爲佳，其中亦以便宜的聚對酞酸乙二酯薄膜爲特佳。支持體可使用販賣者，具體可舉出T6〇 ( Tor ay (股 )製之聚對酞酸乙二酯薄膜）、A4100 (東洋紡（股）製之聚對酞酸乙二酯薄膜）、Q83 ( Teijindupontfilm (股）製之聚2,6-萘二酸乙二醇酯薄膜）、Lintec (股）製之附有醇酸型離型劑（AL-5 )之聚對酞酸乙二酯薄膜、 Diafoil B100 (三菱化學聚酯薄膜（股）製之聚對酞酸乙二酯薄膜）等。於支持體表面上欲使與樹脂組成物層的剝離性良好，可施予氟樹脂、醇酸樹脂、聚矽氧樹脂、聚烯烴樹脂、聚乙烯醇樹脂、丙烯酸樹脂、聚酯樹脂、三聚氰胺樹脂等離型處理，厚度以0.0 1〜0 · 2 y m爲佳。比0.0 1 # m小時，作爲離型劑的機能有難以發揮之傾向，若比0_2 y m大時，由費用上來看有實用性劣化之傾向。支持體的厚度雖無特別，以1 〇〜70 /z m爲佳，以i 5 〜7 0 // m爲較佳。厚度若比1 〇 # m小時，有著處理性劣化的傾向’支持體的剝離性有降低之傾向。又，厚度若比 7 0 # m大時，由費用面及實用性有劣化之傾向。與硬化性樹脂組成物層銜接的支持體表面可施予電暈處理等表面處理。又，未與硬化性樹脂組成物層銜接的支持體表面上，亦可施予消光處理、電暈處理等表面處理。 201124502 [硬化性樹脂組成物層] 使用於硬化性樹脂組成物層之硬化性樹脂組成物若爲適用於多層配線基板的絕緣層者即可，並無特別限定。具體可使用於環氧基樹脂、氰酸酯樹脂、酚樹脂、雙馬來醯亞胺-三嗪樹脂、聚醯亞胺樹脂、丙烯酸樹脂、乙烯苯甲基樹脂等熱硬化性樹脂中至少添加該硬化劑的組成物。含有環氧基樹脂及硬化劑的組成物爲佳，同時於環氧基樹脂及硬化劑中進一步含有熱塑性樹脂的組成物爲特佳。作爲環氧基樹脂，雖無特別限制，具體可舉出雙酚A 型環氧基樹脂、聯苯基型環氧基樹脂、萘酚型環氧基樹脂、萘型環氧基樹脂、雙酚F型環氧基樹脂、含磷環氧基樹脂、雙酚S型環氧基樹脂、脂環式環氧基樹脂、脂肪族鏈狀環氧基樹脂、酚漆用酚醛型環氧基樹脂、甲酚漆用酚醛型環氧基樹脂、雙酚A漆用酚醛型環氧基樹脂、具有丁二稀結構之環氧基樹脂、雙酚的二環氧丙基醚化物、萘二醇的二環氧丙基醚化物、酚類的環氧丙基醚化物、及醇類的二環氧丙基醚化物、以及彼等環氧基樹脂的烷基取代體及氫化物等。亦可組合1種或2種以上的環氧基樹脂使用〇環氧基樹脂爲這些中以耐熱性、絕緣信賴性高的觀點來看，以雙酚A型環氧基樹脂、萘酚型環氧基樹脂、萘型環氧基樹脂、聯苯基型環氧基樹脂、具有丁二稀結構之環氧基樹脂爲佳，以日本環氧樹脂（股）製「jER8 2 8 EL 」（液狀雙酚A型環氧基樹脂）、DIC (股）製「HP403 2 -10- 201124502 」、「HP4032D〕（蔡型2官能環與基樹月日」、DIC (股 )製「HP4700」（萘型4官能環氧基樹目曰）、東都化成 (股）製「ESN-475V」「ESN-185V」（萘酣型環氧基樹脂）、Dai eel化學工業（股）製「PB-3600」（具有丁二稀結構之環氧基樹脂）、日本化藥（股）製「NC3 000H」 ' 「NC3000L」、「NC3100」、「NC3000」（聯苯基型環氧基樹脂）、日本環氧樹脂（股）製「YX4000」（聯苯基型環氧基樹脂）、東都化成（股）製GK3207(聯苯基型環氧基樹脂）、日本環氧樹脂（股）製「ΥΧ8800」 (含有蒽骨架型環氧基樹脂）爲較佳。環氧基樹脂若以黏著薄膜的形態使用時，欲兼具耐熱性或破斷強度與層合性，可合倂於1分子中具有2個以上環氧基，在2 〇 °C下爲液狀的芳香族系環氧基樹脂、或在熔點以上經溶解後，在室溫成爲液狀的結晶性芳香族系環氧基樹脂、與1分子中具有3個以上環氧基，在2 (TC下爲固體狀的芳香族系環氧基樹脂而使用爲佳。又，該固體狀的芳香族系環氧基樹脂欲提高玻璃轉移溫度等物性，以環氧基當量爲230以下者爲佳，以環氧基當量爲15〇〜23〇之範圍者爲較佳。該液狀的芳香族系環氧基樹脂與固體狀的芳香族系環氧基樹脂之比率在質量比（液狀芳香族系環氧基樹脂：固體狀芳香族系環氧基樹脂）以1 : 〇.3〜2的範圍爲佳’以1 : 0.5〜1 · 5的範圍爲較佳，以1 : 〇 . 5〜1 · 2 的範圍爲更佳’以1 : 〇 . 5〜i的範圍爲進一步更佳。作爲硬化劑，雖無特別限制，具體可舉出胺系硬化劑 -11 - 201124502 、胍系硬化劑、咪唑系硬化劑、含有三嗪骨架之酚系硬化劑、酚系硬化劑、含有三嗪骨架之萘酚系硬化劑、萘酚系硬化劑、酸酐系硬化劑或彼等環氧基加成物或經微膠囊化者、活性酯系硬化劑、苯並噁嗪系硬化劑、氰酸酯樹脂等。以酚系硬化劑、萘酚系硬化劑、含有三嗪骨架之酚系硬化劑、含有三嗪骨架之萘酚系硬化劑爲佳。這些硬化劑可單獨使用1種或倂用2種以上。對於酚系硬化劑、萘酚系硬化劑，雖無特別限制，具體可舉出 MEH-7700、MEH-7810、MEH-7851 (明和化成（股）製）、NHN、CBN、GPH (日本化藥（股）製）、SN170 、SN180、SN190、SN47 5、SN48 5、SN49 5、SN3 7 5、 SN395 (東都化成（股）製）、TD2090 ( DIC(股）製）等。含有三嗪骨架之酚系硬化劑雖無特別限制，具體可舉出 LA3018、LA7052、LA7054、LA 1 3 56 ( DIC(股）製）等。活性酯系硬化劑若爲具有作爲環氧基樹脂的硬化劑之機能者即可，並無特別限制，但具體以使用1分子中具有 2個以上酚酯類、硫酚酯類、N -羥基胺酯類、雜環羥基化合物的酯類等反應活性高的酯基之化合物爲佳。活性酯系硬化劑係以藉由羧酸化物及/或硫羧酸化物與羥基化合物及/或硫醇化合物之縮合反應而得者爲佳。由耐熱性等觀點來看，以由羧酸化物與酚化合物或萘酚化合物所得之活性酯系硬化劑爲更佳。作爲羧酸化物，具體可舉出安息香酸、乙酸、琥珀酸、馬來酸、衣康酸、苯二甲酸、異苯二甲酸、對苯二甲酸、均苯四甲酸等。作爲酚化合物或萘酚 -12- 201124502 化合物，可舉出氫醌、間苯二酚、雙酚A、雙酚F、雙酚 S、酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、酸、〇 -甲酣、m -甲酣、ρ -甲酣、兒茶酣，α-萘酣、/3-萘酚、1，5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、間苯三酚、苯三醇、二環戊二烯二酚、酚漆用酚醛等。可使用一種或倂用2種之活性酯系硬化劑。又’作爲活性酯系硬化劑，亦可使用揭示於J Ρ - A - 2 0 0 4 - 4 2 7 7 6 1公報的活性酯系硬化劑，有亦可使用販賣者。作爲經販賣的活性酯系硬化劑，具體可舉出含有二環戊二烯二酚結構者之EXB-945 1 、EXB-9460 (DIC (股）製），作爲酚漆用酚醛的乙醯基化物，可舉出D C 8 0 8 (日本環氧樹脂（股）製），作爲酚漆用酚醛的苯甲醯化物，可舉出 YLH1026(日本環氧樹脂（股）製）等。苯並噁嗓系硬化劑具體可舉出F-a、P-d (四國化成（股）製）、HFB 2006M (昭和高分子（股）製）等。氰酸酯樹脂具體可舉出漆用酚醛型（酚漆用酚醛型、烷基酚漆用酚醛型等）氰酸酯樹脂、雙酚型（雙酚A型 '雙酚F型、雙酚S型等）氰酸酯樹脂及彼一部份經三嗪化的預聚物等。作爲較佳氰酸酯樹脂，具體可舉出雙酚A 二氰酸酯、聚酚氰酸酯（寡（3 -伸甲基-1 , 5 -伸苯基氰酸酯 )、4,4’-伸甲基雙（2,6-二甲基苯基氰酸酯）、4,4’-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙（4-氰酸酯）苯基丙烷、1，1_雙（4-氰酸酯苯基甲烷）、雙（4- -13 - 201124502 氰酸酯-3,5-二甲基苯基）甲烷、1，3-雙（4-氰酸酯苯基-1-(甲基亞乙基））苯、雙（4-氰酸酯苯基）硫醚、雙（4-氰酸酯苯基）醚等2官能氰酸酯樹脂、酚漆用酚醛、甲酚漆用酚醛等所衍生的多官能氰酸酯樹脂、這些氰酸酯樹脂的一部份經三嗪化的預聚物等。作爲經販賣的氰酸酯樹脂，可舉出Lonza Japan (股）製之PT30 (酚漆用酚醛型多官能氰酸醋樹脂、氰酸醋當量124) 、Lonza Japan (股）製之BA2 3 0 (雙酚A二氰酸酯的一部份或全部經三嗪化成爲三聚物的預聚物、氰酸酯當量23 2 ) 、Lonza Japan ( 股）製之DT4000 (二環戊二烯型多官能氰酸酯樹脂、氰酸酯當量140 )等。環氧基樹脂與硬化劑之配合比率以含有三嗪骨架之酚系硬化劑、酚系硬化劑、含有三嗪骨架之萘酚系硬化劑、萘酚系硬化劑的情況爲，對於環氧基樹脂的環氧基當量1 而言，這些硬化劑的酚性羥基當量成爲0.4〜2.0之範圍的比率爲佳’成爲〇·5〜1.0之範圍的比率爲較佳。反應基當量比若爲該範圍外時，硬化物的機械強度或耐水性會有降低之傾向。於本發明中之熱硬化性樹脂組成物中，加入硬化劑，並可進一步添加硬化促進劑。作爲如此硬化促進劑，若具有硬化促進作用即可，並無特別限制，例如可舉出咪唑化合物、二氮雜二環化合物、有機膦.鱗化合物等。具體而言可舉出四國化成（股）製的2ΜΖ(2 -甲基咪唑）、 C11Z(2 -十一烷基咪唑）、C17Z(2 -十七烷基咪唑）、 -14- 201124502 1.2DMZ ( 1,2 -二甲基咪唑）、2E4MZ ( 2 -乙基-4-甲基咪唑 )、2PZ ( 2-苯基咪唑）、2P4MZ ( 2-苯.基-4-甲基咪唑）、1B2MZ ( 1-苯甲基-2-甲基咪唑）、：1B2PZ ( 1-苯甲基- 2-苯基咪唑）、2MZ-CN(1-氰基乙基-2-甲基咪唑）、 C11Z-CN ( 1-氰基乙基-2-十一烷基咪唑）、2E4MZ-CN ( 1-氰基乙基-2-乙基-4-甲基咪唑）、2PZ-CN ( 1-氰基乙基-2 -苯基咪唑）、C11-CNS ( 1-氰基乙基-2-十一烷基咪唑偏苯三酸）、2PZCNS-PW ( 1-氰基乙基-2-苯基咪唑偏苯三酸）、21^2-八（2,4-二胺基-6-〔2’-甲基咪唑基-(1’）〕- 乙基-8-三嗪、（3117-八（2,4-二胺基-6-〔2’-^--烷基咪唑基-(1，）〕-乙基-S-三嗪）、2E4MZ-A ( 2,4-二胺基-6-〔 2’-乙基- 4’-甲基咪唑基-(1，）〕-乙基-s-三嗪）、2MA-01<：(2,4-二胺基-6-〔2’-甲基咪唑基-(1’）〕-乙基-5-三嗪異三聚氰酸付加物）、2PHZ-PW ( 2-苯基-4,5-二羥基甲基咪唑）、2P4MHZ-PW ( 2 -苯基-4-甲基-5-羥基甲基咪唑 )、TBZ(2,3 -二氫-1H-吡咯並〔l，2-a〕苯並咪唑、SFZ (卜十二烷基-2-甲基-3-苯甲基咪唑鑰氯化物）、P-0505 (環氧基-咪唑加成物）等咪唑化合物、San-apro (股）製的 U-CAT S A 1 ( DBU-酚鹽）、U-CAT S A 102 ( DBU-辛基酸鹽）'U-CAT SA 506 (DBU-p -甲苯磺酸鹽）、1；-CAT SA 603 ( DBU-甲酸鹽）、U-CAT SA 810 ( DBU -鄰苯二甲酸鹽、U-CAT SA 831、841、851、U-CAT 881 ( DBU-酚漆用酚醛樹脂鹽）、U-CAT 5002 ( N-苯甲基DBU-四苯基硼酸鹽）等二氮雜二環化合物、北興化學工業（股 -15- 201124502 )製之TPP-S (三苯基膦三苯基硼烷）、ΤΡΡ-Κ (四苯基鱗四苯基硼酸鹽）、TBP-DA (四丁基鱗癸酸鹽）等有機膦·鱗化合物等。使用硬化促進劑時，該使用量雖無特別限定，但對於環氧基樹脂而言在〇.1〜3.0質量％的範圍下使用爲佳。對於本發明所使用之熱硬化性樹脂組成物，由可對於硬化後的組成物賦予適度可撓性的觀點來看，可進一步添加熱塑性樹脂。作爲熱塑性樹脂，雖無特別限制，具體可舉出苯氧基樹脂、聚乙烯縮醛樹脂、聚醯亞胺、聚醯胺醯亞胺、聚醚颯、聚颯等。熱硬化性樹脂可使用1種或倂用 2種以上。將熱硬化性樹脂組成物的不揮發部分作爲100 質量％時，該熱塑性樹脂的配合比率以0.5〜60質量％爲佳，以3〜50質量％爲較佳。熱塑性樹脂的配合比率若未達0.5質量％時，因樹脂組成物黏度變低，有著難以形成均勻熱硬化性樹脂組成物層的傾向，若超過6 0質量％時，樹脂組成物的黏度會過高，有著對基板上的配線圖形之埋入變的困難之傾向。苯氧基樹脂雖無特別限制，具體可舉出東都化成（股 )製FX2 80、FX293、日本環氧樹脂（股）製ΥΧ8100、 YL6954、YL6974、YL7482、YL7553、YL6794、YL7213 、YL7290 等》作爲聚乙烯縮醛樹脂，以聚乙烯丁醛樹脂爲佳，作爲聚乙烯縮醛樹脂，具體可舉出電氣化學工業（股）製的電化 Butyral 4000-2 、 5000-A 、 6000-C 、 6000-EP 、積水化 -16- 201124502 學工業（股）製的s-recl BH系列、BX系列、KS系列、 BL系歹IJ、BM系列等。作爲聚醯亞胺的具體例，可舉出新日本理化（股）製的聚醯亞胺「LiquacoatSN20」、「LiquacoatPN20」等。又可舉出將2官能性羥基末端聚丁二稀、二異氰酸酯化合物及四鹼酸酐經反應所得的線狀聚醯亞胺（ JP-A-2〇〇6-37〇83公報所記載者）、含有聚矽氧烷骨架之聚醯亞胺（JP-A-2002-12667 公報、JP-A-2000-319386 公報等所記載者）等變性聚醯亞胺。作爲聚醯胺醯亞胺的具體例，可舉出東洋紡績（股）製的聚醯胺醯亞胺「 VylomaxHRllNN」、「 Vyl〇maxHR16NN」。又可舉出日立化成工業（股）製的含有聚矽氧烷骨架之聚醯胺醯亞胺「KS9100」、「 KS 93 00」等變性聚醯胺醯亞胺。作爲聚醚碾的具體例，可舉出住友化學（股）製的聚醚颯「PES 5 003 P」等。作爲聚颯的具體例，可舉出Solvay Advanced Polymers (股）製的聚颯「P1700」、「P3500」等。於本發明中之熱硬化性樹脂組成物中，可含有欲使硬化後的組成物低熱膨張化等之無機塡充材。作爲無機塡充材，具體可舉出二氧化矽 '氧化鋁、雲母、mica、矽酸鹽、硫酸鋇、氫氧化鎂、氧化鈦等，以二氧化矽、氧化鋁爲佳’特佳爲無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽等二氧化矽。作爲二氧化矽以球狀者爲 -17- 201124502 佳》且，無機塡充劑由絕緣信賴性的觀點來看，以平均粒徑爲3 μ m以下者爲佳，以平均粒徑以1 · 5 μ m以下者爲較佳。無機塡充材的平均粒徑可藉由依據Mie散射理論的雷射衍射·散射法進行測定。具體爲可藉由雷射衍射式粒度分佈測定裝置，將無機塡充材的粒度分佈以體積爲基準作成，將該等量徑作爲平均粒徑下進行測定。測定樣品爲使用將無機塡充材藉由超音波而分散於水中者爲佳。作爲雷射衍射式粒度分佈測定裝置，可使用（股）堀場製作所製 LA-500 等。無機塡充材欲提高耐濕性、分散性等，可藉由以下表面處理劑進行表面處理爲佳。作爲表面處理劑，可舉出胺基丙基甲氧基矽烷、胺基丙基三乙氧基矽烷、脲基丙基三乙氧基矽烷、N-苯基胺基丙基三甲氧基矽烷、N-2 (胺基乙基）胺基丙基三甲氧基矽烷等胺基矽烷系耦合劑；環氧丙氧基丙基三甲氧基矽烷、環氧丙氧基丙基三乙氧基矽烷、環氧丙氧基丙基甲基二乙氧基矽烷、環氧丙基丁基三甲氧基矽烷、（3,4_環氧基環己基）乙基三甲氧基矽烷等環氧基矽烷系耦合劑；氫硫基丙基三甲氧基矽烷、氫硫基丙基三乙氧基矽烷等氫硫基矽烷系耦合劑；甲基三甲氧基矽烷、十八烷基三甲氧基矽烷 '苯基三甲氧基矽烷、甲基丙烯氧基丙基三甲氧基矽烷、咪唑矽烷、三嗪矽烷等矽烷系耦合劑；六甲基二矽烷基胺、六苯基二矽烷基胺、二甲基胺基三甲基矽烷、三矽氮烷' 環三矽氮烷、1，1，3,3，5,5-六甲基環三矽氮烷等有機矽氮烷化合物；丁基鈦酸鹽二聚物 -18 - 201124502 、鈦辛二醇酸鹽、二異丙氧基鈦雙（氨化三乙醇）、二羥基鈦雙乳酸鹽、二羥基雙（銨乳酸鹽）鈦、雙（二辛基焦磷酸酯）伸乙基鈦酸鹽 '雙（二辛基焦磷酸酯）氧基乙酸酯鈦酸鹽、三-n-丁氧基鈦單硬脂酸鹽、四_n_丁基鈦酸鹽、四（2-乙基己基）鈦酸鹽、四異丙基雙（二辛基磷酸酯 )鈦酸鹽、四辛基雙（雙十三烷基磷酸酯）鈦酸鹽、四（ 2,2-二烯丙基氧基甲基-1-丁基）雙（雙十三烷基）磷酸酯鈦酸鹽、異丙基三辛醯基欽酸鹽、異丙基三枯嫌基苯基欽酸鹽、異丙基三異硬脂醯基鈦酸鹽、異丙基異硬脂醯基二丙烯基鈦酸鹽、異丙基二甲基丙烯基異硬脂醯基鈦酸鹽、異丙基三（二辛基磷酸酯）鈦酸鹽、異丙基參十二烷基苯磺醯基鈦酸鹽、異丙基參（二辛基焦磷酸酯）鈦酸鹽、異丙基三（N -醯胺乙基·胺基乙基）鈦酸鹽等鈦酸鹽系耦合劑等。這些可單獨使用1種或亦可併用2種以上。硬化性樹脂組成物中之無機塡充劑的含有量若爲不阻斷本發明的效果之程度下並無特別限制，將硬化性樹脂組成物的不揮發分作爲100質量％時，以20〜80質量％爲佳，以20〜70質量％爲較佳，以30〜70質量％爲更佳，以40〜70質量％爲進一步更佳，以4〇〜60質量％爲特佳。無機塡充劑的含有量若未達2〇質量％時，有著熱膨張率之降低效果無法充分發揮的傾向，無機塡充劑的含有量若超過80質量％時，有著硬化物之機械強度降低等傾向。又，硬化性樹脂組成物以提高硬化物之機械強度、應力緩和效果等目的下可含有固體狀橡膠粒子。橡膠粒子爲 -19* 201124502 於調製樹脂組成物時的有機溶劑中亦不會溶解，與環氧基樹脂等樹脂組成物中之成分亦不會相溶，於樹脂組成物的清漆中以分散狀態存在者爲佳。如此橡膠粒子一般爲將橡膠成分的分子量增大至不溶解於有機溶劑或樹脂的水準，以粒子狀方式而調製》作爲橡膠粒子，具體可舉出芯殼型橡膠粒子、交聯丁腈丁二稀橡膠粒子、交聯苯乙烯丁二稀橡膠粒子、丙烯酸橡膠粒子等。芯殼型橡膠粒子爲粒子具有芯層與殼層的橡膠粒子，具體可舉出外層的殼層爲玻璃狀聚合物，內層的芯層爲橡膠狀聚合物所構成之2層結構、或外層的殼層爲玻璃狀聚合物，中間層爲橡膠狀聚合物，芯層爲玻璃狀聚合物所構成之3層結構者等。玻璃狀聚合物層具體係由甲基丙烯基酸甲基的聚合物等所構成，橡膠狀聚合物層具體係由丁基丙烯酸酯聚合物（丁基橡膠）等所構成。作爲芯穀型橡膠粒子的具體例，可舉出 StaphyloidAC3 8 3 2 > AC3816N ( ganz 化成（股）商品名）、Metablen KW-4426 ( MITSUBISHI RAYON (股）商品名 )。作爲丙烯醯基丁二稀橡膠（NBR)粒子的具體例，可舉出 XER-91C平均粒徑 0.5;zm、JSR (股）製）等。作爲苯乙烯丁二稀橡膠（SBR )粒子的具體例，可舉出 XSK-500 (平均粒徑0.5 /z m、JSR (股）製）等。作爲丙烯酸橡膠粒子的具體例，可舉出Metablen W3 00A (平均粒徑〇.l#m) 、W450A (平均粒徑〇.5/zm)( MITSUBISHI RAYON (股）製）等。本發明中之橡膠粒子的平均粒徑可使用動態光散射法 -20- 201124502 進行測定。具體爲於適當有機溶劑中藉由超音波等均勻地分散橡膠粒子，使用FPRA-1000 (大塚電子（股）製），以橡膠粒子的粒度分佈作爲質量基準而作成，可將該等量徑作爲平均粒徑下而測定。所添加的橡膠粒子之平均粒徑以0.005〜l#m的範圍爲佳，以0.2〜〇.6/zm的範圍爲較佳。添加橡膠粒子時的含有量對於樹脂組成物中之不揮發分1 00質量％而言’以1〜1 0質量％的範圍爲佳，以2〜 5質量％的範圍爲較佳。本發明所使用的熱硬化性樹脂組成物中，視必要可添加其他成分。作爲其他成分，具體可舉出有機磷系難燃劑、有機系含氮之磷化合物、氮化合物、聚矽氧系難燃劑、金屬氫氧化物等難燃劑、聚矽氧粉末、尼龍粉末、氟粉末等塡充劑、orbene、benton等增黏劑、聚矽氧系、氟系、高分子系消泡劑或均塗劑、咪唑系、噻唑系、三唑系、矽烷系耦合劑等密著性賦予劑、酞腈藍、酞腈綠、碘綠、雙偶氮黃、碳黑等著色劑等。且’硬化性樹脂組成物層亦可爲於由纖維所成的薄片狀補強基材中含浸上述硬化性樹脂組成物的預浸體。使用於預浸體的薄片狀纖維基材並無特別限定，具體爲可使用作爲玻璃布、聚芳醯胺不織布、液晶聚合物不織布等預浸體用基材的常用物。薄片狀纖維基材可適用厚度爲10〜150ym者，特別爲10〜1〇〇#m者爲佳。作爲薄片狀纖維基材的具體例中，作爲玻璃布基材，具體可舉出 -21 - 201124502 ASAHISCHWEBEL (股）製 Stylel027MS (經紗密度 75 根/25mm、緯紗密度75根/25mm、布質量20g/m2、厚度 19# m) 'ASAHISCHWEBEL (股）製 Stylel037MS (經紗密度 70根/25mm、緯紗密度 73根/25mm、布質量 24g/m2、厚度28 /z m )、（股）有澤製作所製1 07 8 (經紗密度54根/2 5mm、緯紗密度54根/25mm、布質量48g/m2 、厚度4 3 /z m )、（股）有澤製作所製2 1 1 6 (經紗密度 50根/2 5mm、緯紗密度58根/25mm、布質量1 03.8g/m2、厚度94//m)等。又，作爲液晶聚合物不織布，可舉出由 (股）Kuraray製的芳香族聚酯藉由溶噴（Melt-Blow)法所製造之不織布的Beckles (單位量6〜15g/m2 )或將（股）Kuraray製的Vectran作爲纖維素材的不織布等。對於本發明的附銅箔之黏著薄膜，硬化性樹脂組成物層之厚度雖依內層回路基板的導體層厚度等而不同，但由可提商在層間的絕緣信賴性等觀點來看，以10〜150// m 爲佳，以15〜80/zm爲較佳》 [銅合金鍍敷層於表面形成之銅箔] (銅箔）作爲銅箔，例如使用電解銅箔或壓延銅箔。形成銅合金鑛敷層之面的表面粗度（Ra)以150nm以下爲佳，以 120nm以下爲較佳。由處理性良好的觀點來看，銅箔厚度的上限以7 0 v m以下爲佳，以5 0 y m以下爲較佳，以3 0 以下爲更佳，以18//m以下爲進~步更佳。又，由 -22- 201124502 若過度薄時’會使處理性降低的觀點來看，銅箔厚度的下限以9 // m以上爲佳。銅箔上因進一步附有載體可使強度補強。所謂載體係爲具有自身支持性的薄膜及極薄片狀的材料，雖無特別限制’具體可舉出銅、鋁等金屬箔、聚對酞酸乙二酯、聚 2,6-萘二酸乙二醇酯等塑質薄膜等。銅箔若爲附有載體時，該銅箱厚度即使未達亦可使用。載體厚度以12〜 50//m爲佳，厚度比薄時有時會降低處理性。且’附有載體的銅箔爲，於載體上形成由鉻系異種金屬所成、或由含氮化合物、含硫化合物等有機物所成之剝離層，於該上面以電鍍形成薄銅膜而製作。 (銅合金鍍敷層）本發明中所謂的「銅合金鍍敷層」爲，於銅箔上藉由進行銅合金的鍍敷處理而得之層。又，所謂銅合金表示係由銅與銅以外的金屬所成之合金，具體爲選自Ni-Co-Cu 、：Ni-Cu、Co-Cu中任一者。銅合金鍍敷層的形成方法雖無特別限制，可依據對銅箔表面之電鍍所進行銅合鍍金方法而進行。由銅合金鍍敷層之表面粗度（Ra )轉印於硬化性樹脂組成物層的表面之觀點來看，銅合金鍍敷層的表面粗度（ Ra)之上限値以300nm以下爲佳，以250nm以下爲較佳，以200nm以下爲更佳，以150nm以下爲進一步更佳。另一方面，若銅合金鍍敷層的表面粗度（Ra )過小時，硬 -23- 201124502 化性樹脂組成物層的表面之表面粗度性樹脂組成物層經硬化所形成之絕緣會有降低之顧慮，由此觀點來看，銅粗度（Ra )的下限値以1 〇nm以上爲較佳，以30nm以上爲更佳。藉由對於銅箔表面之鍍敷金屬的敷層之表面粗度。對於鍍敷金屬的附，形成Ni-Co-Cu層的情況下，進行ί 量（Ni與Co之總附著量）至130 Ni + Co的附著量比1 30mg/m2少時，以形成充分銅合金鍍敷層的傾向，若有著銅合金鍍敷層的表面粗度過大之又，形成Ni-Cu層時，進行鑛敷 200〜1000m g/m2爲佳。Ni的附著量老有著於金屬箔表面難以形成充分銅合過lOOOmg/m2時，有著銅合金鍍敷層向。又，形成Co-Cu層時，進行鍍敷 3 00 - 1 000mg/m2爲佳。Co的附著量，有著於金屬箔表面難以形成充分銅若超過1 000mg/m2時，有著銅合金鍍之傾向。以下表示形成Ni-Co-Cu層、Ni- 的較佳鍍敷條件。 (R a )會變小，硬化層與導體層之密著性合金鑛敷層中之表面佳，以20nm以上爲附著量調整銅合金鍍著量，雖無特別限制度敷至Ni + Co的附著〜1000mg/m2 爲佳。有著於金屬箔表面難超過 1 000mg/m2 時，傾向。至Ni的附著量成爲 ^ 比 200mg/m2 少時，金鎪敷層的傾向，超的表面粗度過大之傾至Co的附著量成爲若比3 0 0mg/m2少時合金鍍敷層的傾向’ 敷層的表面粗度過大 Cu層或Co-Cu層時 -24- 201124502 (Cu-Ni-Co 鍍敷液）201124502 VI. Description of the Invention: [Technical Field of the Invention] A film and a multilayer printing method using the same The present invention relates to a method of manufacturing a wiring board with a copper foil. [Prior Art] Since it has been known that the curable resin matte surface has an anchor effect on the unevenness of the curable resin composition layer, and the adhesion between the copper foil and the fat composition layer can be improved. Further, the copper foil is bonded to the curable tree to remove the copper foil, and the rough surface of the copper foil is printed with the anchor effect of the unevenness of the insulating layer, and the technique of adhering the conductive layer is such that the known unevenness is increased. When the conductor layer is formed into a circuit, the conductor layer of the unnecessary conductive portion is etched, and when the etching is sufficiently removed, there is a problem that the wiring of the circuit is formed. On the other hand, it is known as a plasma to reflect light, and the surface is made of Ni alloy. After the surface of the composition layer is bonded to the roughened copper foil, the insulating layer of the rough surface of the copper foil (the hardened curable copper foil used as the conductive layer is used as a conductive layer and hardened, and the uneven transfer is performed. The insulating layer is formed by plating and plating on the insulating layer. However, generally, if the peeling strength of the surface of the insulating layer is increased, it is difficult to remove the conductive layer of the concave and convex portion when the reverse layer is removed. A copper foil for a fine wiring sub-display panel, and a copper box for blackening treatment, etc. (Special [Technical Disclosure] 201124502 [Patent Document] [Patent Document 1] International Publication No. 2005/〇79 1 SUMMARY OF THE INVENTION [Problem of the Invention] An object of the present invention is to provide a multilayer printed wiring board in which a copper layer can be obtained with a high adhesion strength to an insulating layer even if the surface of the insulating layer formed on the circuit substrate has a very small surface roughness. The adhesive film attached to the copper foil. The inventors have repeated the detailed investigation results and found that the copper foil formed by depositing a specific copper alloy plating layer on the surface is bonded to the surface by a specific method. The present invention can be achieved by solving the above problems by the curable resin composition layer on the support. That is, the present invention contains the following contents: [1] An adhesive film with a copper foil, which is characterized in that it is formed by electroplating on a surface. The copper foil of the copper alloy plating layer is bonded to the curable resin composition layer formed on the support, and is bonded to a layer such as a copper alloy plating layer to bond with the curable resin composition layer. [2] An adhesive film with a copper foil, characterized in that the surface of the copper alloy plating layer is treated with anti-rust treatment. [3] The adhesive film with a copper foil as described in [1] or [2], which is characterized by a copper alloy plating layer. The surface roughness (Ra) is 300 nm or less. [4] A method for producing a multilayer printed wiring board, comprising the following steps (A) to (D); (A) stripping any one of [1] to [3] After the support of the adhesive film with a copper case is described, the step of laminating the curable resin composition layer on the inner stomach -6 - 201124502 circuit substrate, and (B) the hardening resin composition layer are formed to form an insulating layer. Step, (C) remove the copper foil by copper etching solution (D) The step of forming a copper layer by electroless plating on the surface of the insulating layer. [5] The method for producing a multilayer printed wiring board according to [4], which further comprises (E) a copper alloy. [6] The method for producing a multilayer printed wiring board according to the above [4] or [5], wherein the surface roughness (Ra) of the surface of the insulating layer is 300 nm or less. The method for producing a multilayer printed wiring board according to any one of [4] to [6], which further comprises (F) a step of forming a pupil. [8] as in [4] to [7] The method for producing a multilayer printed wiring board according to any one of the above [4] to [8], wherein the multilayer printed wiring board according to any one of [4] to [8] is further provided. The manufacturing method 'is characterized by further comprising (H) a step of forming a conductor layer by electroplating. [10] The method for producing a multilayer printed wiring board according to any one of [4] to [9] wherein the method further comprises (1) forming a loop forming step of the conductor layer forming circuit. 201124502 [11] A method of manufacturing a multilayer printed wiring board characterized by repeating a series of steps of the above steps (A) to (I) to laminate a plurality of build-up layers. [Effects of the Invention] The present invention can provide a curable resin composition layer formed by attaching a copper foil of a copper alloy plating layer to a surface to a support by a specific method, even if it is formed on the circuit substrate. The thickness of the layer surface is extremely small, and a copper foil-attached adhesive film of a multilayer printed wiring board on which a copper layer is formed can be obtained with a high adhesion strength to the insulating layer. [Mode for Carrying Out the Invention] The details will be described below. <Adhesive film with copper foil> The adhesive film of the copper foil of the present invention is a layer of a curable resin formed on a support by a copper foil which is plated on the surface to form a copper alloy plating layer. The upper layer is bonded to a layer such as a copper alloy plating layer and a curable resin composition layer. [Support] The support system is a self-supporting film to sheet, and a plastic film can be applied. Examples of the plastic film include polyethylene terephthalate, polyethylene-2,6-naphthalate, polyimine, polyamidimide, polyamine-8 - 201124502, and poly Films such as tetrafluoroethylene and polycarbonate are preferably polyethylene terephthalate film and polyethylene 2,6-naphthalate film, and the cheap polyethylene terephthalate film is also used. Very good. The support can be used as a supporter, and specifically, T6〇 (a polyethylene terephthalate film made by Tor ay), A4100 (polyethylene terephthalate film made by Toyobo Co., Ltd.), Q83 (Polyethylene 2,6-naphthalate film made by Teijindupontfilm Co., Ltd.), polyethylene terephthalate film with alkyd type release agent (AL-5) made by Lintec Co., Ltd. , Diafoil B100 (polyethylene terephthalate film made by Mitsubishi Chemical Polyester Film Co., Ltd.). In order to improve the releasability with the resin composition layer on the surface of the support, a fluororesin, an alkyd resin, a polyoxymethylene resin, a polyolefin resin, a polyvinyl alcohol resin, an acrylic resin, a polyester resin, a melamine resin may be applied. For the isothermal treatment, the thickness is preferably 0.01 to 0. 2 ym. When it is more than 0.01 #m, the function as a release agent tends to be difficult to exert, and when it is larger than 0_2 y m, there is a tendency to deteriorate in practical use. The thickness of the support is not particularly limited, and is preferably 1 〇 to 70 / z m, and preferably i 5 to 7 0 // m. When the thickness is more than 1 〇 #m, there is a tendency for handling deterioration. The peeling property of the support tends to be lowered. Further, when the thickness is larger than 70 #m, the cost and the practicality tend to deteriorate. The surface of the support which is bonded to the layer of the curable resin composition may be subjected to surface treatment such as corona treatment. Further, a surface treatment such as matting treatment or corona treatment may be applied to the surface of the support which is not bonded to the curable resin composition layer. 201124502 [Curable resin composition layer] The curable resin composition used for the curable resin composition layer is not particularly limited as long as it is an insulating layer suitable for a multilayer wiring board. Specifically, it can be used at least in a thermosetting resin such as an epoxy resin, a cyanate resin, a phenol resin, a bismaleimide-triazine resin, a polyimine resin, an acrylic resin, or a vinyl benzyl resin. The composition of the hardener. A composition containing an epoxy resin and a curing agent is preferred, and a composition further containing a thermoplastic resin in the epoxy resin and the curing agent is particularly preferable. The epoxy resin is not particularly limited, and specific examples thereof include a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, and a bisphenol. F-type epoxy resin, phosphorus-containing epoxy resin, bisphenol S-type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenolic epoxy resin for phenol paint, A phenolic epoxy resin for cresol paint, a phenolic epoxy resin for bisphenol A paint, an epoxy resin having a butyl dibasic structure, a diepoxypropyl etherate of bisphenol, and a naphthalenediol A epoxidized propyl ether compound, a phenolic propyl ether ether compound, an alcoholic diepoxypropyl ether compound, and an alkyl group and a hydrogenated product of the epoxy group. It is also possible to use one or two or more epoxy resins in combination with a fluorene-based epoxy resin, and a bisphenol A-type epoxy resin or a naphthol-type ring from the viewpoint of high heat resistance and high insulation reliability. Oxygen resin, naphthalene type epoxy resin, biphenyl type epoxy resin, epoxy resin having a butyl diene structure, and "jER8 2 8 EL" made of Japanese epoxy resin (liquid) Bisphenol A type epoxy resin), DIC (product) "HP403 2 -10- 201124502", "HP4032D" (Cai type bifunctional ring and base tree moon day), DIC (share) system "HP4700" (naphthalene) "ESN-475V", "ESN-185V" (naphthoquinone type epoxy resin), and "PB-3600" manufactured by Dai eel Chemical Industry Co., Ltd. ("4-functional epoxy group") "Epoxy resin with a dibutyl structure", "NC3 000H" made by Nippon Kayaku Co., Ltd. "NC3000L", "NC3100", "NC3000" (biphenyl type epoxy resin), Japanese epoxy resin (YX4000) (biphenyl type epoxy resin), GK3207 (biphenyl type epoxy resin) manufactured by Toho Chemical Co., Ltd. It is preferable to use "ΥΧ8800" (containing an anthracene skeleton type epoxy resin) made of the epoxy resin (strand). When the epoxy resin is used in the form of an adhesive film, it is intended to have heat resistance or breaking strength and lamination. It can be combined with an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at 2 ° C, or dissolved in a melting point or higher, and then liquid at room temperature. The crystalline aromatic epoxy resin is preferably used in an aromatic epoxy-based resin having 2 or more epoxy groups in one molecule and being solid at 2 (TC). The family epoxy resin is preferably one having an epoxy group equivalent of 230 or less, and preferably having an epoxy group equivalent of 15 Å to 23 Å, in order to increase physical properties such as glass transition temperature. The ratio of the epoxy resin to the solid aromatic epoxy resin is in a mass ratio (liquid aromatic epoxy resin: solid aromatic epoxy resin) of 1:3. The range is preferably '1: 0.5~1 · 5 is preferred, and the range of 1: 〇. 5~1 · 2 is The range of 1:5 is further improved. The curing agent is not particularly limited, and specific examples thereof include an amine curing agent-11 - 201124502, an lanthanum curing agent, an imidazole curing agent, and the like. a phenolic curing agent for a triazine skeleton, a phenolic curing agent, a naphthol-based curing agent containing a triazine skeleton, a naphthol-based curing agent, an acid anhydride-based curing agent, or an epoxy group-containing adduct or a microencapsulated one. An active ester-based curing agent, a benzoxazine-based curing agent, a cyanate resin, etc. A phenol-based curing agent, a naphthol-based curing agent, a benzene-based curing agent containing a triazine skeleton, and a naphthol containing a triazine skeleton. A hardener is preferred. These hardeners may be used alone or in combination of two or more. The phenolic curing agent and the naphthol-based curing agent are not particularly limited, and specific examples thereof include MEH-7700, MEH-7810, MEH-7851 (made by Megumi Kasei Co., Ltd.), NHN, CBN, and GPH (Japanese medicine). (share) system, SN170, SN180, SN190, SN47 5, SN48 5, SN49 5, SN3 7 5, SN395 (Dongdu Huacheng (share) system), TD2090 (DIC system). The phenolic curing agent containing a triazine skeleton is not particularly limited, and specific examples thereof include LA3018, LA7052, LA7054, and LA 1 3 56 (manufactured by DIC). The active ester-based curing agent is not particularly limited as long as it has a function as a curing agent for the epoxy resin, but specifically has two or more phenol esters, thiophenol esters, and N-hydroxyl groups in one molecule. A compound having a highly reactive ester group such as an ester of an amine ester or a heterocyclic hydroxy compound is preferred. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylate and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound. From the viewpoint of heat resistance and the like, an active ester-based curing agent obtained from a carboxylate compound and a phenol compound or a naphthol compound is more preferable. Specific examples of the carboxylate include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol-12-201124502 compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylated bisphenol F. , methylated bisphenol S, acid, hydrazine-methylhydrazine, m-formamidine, ρ-methylhydrazine, catechin, α-naphthoquinone, /3-naphthol, 1,5-dihydroxynaphthalene, 1, 6-Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene Phenol, phenol paint, etc. Two or more active ester-based hardeners may be used. Further, as the active ester-based curing agent, an active ester-based curing agent disclosed in J Ρ - A - 2 0 0 4 - 4 2 7 7 1 1 may be used, and it may be used as a seller. Specific examples of the commercially available active ester-based curing agent include EXB-945 1 and EXB-9460 (manufactured by DIC) containing a dicyclopentadiene diol structure, and an acetamino group as a phenolic phenolic aldehyde. Illustrative examples of the compound include DC 8 0 8 (manufactured by Nippon Epoxy Resin Co., Ltd.), and phenylhydrazine phenolate for phenol paint, and YLH1026 (manufactured by Nippon Epoxy Co., Ltd.). Specific examples of the benzoxanthrene-based curing agent include F-a, P-d (manufactured by Shikoku Chemical Co., Ltd.), and HFB 2006M (manufactured by Showa Polymer Co., Ltd.). Specific examples of the cyanate resin include a phenolic type for a paint (a phenol type for a phenol paint, a phenol type for an alkyl phenol paint), a cyanate resin, and a bisphenol type (bisphenol A type bisphenol F type, bisphenol S). Type, etc.) cyanate resin and a part of the triazine-based prepolymer. Specific examples of the preferred cyanate resin include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methyl-1-, 5-phenylene), 4,4' - Methyl bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4- -13 - 201124502 cyanate-3,5-dimethylphenyl) Methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) a bifunctional cyanate resin such as ether, a phenolic phenolic phenol, a polyfunctional cyanate resin derived from phenolic phenolic or the like, a partially-triazine-based prepolymer of these cyanate resins, and the like. Examples of the commercially available cyanate resin include PT30 manufactured by Lonza Japan Co., Ltd. (phenolic polyfunctional cyanate resin for phenol paint, cyanate equivalent 124), and BA2 3 0 manufactured by Lonza Japan Co., Ltd. (Pre-polymerized or partially cyanated to a prepolymer of a trimer of a bisphenol A dicyanate, or a cyanate equivalent of 23 2 ), Lonza Jap An DT4000 (dicyclopentadiene type polyfunctional cyanate resin, cyanate equivalent 140) manufactured by an. The ratio of the epoxy resin to the hardener is a phenolic hardener containing a triazine skeleton. In the case of a phenolic curing agent, a naphthol-based curing agent containing a triazine skeleton, and a naphthol-based curing agent, the phenolic hydroxyl equivalent of these curing agents is 0.4 to the epoxy equivalent of the epoxy resin. The ratio of the range of 2.0 is preferably 'the ratio of the range of 〇·5 to 1.0 is preferable. When the equivalent ratio of the reaction group is outside the range, the mechanical strength or water resistance of the cured product tends to be lowered. In the thermosetting resin composition, a curing agent is added, and a curing accelerator is further added. The curing accelerator is not particularly limited as long as it has a hardening promoting action, and examples thereof include an imidazole compound and a diazo. a heterobicyclic compound, an organic phosphine, a scaly compound, etc. Specifically, 2 ΜΖ (2-methylimidazole), C11Z (2-undecylimidazole), C17Z (2 -) manufactured by Shikoku Chemical Co., Ltd. Heptadecyl imidazole), -14- 20112450 2 1.2DMZ (1,2-dimethylimidazole), 2E4MZ (2-ethyl-4-methylimidazole), 2PZ (2-phenylimidazole), 2P4MZ (2-Benzyl-4-methylimidazole) ), 1B2MZ (1-benzyl-2-methylimidazole), :1B2PZ (1-benzyl-2-phenylimidazole), 2MZ-CN (1-cyanoethyl-2-methylimidazole) , C11Z-CN (1-cyanoethyl-2-undecylimidazole), 2E4MZ-CN (1-cyanoethyl-2-ethyl-4-methylimidazole), 2PZ-CN ( 1- Cyanoethyl-2-phenylimidazole), C11-CNS (1-cyanoethyl-2-undecylimidazole trimellitic acid), 2PZCNS-PW (1-cyanoethyl-2-benzene) Benzimidazole trimellitic acid), 21^2-octa(2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-8-triazine, (3117- Octa(2,4-diamino-6-[2'-^--alkylimidazolyl-(1,))-ethyl-S-triazine), 2E4MZ-A (2,4-diamino) -6-[ 2'-ethyl-4'-methylimidazolyl-(1,)]-ethyl-s-triazine), 2MA-01<:(2,4-diamino-6-[ 2'-Methylimidazolyl-(1')]-ethyl-5-triazine isocyanuric acid addition), 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole), 2P4MHZ-PW ( 2 -phenyl-4- 5--5-hydroxymethylimidazole), TBZ (2,3-dihydro-1H-pyrrolo[l,2-a]benzimidazole, SFZ (budecyl-2-methyl-3-benzene) Imidazole compound such as methylimidazolium chloride), P-0505 (epoxy-imidazole adduct), U-CAT SA 1 (DBU-phenolate) manufactured by San-apro Co., Ltd., U-CAT SA 102 (DBU-octyl acid salt) 'U-CAT SA 506 (DBU-p-toluenesulfonate), 1; -CAT SA 603 (DBU-formate), U-CAT SA 810 (DBU-o-phenylene) Formate, U-CAT SA 831, 841, 851, U-CAT 881 (DBU-phenolic resin phenolic resin salt), U-CAT 5002 (N-benzyl DBU-tetraphenylborate) Heterobicyclic compounds, TPP-S (triphenylphosphine triphenylborane), bismuth-tellurium (tetraphenylphosphinium tetraphenylborate), TBP-DA manufactured by Beixing Chemical Industry Co., Ltd. (Stock-15-201124502) An organic phosphine scale compound such as (tetrabutyl sulfonate). When the curing accelerator is used, the amount used is not particularly limited, but it is preferably used in the range of from 0.1 to 3.0% by mass based on the epoxy resin. The thermosetting resin composition used in the present invention may further contain a thermoplastic resin from the viewpoint of imparting moderate flexibility to the cured composition. The thermoplastic resin is not particularly limited, and specific examples thereof include a phenoxy resin, a polyvinyl acetal resin, a polyimine, a polyamine oxime, a polyether oxime, and a polyfluorene. The thermosetting resin may be used alone or in combination of two or more. When the non-volatile portion of the thermosetting resin composition is 100% by mass, the compounding ratio of the thermoplastic resin is preferably 0.5 to 60% by mass, more preferably 3 to 50% by mass. When the blending ratio of the thermoplastic resin is less than 0.5% by mass, the viscosity of the resin composition tends to be low, and it tends to be difficult to form a uniform thermosetting resin composition layer. When the content exceeds 60% by mass, the viscosity of the resin composition may pass. It is high and has a tendency to become difficult to embed the wiring pattern on the substrate. The phenoxy resin is not particularly limited, and specific examples thereof include FX2 80, FX293 manufactured by Tohto Kasei Co., Ltd., ΥΧ8100, YL6954, YL6974, YL7482, YL7553, YL6794, YL7213, YL7290, etc. as the Japanese epoxy resin (stock). The polyvinyl acetal resin is preferably a polyvinyl butyral resin. Specific examples of the polyvinyl acetal resin include an electrified Butyral 4000-2, 5000-A, 6000-C, 6000- by the Electrochemical Industry Co., Ltd. EP, Sekisui-16- 201124502 s-recl BH series, BX series, KS series, BL series 歹IJ, BM series, etc. Specific examples of the polyimine are Polyimine amide "Liquacoat SN20" and "Liquacoat PN20" manufactured by Shin-Nihon Chemical Co., Ltd. Further, a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutylene dichloride, a diisocyanate compound, and a tetrabasic acid anhydride (described in JP-A-2〇〇6-37〇83) Denatured polyimine, such as a polyfluorene skeleton having a polyoxyalkylene skeleton (described in JP-A-2002-12667, JP-A-2000-319386, etc.). Specific examples of the polyamidoximine are the polyamidoquinone imines "VylomaxHRllNN" and "Vyl〇maxHR16NN" manufactured by Toyobo Co., Ltd. Further, a modified polyamidoquinone imine such as "polyacrylamide"-containing polyamine amidoxime "KS9100" or "KS 93 00" manufactured by Hitachi Chemical Co., Ltd. can be cited. Specific examples of the polyether mill include polyether oxime "PES 5 003 P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyfluorene include "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd. The thermosetting resin composition of the present invention may contain an inorganic enamel filler which is intended to be low-expansion of the hardened composition. Specific examples of the inorganic cerium filling material include cerium oxide, aluminum oxide, mica, mica, ceric acid salt, barium sulfate, magnesium hydroxide, titanium oxide, etc., and cerium oxide and aluminum oxide are preferred. Forming cerium oxide, molten cerium oxide, crystalline cerium oxide, and synthetic cerium oxide such as cerium oxide. As the cerium oxide is spherical, it is -17-201124502, and the inorganic ceramium is preferably an average particle diameter of 3 μm or less, and an average particle diameter of 1 Å from the viewpoint of insulation reliability. Those below 5 μm are preferred. The average particle diameter of the inorganic cerium filler can be measured by a laser diffraction/scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic cerium filling material can be prepared on the basis of volume by a laser diffraction type particle size distribution measuring apparatus, and the same diameter can be measured as an average particle diameter. The measurement sample is preferably one in which the inorganic cerium filling material is dispersed in water by ultrasonic waves. As the laser diffraction type particle size distribution measuring apparatus, a LA-500 or the like can be used. The inorganic ruthenium filler is preferably subjected to surface treatment by the following surface treatment agent in order to improve moisture resistance, dispersibility, and the like. Examples of the surface treatment agent include aminopropyl methoxy decane, aminopropyl triethoxy decane, ureidopropyl triethoxy decane, and N-phenylaminopropyl trimethoxy decane. An amine decane-based coupling agent such as N-2 (aminoethyl)aminopropyltrimethoxydecane; glycidoxypropyltrimethoxydecane, glycidoxypropyltriethoxydecane, Epoxy decane coupling such as glycidoxypropylmethyldiethoxydecane, propylenepropyl butyl trimethoxy decane, (3,4-epoxycyclohexyl)ethyltrimethoxydecane Hydroxythiodecane-based coupling agent such as thiopropylpropyltrimethoxydecane or thiopropylpropyltriethoxydecane; methyltrimethoxydecane, octadecyltrimethoxydecane-phenyltrimethyl a decane-based coupling agent such as oxydecane, methacryloxypropyltrimethoxynonane, imidazolium or triazine decane; hexamethyldidecylamine, hexaphenyldioxanylamine, dimethylamino group III Organic sulfonium compounds such as methyl decane, triazane' cyclotriazane, 1,1,3,3,5,5-hexamethylcyclotriazane; butyl Titanate Dimer-18 - 201124502, Titanium Octate, Diisopropoxide Titanium (Ammonia Triethanol), Dihydroxy Titanium Lactate, Dihydroxybis(Ammonium Lactate) Titanium, Double (dioctyl pyrophosphate) exoethyl titanate 'bis(dioctyl pyrophosphate)oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n _Butyl titanate, tetrakis(2-ethylhexyl) titanate, tetraisopropylbis(dioctylphosphonate) titanate, tetraoctylbis(ditridecyl phosphate) titanic acid Salt, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphate titanate, isopropyl trioctyl decylate, isopropyl triacetate Acetyl phenyl acid salt, isopropyl triisostearyl strontium titanate, isopropyl isostearyl decyl dipropenyl titanate, isopropyl dimethyl propylene isostearyl fluorenyl titanium Acid salt, isopropyl tris(dioctyl phosphate) titanate, isopropyl dodecyl benzene sulfonate titanate, isopropyl ginseng (dioctyl pyrophosphate) titanate, Titanic acid such as isopropyl tris(N-nonylaminoethylaminoethyl) titanate Salt coupling agent, etc. These may be used alone or in combination of two or more. The content of the inorganic chelating agent in the curable resin composition is not particularly limited as long as the effect of the present invention is not inhibited, and when the nonvolatile content of the curable resin composition is 100% by mass, 20~ 80% by mass is preferable, preferably 20 to 70% by mass, more preferably 30 to 70% by mass, still more preferably 40 to 70% by mass, and particularly preferably 4 to 60% by mass. When the content of the inorganic chelating agent is less than 2% by mass, the effect of lowering the thermal expansion ratio tends not to be sufficiently exhibited, and when the content of the inorganic chelating agent exceeds 80% by mass, the mechanical strength of the cured product is lowered. And so on. Further, the curable resin composition may contain solid rubber particles for the purpose of improving the mechanical strength of the cured product, the stress relieving effect, and the like. The rubber particles are -19*201124502 and are not dissolved in the organic solvent in the preparation of the resin composition, and are not compatible with the components in the resin composition such as the epoxy resin, and are dispersed in the varnish of the resin composition. The survivor is better. The rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level that does not dissolve in the organic solvent or the resin, and are prepared as a rubber particle. Specifically, the core-shell rubber particles and the cross-linked nitrile butadiene are exemplified. Dilute rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and specifically, the shell layer of the outer layer is a glassy polymer, and the core layer of the inner layer is a two-layer structure or outer layer composed of a rubbery polymer. The shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glassy polymer layer is specifically composed of a polymer of methacrylic acid methyl group or the like, and the rubbery polymer layer is specifically composed of a butyl acrylate polymer (butyl rubber) or the like. Specific examples of the core-type rubber particles include Staphyloid AC3 8 3 2 > AC3816N (Ganz Chemicals Co., Ltd.) and Metablen KW-4426 (MITSUBISHI RAYON Co., Ltd.). Specific examples of the acrylonitrile butyl rubber (NBR) particles include XER-91C average particle diameter of 0.5; zm and JSR (manufactured by JSR). Specific examples of the styrene butyl rubber (SBR) particles include XSK-500 (average particle diameter 0.5 / z m, manufactured by JSR). Specific examples of the acrylic rubber particles include Metablen W3 00A (average particle diameter 〇.l#m) and W450A (average particle diameter 〇.5/zm) (manufactured by MITSUBISHI RAYON Co., Ltd.). The average particle diameter of the rubber particles in the present invention can be measured by dynamic light scattering method -20-201124502. Specifically, the rubber particles are uniformly dispersed by ultrasonic waves or the like in a suitable organic solvent, and FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.) is used, and the particle size distribution of the rubber particles is used as a mass basis, and the same diameter can be used as Measured under the average particle size. The average particle diameter of the rubber particles to be added is preferably in the range of 0.005 to 1 #m, and more preferably in the range of 0.2 to 6.6/zm. The content of the rubber particles is preferably in the range of 1 to 10% by mass, and preferably in the range of 2 to 5% by mass, based on the non-volatile content of the resin composition of 100% by mass. In the thermosetting resin composition used in the present invention, other components may be added as necessary. Specific examples of the other components include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyfluorene-based flame retardant, a metal hydroxide-based flame retardant, a polyoxygenated powder, and a nylon powder. , fluorinated powder and other chelating agents, orbene, benton and other tackifiers, polyfluorene-based, fluorine-based, polymeric antifoaming or leveling agents, imidazole, thiazole, triazole, decane coupling agents, etc. Coloring agent such as adhesion imparting agent, phthalonitrile blue, phthalonitrile green, iodine green, disazo yellow, carbon black, and the like. Further, the "curable resin composition layer" may be a prepreg in which the above-mentioned curable resin composition is impregnated into a sheet-like reinforcing substrate made of fibers. The sheet-like fibrous base material to be used for the prepreg is not particularly limited, and specifically, a conventional substrate for a prepreg such as a glass cloth, a polyarylamine nonwoven fabric, or a liquid crystal polymer nonwoven fabric can be used. The sheet-like fibrous substrate can be applied to a thickness of 10 to 150 μm, particularly preferably 10 to 1 Å #m. Specific examples of the sheet-like fiber base material include, as a glass cloth substrate, Stylel027MS manufactured by ASA HI HI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI SHI M2, thickness 19# m) Stylel037MS made by ASAHISCHWEBEL (warp density 70 pieces/25mm, weft density 73 pieces/25mm, cloth quality 24g/m2, thickness 28/zm), (shares) made by Ozawa Manufacturing Co., Ltd. 1 07 8 (The warp density is 54 /2 5 mm, the weft density is 54/25 mm, the cloth quality is 48 g/m2, the thickness is 4 3 /zm), and the (stock) is manufactured by Ozawa Manufacturing Co., Ltd. 2 1 16 (warp density 50 /2 5 mm, weft density) 58 pieces / 25 mm, cloth quality 1 03.8 g / m 2 , thickness 94 / / m) and the like. Further, examples of the liquid crystal polymer nonwoven fabric include a Beckles (unit amount: 6 to 15 g/m 2 ) of a nonwoven fabric produced by a Melt-Blow method of an aromatic polyester manufactured by Kuraray. Co., Ltd. Vectran made of Kuraray as a non-woven fabric of fiber material. In the adhesive film with a copper foil of the present invention, the thickness of the curable resin composition layer varies depending on the thickness of the conductor layer of the inner layer circuit board, etc., but from the viewpoint of insulation reliability between layers, etc., 10 to 150 / / m is preferable, preferably 15 to 80 / zm" [copper alloy plating layer formed on the surface of copper foil] (copper foil) As the copper foil, for example, an electrolytic copper foil or a rolled copper foil is used. The surface roughness (Ra) of the surface on which the copper alloy ore layer is formed is preferably 150 nm or less, and preferably 120 nm or less. From the viewpoint of good handleability, the upper limit of the thickness of the copper foil is preferably 70 vm or less, preferably 50 ym or less, more preferably 30 or less, and 18/m or less. good. Further, from the viewpoint that the -22-201124502 is too thin, the handleability is lowered, and the lower limit of the thickness of the copper foil is preferably 9 // m or more. The copper foil can be reinforced by further attaching a carrier. The carrier is a self-supporting film and a sheet-like material, and is not particularly limited. Specific examples thereof include a metal foil such as copper or aluminum, polyethylene terephthalate, and poly 2,6-naphthalenediate B. A plastic film such as a glycol ester. If the copper foil is provided with a carrier, the thickness of the copper box may be used even if it is not reached. The thickness of the carrier is preferably from 12 to 50/m, and the thickness is sometimes thinner and the handleability is sometimes lowered. Further, the copper foil with a carrier is formed by forming a release layer made of a chromium-based dissimilar metal or an organic substance such as a nitrogen-containing compound or a sulfur-containing compound on the carrier, and forming a thin copper film by electroplating thereon. . (Copper alloy plating layer) The "copper alloy plating layer" in the present invention is a layer obtained by plating a copper alloy on a copper foil. Further, the copper alloy is an alloy formed of a metal other than copper and copper, and is specifically selected from the group consisting of Ni-Co-Cu, Ni-Cu, and Co-Cu. The method for forming the copper alloy plating layer is not particularly limited, and may be carried out by a copper plating method for plating the surface of the copper foil. The upper limit 表面 of the surface roughness (Ra) of the copper alloy plating layer is preferably 300 nm or less from the viewpoint that the surface roughness (Ra ) of the copper alloy plating layer is transferred to the surface of the curable resin composition layer. It is preferably 250 nm or less, more preferably 200 nm or less, and still more preferably 150 nm or less. On the other hand, if the surface roughness (Ra) of the copper alloy plating layer is too small, the surface roughness of the surface of the hard -23-201124502 resin composition layer is hardened to form an insulation. From the viewpoint of the reduction, the lower limit 铜 of the copper roughness (Ra ) is preferably 1 〇 nm or more, more preferably 30 nm or more. By the surface roughness of the metallized coating on the surface of the copper foil. In the case of forming a Ni-Co-Cu layer with a plating metal, when the amount of adhesion (the total adhesion amount of Ni and Co) to 130 Ni + Co is less than 1 30 mg/m 2 , sufficient copper is formed. In the tendency of the alloy plating layer, if the surface roughness of the copper alloy plating layer is too large, when the Ni-Cu layer is formed, it is preferable to carry out the mineralization of 200 to 1000 m g/m 2 . The adhesion amount of Ni is old, and it is difficult to form a sufficient copper bond on the surface of the metal foil. When it is over 1000 mg/m2, it has a copper alloy plating layer. Further, when the Co-Cu layer is formed, it is preferable to carry out plating of 300 to 1 000 mg/m2. The adhesion amount of Co is difficult to form sufficient copper on the surface of the metal foil. When it exceeds 1,000 mg/m2, it tends to be plated with a copper alloy. Preferred plating conditions for forming a Ni-Co-Cu layer and Ni- are shown below. (R a ) will become smaller, the surface of the hardened layer and the conductive layer in the adhesive alloy deposit layer is better, and the amount of copper alloy plating is adjusted by the adhesion amount of 20 nm or more, although it is applied to Ni + Co without special limitation. Attaching ~1000mg/m2 is preferred. When the surface of the metal foil is difficult to exceed 1 000 mg/m2, it tends to be. When the amount of adhesion to Ni is less than 200 mg/m2, the tendency of the gold-coated layer is too high, and the excessive surface roughness is too large, and the amount of Co deposited is less than 300 mg/m2. 'When the surface roughness of the coating is too large for the Cu layer or the Co-Cu layer-24- 201124502 (Cu-Ni-Co plating solution)

Cu ： 5 〜3 Og/LCu : 5 ～ 3 Og/L

Ni : 5 - 3 Og/LNi : 5 - 3 Og/L

Co : 5 〜30g/L pH : 2 〜4Co : 5 ~ 30g / L pH : 2 ~ 4

液溫：2 0〜6 0 °C 電流密度：30〜60A/dm2 (Cu-Co鍍敷液）Liquid temperature: 2 0~6 0 °C Current density: 30~60A/dm2 (Cu-Co plating solution)

Cu ： 5 〜3 Og/L Co ： 1 0 〜3 Og/L ρ Η : 2 〜4 液溫：2 0〜6 0 °C 電流密度：30〜50A/dm2 (Cu-Ni鍍敷液）Cu : 5 〜 3 Og / L Co : 1 0 〜 3 Og / L ρ Η : 2 〜 4 Liquid temperature : 2 0~6 0 °C Current density : 30~50A/dm2 (Cu-Ni plating solution)

Cu: 5 ~ 3 Og/L Ni ： 1 0 ~ 3 Og/L pH : 2 〜4 液溫：2 0〜5 5 t 電流密度：30〜55A/dm2 (防鏽處理層） -25- 201124502 本發明的銅合金鍍敷層形成於表面之銅的氧化之觀點來看，於銅合金鍍敷層進理爲佳。於防鏽處理時可使用鋅（Zn)、 (具體爲Zn-Ni、Zn-Ni-P等）等無機防爲1種或亦可混合使用2種以上。又，使鏽處理之方法並無特別限制，可採用電鍍法、濺鍍法等。其中以Ζη·鉻酸鹽處理爲鍍之鍍敷條件，具體可舉出以下條件。 (Zn、鉻酸鹽處理液） K2Cr207 : 2 〜10g/L Zn: 0.1 〜0.5g/L Na2S04 ： 5 〜20g/L pH : 3.5 〜5.0 液溫：2 0〜6 0 °C 電流密度：0.1〜3.0A/dm2 鍍敷時間：1〜3秒且，即使藉由防鏽處理，銅合金鑛敷無實質變化，防鏽處理後的銅合金鍍敷層 (Ra)以 300nm以下爲佳，以 250nm 200nm以下爲更佳，以150nm爲進一j l〇nm以上爲佳，以20nm以上爲較佳，以佳。銅箔，由可抑制一步施予防鏽處鉻酸鹽、鋅合金鏽劑，防鏽劑可用該防鏽劑的防法、無電解鍍敷佳，作爲藉由電層之表面粗度並表面之表面粗度以下爲較佳，以步更佳。又，以 ,3〇nm以上爲更 -26- 201124502 本發明的附銅箔之黏著薄膜的製造方法雖無特別限_ ’以以下方法爲佳。製作於支持體上形成硬化性樹脂組成物層的黏著薄月莫 ’藉由於該硬化性樹脂組成物層貼合黏著薄膜與銅箔成接觸銅箔表面的銅合金鍍敷層的方法而製作。具體爲於黏著薄膜的硬化性樹脂組成物層，重疊銅箔成接觸銅箔的銅合金鍍敷層，再以熱加壓、熱輥等進行層合。此時的加熱溫度較佳爲選自6 0〜1 4 0 °C的範圍，較佳爲選自80〜120°C的範圍。又，壓著壓力較佳爲選自1〜 llkgf/cm2 ( 9.8x104~ 1 0 7.9 x 1 0 4 N / m 2 )的範圍，更佳爲選自 2 〜7kgf/cm2 ( 19.6M04〜68.6xl04N/m2)的範圍。時間以5秒〜3分鐘的範圍爲佳，以1 5秒〜1分鐘的範圍爲較佳。又，空氣壓爲20mmHg ( 26.7hPa )以下的減壓下進行層合爲佳。本發明中之「銅合金鍍敷層於表面形成的銅箔」可使用販賣品。具體可舉出日鑛金屬（股）製的「HLPFN」（銅合金鍍敷層：Ni-Co-Cu、防鏽處理：Zn ·鉻酸鹽處理、表面粗度（Ra ):約2 5 0nm )、日鑛金屬（股）製的「 BHY-HA j (銅合金鍍敷層：Ni-Co-Cu、防鏽處理：Zn _ 鉻酸鹽處理 '表面粗度（Ra ):約30〇nm )。另一方面，黏著薄膜係可藉由調製於有機溶劑溶解前述硬化性樹脂組成物的樹脂清漆，將該樹脂清漆使用模具塗佈等，塗佈於前述支持體上，進一步經加熱、或吹熱風等乾燥有機溶劑後形成樹脂組成物層而得。 -27- 201124502 作爲有機溶劑，具體可舉出丙酮、甲基乙基酮、環己酮等酮類、乙酸乙酯、乙酸丁酯、賽路蘇乙酸酯、丙二醇單甲醚乙酸酯、卡必醇乙酸酯等乙酸酯類、賽路蘇、丁基卡必醇等卡必醇類、甲苯、二甲苯等的芳香族烴類、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等。有機溶劑可使用1種或組合2種以上使用。乾燥條件雖無特別限定，對於乾燥終點，乾燥至樹脂組成物層中之有機溶劑的含有量達到1 0質量％以下，較佳爲達到5質量％以下。因依據清漆中之有機溶劑量、有機溶劑的沸點而相異，故可設定適宜乾燥條件。具體爲含有30〜60質量％的有機溶劑之清漆的情況爲在50〜150 °C 下乾燥3〜10分鐘的方法爲佳。又，欲得到硬化性樹脂組成物層係由預浸體所成的附銅箔之黏著薄膜時，雖無特別限制，具體爲於支持體上將預浸體藉由真空層合法進行層合而製作黏著薄膜，將該黏著薄膜與銅箔以前述條件下進行貼合爲佳。其中，預浸體可藉由公知熱熔法、溶劑法等而製造。熱熔法爲，無須將樹脂組成物溶解於有機溶劑，將樹脂組成物一旦塗佈於剝離性良好的離型紙後，將此層合於薄片狀纖維基材、或藉由模具塗佈進行直接塗佈等製造預浸體之方法。又，溶劑法爲於將樹脂組成物溶解於有機溶劑的清漆中浸漬薄片狀纖維基材後，使清漆含浸於薄片狀纖維基材後，使其乾燥之方法。又，可將由於支持體上層合的硬化性樹脂組成物所成之黏著薄膜，自薄片狀補強基材的 -28- 201124502 兩面進行加熱’加壓條件下進行連續性層合後而調製。以溶劑法製作時’於清漆使用前述樹脂清漆，雖乾燥條件並無特別限定，但將多層印刷配線板於製造步驟，將附銅箔之黏著薄膜層合於內層回路基板時，硬化性樹脂組成物必須具有流動性及黏著性。因此，乾燥時儘可能不進行硬化性樹脂組成物的硬化成爲重要事項。另一方面，若於預浸體內殘留過多有機溶劑時，會成爲硬化後產生膨脹的原因’乾燥終點中硬化性樹脂組成物中之有機溶劑的含有比率之上限係以5質量％以下爲差，以2質量％以下爲較佳。具體的乾燥條件依據硬化性樹脂組成物的硬化性或清漆中之有機溶劑量而相異，故可設定適宜乾燥條件，但具體爲對於含有30〜60質量％的有機溶劑之清漆中，在 8 0〜1 8 0 °C下乾燥3〜1 3分鐘爲佳。又，可直接於銅箔塗佈清漆製造附銅箔之黏著薄膜。此時的塗佈方法與上述記載的黏著薄膜製作方法相同，乾燥條件亦可設定爲相同。 <使用附銅箔之黏著薄膜的多層印刷配線板之製造> 本發明的多層印刷配線板的製造方法含有以下（A ) 〜（D )之步驟。 (A )剝離本發明的附銅箔之黏著薄膜的支持體’將硬化性樹脂組成物層層合於內層回路基板之步驟、 (B )將硬化性樹脂組成物層硬化後形成絕緣層之步Cu: 5 ~ 3 Og / L Ni : 1 0 ~ 3 Og / L pH : 2 ~ 4 Liquid temperature: 2 0~5 5 t Current density: 30~55A/dm2 (rust-proof layer) -25- 201124502 The copper alloy plating layer of the invention is preferably formed on the copper alloy plating layer from the viewpoint of oxidation of copper on the surface. In the rust-preventing treatment, one type of inorganic control such as zinc (Zn), (specifically, Zn-Ni, Zn-Ni-P, or the like) may be used, or two or more types may be used in combination. Further, the method of the rust treatment is not particularly limited, and an electroplating method, a sputtering method, or the like can be used. Among them, Ζη·chromate treatment is used as plating conditions for plating, and specific examples thereof include the following conditions. (Zn, chromate treatment solution) K2Cr207 : 2 ~ 10g / L Zn: 0.1 ~ 0.5g / L Na2S04 : 5 ~ 20g / L pH : 3.5 ~ 5.0 Liquid temperature: 2 0~6 0 °C Current density: 0.1 ~3.0A/dm2 Plating time: 1 to 3 seconds, even if the rust-preventing treatment, the copper alloy ore does not change substantially, and the copper alloy plating layer (Ra) after the rust-preventing treatment is preferably 300 nm or less. 250 nm or less is preferable, and 150 nm is preferably more than jl 〇 nm or more, and more preferably 20 nm or more. The copper foil is made of a chromate and a zinc alloy rust agent which can be inhibited from being applied in one step. The anti-rust agent can be used for the anti-corrosion and electroless plating of the anti-rust agent as the surface roughness and surface of the electric layer. The surface roughness is preferably as follows, and the step is better. Further, the method of producing a copper foil-attached adhesive film of the present invention is not particularly limited to the following method. The adhesive thin film which is formed on the support to form the curable resin composition layer is produced by a method in which the curable resin composition layer is bonded to the copper foil to form a copper alloy plating layer on the surface of the copper foil. Specifically, the copper alloy plating layer which is in contact with the copper foil is laminated on the curable resin composition layer of the adhesive film, and then laminated by hot pressing, a hot roll or the like. The heating temperature at this time is preferably selected from the range of from 60 to 140 ° C, preferably from 80 to 120 ° C. Further, the pressing pressure is preferably selected from the range of 1 to llkgf/cm2 (9.8x104 to 1 0 7.9 x 1 0 4 N / m 2 ), more preferably 2 to 7 kgf/cm 2 ( 19.6 M 04 to 68.6 x 10 4 N) /m2) range. The time is preferably in the range of 5 seconds to 3 minutes, and preferably in the range of 15 seconds to 1 minute. Further, it is preferred to carry out lamination under a reduced pressure of 20 mmHg (26.7 hPa) or less. In the present invention, the "copper alloy plating layer formed on the surface of the copper foil" can be used as a retail product. Specifically, "HLPFN" manufactured by Nippon Minerals Co., Ltd. (copper alloy plating layer: Ni-Co-Cu, rust-preventing treatment: Zn-chromate treatment, surface roughness (Ra): about 205 nm) ) BHY-HA j (copper alloy plating layer: Ni-Co-Cu, rust-proof treatment: Zn _ chromate treatment) surface roughness (Ra): about 30 〇 nm On the other hand, the adhesive film is a resin varnish prepared by dissolving the curable resin composition in an organic solvent, and the resin varnish is applied onto the support by die coating or the like, and further heated, or A dry organic solvent such as hot air is blown to form a resin composition layer. -27- 201124502 Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and ethyl acetate and butyl acetate. Acetate such as cyproacetate, propylene glycol monomethyl ether acetate, carbitol acetate, carbitol such as serosol, butyl carbitol, aromatic hydrocarbons such as toluene and xylene Class, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Organic solvents can be used in 1 or in combination 2 The drying conditions are not particularly limited, and the content of the organic solvent to be dried in the resin composition layer is 10% by mass or less, preferably 5% by mass or less, based on the organic matter in the varnish. The solvent amount and the boiling point of the organic solvent are different, so that suitable drying conditions can be set. Specifically, in the case of a varnish containing 30 to 60% by mass of an organic solvent, it is preferred to dry at 50 to 150 ° C for 3 to 10 minutes. Further, in order to obtain an adhesive film of a copper foil to be formed of a prepreg, the curable resin composition layer is not particularly limited, and specifically, the prepreg is laminated by vacuum lamination on the support. The adhesive film is preferably formed by laminating the adhesive film and the copper foil under the above-mentioned conditions. The prepreg can be produced by a known hot melt method, a solvent method, etc. The hot melt method does not require the resin to be composed. The product is dissolved in an organic solvent, and the resin composition is applied to a release paper having good releasability, and then laminated to a sheet-like fibrous base material or directly coated by a die coating to prepare a prepreg. Further, the solvent method is a method in which a varnish is impregnated into a flaky fiber base material by dissolving a resin composition in a varnish of an organic solvent, and then the varnish is impregnated into a flaky fiber base material, and then dried. The adhesive film formed by the curable resin composition laminated on the support layer is heated from both sides of the flaky reinforcing substrate -28-201124502 under the condition of continuous lamination under pressure, and is prepared by a solvent method. In the varnish, the resin varnish is used, and the drying conditions are not particularly limited. However, when the multilayer printed wiring board is laminated on the inner layer circuit substrate in the production step, the curable resin composition must have fluidity. And adhesion. Therefore, it is important to harden the hardening resin composition as much as possible during drying. On the other hand, when the organic solvent remains in the prepreg, the upper limit of the content ratio of the organic solvent in the curable resin composition in the drying end is 5% by mass or less. It is preferably 2% by mass or less. The specific drying conditions differ depending on the curability of the curable resin composition or the amount of the organic solvent in the varnish, so that suitable drying conditions can be set, but specifically, for the varnish containing 30 to 60% by mass of the organic solvent, at 8 0~1 8 0 °C drying 3~1 3 minutes is better. Further, an adhesive film with a copper foil can be produced directly from a copper foil-coated varnish. The coating method at this time is the same as the above-described method for producing an adhesive film, and the drying conditions may be set to be the same. <Production of Multilayer Printed Wiring Board Using Adhesive Film Attached with Copper Foil> The method for producing a multilayer printed wiring board of the present invention comprises the following steps (A) to (D). (A) a support for peeling off the adhesive film of the copper foil-attached adhesive film of the present invention, a step of laminating the curable resin composition layer on the inner layer circuit substrate, and (B) curing the curable resin composition layer to form an insulating layer. step

-29 - 201124502 (C) 將銅箔以銅蝕刻液除去的步驟、 (D) 於絕緣層表面藉由無電解鍍敷形成銅層的步驟〇所謂本發明之「內層回路基板」，係於玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚伸苯基醚基板的單面或兩面上具有經圖形加工 (回路形成）之導體層，製造多層印刷配線板時，必須進一步形成絕緣層及導體層的中間製造物。步驟（A )中，剝離附銅箔之黏著薄膜的支持體，將硬化性樹脂組成物層的露出面以向著內層回路基板之方向層合。對於該附銅箔之黏著薄膜的內層回路基板之層合，由容易得到作業性及一樣接觸狀態之觀點來觀點來看，進行輥、加壓壓著等。又，以真空層合法，即減壓下進行層合者爲佳。又，層合的方法可爲分批式、亦可藉由輥施予連續方式。該層合條件的較佳溫度選自6 0〜1 4 0 °C的範圍，更佳爲選自.80〜120 °C的範圍。又，加壓之壓力較佳爲選自1 〜1“8£/(；1112(9.8><104〜107.9><104]^/1112)的範圍，更佳爲選自2〜7让§£/〇1112(19.6><104〜68.6\104]^/1112)的範圍。時間以5秒〜3分鐘的範圍爲佳，以丨5秒〜1分鐘的範圍爲較佳。又’空氣壓在20mmHg ( 26.7hPa )以下的減壓下進行層合爲佳。該（A)步驟爲將附銅箔之黏著薄膜黏著於內層回路基板並使其一體化的步驟，該步驟後之硬化性樹脂組成物層係爲硬化反應之中間段階（B階段）的狀態。 -30- 201124502 真空層合可使用販賣的真空層合器進行。作爲販賣的真空層合器，具體可舉出（股）名機製作所製分批式真空加壓層合器 MVLP-500 ' Nichigo-Morton (股）製真空噴頭器、（股）Hitachi Plant Technologies製輕式乾燥塗佈機、日立A 1C (股）製真空層合器等。步驟（B )係爲硬化硬化性樹脂組成物層並形成絕緣層的步驟（即，使其硬化至使硬化性樹脂組成物層成爲硬化的最終段階之C階段的步驟），該硬化方法並無特別限制，使用熱硬化處理爲佳。在熱硬化處理的硬化條件雖依硬化性樹脂的種類等而不同，但硬化溫度以120〜2 00°C，硬化時間以1 5〜90分鐘的條件下進行爲佳。且，由防止所形成之絕緣層表面的縐折之觀點來看，以由比較低的硬化溫度至高硬化溫度的段階性硬化之方法、或自比較低的硬化溫度上升至高硬化溫度下進行硬化的方法爲佳。步驟 (B )在步驟（A )之後爲佳。又，（A)步驟與（B)步驟可使用一般真空熱加壓機以連續方式進行。例如可藉由將經加熱的S U S板等金屬板由銅箔側加壓而進行。作爲販賣的真空熱加壓機’例如可舉出 MNPC-V-750-5-200 (股）名機製作所製）、 VH 1 - 1 603 (北川精機（股）製）等。在步驟（C )之銅箔的除去若可達成目的即可，並無特別限制，具體可藉由氯化第二鐵水溶液、氯化第二銅水溶液、過氧二硫酸鈉與硫酸之水溶液等銅蝕刻液進行。作爲販賣的銅蝕刻液，可舉出MEC (股）製的CF-6000、 -31 - 201124502-29 - 201124502 (C) The step of removing the copper foil with a copper etching solution, and (D) the step of forming a copper layer on the surface of the insulating layer by electroless plating. The "inner layer circuit substrate" of the present invention is attached to A glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate having a conductor layer formed by patterning (loop formation) on one or both sides In the case of a multilayer printed wiring board, it is necessary to further form an intermediate product of the insulating layer and the conductor layer. In the step (A), the support of the adhesive film with a copper foil is peeled off, and the exposed surface of the curable resin composition layer is laminated in the direction toward the inner layer circuit substrate. The lamination of the inner layer circuit board of the copper foil-attached adhesive film is carried out by a roll, press-pressing, or the like from the viewpoint of easy workability and the same contact state. Further, it is preferred to carry out lamination under vacuum lamination, that is, under reduced pressure. Further, the laminating method may be batchwise or may be carried out by a roller in a continuous manner. The preferred temperature for the lamination conditions is selected from the range of from 60 to 140 ° C, more preferably from the range of from 80 to 120 °C. Further, the pressure of the pressurization is preferably selected from the range of 1 to 1 "8 £ / (; 1112 (9.8 >< 104 to 107.9 >< 104] / 1112), more preferably selected from 2 to 2 7 Let §£/〇1112 (19.6><104~68.6\104]^/1112) range. The time is preferably in the range of 5 seconds to 3 minutes, preferably in the range of 5 seconds to 1 minute. Further, it is preferred that the air pressure is laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. The step (A) is a step of adhering and bonding the adhesive film of the copper foil to the inner layer substrate. The layer of the curable resin composition after the step is in the middle stage of the hardening reaction (stage B). -30- 201124502 The vacuum lamination can be carried out using a vacuum laminator sold as a vacuum laminator for sale, specifically A batch vacuum pressure laminate MVLP-500 manufactured by Nippon Seiki Co., Ltd. 'Nichigo-Morton vacuum nozzle, Hitachi Plant Technologies light drying coater, Hitachi A 1C a vacuum laminator made of (strand), etc. Step (B) is a step of hardening the curable resin composition layer and forming an insulating layer (ie, hardening it to The hardening resin composition layer is a step of the C stage of the final stage of curing. The curing method is not particularly limited, and it is preferably a thermal curing treatment. The curing conditions of the thermosetting treatment differ depending on the type of the curable resin. However, the curing temperature is preferably 120 to 200 ° C, and the curing time is preferably 15 to 90 minutes. Moreover, from the viewpoint of preventing the formation of the surface of the insulating layer formed, it is relatively low. The method of hardening from the hardening temperature to the high hardening temperature, or the method of hardening from a relatively low hardening temperature to a high hardening temperature is preferred. The step (B) is preferably after the step (A). Further, the step (A) The step (B) can be carried out in a continuous manner using a general vacuum heat presser, for example, by pressurizing a metal plate such as a heated SUS plate from the side of the copper foil. As a vacuum heat press machine for sale, for example MNPC-V-750-5-200 (manufactured by Nihon Seiki Co., Ltd.), VH 1 - 1 603 (made by Kitagawa Seiki Co., Ltd.), etc. The removal of copper foil in step (C) can be achieved. Yes, there are no special restrictions. Specifically, it can be carried out by a copper etching solution such as a second aqueous solution of chlorinated chloride, a second aqueous solution of copper chloride, or an aqueous solution of sodium peroxodisulfate and sulfuric acid. The commercially available copper etching solution is a CF manufactured by MEC (share). -6000, -31 - 201124502

Meltex (股）製的E-製程一WL等鹼性蝕刻液。依據銅范的厚度等雖不同，但可藉由銅箔的除去爲將銅箔含浸於蝕刻液（2〇〜60°C )中1〇〜60分鐘的浸漬法而進行。又，亦可使用將蝕刻液成爲噴霧狀，吹入形成絕緣層的內層回路基板而進行蝕刻的方法。條件與浸漬法相同。對於藉由該銅蝕刻液的銅箔之除去處理，於銅箔的除去處理後露出的絕緣層之表面，轉印成具有銅合金鍍敷層的銅箔之表面粗度（Ra)爲300nm以下的微細粗面。因此，絕緣層的表面粗度（Ra )之上限以300nm以下爲佳，以 250nm以下爲較佳，以 200nm以下爲更佳，以 150nm以下爲進一步更佳。又，下限.以l〇nm以上爲佳，以2 0nm以上爲較佳，以30nm以上爲更佳。於銅箔表面我形成之銅合金鍍敷層可藉由銅箔之除去處理而與銅箔同時幾乎除去，但於絕緣層的表面亦可殘存一部份。本發明的預浸體之表面中的銅合金鍍敷層之殘存量可藉由X線光電子分光（XPS )測定。銅合金鍍敷層的殘存量可藉由X線光電子分光（XPS)所得之測定値爲 l.Oatomic%以上。且，即使銅合金鍍敷層的殘存量相異，絕緣層的表面粗度（Ra)爲一定。又，銅合金鍍敷層之表面並未經防鏽處理的情況爲多，但此所謂銅合金鍍敷層之殘存量爲銅合金鍍敷層的表面經防鏽處理的情況時，銅合金鍍敷層與防鏽處理被膜的合計量。且，即使殘存防鏽處理被膜亦無特別問題。於步驟（B )之後進行步驟（C )爲佳。 -32- 201124502 本發明之多層印刷配線板的製造方法中因進一步含有 (E)除去銅合金鍍敷層的步驟，可除去成爲在高周波之噪音的原因之顧慮的銅合金鍍敷層，減量殘存於絕緣層表面之銅合鍍金，並可提高在高周波之電氣特性。又，回路形成後在銅片（copper land)上形成突塊，於銅片（ copper land)上進行Au-Ni無電解鍍敷時，即使在本來無電解鍍敷未析出的樹脂表面上可迴避將微小銅合鍍金作爲核的鑛敷析出等不佳情況的產生。步驟（E )可藉由氧化劑溶液處理而進行，雖無特別限制，該氧化劑溶液處理具體以（a )藉由膨潤液之膨潤處理、（b )藉由氧化劑溶液之粗化處理及（c )藉由中和液之中和處理的順序進行爲佳。作爲膨潤液’雖無特別限制，但可舉出鹼溶液、界面活化劑溶液等，鹼溶液爲佳，以氫氧化鈉溶液、氫氧化鉀溶液爲較佳。又’亦可使用 Atotech Japan (股）製的 Swelling Dip Securiganth P、Swelling Dip Securiganth S B U等販賣的膨潤液。藉由膨潤液之膨潤處理雖無特別限制，具體爲可使用於除去銅箔的處理面將2 0〜5 0 r的膨潤液賦予1 〇秒〜2分鐘的方法。由作業性、樹脂不會過度膨潤的觀點來看’以將除去銅箱的對象物於2 0〜5 0。(：的膨潤液中進行1 〇秒〜1分鐘的浸漬方法爲佳。作爲氧化劑溶液’雖無特別限制，具體可舉出於氫氧化鈉的水溶液中溶解過錳酸鉀或過錳酸鈉之鹼性過錳酸溶液。鹼性過錳酸溶液中之過錳酸鹽的濃度以5〜1 0質量％ -33- 201124502 爲佳。又，亦可使用 Atotech Japan (股 CONCENTRATE · COMPACT CP ' Dosing solution SecuriganthP等販賣的氧化劑溶液。藉由氧化劑化處理雖無特別限制，具體可使用於藉由膨潤液處理之處理面將20〜60°C的氧化劑溶液施予10 鐘的方法。由作業性、樹脂不會過度粗化的觀點進行膨濕處理的對象物於20〜50°C的氧化劑溶济秒〜1分鐘的浸漬之方法爲佳。作爲中和液，雖無特別限制，以酸性水溶液可使用Atotech Japan (股）製的還原溶液.Secu: 等販賣的中和液。藉由中和液之處理可使用於藉溶液進行粗化處理的處理面，將20〜60°C的中 1 0秒〜2分鐘的方法。由作業性等觀點來看，將劑溶液進行粗化處理之對象物於20〜5 0°C的中 10秒〜1分鐘的方法爲佳。藉由進行以上之氧化劑溶液處理，銅合金鍍完全被除去，於氧化劑溶液處理後之絕緣層的露存在銅合鍍金、或即使存在但藉由 XPS的ί 0.1 atomic%以下。於步驟（C )之後，進行步驟佳。又’步驟（E)於步驟（D)前進行爲佳。對於本發明之多層印刷配線板的製造方法， D)的絕緣層表面藉由無電解鍍敷形成銅層的步別限制，可進行公知方法。具體爲將絕緣層表面化劑等進行處理，賦予鈀等鑛敷觸媒後，以浸漬 )製的溶液的粗進行膨濕秒〜2分來看，將 g進行10 爲佳。亦 re GanttP 由氧化劑和液施予藉由氧化和液浸漬敷層大槪出面上不則定値爲丨（E )爲於步驟（驟雖無特以界面活於無電解 -34- 201124502 鍍敷液之方式形成銅層爲佳。銅層的厚度以〇 . 1〜5.0 # m 爲佳，以0.2〜2.5"m爲較佳，以0.2〜1.5//m爲更佳。且’銅層可藉由一種無電解鍍敷之直接印刷法而形成。步驟（D )爲施予於經由步驟（C 〇而露出的絕緣層表面爲佳’施予於經由步驟（E )而露出的絕緣層表面爲更佳。本發明之多層印刷配線板的製造方法中因進一步含有形成步驟（F )的盲孔之步驟，可進行層間之導通。步驟 (F )若可達到目的即可，並無特別限制，具體可藉由碳酸氣雷射、YAG雷射等進行。步驟（F )於步驟（B )或步驟（C )或步驟（E )之後進行爲佳。於盲孔形成後藉由去膠渣液爲粗化絕緣層表面，由可微細配線化的觀點來看，步驟（F )於步驟（C )之前進行爲較佳。本發明之多層印刷配線板的製造方法因進一步含有步驟（G)的去膠渣步驟，除去因盲孔形成所產生的孔底（ via-bottom )殘渣，而可進行孔壁面之粗化。步驟（G ) 雖無特別限制，可藉由公知之方法而進行。具體以藉由等離子等乾燥法、鹼性過錳酸溶液等氧化劑處理的加濕法爲佳。由與除去孔底（via-bottom)之炫脈（smear)的同時，孔壁面可藉由氧化劑粗化，提高鍍敷密著強度的觀點來看，藉由氧化劑溶液進行處理爲較佳。步驟（G )的氧化劑溶液處理雖無特別限制’以（a ) 藉由膨潤液之膨潤處理、（b )藉由氧化劑溶液之粗化處理及（c )藉由中和液之中和處理的順序進行爲佳。作爲膨潤液，雖無特別限制，可舉出鹼溶液、界面活 -35- 201124502 化劑溶液等，以鹼溶液爲佳，以氫氧化鈉溶液、氫氧化鉀溶液爲較佳。又，亦可使用 Atotech Japan (股）製的 Swelling Dip Securiganth P ' Swelling Dip Securiganth SBU等販賣的膨潤液。藉由膨潤液之膨潤處理雖無特別限制，具體爲將30〜90°C的膨潤液賦予1分鐘〜15分鐘下進行。由作業性、樹脂不會過度膨潤的觀點來看，於40 〜8(TC之膨潤液浸漬5秒〜1 0分鐘的方法爲佳。作爲氧化劑溶液，雖無特別限制，具體可舉出於氫氧化鈉的水溶液溶解過錳酸鉀或過錳酸鈉之鹼性過錳酸溶液。鹼性過錳酸溶液中之過錳酸鹽的濃度以5〜1 0質量％爲佳。又，可使用AtotechJapan (股）製的 CONCENTRATE · COMPACT CP 、 Dosing solution SecuriganthP等販賣的氧化劑溶液。藉由氧化劑溶液之粗化處理雖無特別限制，具體可使用藉由膨潤液進行膨濕處理的處理面上將50〜90°C的氧化劑溶液賦予1〇分鐘〜40分鐘的方法。由作業性、樹脂不會過度粗化的觀點來看，將經膨濕處理的對象物在60〜 85 °C的氧化劑溶液中浸漬20分鐘〜30分鐘的方法爲佳。作爲中和液，雖無特別限制，以酸性水溶液爲佳。可使用Atotech Japan (股）製的還原溶液.Secure GanttP等販賣的中和液。藉由中和液之處理可使用藉由氧化劑溶液的粗化處理之處理面上將3 0〜8 0 °C的中和液賦予5分鐘〜 3 0分鐘的方法。由作業性等觀點來看’將藉由氧化劑溶液的粗化處理之對象物於4 0〜7 0。(：之中和液浸漬5分鐘〜 -36- 201124502 2 0分鐘的方法爲佳。於步驟（F )之後進行步驟（G )爲佳。此後無進行電鍍，提高盲孔之接續信賴性的觀點來看，步驟（G )於步驟（D )之前進行爲佳。於步驟（C )時，孔底（via_ bottom)的基質銅層表面被蝕刻，可將孔底（via-bottom )之炫脈（smear )更完全地除去，且由防止絕緣層表面被粗化的觀點來看，步驟（G)於步驟（C)之前進行爲更佳。本發明之多層印刷配線板的製造方法中可進一步可含有（H)藉由電鍍形成導體層之步驟。步驟（η)中之導體層形成方法雖無特別限制，可藉由半加成法等公知方法進行。具體以形成鍍敷抗阻，將以上述的步驟（D )所形成之銅層作爲鍍敷種（planting seed)層，藉由電鍍形成導體層爲佳。藉由電鍍的導體層以銅爲佳。導體層之厚度雖依所望回路基板的設計而不同，以3〜3 5 y m爲佳，5 〜3 0 // m爲較佳。於步驟（d )之後進行步驟（η )爲佳〇本發明的多層印刷配線板的製造方法中可進一步含有 (I )於導體層形成回路的回路形成步驟。步驟（I )中之回路形成方法雖無特別限制，鍍敷抗阻以鹼性水溶液等鍍敷抗阻剝離液除去，藉由進行鍍敷種層之除去可形成回路。且，鍍敷種層之除去方法可進行與前述的步驟（C)之相同方法。於步驟（Η )之後進行步驟（I )爲佳。所謂本發明方法，得知於表面粗度（R a )極低的絕緣 -37- 201124502 層表面上可形成高密著強度之導體層。絕緣層的表面粗度 (Ra)之下限由絕緣層與鍍銅層之黏著性良好的觀點來看，以5nm以上爲佳，以10nm以上爲較佳，以15nm以上爲更佳。另一方面，絕緣層之表面粗度（Ra)的上限由藉由回路形成時的不需要導體層之蝕刻的作業性與微細配線形成性良好的觀點來看，以3 00nm以下爲佳，以250nm 以下爲較佳，以200nm以下爲更佳，以150nm以下爲進一步更佳。所謂本發明方法，剝離強度之下限由對絕緣層之黏著安定性優良且可形成高信賴性之回路的觀點來看，以〇.50kgf/cm以上爲佳，以〇.55kgf/cm以上爲較佳.，以〇.60kgf/cm以上爲更佳，以〇.65kgf/cm以上爲進一步更佳。另一方面，剝離強度越高越佳，該上限値並無特別限制，但剝離強度之上限由充分性能之觀點來看，以 2kgf/cm以下爲佳，以5kgf/cm以下爲較佳，以l〇kgf/cm 以下爲更佳，以lOOkgf/cm以下爲進一步更佳。對於本發明，於如此高平滑性（即，表面粗度極低）之絕緣層表面上可形成剝離強度高之導體層的理由可考慮爲，於銅箔除去後之樹脂表面上，形成適合於提高銅層之密著性的非常緻密的粗面之故。且，本發明之多層印刷配線板的製造方法中亦含有數次重複自上述附銅箔之黏著薄膜的層合步驟至回路形成步驟（即步驟（A )〜步驟（I ))爲止的一連串步驟，層合多段增層（build-up layer)之增層工法。由有效率地進行 -38 - 201124502 多層印刷配線板的製造之觀點來看，各步驟之順序以步驟 (A )、步驟（B )、步驟（F )、步驟（G )、步驟（C ) 、步驟（E )、步驟（D )、步驟（Η )、步驟（I )之順序爲佳。【實施方式】 [實施例] 以下表示實施例，更具體說明本發明，但本發明並未受到以下實施例之任何限定。且，以下記載中之「份」表不「質量份」。首先，對於本說明書中的物性評估之測定方法做說明。 <導體層之剝離強度> 將導體層的剝離強度依據】IS C648 1，以以下方法進行測定。將下述實施例及比較例中所得之多層印刷配線板切成 15 0mm X 3 0mm之小片。於小片之銅箔部分以切割器切成寬度1 0 m m、長度1 0 0 m m，剝開銅箔之一端以綑具進行綑綁，使用Instron萬能試驗機在室溫中，測定以50mm/分鐘的速度於垂直方向拉開剝離3 5mm時的荷重，作爲剝離強度。導體層之厚度約30μπι。 <絕緣層表面粗度> 將回路基板上的無電解鍍銅層及電解鍍銅層以銅蝕刻 -39- 201124502 液除去，使用非接觸型表面粗度計（Veeco Instruments製 WYKO NT3300 )，藉由VSI接觸型、50倍透鏡將測定範圍設定爲1 2 1 /z m X 92 /z m，測定將銅箔經蝕刻除去後或除去銅合金鍍敷層後之絕緣層表面，求得表面粗度（Ra)。且Ra値以隨機方式將測定範圍設定爲3處，採用3處的測定値之平均値。 [絕緣層表面中之銅合鍍金的殘存量測定方法] <測定裝置> 裝置型式：QUANTERA SXM (全自動掃描型X線光電子分光分析裝置）到達真空度：7.〇xlO_1()Torr X 線源：單色化 Α1 Κ α ( 1 4 8 6.6 e V ) 分光器：靜電同心半球型分析器檢測器：多通道式（32 Multi-Channel Detector) 中和槍設定電子：1.0V(20；aA)、離子：l〇.〇V(7mA) <測定條件> <測量光譜> X 光束徑：1〇〇μηιΦ(ΗΡ 模型、100.6W、20kV) 測定區域：1400ymxl00"m 信號之讀取角：45.0°Meltex (E) process E-process an alkaline etching solution such as WL. Although the thickness of the copper is different, the copper foil can be removed by impregnation of the copper foil in an etching solution (2 to 60 ° C) for 1 to 60 minutes. Further, a method in which the etching liquid is sprayed and blown into the inner layer substrate on which the insulating layer is formed may be used for etching. The conditions are the same as the dipping method. In the removal process of the copper foil by the copper etching solution, the surface of the insulating layer exposed after the copper foil removal treatment is transferred to a copper foil having a copper alloy plating layer having a surface roughness (Ra) of 300 nm or less. The fine rough surface. Therefore, the upper limit of the surface roughness (Ra) of the insulating layer is preferably 300 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less, and still more preferably 150 nm or less. Further, the lower limit is preferably 10 nm or more, more preferably 20 nm or more, and still more preferably 30 nm or more. On the surface of the copper foil, the copper alloy plating layer I formed can be removed almost simultaneously with the copper foil by the removal of the copper foil, but a part of the surface of the insulating layer can remain. The residual amount of the copper alloy plating layer in the surface of the prepreg of the present invention can be measured by X-ray photoelectron spectroscopy (XPS). The residual amount of the copper alloy plating layer can be determined by X-ray photoelectron spectroscopy (XPS) to be .Oatomic% or more. Further, even if the residual amount of the copper alloy plating layer is different, the surface roughness (Ra) of the insulating layer is constant. Moreover, the surface of the copper alloy plating layer is not subjected to rustproof treatment. However, when the residual amount of the copper alloy plating layer is the surface of the copper alloy plating layer subjected to rustproof treatment, copper alloy plating is performed. The total amount of the coating layer and the rust-preventing treatment film. Further, there is no particular problem even if the rust-preventing film remains. It is preferred to carry out step (C) after step (B). -32-201124502 In the method for producing a multilayer printed wiring board of the present invention, the step of removing the copper alloy plating layer is further included (E), and the copper alloy plating layer which is a cause of high-frequency noise can be removed, and the amount of reduction remains. The copper is plated on the surface of the insulating layer and can improve the electrical characteristics at high frequency. Further, after the circuit is formed, a bump is formed on the copper land, and when the Au-Ni electroless plating is performed on the copper land, the surface of the resin which is not precipitated by the electroless plating can be avoided. The occurrence of poor conditions such as precipitation of fine copper and gold plating as a core. Step (E) can be carried out by treatment with an oxidizing agent solution, and the oxidizing agent solution is specifically treated by (a) swelling treatment by swelling liquid, (b) roughening treatment by oxidizing agent solution, and (c) It is preferred to carry out the treatment by the neutralization liquid. The swelling liquid is not particularly limited, and examples thereof include an alkali solution and an interfacial activator solution. The alkali solution is preferred, and a sodium hydroxide solution or a potassium hydroxide solution is preferred. Also, 'Swelling Dip Securiganth P, Swelling Dip Securiganth S B U, etc., manufactured by Atotech Japan Co., Ltd., may be used. The swelling treatment by the swelling liquid is not particularly limited, and specifically, a method of applying a swelling liquid of 20 to 50 μr to the treated surface for removing the copper foil for 1 to 2 minutes. From the viewpoint of workability and resin from excessive swelling, the object to be removed from the copper box is 20 to 50. It is preferable to carry out the immersion method of 1 sec. to 1 minute in the swelling liquid of the following: The oxidizing agent solution is not particularly limited, and specifically, potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. Alkaline permanganic acid solution. The concentration of permanganate in alkaline permanganic acid solution is preferably 5~10% by mass -33- 201124502. Also, Atotech Japan (CONCENTRATE · COMPACT CP ' Dosing) The oxidizing agent solution sold by Securiganth P, etc. is not particularly limited, and a method of applying an oxidizing agent solution of 20 to 60 ° C for 10 hours on a treated surface treated with a swelling liquid can be specifically used. In the case where the resin is not excessively roughened, it is preferred that the object to be swelled is immersed in an oxidizing agent at 20 to 50 ° C for a period of 1 minute to 1 minute. The neutralizing liquid is not particularly limited, and an acidic aqueous solution may be used. Use a reducing solution made by Atotech Japan Co., Ltd. Secu: Neutralizing liquid for sale, etc. The treatment surface for roughening treatment by the treatment of the neutralizing solution can be used in a medium of 20 to 60 ° C. Seconds ~ 2 minutes square From the viewpoint of workability, etc., it is preferred that the object to be subjected to the roughening treatment is subjected to a treatment at 20 to 50 ° C for 10 seconds to 1 minute. The copper alloy is treated by the above oxidizing agent solution. The plating is completely removed, and the exposed layer of the insulating layer after the treatment with the oxidizing agent solution is copper-plated or, if present, ε 0.1 atomic% or less by XPS. After the step (C), the step is performed. Further, the step (E) In the step (D), the advancement behavior is good. In the method for producing a multilayer printed wiring board of the present invention, the surface of the insulating layer of D) is restricted by the step of forming a copper layer by electroless plating, and a known method can be carried out. After the treatment of the surface layering agent or the like of the insulating layer and the application of the mineralizing catalyst such as palladium, it is preferable to carry out the growth of the solution by immersion in the second to 2 minutes. ReganttP is also applied by oxidizing agent and liquid by oxidizing and liquid impregnation. The surface of the large sputum is not determined as 丨(E) in the step (there is no special interface to live in electroless-34-201124502 plating solution Preferably, the copper layer is formed. The thickness of the copper layer is preferably from 1 to 5.0 #m, preferably from 0.2 to 2.5 "m, more preferably from 0.2 to 1.5//m. It is formed by a direct printing method of electroless plating. Step (D) is applied to the surface of the insulating layer exposed through the step (E) by applying the surface of the insulating layer exposed through the step (C 为 is preferred) Further, in the method for producing a multilayer printed wiring board of the present invention, since the step of forming the blind via of the step (F) is further included, the interlayer conduction can be performed. The step (F) can be achieved without particular limitation. Specifically, it can be carried out by carbonic acid gas laser, YAG laser, etc. Step (F) is preferably carried out after step (B) or step (C) or step (E). Desmear after formation of blind holes The liquid is the surface of the roughened insulating layer, and the step (F) is stepped from the viewpoint of fine wiring. It is preferable to carry out the process before the step (C). The method for producing a multilayer printed wiring board according to the present invention further comprises the desmear step of the step (G) to remove the via-bottom residue caused by the blind hole formation. The step (G) can be carried out by a known method, and the humidification method by an oxidizing agent such as a plasma drying method or an alkaline permanganic acid solution is used. Preferably, the pore wall surface can be treated by the oxidizing agent solution from the viewpoint of coarsening the oxidizing agent and increasing the adhesion strength of the plating layer while removing the smear of the via-bottom. The treatment of the oxidizing agent in the step (G) is not particularly limited 'by (a) swelling treatment by swelling liquid, (b) roughening treatment by oxidizing agent solution, and (c) neutralization treatment by neutralizing liquid. The order of the swelling solution is not particularly limited, and examples thereof include an alkali solution and an interfacial activity-35-201124502 solution, preferably an alkali solution, and a sodium hydroxide solution or a potassium hydroxide solution. Good. Also, you can use Atotec. The swelling liquid sold by Swelling Dip Securiganth P 'Swelling Dip Securiganth SBU, etc., manufactured by h Japan. The swelling treatment by the swelling liquid is not particularly limited, and specifically, the swelling liquid of 30 to 90 ° C is given for 1 minute to 15 minutes. In the case of the workability, the resin does not excessively swell, it is preferably 40 to 8 (the immersion liquid of TC is immersed for 5 seconds to 10 minutes. The oxidizing agent solution is not particularly limited, specifically An alkaline permanganic acid solution of potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Further, an oxidizing agent solution such as CONCENTRATE · COMPACT CP or Dosing solution Securiganth P manufactured by Atotech Japan Co., Ltd. can be used. The roughening treatment by the oxidizing agent solution is not particularly limited, and a method of applying an oxidizing agent solution of 50 to 90 ° C for 1 minute to 40 minutes on the treated surface which is swelled by the swelling liquid can be specifically used. From the viewpoint of workability and resin from being excessively roughened, it is preferred to immerse the object to be immersed in an oxidizing agent solution at 60 to 85 ° C for 20 minutes to 30 minutes. The neutralizing liquid is not particularly limited, and an acidic aqueous solution is preferred. A neutralizing solution such as a reducing solution manufactured by Atotech Japan Co., Ltd., Secure GanttP, etc. can be used. By the treatment of the neutralizing solution, a method of imparting a neutralizing solution of 30 to 80 ° C for 5 minutes to 30 minutes on the treated surface by the roughening treatment of the oxidizing agent solution can be used. From the viewpoint of workability and the like, the object to be roughened by the oxidizing agent solution is from 40 to 70. (: The neutralization solution is immersed for 5 minutes~-36-201124502 2 0 minutes is preferred. Step (G) is preferred after step (F). After that, no plating is performed to improve the reliability of the blind hole. It should be noted that the step (G) is preferably performed before the step (D). In the step (C), the surface of the matrix copper layer of the via_bottom is etched, and the via-bottom is immersed. (smear) is more completely removed, and step (G) is preferably performed before step (C) from the viewpoint of preventing the surface of the insulating layer from being roughened. Further, in the method for producing a multilayer printed wiring board of the present invention, The step of forming a conductor layer by electroplating may be contained (H). The method of forming the conductor layer in the step (n) is not particularly limited, and may be carried out by a known method such as a semi-additive method, specifically to form a plating resist. The copper layer formed by the above step (D) is preferably used as a plating seed layer to form a conductor layer by electroplating. The electroplated conductor layer is preferably copper. The thickness of the conductor layer depends on the desired circuit. The design of the substrate is different, preferably 3 to 3 5 ym, 5 ~ It is preferable that the step (n) is carried out after the step (d). The method for producing a multilayer printed wiring board of the present invention may further comprise (I) a loop forming step of forming a loop of the conductor layer. The method for forming the circuit in the step (I) is not particularly limited, and the plating resistance is removed by plating an anti-blocking liquid such as an alkaline aqueous solution, and a circuit can be formed by removing the plating layer. The removal method can be carried out in the same manner as the above step (C). It is preferred to carry out the step (I) after the step (Η). The method of the present invention is known to have an extremely low surface roughness (R a ). 37- 201124502 A conductor layer with high density can be formed on the surface of the layer. The lower limit of the surface roughness (Ra) of the insulating layer is preferably 5 nm or more, and 10 nm, from the viewpoint of good adhesion between the insulating layer and the copper plating layer. The above is preferable, and it is more preferably 15 nm or more. On the other hand, the upper limit of the surface roughness (Ra) of the insulating layer is excellent in workability and fine wiring formation property of the etching of the unnecessary conductor layer when the circuit is formed by the circuit. From the point of view, it is better to be below 300 nm. It is preferably 250 nm or less, more preferably 200 nm or less, and still more preferably 150 nm or less. In the method of the present invention, the lower limit of the peel strength is excellent in adhesion stability to the insulating layer and can form a circuit with high reliability. In view of the above, it is preferably 5050kgf/cm or more, more preferably 〇55kgf/cm or more, more preferably 〇60kgf/cm or more, and further preferably 〇.65kgf/cm or more. In the aspect of the present invention, the upper limit is not particularly limited, but the upper limit of the peel strength is preferably 2 kgf/cm or less, more preferably 5 kgf/cm or less, from the viewpoint of sufficient performance. It is more preferably kgf/cm or less, and further preferably 100 kgf/cm or less. In the present invention, the reason why a conductor layer having a high peeling strength can be formed on the surface of the insulating layer having such high smoothness (that is, the surface roughness is extremely low) can be considered to be suitable for forming a surface of the resin after removal of the copper foil. A very dense rough surface that enhances the adhesion of the copper layer. Further, the method for producing a multilayer printed wiring board of the present invention also includes a series of steps of repeating the laminating step from the copper foil-attached adhesive film to the loop forming step (ie, steps (A) to (I)). , layering multi-stage build-up layer layering method. From the viewpoint of efficiently manufacturing the multilayer printed wiring board of -38 - 201124502, the order of each step is step (A), step (B), step (F), step (G), step (C), The order of step (E), step (D), step (Η), and step (I) is preferred. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the following examples. Further, the "parts" in the following description are not "parts by mass". First, the measurement method of the physical property evaluation in this specification will be described. <Peel strength of the conductor layer> The peel strength of the conductor layer was measured by the following method in accordance with IS C6481. The multilayer printed wiring board obtained in the following examples and comparative examples was cut into small pieces of 150 mm × 30 mm. The copper foil portion of the small piece was cut into a width of 10 mm and a length of 100 mm by a cutter, and one end of the copper foil was peeled off and bundled with a bundle, and the temperature was measured at room temperature using an Instron universal testing machine at 50 mm/min. The speed was pulled in the vertical direction and the load at the peeling of 3 5 mm was taken as the peeling strength. The thickness of the conductor layer is about 30 μm. <Insulation layer surface roughness> The electroless copper plating layer and the electrolytic copper plating layer on the circuit substrate were removed by a copper etching-39-201124502 liquid, and a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments) was used. The measurement range was set to 1 2 1 /zm X 92 /zm by a VSI contact type, 50-fold lens, and the surface of the insulating layer after removing the copper foil by etching or removing the copper alloy plating layer was measured to obtain the surface roughness. (Ra). And Ra値 set the measurement range to 3 in a random manner, and measured the average enthalpy of enthalpy at three places. [Method for Measuring Residual Amount of Copper-Coated Gold in the Surface of Insulating Layer] <Measuring Device> Device Type: QUANTERA SXM (Full-Automatic Scanning X-ray Photoelectron Spectroscopic Analysis Device) Reaching Vacuum: 7. 〇xlO_1() Torr X Line source: Monochrome Α1 Κ α (1 4 8 6.6 e V ) Beam splitter: Electrostatic concentric hemispheric analyzer Detector: Multi-channel Detector Neutral gun setting electron: 1.0V (20; aA), ion: l〇.〇V (7 mA) <Measurement conditions><Measurementspectrum> X Beam diameter: 1 〇〇μηιΦ (ΗΡ model, 100.6 W, 20 kV) Measurement area: 1400 ym x l00 " m signal Reading angle: 45.0°

通行能：280.0eV -40- 201124502 [實施例1 ] <具有硬化性樹脂組成物層之黏著薄膜的製作> 將液狀雙酚A型環氧基樹脂（環氧基當量180、日本環氧樹脂（股）製「EPIKOTE828EL」）28份、萘型4官能環氧基樹脂（環氧基當量163、大日本油墨化學工業（股）製「HP47 00」）28份、及苯氧基樹脂（日本環氧樹脂（股）製「YX6954BH30」、固體成分 30質量％的 MEK與環己酮之1: 1溶液）20份於MEK15份與環己酮 1 5份之混合液中一邊攪拌一邊使其加熱溶解。於此混合以含有三嗪的酚漆用酚醛樹脂（羥基當量1 25、DIC (股 )製「LA7054」、固體成分60質量％之MEK溶液、氮含有量約1 2質量％ ) 2 7份、萘酚系硬化劑（羥基當量 215、東都化成（股）製「SN-485」）之固體成分50質量 %之MEK溶液27份、硬化觸媒（四國化成工業（股）製之「2E4MZ」）0.1份、球形二氧化矽（平均粒徑0.5 # m 、（股）Admatechs製「SOC2」）70份、菲型磷化合物 (三光（股）製「HCA-HQ」）6份、及聚乙烯丁醛樹脂 (積水化學工業（股）製「KS-1」）溶解於乙醇與甲苯的質量比爲1 : 1之混合溶劑的固體成分1 5 %之溶液1 0份，以高速轉動攪拌機均勻地分散後製作出樹脂清漆。於附有厚度38//m之醇酸型離型劑（AL-5 )的聚對酞酸乙二酯薄膜（Lintec (股）製）上將上述清漆藉由模具塗佈進行塗佈，使用熱風乾燥爐除去溶劑，製作出硬化性樹脂組成物層的厚度爲40 之黏著薄膜。 -41 - 201124502 <附銅箔之黏著薄膜的製作> 於上述黏著薄膜之硬化性樹脂組成物層，於表面具有藉由電鍍之Ni-Co-Cu的銅合金鍍敷層，於該表面上經Zn 及鉻酸鹽的防鏽處理，將該Ra値爲2 5 0nm之銅箔（厚度 18#m之電解銅箔）（日鑛金屬（股）製「HLPFN」）在溫度90°C貼合成該銅合金鍍敷層接觸於硬化性樹脂組成物層而捲取後得到附銅箔之黏著薄膜。 <對於內層回路基板上的附銅箔之黏著薄膜的層合及硬化〉在厚度的銅層形成回路之玻璃環氧基板的銅層上以MEC (股）製CZ8100C含有唑類之銅錯體、有機酸之表面處理劑處理）施予粗化。其次，剝離上述附銅箔之黏著薄膜的離型PET，使硬化性樹脂組成物層與銅回路表面銜接，使用分批式真空加壓層合器MVLP-5 00 ((股 )名機製作所製商品名），在壓力0.7MPa、溫度100°C、時間30秒下層合於基板之兩面。層合爲30秒減壓後將氣壓設定爲13hPa以下進行。此後’在180°C進行30分鐘熱硬化而形成絕緣層。 <銅箔及銅合金鍍敷層之除去> 將藉由上述熱硬化形成絕緣層的基板上之銅箔以氯化第二鐵水溶液在40 °C進行30分鐘處理而除去’再藉由氧化劑溶液進行銅合金鍍敷層之除去處理。藉由該氧化劑溶 -42- 201124502 液之處理爲，經 Atotech Japan (股）製的 Swelling Dip Securiganth P進行膨潤（條件爲在40°C進行1分鐘），水洗後藉由 Atotech Japan (股）製的 CONCENTRATE . COMPACT CP (鹼性過猛酸溶液）進行粗化處理（條件爲在 40°C進行1分鐘），進一步水洗後，藉由 Atotech Japan (股）製的還原溶液· Secure Gan UP (中和液）進行中和處理（條件爲在40°C進行1分鐘）而進行。且，在絕緣層表面殘存銅合金鍍敷層約l.Oatomic%。 <導體層之形成> 此後使用使用下述Atotech Japan (股）製藥液之無電解鍍銅製程進行無電解鍍銅，形成膜厚的銅層。此後進行電解鍍銅，形成合計3 0 # m厚度的導體層而得到多層印刷配線板。 <使用Atotech Japan (股）製藥液之無電解鍍銅製程〉 1 .鹼洗淨（樹脂表面之洗淨與電荷調整）商品名:Cleaning cleaner Securiganth 902 條件：在60°C下進行5分鐘 2.軟蝕刻（孔底（via-bottom)、導體之銅的洗淨）硫酸酸性過氧二硫酸鈉水溶液條件：在30°C進行1分鐘 -43- 201124502 3.預浸（使用於下步驟的Pd賦予的表面電荷之調整爲目的）Passing energy: 280.0 eV -40 - 201124502 [Example 1] <Preparation of adhesive film having a curable resin composition layer> Liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, Japanese ring) 28 parts of "EPIKOTE 828EL" made of oxygen resin (stock), 28 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, "HP47 00" manufactured by Dainippon Ink Chemicals Co., Ltd.), and phenoxy resin (YX6954BH30, manufactured by Nippon Epoxy Resin Co., Ltd., a 1:1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) 20 parts of a mixture of 15 parts of MEK and 15 parts of cyclohexanone while stirring It is heated to dissolve. In this case, a phenol resin for phenol paint containing a triazine (hydroxyl equivalent of 25, "LA7054" manufactured by DIC Co., Ltd., a MEK solution of 60% by mass of a solid component, and a nitrogen content of about 12% by mass) of 27 parts, 27 parts of a MEK solution containing 50% by mass of a solid component of a naphthol-based curing agent (hydroxyl equivalent 215, "SN-485" manufactured by Tohto Kasei Co., Ltd.), and a curing catalyst (2E4MZ manufactured by Shikoku Chemicals Co., Ltd.) ) 0.1 parts, spherical cerium oxide (average particle size 0.5 # m, (stock) made by Admatechs "SOC2") 70 parts, phenanthrene-type phosphorus compound (Sanko (HCA-HQ) made of 6 parts), and polyethylene Butyl aldehyde resin ("KS-1" manufactured by Sekisui Chemical Co., Ltd.) is dissolved in 10 parts of a solid solution of 15% by mass of a mixed solvent of ethanol and toluene, and the mixture is uniformly rotated at a high speed. After dispersion, a resin varnish was produced. The varnish was coated by a die coating on a polyethylene terephthalate film (manufactured by Lintec Co., Ltd.) having an alkyd type release agent (AL-5) having a thickness of 38/m. The solvent was removed by a hot air drying oven to prepare an adhesive film having a thickness of 40 of the curable resin composition layer. -41 - 201124502 <Preparation of Adhesive Film Attached to Copper Foil> The curable resin composition layer of the above-mentioned adhesive film has a copper alloy plating layer by plating Ni-Co-Cu on the surface, on the surface The anti-rust treatment of Zn and chromate is carried out, and the copper foil having a Ra値 of 250 nm (electrolyzed copper foil of thickness 18#m) ("HLPFN" manufactured by Nippon Mining Co., Ltd.) is at a temperature of 90 ° C. The copper alloy plating layer is bonded to the curable resin composition layer and wound up to obtain an adhesive film with a copper foil. <Lamination and hardening of the adhesive film of the copper foil on the inner layer substrate> The copper layer of the glass epoxy substrate on which the copper layer of the thickness is formed is made of MEC (stock) CZ8100C containing the azole copper The surface treatment of the body and the organic acid is applied to roughen. Next, the release PET of the above-mentioned copper foil-attached adhesive film was peeled off, and the curable resin composition layer was bonded to the surface of the copper circuit, and a batch type vacuum pressure laminate MVLP-5 00 (manufactured by Seiki Co., Ltd.) was used. The product name was laminated on both sides of the substrate at a pressure of 0.7 MPa, a temperature of 100 ° C, and a time of 30 seconds. After laminating for 30 seconds, the pressure was set to 13 hPa or less. Thereafter, heat hardening was performed at 180 ° C for 30 minutes to form an insulating layer. <Removal of Copper Foil and Copper Alloy Plating Layer> The copper foil on the substrate on which the insulating layer was formed by the above thermosetting was removed by treatment with a second aqueous solution of chlorinated iron at 40 ° C for 30 minutes to remove The oxidant solution is subjected to removal treatment of the copper alloy plating layer. The oxidizing agent was dissolved in -42-201124502, and was swelled by Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd. (conditions were carried out at 40 ° C for 1 minute), and washed with Atotech Japan (manufactured by Atotech Japan Co., Ltd.). CONCENTRATE . COMPACT CP (alkaline excess acid solution) for roughening (conditions at 40 ° C for 1 minute), further water washing, with Atotech Japan (stock) reduction solution · Secure Gan UP (medium The liquid phase was subjected to a neutralization treatment (conditions were carried out at 40 ° C for 1 minute). Further, a copper alloy plating layer was left on the surface of the insulating layer by about 1.0 atomic%. <Formation of Conductor Layer> Thereafter, electroless copper plating was performed using an electroless copper plating process using the following Atotech Japan pharmaceutical liquid to form a copper layer having a film thickness. Thereafter, electrolytic copper plating was carried out to form a conductor layer having a total thickness of 30 μm to obtain a multilayer printed wiring board. <Electroless copper plating process using Atotech Japan (stock) pharmaceutical liquid> 1. Alkali washing (resin surface cleaning and charge adjustment) Trade name: Cleaning cleaner Securiganth 902 Condition: 5 minutes at 60 ° C 2 Soft etching (via-bottom, copper cleaning of the conductor) Acidic acid sodium peroxodisulfate aqueous solution conditions: 1 minute at 30 ° C -43 - 201124502 3. Pre-dip (used in the next step The adjustment of the surface charge imparted by Pd is for the purpose)

商品名：Pre. Dip Neoganth B 條件：在室溫下進行1分鐘 4. 活化劑（對樹脂表面之Pd的賦予）商品名：Activator Neoganth 834 條件：在3 5 t下進行5分鐘 5. 還原（還原附有樹脂之Pd )Product name: Pre. Dip Neoganth B Condition: 1 minute at room temperature 4. Activator (granting Pd on resin surface) Trade name: Activator Neoganth 834 Condition: 5 minutes at 3 5 t 5. Reduction ( Reducing Pd with resin)

商品名：Reducer Neoganth WA :Reducer Acceralator 810 mod.之混合液條件：在30°C下進行5分鐘 6·無電解鍍銅（將Cu析出於樹脂表面（Pd表面））商品名：B as i c S ο 1 uti on P r i nt ganth M S K-D K ：Copper solution Printganth MSK ：Stabilizer Printganth MSK-DK :Reducer Cu之混合液條件：在35°C進行20分鐘 [實施例2] 除未藉由氧化劑溶液進行銅合金鍍敷層的除去處理以外，與實施例1同樣下製作多層印刷配線板。 -44 - 201124502 [實施例3] <具有硬化性樹脂組成物層之黏著薄膜的製作> 將液狀雙酚A型環氧基樹脂（環氧基當量180、曰本環氧樹脂（股）製「EPIKOTE828EL」）28份、萘型4官能環氧基樹脂（環氧基當量163、大日本油墨化學工業（股）製「HP4700」）28份、與苯氧基樹脂（日本環氧樹脂（股）製「YX6954BH30」、固體成分30質量％之 MEK與環己酮之1: 1溶液）20份，於MEK15份與環己酮1 5份的混合液中一邊攪拌一邊使其加熱溶解。於此將三嗪含有酚漆用酚醛樹脂（羥基當量125、DIC (股）製「LA7054」、固體成分60質量％之MEK溶液、氮含有量約1 2質量％ ) 2 7份、萘酚系硬化劑（羥基當量2 1 5、東都化成（股）製「SN-48 5」）之固體成分50質量％的 MEK溶液27份、硬化觸媒（四國化成工業（股）製之「 2E4MZ」）0.1份、球形二氧化矽（平均粒徑〇·5 # m、( 股）Admatechs製「SOC2」）120份、菲型磷化合物（三光（股）製「HCA-HQ」）6份、聚乙烯丁醛樹脂（積水化學工業（股）製「K S - 1」）混合於溶解於乙醇甲苯的質量比爲1 : 1之混合溶劑的固體成分1 5質量％之溶液3 〇份，以高速轉動攪拌機均勻地分散，製作出樹脂清漆。於厚度38"m之附有醇酸型離型劑（AL-5)的聚對酞酸乙二酯薄膜（Lintec (股）製）上將上述清漆藉由模具塗佈進行塗佈’使用熱風乾燥爐除去溶劑，製作出硬化性樹脂 -45 - 201124502 組成物層之厚度爲40/zm的黏著薄膜。與實施例1同樣地，於表面具有藉由電鍍之Ni-Co_ Cu的銅合金鍍敷層，該表面以Zn及鉻酸鹽進行防鏽處理 ’製作出貼合Ra爲250nm之厚度18em的電解銅箔（曰鑛金屬（股）製「HLPFN」）、與上述黏著薄膜的附銅箔之黏著薄膜。此後將該附銅箔之黏著薄膜於形成開口徑爲 300 v m之通孔的〇.3mm厚度之玻璃環氧基板藉由分批式真空加壓層合器進行層合。層合之條件與實施例1相同。此後在190°C進行90分鐘硬化。此時，未觀察到通孔上之凹部分等。 <盲孔之形成> 進行藉由氯化第二鐵水溶液之蝕刻處理使銅箔之厚度成爲約 lym後，自銅箔上藉由日立 Hitachi Via Mechanics (股）製的碳酸氣雷射，以出力0.6w、脈衝幅 3 y s、注射數2次之條件下形成頂部的開口徑爲65 y m之盲孔。 <藉由去膠渣處理之孔底（via-bottom)的洗淨> 於形成盲孔的基板上，藉由 Atotech Japan (股）製的Swelling Dip Securiganth P進行膨潤處理（條件爲在 60 °C進行5分鐘）。且，經水洗後藉由Atotech Japan (股 )製的CONCENTRATE . C Ο Μ P A C T C P (鹼性過锰酸溶液 )進行粗化處理（條件爲在80°C進行20分鐘）。水洗後 -46- 201124502 藉由 Atotech Japan (股）製的還原溶液.Secure GanttP( 中和液）進行中和處理（條件爲在40 °C進行5分鐘）。 <銅箔的除去、導體層的形成> 其次，將銅箔在40°C之氯化第二鐵水溶液中進行5分處理而除去，其後與實施例1同樣地，將無電解鍍銅與電解鍍銅依序進行，形成計3 0 // m厚之導體層而得到多層印刷配線板。 [比較例1 ] 於電解銅箔（（股）日鑛materials製「JTC箔」、 18#m)之消光處理面（絕緣層表面粗度（Ra) : 1 200nm )上，形成與實施例1相同的硬化性樹脂組成物層，得到附銅箔之黏著薄膜。使用該附銅箔之黏著薄膜藉由與實施例1的相同操作，製作出多層印刷配線板。在無電解鍍銅、電解鍍銅後，不會產生鑛敷膨脹等不佳情況，剝離強度爲如0 · 9 kgf/cm之高値，但R a爲如1 0 0 0 nm以上的大値。 [比較例2] 於電解銅箔（（股）日鑛materials製「丨TC箔」、 18 v m )之發光面（絕緣層表面粗度（Ra ) : 3 5 0nm ) ’ 形成與實施例1之相同硬化性樹脂組成物層’得到附銅箱之黏著薄膜。使用該附銅箔之黏著薄膜藉由與實施例1之相同操作，製作出多層印刷配線板。於無電解鍍銅後因產 -47- 201124502 生多數鍍敷膨脹故無法進行其後的評估。 [表 π__ 實施例1 實施例2 實施例3 比較例1 Ra(nm) 135 140 120 1200 剝離強度(kgfi^cni) 0.79 0.85 0.82 0.90 由表1得知在實施例1〜3可製造於絕緣層表面粗度 (Ra )較小之絕緣層表面具有高剝離強度的導體層之多層印刷配線板。另一方面，使用於表面未藉由銅合金鏟敷層處理的電解銅箔的附銅箔之黏著薄膜，對於製作多層印刷配線板的比較例1，導體層的剝離強度爲如〇.90kgf/cm之高値，但絕緣層表面粗度（Ra )超過lOOOnm，其爲極大値。又，使用於表面未藉由銅合金鍍敷層處理的電解銅箔之發光面上層合硬化性樹脂組成物層的附銅箔之黏著薄膜，對於製作多層印刷配線板的比較例2，無法得到無電解鍍銅與樹脂之間的密著，在該界面無電解鑛銅會浮上且膨脹。產業上可利用性本發明爲可製作於低粗度的絕緣層表面以高密著強度下形成銅層之多層印刷配線板。進一步亦可提供裝置此之電腦、行動電話、數位照相機、電視、等電氣製品、或電動自行車、汽車、電車、船舶、航空機等交通工具。本申請案係以日本申請的特願2009-165781作爲基礎申請案，該內容皆包含於本說明書中。 -48-Product name: Reducer Neoganth WA : Reducer Acceralator 810 mod. Mixing conditions: 5 minutes at 30 ° C. 6. Electroless copper plating (Cu is deposited on the resin surface (Pd surface)) Trade name: B as ic S ο 1 uti on P ri nt ganth MS KD K :Copper solution Printganth MSK :Stabilizer Printganth MSK-DK :Reducer Cu mixture condition: 20° C. at 35° C. [Example 2] Except for copper without oxidizing agent solution A multilayer printed wiring board was produced in the same manner as in Example 1 except that the alloy plating layer was removed. -44 - 201124502 [Example 3] <Preparation of an adhesive film having a curable resin composition layer> Liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, bismuth epoxy resin) 28 parts of "EPIKOTE828EL"), 28 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, "HP4700" manufactured by Dainippon Ink Chemicals Co., Ltd.), and phenoxy resin (Japanese epoxy resin) 20 parts of "YX6954BH30" (manufactured by "XX6954BH30", 30% by mass of MEK and cyclohexanone 1:1 solution), and heated and dissolved while stirring in a mixture of 15 parts of MEK and 15 parts of cyclohexanone. Here, the triazine contains a phenol resin for phenol paint (hydroxyl equivalent 125, "LA7054" manufactured by DIC Co., Ltd., a MEK solution of 60% by mass of a solid component, and a nitrogen content of about 12% by mass), 27 parts, and a naphthol type. 27 parts of a MEK solution having a solid content of 50% by mass of a curing agent (hydroxyl equivalent of 215, "SN-48 5" manufactured by Tosei Chemical Co., Ltd.), and a curing catalyst ("EE 4MZ" manufactured by Shikoku Chemicals Co., Ltd.) ) 0.1 parts, spherical cerium oxide (average particle size 〇·5 # m, (stock) made by Admatechs "SOC2"), 120 parts, phenanthrene-type phosphorus compound ("Huang-HQ") A vinyl butyral resin ("KS-1" manufactured by Sekisui Chemical Co., Ltd.) was mixed with a solution of a solid component of 15% by mass of a mixed solvent of ethanol toluene in a mass ratio of 1:1, and was rotated at a high speed. The mixer was uniformly dispersed to prepare a resin varnish. The above varnish was coated by die coating on a polyethylene terephthalate film (manufactured by Lintec Co., Ltd.) having an thickness of 38"m with an alkyd type release agent (AL-5). The solvent was removed in a drying oven to prepare an adhesive film having a thickness of 40/zm of a composition layer of a curable resin-45 - 201124502. In the same manner as in the first embodiment, a copper alloy plating layer of Ni-Co_Cu plated on the surface was used, and the surface was subjected to rust-preventing treatment with Zn and chromate to prepare an electrolysis having a thickness of 18 nm bonded to Ra of 250 nm. A copper foil ("HLPFN" made of bismuth ore metal) and an adhesive film attached to the copper foil of the above-mentioned adhesive film. Thereafter, the copper foil-attached film was laminated on a glass epoxy substrate having a through-hole of 300 m in opening diameter by a batch vacuum pressure laminate. The conditions for lamination were the same as in Example 1. Thereafter, hardening was carried out at 190 ° C for 90 minutes. At this time, a concave portion or the like on the through hole was not observed. <Formation of blind holes> After the etching of the chlorinated second iron aqueous solution is carried out to make the thickness of the copper foil approximately lym, a carbon dioxide laser made by Hitachi Hitachi Via Mechanics (share) is used from the copper foil. A blind hole having an opening diameter of 65 μm at the top was formed under the conditions of a force of 0.6 w, a pulse amplitude of 3 ys, and an injection number of 2 times. <washing of via-bottom by desmear treatment> On a substrate on which a blind hole is formed, swelling treatment is performed by Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd. (condition is 60 °C for 5 minutes). Further, after washing with water, it was subjected to a roughening treatment by CONCRATE.C Ο Μ P A C T C P (alkaline permanganic acid solution) manufactured by Atotech Japan Co., Ltd. (conditions were carried out at 80 ° C for 20 minutes). After washing -46- 201124502 Neutralization treatment was carried out by a reduction solution.Secure GanttP (neutralization solution) manufactured by Atotech Japan Co., Ltd. (conditions were carried out at 40 ° C for 5 minutes). <Removal of Copper Foil and Formation of Conductor Layer> Next, the copper foil was removed by treatment in a second aqueous solution of chlorinated iron at 40 ° C for 5 minutes, and thereafter, electroless plating was carried out in the same manner as in Example 1. Copper and electrolytic copper plating were sequentially performed to form a conductor layer having a thickness of 30 // m to obtain a multilayer printed wiring board. [Comparative Example 1] Example 1 was formed on the matte finish surface (thickness (Ra) of insulating layer: 1 200 nm) of electrolytic copper foil ("JTC foil", 18#m) manufactured by Nippon Mining Materials Co., Ltd. The same curable resin composition layer was obtained to obtain an adhesive film with a copper foil. Using the copper foil-attached adhesive film, a multilayer printed wiring board was produced by the same operation as in Example 1. After electroless copper plating or electrolytic copper plating, there is no problem such as poor expansion of the mineral deposit, and the peel strength is as high as 0. 9 kgf/cm, but Ra is a large enthalpy such as 100 nm or more. [Comparative Example 2] The light-emitting surface (the surface roughness (Ra) of the insulating layer: 305 nm) of the electrolytic copper foil ("丨TC foil", 18 vm) made of the electrolytic copper foil (formed by Nissan Materials Co., Ltd.) was formed as in Example 1. The same hardenable resin composition layer 'obtained an adhesive film with a copper box. A multilayer printed wiring board was produced by the same operation as in Example 1 using the copper foil-attached adhesive film. After the electroless copper plating, the majority of the plating was expanded due to the production of -47- 201124502, so the subsequent evaluation could not be carried out. [Table π__ Example 1 Example 2 Example 3 Comparative Example 1 Ra (nm) 135 140 120 1200 Peel strength (kgfi^cni) 0.79 0.85 0.82 0.90 It is understood from Table 1 that the insulating layers can be produced in Examples 1 to 3. A multilayer printed wiring board having a conductor layer having a high peel strength on the surface of the insulating layer having a small surface roughness (Ra). On the other hand, in the case of the copper foil-attached adhesive film of the electrolytic copper foil which was not treated with the copper alloy shovel layer on the surface, in Comparative Example 1 for producing a multilayer printed wiring board, the peeling strength of the conductor layer was, for example, 90.90 kgf/ The height of cm is high, but the surface roughness (Ra) of the insulating layer exceeds 100 nm, which is extremely large. Moreover, the adhesive film of the copper foil which laminated the hardening resin composition layer on the light-emitting surface of the electrolytic copper foil which was not processed by the copper alloy plating layer on the surface was not able to obtain the comparative example 2 of the multilayer printed wiring board. The adhesion between the electroless copper plating and the resin, at this interface, the electroless copper will float and expand. Industrial Applicability The present invention is a multilayer printed wiring board which can be formed on a surface of a low-thickness insulating layer to form a copper layer with high adhesion strength. Further, it is also possible to provide such a computer, a mobile phone, a digital camera, a television, an electric appliance, or an electric bicycle, a car, a tram, a ship, an aircraft, and the like. The present application is based on Japanese Patent Application No. 2009-165781, the entire contents of which are incorporated herein. -48-

Claims

201124502 VII. Patent application scope: 1. An adhesive film with a copper foil, which is characterized in that a layer of a hardening resin formed by bonding a copper foil plated on a surface of a copper alloy plating layer to a support is used. The copper alloy plating layer is brought into contact with the curable resin composition layer. 2. The adhesive film of the copper foil attached to the first application of the patent scope, wherein the surface of the copper alloy plating layer is rust-proofed. 3. The adhesive film of the copper foil attached to the first aspect of the patent application, wherein the copper alloy plating layer has a surface roughness (Ra) of 300 nm or less. A method for producing a multilayer printed wiring board, which comprises the following steps (A) to (D); (A) stripping the copper foil of any one of claims 3 to 3; The support for adhering the film, the step of laminating the curable resin composition layer to the inner layer circuit substrate, (B) the step of hardening the curable resin composition layer to form an insulating layer, and (C) etching the copper foil with copper a step of removing the liquid, (D) a step of forming a copper layer by electroless plating on the surface of the insulating layer, and a method for producing a multilayer printed wiring board according to claim 4, further comprising (E) removing copper The step of alloying ore coating. 6. The method of producing a multilayer printed wiring board according to the fourth aspect of the invention, wherein the surface roughness (Ra) of the surface of the insulating layer is 300 nm or less. 1 Manufacture of a multilayer printed wiring board according to item 4 of the patent application - 49 - 201124502 The method further comprises (F) a step of forming a blind hole. 8. The method of manufacturing a multilayer printed wiring board according to claim 4, further comprising (G) a desmear step. 9. The method of manufacturing a multilayer printed wiring board according to claim 4, wherein the step (H) comprises forming a conductor layer by electroplating. The manufacturing method of the multilayer printed wiring board of the fourth aspect of the invention is further included (I) a loop forming step of forming a loop of the conductor layer. A method for producing a multilayer printed wiring board, characterized in that a series of steps from the following steps (A) to (I) are repeated a plurality of times to laminate a plurality of build-up layers; (A) A support for adhering a copper foil-attached adhesive film according to any one of claims 1 to 3, a step of laminating a curable resin composition layer to an inner layer circuit substrate, and (B) a hardenability a step of forming an insulating layer after the resin composition layer is cured, (C) a step of removing the copper foil with a copper etching solution, (D) a step of forming a copper layer by electroless plating on the surface of the insulating layer, and (E) removing copper a step of alloy plating, (F) a step of forming a pupil, (G) a desmear step, (H) a step of forming a conductor layer by electroplating, and (I) a loop forming step of forming a loop in the conductor layer. -50- 201124502 无明说单无简••号 is the symbol of the map element on behalf of the map: the table design represents the book one or two fingers c C 'four 201124502 five cases if there is a chemical formula, please reveal the best display Chemical formula of the inventive feature: none