592011 A7 _ B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（1 ) MJB領域 本發明係關於印刷電路板上銅表面的處理與解決方法 。較特別的是，本發明所關聯的處理與解決方法爲藉由增 加印刷電路板上的銅箔表面及線路圖上的有機金屬轉化塗 膜的化學性抵抗力，以改進銅對介電材質之鍵結完整性。 發明背景 多層印刷電路板（Μ L B s )典型含有交錯陳列的銅 層及介電材料，且平鋪層在一起。現今市面上有許多種 ML B s ，依其製造的材質有所不同，可以是硬的（如果 是以硬的材料如玻璃再強化的環氧樹脂、B T、C E、 P T F E等所製成），可以是彈性的（如果是以彈性的材 料如聚酯或聚醯胺所製成），或可以是組合的（即所謂的 ''硬-彈性〃）。如果交錯陳列的銅層及介電材料是在依 序的程序中疊在彼此之上，而不是同時平鋪湊在一起，則 歸類爲順序架構板（Sequential Build-Up (SBU) Boards )， 此M L B的完整性與銅及介電材質間所形成的可靠鍵結有 關。在習知的M L B製造方法中，銅層係以氫氧化物/亞 氯酸鹽鹼性處理液處理，此謂“黑色氧化物製程”提供一 個強化的銅對介電材質的鍵結，黑色氧化物製程的例子與 細節已在如 U.S.Patents 4，3 5 8，4 7 9 ; 4，409，037;4，512，818; 4，844981 及 4，969 ，958 中說明。然而， 黑色氧化物製程遇到許多限制，包含如下： I I I ___ (請先閱讀背面之注意事項再填寫本頁)592011 A7 _ B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (1) MJB field This invention relates to the treatment and solution of copper surface on printed circuit boards. More specifically, the treatment and solution associated with the present invention is to improve the chemical resistance of copper to the dielectric material by increasing the chemical resistance of the organometal conversion coating film on the surface of the copper foil on the printed circuit board and the circuit diagram. Bonding integrity. BACKGROUND OF THE INVENTION Multilayer printed circuit boards (MLBs) typically contain staggered copper layers and dielectric materials and are tiled together. There are many types of ML B s on the market today. Depending on the material they are made of, they can be hard (if they are made of hard materials such as glass-reinforced epoxy, BT, CE, PTFE, etc.), It can be elastic (if made of an elastic material such as polyester or polyamide), or it can be a combination (so-called `` hard-elastic ''). If the staggered copper layers and dielectric materials are stacked on top of each other in a sequential process instead of being tiled together at the same time, they are classified as Sequential Build-Up (SBU) Boards. The integrity of this MLB is related to the reliable bonding formed between the copper and the dielectric material. In the conventional MLB manufacturing method, the copper layer is treated with a hydroxide / chlorite alkaline treatment solution. This "black oxide process" provides a strengthened copper-to-dielectric bond, black oxide. Examples and details of the manufacturing process have been described in US Patents 4, 3 5 8, 4 7 9; 4,409,037; 4,512,818; 4,844981 and 4,969,958. However, the black oxide process encounters many limitations, including the following: I I I ___ (Please read the notes on the back before filling this page)
0 t I n I . -轉- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -4 - 592011 A7 -B7 五、發明說明（2 ) 1 ·此製程只能在華式溫度約1 6 0至1 7 0下的具 腐蝕性的強鹼溶液中進行。 2 ·處理時間長，所以會在製造程序中產生瓶頸。 3 ·黑色氧化物塗膜容易溶於酸，使其在後續的處理 步驟中容易受酸所侵蝕，常導致一種不好的現象，常謂爲 ''粉紅環〃，且有時會導致、、楔形空隙〃，最後會在銅與 相鄰的介電層間出現不平整。 4 ·剛開始在黑色氧化物塗佈的銅與介電材質間的鍵 結強度很強，但會隨著M L B通過後續製造與包裝的程序 中的熱的生產線而快速劣化。 可靠的銅對介電材質的鍵結對彈性的及S B U電路板 而言特別重要。用來製造彈性板的聚醯胺，及用來製造 S B U電路板的光顯像（photo-imageable )介電物質，已 知其銅對介電材質之鍵結強度低於習知的以環氧玻璃爲基 礎的硬的電路板。 黑色氧化物塗膜由銅、亞銅的氧化物所組成，此塗膜 以主要形成氧化銅爲基礎，使得其展現弱的化學阻力。相 對而言，氧化亞銅（紅色至棕色）較不具化學活性，不像 氧化銅容易受酸所侵蝕。 爲了要消除 ''粉紅環〃，及避免鍵強度的劣化，對黑 色氧化物製程已發展二種型態的後處理。第一種型態是以 還原方法爲基礎，揭露於如U.S· Patent 4,642，161 ; 4，902，551;5，〇06，200; 5，076，864;5，147’492; 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I -------------裝--- (請先閱讀背面之注意事項再填寫本頁) · —線— 經濟部智慧財產局員工消費合作社印製 -5- 592011 A7 _____ B7 五、發明說明（3 ) 5，382，333;5，492，595; 5，556 ，532 及 5，721 ，014。第一種黑色 氧化物的後處理型態的基礎是將氧化物塗膜做部份溶解， 說明於如 U.S. Patent 4，7 1 7，4 3 9 ; 4 ’ 775，444:5，106，454; 5’61，154;5，289，630 及 5 ’ 5 0 1 ，3 5 0中。雖然這二種技術所進行的化學機 制如此不同，但都可以達到近似的結果。第一個機制是一 種還原方法，係將銅的氧化物部份轉化成氧化亞銅與金屬 銅的混合物；第二個機制是一種溶解方法，選擇性地溶解 氧化銅，在表面上留下氧化亞銅。二種方法都是將黑色氧 化物（主要爲銅的氧化物）轉化成表面富含氧化亞銅。然 而，不幸的是，雖然黑色氧化物的還原與溶解的後處理可 以消除 ''粉紅環〃，且在某種程度上改進塗膜對酸的抵抗 力，但仍然無法解決上述與黑色氧化物相關的所有問題。 再者，已經發現用在ML B製造程序中爲了移除在鋪 層步驟前由介電材質所吸收的水分的烘乾步驟中，還原的 黑色氧化物在表面會有快速的再氧化。烘乾步驟後，表面 的再氧化會使塗膜出現明顯的黑暗處，而塗膜較暗的顏色 表示氧化銅又再度出現，使得塗膜又會在後續的處理程序 中更容易受化學性侵蝕。 因爲用在溶解的化學浸泡中的下切動作，部份溶解的 黑色氧化物容易在表面上形成粉狀的、附著力差的氧化亞 銅層，塗膜的粉狀物部份使得銅對介電材質無法形成強的 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） if-----------裝--- (請先閱讀背面之注意事項再填寫本頁) · 經濟部智慧財產局員工消費合作社印製 -1 I I J— . -6 - 592011 Α7 _ Β7 i、發明說明（4 ) 鍵結。此外，因爲會在粉狀表面發生滾筒的印痕，以水平 輸送方式便不可能使用此方法。 11---------裝--- (請先閱讀背面之注意事項再填寫本頁) 近來已引進一種對前述黑色氧化物製程的新的替代方. 法，係在銅表面生成有機金屬轉化塗膜（OMCC)，而 非形成銅氧化物。通常，有機金屬轉化塗膜的目的是爲了 在其下面的金屬表面上形成一個阻絕層，因此，可保護此 表面不受氧化及腐蝕，及/或增加對介電材質的鍵結。 0 M C C s爲金屬離子（單價或多價狀態）與有機化合物 間的化學反應產物，如此，容易與無機的黑色氧化物分辨 。〇MC C由金屬離子與錯合物連接、或與一種或多種有 機材料鍵結所形成的薄膜所組成。此形成0 M C C的方法 已揭露於 U.S. Patent 5，800.859 及 5，8 6 9，1 3 0。 在此方法中所生成的有機金屬轉化塗膜對酸的抵抗力 遠超過黑色氧化物塗膜，然而，因爲它的組成中仍然含有 以銅爲基礎的有機金屬化合物，它也並非能夠完全不受化 學性侵蝕。 經濟部智慧財產局員工消費合作社印製 下文中所討論的 > 楔形空隙〃形成機制，會說明本發 明的後處理步驟的重要性。 M L B板在鋪層後會加以打洞，在打洞操作中，打洞 器刃部的振動會在銅/介電材質界面產生微小裂痕，然後 溶劑調理劑便會被吸收進入銅與介電材質間的微小間隙中 ，後續以過錳酸根溶液的處理會氧化、亦即移除此已經膨 脹的樹脂，會產生一個 ''楔形〃。微蝕刻溶液會侵飩銅， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 592011 Α7 Β7 五、發明說明（5 ) 且使此間隙變寬，預浸漬及活化溶液典型爲相當濃的、以 鹽酸爲基礎的溶液，會進一步移除此銅處理層。若無電的 銅無法完全封住此、、楔形〃，則當此物浸泡於酸淸潔液、 微蝕刻溶液、酸浸漬及酸銅中’化學性侵鈾仍將持續。當 、、楔形〃相對的小，酸銅可以完全地塡補此間隙’而形成 典型的、、粉紅環〃外觀；若此間隙足夠大’可能只能部份 橫跨或一點也不能橫跨，而導致〜楔形空隙〃的缺陷。在 最嚴重的情形下，其結果爲出現不平整。 摘要說明： 本發明係關於一種處理與解決方法’以克服製造印刷 電路板時，已知的增強銅與介電材質間鍵結方法的問題。 較特別的是，本發明所關聯的方法爲藉由將銅表面上以銅 爲基礎的有機金屬化合物轉化成以亞銅爲基礎的有機金屬 轉化塗膜，以增加此黏著的、改進的銅塗膜的化學性抵抗 力，進而改進鍵結完整性。其達成方式爲還原及/或以部 份溶解有機金屬塗膜，及選擇性地同時添加銅氧化抑制劑 詳細說明= 本發明的基礎爲明顯地改進有機金屬轉化塗膜（ 〇M C C )的化學性抵抗力，使其在去斑點、無電銅及酸 銅電鍍製法中可以抵抗化學性侵蝕，因此，可消除因爲化 學性侵蝕造成的 ''粉紅環〃 、楔形空隙〃及不平整的傾 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -8- (請先閱讀背面之注咅？事項再填寫本頁) 裝 · 592011 A7 _ B7 五、發明說明（6 ) 向，並強化鍵結的完整性。將表面上大部份以銅爲基礎的 有機金屬化合物轉化成爲以亞銅爲基礎的有機金屬轉化塗 膜，可以改進其化學性抵抗力，此轉化可藉由還原及/或· 溶解而達成。後處理的OMC C可以很容易地由還原的或 部份溶解的黑色氧化物中分辨出來，後者聲稱主要由金屬 銅所組成。還原的0 M C C成爲一種有機金屬錯合物，其 中大部分的雙價銅皆還原成單價。同理，部份溶解的黑色 氧化物仍然是亞銅與銅氧化物的混合物，而部份溶解的 〇M C C爲主要以單價銅爲基礎的有機金屬錯合物。此組 成視情況可含有一種銅氧化抑制劑或數種抑制劑的組合物 ，以避免〇M C C在後續的處理步驟中再度氧化。所得的 以亞銅爲基礎的OMC C實質上比後處理的黑色氧化物或 未處理的〇M C C更能彈回及抵抗後續的M L Β處理步驟 〇 許多物質皆可用來還原或溶解OMC C，雖然使用其 他的氨基硼烷亦有效（例如二乙基氨基硼烷、嗎啉硼烷等 )，DMAB (二甲基氨基硼烷）爲最有效的還原劑之一 ，其他可應用在這裡的還原劑有：氨、鹼金及/或鹼土金 屬的氫化硼、次磷酸鹽、亞硫酸鹽類、亞硫酸氫鹽類（ bisulfite及hydrosulfite)、偏亞硫酸氫鹽類、二硫磺酸鹽類 、四硫磺酸鹽類、硫代硫酸鹽類、硫脲類、胼類、羥胺類 、醛類（包括甲醛及乙二醛）、乙醛酸類、及還原的糖類 ，電流也可用來還原。 如果使用溶解劑，任何已知的銅離子螯合物（錯合物 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9 - it-----------裝— (請先閱讀背面之注意事項再填寫本頁) · 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 592011 Α7 Β7 五、發明說明（7 ) )、有機或無機酸及/或其鹽類（或爲其組合）皆可應用 在這裡，這些包括 EDTA、HEEDTA、NTA、DTPA、DCTA 、Quadrol、有機膦酸鹽類（Dequests)、有機酸（檸檬酸、 酒石酸、葡萄庚酸、魅胺酸、磺胺酸、經乙酸、甘胺酸、 羥丁二酸、順丁烯二酸、柳酸、抗壞血酸、甲酸等）、無 機酸（氫氯酸、氫氟酸、氫溴酸、硝酸、鉻酸等）及/或 其銨鹽、鹼金、鹼土金屬及/或胺鹽、胺類（MEA、D EA、TEA、TMAH、EDA、DETA、 TETA、TEPA等）、氫氧化銨、焦磷酸鹽類等；最 好是用Qu a d r ο 1 、EDTA及膦酸鹽類。此外，合 倂使用溶解劑及一種或多種還原劑可能會有利。 如上所述，亦可視情況使用銅氧化抑制劑。如此，可 將如下一種或多種銅氧化抑制劑納入組成中，如：未取代 的及/或烷基、芳基、烷基芳基取代的唑衍生物（在此包 括鹵素取代的衍生物），如、苯並三唑（B T A )、甲苯 三唑（TTA) 、5 —甲基苯咪唑、2 —溴苄基苯咪唑、 2 -氯苄基苯咪唑、2 -溴苯基苯咪唑、2 -氯苯基苯咪 唑、2 -溴乙基苯基苯咪唑、2 -氯乙基苯基苯咪唑、及 2 -十一烷基- 4 -甲基咪唑，最好是用苯並三唑及甲苯 三唑。陽離子、兩性離子、陰離子及/或非離子性界面活 性劑皆可用來增強後處理劑的功效。 還原物的組合物（或任何數量的還原物）可與溶解劑 (或任何數量的溶解劑）合倂使用。應該適當調整p Η、 溫度、濃度及處理時間，以確保有效的還原及/或溶解銅 本紙張尺度適用中關家鮮（CNS)A4規格（210 X 297公爱)Π〇Τ " ------------裝--- (請先閱讀背面之注意事項再填寫本頁) . 592011 A7 B7 五、發明說明（8 ) 離子，此溶液視情況可含有一種氧化抑制劑或數種抑制劑 的組合物。 同時，應該被暸解的是，將上述物質作爲有機金屬轉. 化塗膜生成後的後處理，並不須只受限於後處理的應用， 而是，可將這些物質直接納入溶液中，用以形成原來的有 機金屬轉化塗膜，以完成處理。 實施例 例 1 一片 1 盘斯的 DSTFoil(可購自 Polyclad Laminates)及一 個兩側皆以相同的DSTFoil(Polyclad Laminates )護套的環 氧玻璃薄層板以如下順序的步驟處理： 1 .PC 7036微蝕刻（可購自 Alpha PC Fab) 華氏90度，1分鐘 2.淸洗 室溫，1分鐘 3 .PC 7086鹼性淸潔劑（Alpha PC Fab) 華氏130度，1分 鐘 4. 去離子水淸洗 室溫，1分鐘 5. 預浸漬（5% PC 7023) 華氏105度，30秒 6. PC 7023黏著促進劑（Alpha PC Fab) 華氏105度，1分 鐘 7. 去離子水淸洗 室溫，1分鐘 8. 熱空氣乾燥 華氏160度，1分鐘 接著，箔片（指foil)再覆以兩層Polyclad 1080 B-stage 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 · 經濟部智慧財產局員工消費合作社印製 -11 - 592011 A7 ___________ B7 五、發明說明（9 ) pre-preg(可購自Polyclad Laminates)及在一側覆以兩層 Polyclad 7628 pre-preg，處理層則面向 1 080 pre-preg;而以 DSTFoil護套的銅/環氧玻璃薄層則在每一側覆以雙層· Polyclad 2313。然後將此完成上覆的箔片與薄層在溫度華氏 370度、壓力350ps i下，壓60分鐘。 以1 / 8英吋寬的帶子遮住鋪層的箔片板，在華氏 1 3 0度下，以5 0 0公克/公升氯化鐵溶液蝕刻暴露的 銅，板子再經淸洗、乾燥、及去除遮帶。用C E C〇 ΤΑ 6 2 0 - 3 0剝皮測試器由1 / 8英吋寬的銅條背 面剝皮，以測試銅箔與調理過的環氧樹脂的黏合，發現黏 合度達6 . 76磅/英吋。 將此銅鋪層護套板切成2英吋寬的帶狀物浸在P C 7 4 5 7 HASL (可購自Alpha PC Fab )中迴流，然 後在華氏5 0 0度下，置入熔化的焊錫中。每分鐘皆自焊 錫中取出帶狀物，並檢查是否有不平整的跡象，發現出現 不平整的時間爲9分鐘。 例2 重複例1 ，但不同的是，將以P C 7 0 2 3黏著促 進劑處理後的DSTFoil及銅護套薄層在華氏105 度下，以6公克/公升DMAB及7·5公克/公升氫氧 化鉀所組成的溶液浸泡2分鐘。發現黏合度達7 · 3 6磅 /英吋且出現不平整的時間爲9分3 0秒。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -11---------裝--- (請先閱讀背面之注意事項再填寫本頁) 1 . 經濟部智慧財產局員工消費合作社印製 -12- 592011 A7 ------- B7 五、發明說明（10 ) 例3 一片標準的1盎斯的箔片貼在電路板上，在Coates-ASI 水平式輸送的濕式處理噴霧機器中，以相同於例1的步驟· 胃理。除去貼帶，箔片已鋪層，然後如例1測試黏合度。 發現黏合度達4·6磅/英吋。 例4 重複例3，但不同的是，在水平設備的處理後，在室 溫下’再將箔片於5 % (體積）氯化氫溶液中浸泡1分鐘 。發現黏合度達5 . 1磅/英吋。 例5 重複例4，但不同的是，在華氏130度下，以PH 4 . 1、38公克/公升NazEDTA溶液浸泡6分鐘， 作爲後處理。發現黏合度達6 · 2磅/英吋。 例6 重複例4，但不同的是，在華氏130度下，以PH 4 · 1、76公克/公升NasEDTA溶液浸泡1分鐘， 作爲後處理。發現黏合度達6 · 6磅/英吋。 例7 重複例4，但不同的是，在華氏1 3 0度下，以P Η 1 0、1 〇 ％ (體積）Versene 1〇〇 (EDTA 溶液， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--- (請先閱讀背面之注意事項再填寫本頁) 訂·· 線· 經濟部智慧財產局員工消費合作社印製 -13- 592011 A7 -- B7 五、發明說明⑴） 可購自Dqw Chemical)溶液浸泡1分鐘，作爲後處理。發現 黏合度達6·8磅/英吋。 -----------丨· -裝--- (請先閱讀背面之注咅？事項再填寫本頁) 例8 重複例4，但不同的是，在華氏1 3 0度下，以p Η 1 3、1 〇 % (體積）Versene 1 0 0溶液浸泡1分鐘， 作爲後處理。發現黏合度達6 · 9磅/英吋。 例9 重複例4，但不同的是，在華氏1 3 0度下，以p Η 1 〇、1 0 % (體積）Quadrol (乙氧基化/丙氧基化的乙 二胺衍生物，可購自B A S F )溶液浸泡1分鐘，作爲後 處理。發現黏合度達6 · 9磅/英吋。 -1線· 例1〇0 t I n I.-Turn-This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -4-592011 A7 -B7 V. Description of Invention (2) 1 · This process can only be performed in China It is carried out in a caustic strong alkaline solution at a temperature of about 160 to 170. 2 · The processing time is long, so it will cause bottlenecks in the manufacturing process. 3 · The black oxide coating film is easily soluble in acid, which makes it easy to be attacked by acid in the subsequent processing steps, which often leads to a bad phenomenon, often referred to as `` pink ring tincture, and sometimes, The wedge-shaped void 〃 eventually causes unevenness between the copper and the adjacent dielectric layer. 4 · The bonding strength between the black oxide-coated copper and the dielectric material is very strong at first, but it will deteriorate rapidly as M L B passes through the hot production line in the subsequent manufacturing and packaging process. Reliable copper-to-dielectric bonding is particularly important for flexible and S B U boards. Polyamines used to make elastic plates and photo-imageable dielectric materials used to make SBU circuit boards are known to have lower copper-to-dielectric bond strength than conventional epoxy-based materials. Glass-based rigid circuit board. The black oxide coating film is composed of copper and cuprous oxide. This coating film is based on the formation of copper oxide, which makes it exhibit weak chemical resistance. In contrast, cuprous oxide (red to brown) is less chemically active and unlike copper oxide, it is more susceptible to acid attack. In order to eliminate the "pink ring" and avoid the deterioration of bond strength, two types of post-treatment have been developed for the black oxide process. The first type is based on a reduction method and is disclosed in, for example, US Patent 4,642,161; 4,902,551; 5,00,06; 200; 5,076,864; 5,147'492; Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) I ------------- install --- (please read the precautions on the back before filling this page) · -line — Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -5- 592011 A7 _____ B7 V. Description of the invention (3) 5,382,333; 5,492,595; 5,556,532 and 5,721,014. The basis of the first type of post-treatment of black oxide is to partially dissolve the oxide coating film, as described in US Patent 4,7 1 7,4 3 9; 4 '775,444: 5,106,454 5'61,154; 5,289,630 and 5 '5 0 1, 3 5 0 .; Although the chemical mechanisms used by these two technologies are so different, they can achieve similar results. The first mechanism is a reduction method that converts the copper oxide portion to a mixture of cuprous oxide and metallic copper. The second mechanism is a dissolution method that selectively dissolves copper oxide and leaves oxidation on the surface. Asian copper. Both methods convert black oxides (mainly copper oxides) to cuprous oxide-rich surfaces. However, unfortunately, although the reduction and dissolution of the black oxide can eliminate the `` pink ring '' and improve the resistance of the coating to acid to some extent, it still cannot solve the above-mentioned black oxide related All questions. Furthermore, it has been found that the reduced black oxide is rapidly reoxidized on the surface during the drying step used in the ML B manufacturing process in order to remove the moisture absorbed by the dielectric material before the layup step. After the drying step, re-oxidation of the surface will cause obvious dark areas in the coating film, and the darker color of the coating film indicates that copper oxide reappears, making the coating film more susceptible to chemical attack in subsequent processing procedures. . Because of the undercutting action in the dissolved chemical immersion, the partially dissolved black oxide easily forms a powdery, poorly adhered cuprous oxide layer on the surface. The powdery part of the coating film makes the copper dielectric. The material cannot form a strong paper size. Applicable to China National Standard (CNS) A4 (210 X 297 mm) if ----------- install --- (Please read the precautions on the back before filling (This page) · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -1 IIJ—. -6-592011 Α7 _ Β7 i. Description of the invention (4) Bonding. In addition, it is not possible to use this method with a horizontal conveying method because the impression of a cylinder may occur on a powdery surface. 11 --------- Packing --- (Please read the precautions on the back before filling out this page) Recently, a new alternative to the black oxide process has been introduced. The method is to generate on the copper surface Organic metal conversion coating (OMCC) instead of forming copper oxide. In general, the purpose of an organometallic conversion coating is to form a barrier layer on the metal surface underneath it. Therefore, this surface can be protected from oxidation and corrosion, and / or increased bonding to dielectric materials. 0 M C C s is the chemical reaction product between metal ions (monovalent or multivalent state) and organic compounds. In this way, it is easy to distinguish from inorganic black oxides. OMC C consists of a thin film formed by metal ions connected to a complex or bonded to one or more organic materials. This method of forming 0 M C C has been disclosed in U.S. Patent 5,800.859 and 5,8 6 9,1 3 0. The organic metal conversion coating film generated in this method is far more resistant to acids than the black oxide coating film. However, because its composition still contains copper-based organometallic compounds, it is not completely immune to it. Chemical attack. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs > The wedge-shaped void formation mechanism discussed below will illustrate the importance of the post-processing steps of the present invention. The MLB board will be punched after lamination. During the punching operation, the vibration of the edge of the punch will generate micro-cracks at the copper / dielectric material interface, and then the solvent conditioner will be absorbed into the copper and dielectric material. In the small gap between them, the subsequent treatment with the permanganate solution will oxidize, that is, remove the swollen resin, and a `` wedge shape '' will be generated. The micro-etching solution will attack copper. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 592011 Α7 Β7 5. Inventory (5) The gap becomes wider, and the pre-impregnation and activation solution is typically a fairly concentrated, hydrochloric acid-based solution, which will further remove this copper treatment layer. If the non-electric copper cannot completely seal this, wedge-shaped plutonium, the chemical uranium invasion will continue when this material is immersed in acid cleaning solution, micro-etching solution, acid immersion and acid copper. When the wedge is relatively small, the acid copper can completely fill this gap 'to form a typical, pink ring-shaped appearance; if the gap is large enough, it may only partially or at least span, Which leads to the defect of ~ wedge-shaped void 〃. In the worst cases, the result is unevenness. Abstract description: The present invention relates to a method of processing and solving method 'to overcome the problems of the known bonding method between copper and dielectric materials when manufacturing printed circuit boards. More specifically, the method associated with the present invention is to increase the adhesion and improved copper coating by converting a copper-based organometallic compound on a copper surface into a cuprous-based organometal conversion coating film. The chemical resistance of the film improves bond integrity. The way to achieve this is to reduce and / or partially dissolve the organometallic coating film and optionally add copper oxidation inhibitors at the same time. Detailed description = The basis of the present invention is to significantly improve the chemical properties of the organometallic conversion coating film (〇MCC) Resistance makes it resistant to chemical attack in spotting, electroless copper and acid copper electroplating. Therefore, it can eliminate `` pink ring 〃, wedge-shaped 〃 〃 and uneven flat paper sizes caused by chemical attack. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -8- (Please read the note on the back? Matters before filling out this page) Installation · 592011 A7 _ B7 V. Description of the invention (6), and Strengthen the integrity of the bond. The conversion of most of the copper-based organometallic compounds on the surface to cuprous-based organometal conversion coatings can improve their chemical resistance. This conversion can be achieved by reduction and / or dissolution. Post-processed OMC C can be easily distinguished from reduced or partially dissolved black oxide, which claims to consist mainly of metallic copper. The reduced 0 M C C becomes an organometallic complex, and most of the bivalent copper is reduced to the monovalent. In the same way, the partially dissolved black oxide is still a mixture of cuprous and copper oxides, while the partially dissolved OM C C is an organometallic complex mainly based on monovalent copper. This composition may optionally contain a copper oxidation inhibitor or a combination of several inhibitors to prevent OM C C from being oxidized again in subsequent processing steps. The resulting cuprous-based OMC C is substantially more resilient than post-treated black oxide or untreated OMCC and resists subsequent ML Β processing steps. Many substances can be used to reduce or dissolve OMC C, although It is also effective to use other aminoboranes (such as diethylaminoborane, morpholineborane, etc.). DMAB (dimethylaminoborane) is one of the most effective reducing agents. Other reducing agents that can be used here There are: boron hydride of ammonia, alkali gold and / or alkaline earth metal, hypophosphite, sulfite, bisulfite and hydrosulfite, metabisulfite, disulfide, tetrasulfide Acid salts, thiosulfates, thioureas, amidines, hydroxylamines, aldehydes (including formaldehyde and glyoxal), glyoxylic acids, and reduced sugars can also be used for reduction. If a dissolving agent is used, any known copper ion chelate (complex is applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) on this paper scale) -9-it --------- --Install— (Please read the notes on the back before filling this page) · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 592011 Α7 Β7 V. Description of Invention (7)), Organic or inorganic acids and / or their salts (or combinations thereof) can be used here, these include EDTA, HEEDTA, NTA, DTPA, DCTA, Quadrol, organic phosphonates (Dequests), organic acids (citric acid , Tartaric acid, grape heptanoic acid, melamine acid, sulfanilic acid, acetic acid, glycine, hydroxysuccinic acid, maleic acid, salicylic acid, ascorbic acid, formic acid, etc.), inorganic acids (hydrochloric acid, hydrofluoric acid) Acid, hydrobromic acid, nitric acid, chromic acid, etc.) and / or its ammonium salt, alkali gold, alkaline earth metal and / or amine salt, amines (MEA, D EA, TEA, TMAH, EDA, DETA, TETA, TEPA, etc. ), Ammonium hydroxide, pyrophosphates, etc .; preferably use Quadr ο 1, EDTA and phosphonates . In addition, it may be advantageous to combine the use of a dissolving agent and one or more reducing agents. As mentioned above, copper oxidation inhibitors may also be used as appropriate. In this way, one or more of the following copper oxidation inhibitors can be incorporated into the composition, such as: unsubstituted and / or alkyl, aryl, alkylaryl substituted azole derivatives (including halogen substituted derivatives), For example, benzotriazole (BTA), toluene triazole (TTA), 5-methylbenzimidazole, 2-bromobenzylbenzimidazole, 2-chlorobenzylbenzimidazole, 2-bromophenylbenzimidazole, 2- Chlorophenylbenzimidazole, 2-bromoethylphenylbenzimidazole, 2-chloroethylphenylbenzimidazole, and 2-undecyl-4-methylimidazole, preferably benzotriazole and toluene Triazole. Cationic, zwitterionic, anionic, and / or nonionic surfactants can be used to enhance the effectiveness of the post-treatment agent. The composition of the reduced product (or any number of reduced products) can be used in combination with a dissolving agent (or any number of dissolving agents). The pΗ, temperature, concentration, and processing time should be adjusted appropriately to ensure effective reduction and / or dissolution of copper paper. The paper size applies to Zhongguan Jiaxian (CNS) A4 (210 X 297 public love) Π〇Τ "- ---------- Packing --- (Please read the precautions on the back before filling this page). 592011 A7 B7 V. Description of the invention (8) Ion, this solution may contain an oxidation inhibitor as appropriate Or a combination of several inhibitors. At the same time, it should be understood that the above-mentioned substances are used as organometallics. The post-treatment after the formation of the coating film is not limited to the application of the post-treatment. Instead, these substances can be directly incorporated into the solution and used. In order to form the original organic metal conversion coating film, the process is completed. EXAMPLES Example 1 One piece of DSTFoil (commercially available from Polyclad Laminates) and one epoxy glass sheet with the same DSTFoil (Polyclad Laminates) sheath on both sides were processed in the following sequence: 1. PC 7036 Microetching (available from Alpha PC Fab) 90 degrees Fahrenheit, 1 minute 2. Rinse at room temperature, 1 minute 3. PC 7086 alkaline detergent (Alpha PC Fab) 130 degrees Fahrenheit, 1 minute 4. Deionized water Rinse at room temperature, 1 minute 5. Pre-dip (5% PC 7023) 105 ° F, 30 seconds 6. PC 7023 Adhesion Promoter (Alpha PC Fab) 105 ° F, 1 minute 7. Rinse room temperature with deionized water , 1 minute 8. Hot air drying at 160 degrees Fahrenheit for 1 minute. Then, the foil (referring to foil) is covered with two layers of Polyclad 1080 B-stage. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ) (Please read the precautions on the back before filling out this page) Packing · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -11-592011 A7 ___________ B7 V. Invention Description (9) pre-preg (available from Polyclad Laminates) With two layers of Polyclad 7628 pre-preg on one side and the treatment layer facing 1 080 pre-preg; and a thin layer of copper / epoxy glass sheathed with DSTFoil is covered with a double-layer Polyclad 2313 on each side. The finished foil and thin layer were then pressed at a temperature of 370 degrees Fahrenheit and a pressure of 350 ps for 60 minutes. Cover the laminated foil board with a 1/8 inch wide tape, and etch the exposed copper at 500 grams / liter of ferric chloride solution at 130 degrees Fahrenheit. The board is then rinsed, dried, And remove the masking. A CEC〇ΤΑ 6 2 0-30 peeling tester was used to peel the back of a 1/8 inch wide copper strip to test the adhesion of the copper foil to the conditioned epoxy. The adhesion was found to be 6.76 pounds. / Inch. This copper-clad sheathing board was cut into 2 inch wide ribbons and dipped in PC 7 4 5 7 HASL (available from Alpha PC Fab) for reflow, and then placed at 500 degrees Fahrenheit into the molten In solder. Remove the ribbon from the solder every minute and check for signs of unevenness. It was found that the unevenness took 9 minutes. Example 2 Example 1 was repeated, but the difference was that a thin layer of DSTFoil and copper sheath treated with a PC 7 0 2 3 adhesion promoter was treated at 105 degrees Fahrenheit with 6 g / L DMAB and 7.5 g / L DMAB Soak the solution of potassium hydroxide for 2 minutes. It was found that the adhesion reached 7.36 pounds per inch and the unevenness time was 9 minutes and 30 seconds. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -11 --------- install --- (Please read the precautions on the back before filling this page) 1. Economy Printed by the Consumers' Cooperative of the Ministry of Intellectual Property Bureau-12- 592011 A7 ------- B7 V. Description of the invention (10) Example 3 A standard 1 ounce foil is pasted on a circuit board, and the Coates-ASI In the wet-processed spraying machine for horizontal conveyance, the same procedures as in Example 1 were used. Remove the tape, the foil has been laminated, and then test the adhesion as in Example 1. Adhesion was found to be 4.6 pounds per inch. Example 4 Example 3 was repeated, but the difference was that after processing by a horizontal device, the foil was immersed in a 5% (volume) hydrogen chloride solution at room temperature for 1 minute. Adhesion was found to be 5.1 pounds per inch. Example 5 Example 4 was repeated, but the difference was that it was immersed in a NazEDTA solution at pH 4.1, 38 g / L for 6 minutes at 130 degrees Fahrenheit as a post-treatment. Adhesion was found to be 6.2 lbs / inch. Example 6 Example 4 was repeated, but the difference was that it was immersed in a pH 4 · 1, 76 g / L NasEDTA solution for 1 minute at 130 degrees Fahrenheit as a post-treatment. Adhesion was found to be 6.6 pounds per inch. Example 7 Example 4 was repeated, but the difference was that at 130 degrees Fahrenheit, P Η 10, 10% (volume) Versene 100 (EDTA solution, this paper size applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) ----------- install --- (please read the precautions on the back before filling out this page) Preparation -13- 592011 A7-B7 V. Description of the invention ⑴) Can be purchased from Dqw Chemical) soaked for 1 minute as post-treatment. It was found to have a degree of adhesion of 6.8 pounds per inch. ----------- 丨 · -install --- (Please read the note on the back? Matters before filling out this page) Example 8 Repeat Example 4 but the difference is that at 130 degrees Fahrenheit Next, soak with p Η 1 3, 10% (volume) Versene 100 solution for 1 minute, as a post-treatment. Adhesion was found to be 6.9 lbs / inch. Example 9 Example 4 was repeated, but the difference was that at 130 degrees Fahrenheit with p Η 10, 10% (volume) Quadrol (ethoxylated / propoxylated ethylenediamine derivative, but Soaked from BASF) solution for 1 minute as post-treatment. Adhesion was found to be 6.9 lbs / inch. -1 line · Example 1〇
經濟部智慧財產局員工消費合作社印製 _ L 重複例4，但不同的是，在華氏130度下，以pH 1 3、1 0 % (體積）Q u a d r ο 1溶液浸泡1分鐘， 作爲後處理。發現黏合度達6 · 9磅/英吋。Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs_L Repeat Example 4 but the difference is that it is immersed in pH 1 3, 10% (volume) Q uadr ο 1 solution for 1 minute at 130 degrees Fahrenheit for post-processing . Adhesion was found to be 6.9 lbs / inch.
Equivalents 由前述對本發明的特定實施例的詳細說明，一種將以 銅爲基礎的有機金屬轉化塗膜轉化成以亞銅爲基礎的有機 金屬轉化塗膜的獨特方法，應該顯而易見’雖然特殊的實 施例已在其中詳細揭露，但只以示意目的舉例’並無意限 -14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 592011 A7Equivalents From the foregoing detailed description of specific embodiments of the present invention, a unique method of converting a copper-based organometal conversion coating film to a cuprous-based organometal conversion coating film should be apparently 'although a particular embodiment It has been disclosed in detail, but for the purpose of illustration only. It is not intended to be limited. -14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 592011 A7
五、發明說明（12 ) 制後述所附的申請專利範圍所關聯的範疇。特別是本發明 人期望不偏離本發明申請專利範圍所定義的精神與範疇的 各式替代、改變、及修正皆可用在本發明中。 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention (12) The scope related to the scope of the patent application appended later will be made. In particular, the inventor expects that various substitutions, changes, and modifications that do not depart from the spirit and scope defined by the scope of the patent application of the present invention can be used in the present invention. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -15- (Please read the precautions on the back before filling this page)