583339 A7 _____B7 五、發明説明（1 ) 發明範圍 (請先閲讀背面之注意事項再填寫本頁) 本發明係關於一種用於使用包含銅離子及還原劑但不 含甲醛之無電鍍銅溶液之無電鍍銅方法。 本發明也關於一種用於上述方法之無電鍍銅溶液及藉 由此方法製得之銅-樹脂複合材料。 發明背景 製備印刷電路板時，使用一種利用無電鍍銅溶液之無 電鍍銅方法以非導電性塑膠基材之貫穿孔中的導電性銅層 。接著在該貫穿孔之導電性銅層上施行電解銅電鍍。 發明所欲解決的間題 先前技藝之方法中固有的顯著問題係無電鍍銅溶液中 使用的甲醛。甲醛與致畸形性、致突變性及致癌性有關聯 。因此，已有人開發出一些不含甲醛之無電鍍銅溶液。 經濟部智慧財產局員工消費合作社印製 再者，在利用包含甲醛之無電鍍銅溶液之先前技藝無 電鍍銅方法中’會遇到一個問題，除非使用觸媒，否則沈 積銅所需之時間係冗長的。由於其高反應性，大部分習知 不含甲醛之無電鑛銅溶液皆具有不良的安定性，並且使用 時會快速地分解。因此所欲爲硏發爲具有高浴液安定之不 含甲醛之無電鍍銅溶液，並且該無電鍍銅溶液可用以快速 地完成無電鑛銅方法。 本發明之目的在於提供不需使用甲醛之無電鍍銅方法 ，藉由免除與使用該化學藥品有關之環境影響。甲醛與致 023151 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) 77^ ^ 583339 A7 B7 五、發明説明（2 ) 畸形性、致突變性及致癌性有關聯。本發明之另一目的在 於提供不含曱醛之無電鍍銅溶液’該溶液可快速地沈積銅 ;並且，本發明又另一目的在於提供具有高浴液安定性之 不含甲醛、快速反應之無電鍍銅溶液。 解決該等問題之方法 本發明提供一種用於無電鍍銅之方法，其包括以下之 步驟： 使鈀或鈀-錫觸媒沈積在樹脂基材上；以及 利用包含銅離子及還原劑但不含甲醛之無電鍍銅溶液 處理該基材。 本發明同樣也關於用於所請求方法中之不含曱醒之無 電鍍銅溶液，以及根據該方法製備之複合材料。. 本發明另外關於在根據該方法製備之複合材料上電解 銅電鍍之方法，以及根據該方法製備之複合材料。 較佳具體實施例 在本發明中，「無電鍍銅」表示一種化學方法，藉以 在樹脂基材上形成導電性銅層。此沈積係於接下來的電鍍 處理’例如硫酸銅電鍍，之前先進行。在本發明中，高導 電性銅薄層在表面上經施塗鈀或鈀-錫觸媒之樹脂基材上 快速地形成。不含甲醛之無電鍍銅浴液係於本發明中製備 以用於該方法。該浴液包括銅離子及還原劑，並且可利用 鈀或鈀-錫觸媒在樹脂基材表面上形成薄的銅層，其中對 細靖 — _ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） jl· 1——碎裝II (請先閱讀背面之注意事項再填寫本頁) 訂 -豐 經濟部智慧財產局員工消費合作社印製 583339 A7 ____B7_ 五、發明説明（3 ) (請先閲讀背面之注意事項再填寫本頁) 於該觸媒之加速處理已事先進行。在本發明中，「無電鍍 銅溶液」表示可藉由與該基材接觸而在該基材上形成薄銅 層之浴液，其中並未在該基材表面上進行該鈀或鈀-錫觸 媒之加速處理。 在該基材表面上使用此觸媒可排除加速處理之需求。 該溶液中存有之銅離子可由任何適當之來源衍化而成 。例如，溶於該浴液時可產生銅離子之銅化合物皆可使用 。或者，可溶於水中形成含銅離子接著應用於該浴液之化 合物。有用於充當銅來源之銅化合物包含水溶性者；包含 銅離子者；以及習知用於該技藝中者。較佳地，該等化合 物包含：硫酸銅；硝酸銅；氯化銅；氫氧化銅；胺基磺酸 銅；碳酸亞銅；氧化銅等。更佳爲硫酸銅及氯化銅。適當 的銅化合物可單獨使用或合倂使用。該溶液中之銅離子濃 度通常係0.5至5克/升，較佳爲1至2克/升，以銅金屬 爲基準計算。然而，如果本發明之無電鍍銅溶液包含錯合 劑並且該錯合劑之濃度係高的時，銅離子之濃度可爲2克 /升或更高。例如，銅離子之濃度可高達10克/升或更高 〇 經濟部智慧財產局員工消費合作社印製 用於本發明之無電鍍銅溶液之還原劑係水溶性並且可 使銅離子還原俾於樹脂基材上沈積金屬銅。除了甲醛之外 .，任何還原劑皆可使用。較佳還原劑之實施例包含，但不 限於：硼氫化鈉；硼氫化鉀；二甲胺基甲硼烷；三甲胺基 甲硼烷；肼；以及其衍生物。.又更適宜用作還原劑者係硼 氫化鈉及硼氫化鉀；最佳爲硼氫化鈉。上述之還原劑可單 023153 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 7r _ 583339 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（4 ) 獨使用或合倂使用。 本發明之無電鍍銅溶液中還原劑之濃度通常爲〇. 1至 10克/升，較佳爲0.5至2克/升。濃度超過1〇克/升時， 該浴液將變得不安定並且該還原劑傾向被耗盡。 本發明之無電鍍銅溶液可視情況需要包含錯合劑。所 用之錯合劑必須可錯合銅離子。實施例包含，但不限於： 多元胺及其鹽類；胺基羧酸及其鹽類；氧羧酸及其鹽類； 醇胺及其鹽類等等。在本發明中，無論單一錯合劑或複數 種試劑之合倂皆可使用。 多元胺及其鹽類包含，例如，乙二胺、二乙三胺、二 乙四胺、三乙四胺等，以及氫氯化物、硫酸鹽等；但不限 於此。 該無電鍍銅溶液中之多元胺及其鹽類通常係以1至 100克/升之濃度使用，較佳爲5至50克/升。 胺基羧酸及其鹽類包含，但不限於：亞胺基二醋酸及 其鈉鹽；腈基三醋酸及其鈉鹽；以及，羥乙基乙二胺三醋 酸；四羥基乙二胺醋酸；二羥甲基乙二胺二醋酸；乙二胺 四醋酸；環己烷-1,2-二胺四醋酸；乙二醇二乙醚二胺四醋 酸；乙二胺四丙酸；Ν,Ν,Ν’，Ν’-肆（2-羥丙基）乙二胺等， 以及其鈉鹽及鉀鹽。 醇胺化合物較佳爲包含：一、二及三乙醇胺，但不限 於此。醇胺化合物通常係以5至200毫升/升之濃度用於 該無電鍍銅溶液中，較佳爲50至1〇〇克/升。 氧羧酸之實施例包含：酒石酸；檸檬酸；及古洛糖酸 023i54 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I J ""裝 „ 訂 · 線 (請先閱讀背面之注意事項再填寫本頁) 583339 A7 B7 五、發明説明（5 ) (請先閲讀背面之注意事項再填寫本頁) 。氧羧酸鹽類之實施例包含，酒石酸鈉；酒石酸鉀、酒石 酸鈉鉀；檸檬酸鈉；檸檬酸鉀；檸檬酸銨；古洛糖酸鈉； 以及古洛糖酸鉀；但不限於此。上述化合物通常係以丨至 100克/升之濃度用於本發明之無電鍍銅溶液中，較佳爲5 至50克/升。 本發明之無電鍍銅溶液視情況需要可包含：水溶性鉈 化合物；水溶性鈽化合物；及/或水溶性硫化物。藉由將 水溶性鉈化合物、水溶性鈽化合物及/或水溶性硫化物包 含於該無電鍍銅溶液中，可顯著改善該浴液之安定性。最 佳爲水溶性鉈化合物及/或水溶性鈽化合物。 任何水溶性鉈或鈽化合物皆可用於本發明之無電鍍銅 溶液。關於水溶性硫化物，可使用任何可溶於溶液之化合 物，該化合物以硫化物之形式包含硫元素。該水溶性銘化 合物、铈化合物或硫化物可包括含鈽元素、銘元素或硫化 物形式之硫元素其中任一種之化合物；或可包括含鈽、銳 及硫化物形式之硫其中複數種元素之化合物。另外，此等 化合物可單獨使用或合倂使用。 經濟部智慧財產局員工消費合作社印製 該水溶性鉈化合物' 該水溶性鈽化合物及/或該水溶 性硫化物皆可直接溶於該無電鍍銅溶液或可一次全都溶於 水中；接著可添加該最終的溶液至該浴液。 可用於本發明之水溶性鈽化合物包含，例如，醋酸鈽 ，硝酸姉，硫酸鋪，漠化鋪；碳酸鋪；氯化姉；氯化鈽； 草酸鈽等鹽類及其水合物；但不限於此。可用於本發明之 水溶性鉈化合物包含，例如氯化鉈；甲酸鉈；硝酸銳；氧 Q2JL55_ 本紙張尺度適用中國國家標準（CNS ) A4規格(210X297公釐） 一~ -'一~ --- 583339 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（6 ) 化鉈；硫酸鉈；及醋酸鉈等之鹽類，或其水合物，但不限 於此。可用於本發明之硫化物包含鹼金屬或鹼土金屬之硫 化物，但不限於此。水溶性硫化物較佳爲包含硫化鈉；氫 硫化鈉；硫化鉀；氫硫化鉀；硫化鋇；氫硫化鋇；硫化鎂 ;氫硫化鎂等等。水溶性硫化物更佳爲包含硫化鈉；氫硫 化鈉；硫化鉀；及氫硫化鉀。 該無電鍍銅溶液中包含之水溶性鉈化合物、水溶性鈽 化合物及/或水溶性硫化物之用量可爲足以使該無電鍍銅 溶液安定化之用量。該水溶性鈽化合物之用量通常係1毫 克/升至1000毫克/升，較佳爲5毫克/升至30毫克/升， 並且該水溶性硫化物之用量通常係1毫克/升至1 〇〇〇毫克 /升，較佳爲5毫克/升至20毫克/升。 本發明之無電鍍銅溶液視情況需要可包含碘及/或水 溶性碘化合物。本發明之無電鍍銅溶液較佳爲包含碘及/ 或水溶性碘化合物。如果碘或碘化合物係包含於該無電鍍 銅溶液時，將會該無電鍍銅浴之安定性並且會增進銅之沈 積速率。該無電鍍銅溶液中包含碘元素所獲得之優點爲能 夠增進該無電鍍銅浴之安定性及銅之沈積速率。此等功效 可以本發明之方法在常態條件下完成。 如果該無電鍍銅溶液中包含碘或水溶性碘化合物，將 獲得另一優點，藉以使沈積銅變得密質化並且使所獲得之 銅層具有光澤及金屬銅色調。本發明之無電鍍銅方法中， 如果該無電鍍銅溶液不含碘離子，沈積銅層將具有無光澤 之相反金屬外觀。該無電鍍銅領域中，沈積銅層之外觀係 :適用中國國家標準（CNS ) A4規格（210X297公釐） -9- IJ1L---^---裝----^---訂------·線 (請先閲讀背面之注意事項再填寫本頁) 583339 A7 B7 五、發明説明（7 ) 重要的，因此，特別需要有光澤的金屬表觀之銅層。 (請先閱讀背面之注意事項再填寫本頁) 任何分子中包含碘並且可溶於該無電鍍銅溶液之化合 物皆可用作本發明之水溶性碘化合物，但並非特別限定於 此。對於該水溶性碘化合物，碘可以任何形式存在，例如 ’以碘離子鹽的形式，如碘化鉀、碘化銨、碘化鉈；或以 碘與有機化合物之共價鍵的形式，如1，3-二氯-4-碘基苯 、8-羥基-7-碘基-5-喹啉磺酸及苯甲酸碘。本發明所包含 之水溶性碘化合物可單獨使用或合倂使用。 該水溶性碘化合物可同時包含另一有用於本發明之組 成部分，例如碘化鉈。 碘及/或該水溶性碘化合物可直接溶在該無電鍍銅溶 液或可一次全都溶在水中，接著將結果的溶液添加至該浴 液。 在本發明之無電鍍銅溶液中，碘元素可以碘離子的形 式或構成分子之一部分而存在，例如碘係共價鍵結至上述 有機化合物所構成之化合物。本發明之無電鍍銅溶液較佳 包含碘化合物。 經濟部智慧財產局員工消費合作社印製 據推測碘會加速該無電鍍銅處理期間之銅沈積反應， 藉由將碘吸附在鈀觸媒或鈀-錫觸媒之機構，該等觸媒並 未用於加速處理。因爲碘無論在離子態或共價鍵結至該化 合物之狀態皆具有上述功效，所以據推測碘元素本身也會 對該鈀觸媒或該鈀-錫觸媒起作用。 使用量太小時，本發明之無電鍍銅溶液中所含之碘及 /或水溶性碘化合物不具有有加速銅沈積之功效，然而使 〇 C本，適用中國國家標準（CNS ) A4規格（210X 297公釐） _ ’ 〇 583339 A7 B7 五、發明説明（8 ) 用過量時，該等化合物會造成該鈀觸媒或該鈀-錫觸媒不 具活性。因此，碘及/或水溶性化合物之用量以碘之重量 爲基準，通常係1毫克/升至1000毫克/升，較佳爲5毫 克/升至30毫克/升並且更佳爲1〇毫克/升至20毫克/升。 本發明之無電鍍銅溶液可視情況需要包含乙內醯脲及 /或乙內醯脲衍生物。如果該無電鑛銅溶液中包含乙內醯 脲及/或乙內醯脲衍生物，將會加速銅之沈積速率。本發 明之無電鍍銅溶液較佳包含乙內醯脲之衍生物。 至於本發明之無電鍍銅溶液中所含之乙內醯脲衍生物 之具體實施例，任可具有乙內醯脲結構之化合物皆可使用 。本發明另一具體實施例包含由脲基醋酸等具有乙內醯脲 結構之化合物的乙內醯脲環斷裂所獲得之化合物。此等乙 內醯脲衍生物可包含任何適用於該無電鍍銅溶液之化合物 。此等乙內醯脲及/或乙內醯脲衍生物可單獨使用或合倂 使用。 有用於本發明之乙內醯脲及/或乙內醯脲衍生物包含 乙內醯脲、脲基醋酸、1-甲基-乙內醯脲、5,5’-二苯基乙 內醯脲、5,5’ -二甲基乙內醯脲、ι，5,5 -三甲基乙內醯脲及 其衍生物，但不限於此。較佳爲5，5 ’ -二甲基乙內醯脲及 5,5’-二苯基乙內醯脲。本發明之無電鍍銅溶液中之乙內醯 脲及/或乙內醯脲衍生物通常可以1至1〇〇克/升之濃度使 用，較佳爲5至50克/升。 各種添加物皆可摻入本發明之無電鍍銅溶液中。此等 添加物包含，例如，pH調整劑、層改質劑，但不限於此 IJ.L---r ——，0_裝—丨 (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 Π 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 583339 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（9 ) 〇 pH調整劑使本發明之無電鍍銅溶液保持在較佳値並 且加速銅離子沈積成銅之還原反應。此等pH調整劑包含 如硫酸、氫氯酸、磷酸等之無機酸類，以及如氫氧化鈉、 氫氧化鉀等氫氧化物，但不限於此。該pH調整劑可以足 於調整該無電鍍銅溶液之用量添加。用於本發明之無電鍍 銅方法之無電鍍銅溶液的pH較佳爲10或更高，更佳爲 13或更高。 添加該層改質劑以達到改質藉由本發明之方法製造之 銅薄層性質的目的，例如脆性、抗張強度、硬度、內應力 等；或用以達到沈積精製銅顆粒的目的。此等層改質劑包 含，例如，硫代化合物、2,2乂聯吡啶、1，1-啡啉、鐵氰化 鉀、環氧乙烷型界面活性劑、聚乙二醇等之含硫化合物， 但不限於此。此等添加物可單獨使用或合倂使用。 此等添加物添加至本發明之無電鍍銅溶液之用量係依 習知設定使各添加物具有所欲之功效。例如該硫代化合物 之濃度通常爲1至100毫克/升，較佳爲5至10毫克/升； 該聯吡啶化合物之濃度通常爲1至5 0毫克/升，較佳爲5 至15毫克/升；而該界面活性劑之濃度通常爲1至500毫 克/升，較佳爲10至20毫克/升。 關於本發明之樹脂基材，任何具有適用於該應用目的 之性質，例如，強度及抗腐蝕性的基材皆可使用；該樹脂 基材可爲任何形式而無特別限制。可用於本發明之樹脂基 材並未特別限制於樹脂成型物但可爲包含補強材料，例如 (請先閱讀背面之注意事 蚌 ，項再填· 裝—— :寫本頁) 用中國國家標準（CNS ) A4規格（210X297公釐） -12- 583339 A7 B7 五、發明説明（1Q) 摻入該樹脂之玻璃纖維，之複合材料；或各種材料，例如 陶瓷、玻璃、金屬等，上具有樹脂層之複合材料。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 任何樹脂f旨可用作樹脂基材，例如聚烯烴樹脂，舉例 來說，聚乙烯樹脂’例如局密度聚乙烯；中密度聚乙丨希； 分支的低密度聚乙烯；線性低密度聚乙烯；超高分子量聚 乙烯等；聚丙烯樹脂；聚丁二烯樹脂；聚丁烯樹脂；聚苯 乙烯樹脂等。也可使用含鹵素樹脂，例如聚氯乙烯；聚偏 二氯乙烯；聚偏二氯乙烯-氯乙烯共聚物樹脂；氯化聚乙 烯；氯化聚丙烯；四氟乙烯等。另外，可使用AS樹脂； A B S樹脂；Μ B S樹脂；聚乙烯醇樹脂；聚丙烯酸酯樹脂 ，例如聚丙烯酸甲酯；聚甲基丙烯酸酯樹脂，例如聚甲基 丙烯酸甲酯；甲基丙烯酸甲酯-苯乙烯共聚物樹脂；馬來 酸酐-苯乙烯共聚物樹脂；聚醋酸乙烯酯樹脂；纖維素樹 脂’例如丙丙炔酸纖維素樹脂、醋酸纖維素樹脂；環氧樹 脂；聚醯亞胺樹脂；聚醯胺樹脂，例如耐龍；聚醯胺亞胺 樹脂；聚丙烯酸樹脂；聚醚亞胺樹脂；聚醚-醚酮樹脂； 聚環氧乙烷樹脂；各種聚酯樹脂，例如ΡΕΤ樹脂；聚碳 酸酯樹脂；聚阐樹脂；聚乙烯醚樹脂；聚乙烯丁醛；聚乙 烯醚樹脂，例如聚苯醚；聚苯硫醚樹脂；聚對苯二甲酸丁 二酯樹脂；聚甲基戊烯樹脂；聚縮醛樹脂；氯乙烯-醋酸 乙烯酯共聚物樹脂；乙烯-醋酸乙烯酯共聚物；乙烯-氯乙 烯共聚物；以及熱塑性樹脂，例如其共聚物以及其摻混物 ;熱固性樹脂，例如環氧樹脂；二甲苯樹脂；鳥糞胺樹脂 ;苯二甲酸二丙烯酯樹脂；乙烯酯樹脂；酚樹脂；不飽和 f中國國家標準（CNS)A4規格（210x297公釐) 583339 經濟部智慧財產局員工消費合作社印製 A7 ____B7五、發明説明（11 ) 聚酯樹脂；呋喃樹脂；聚醯亞胺樹脂；聚胺基甲酸酯樹脂 ;馬來酸樹脂；三聚氰胺樹脂；尿素樹脂等，以及其摻混 物，但不限於此。較佳的樹脂包含環氧樹脂、聚醯亞胺樹 月旨、乙烯基樹脂、酚樹脂、耐龍樹脂、聚苯醚樹脂、聚丙 烯樹脂、氟型樹脂及A B S樹脂，更佳之樹脂包含環氧樹 脂、聚醯亞胺樹脂、聚苯醚樹脂、氟型樹脂及A B S樹脂 ，又更佳爲環氧樹脂及聚醯亞胺樹脂。樹脂基材可由單一 樹脂或複數種樹脂構成。其它基材上含被覆樹脂或積層樹 脂之複合材料皆可使用。 至於本發明所用之鈀或-錫觸媒，市面上可購得之習 知鈀或-錫觸媒皆可使用。所用之觸媒係液態觸媒形成者 ，其中該介質中包含之鈀或-錫觸媒呈膠體狀。例如， Crimson Activat〇r-5300型水稀釋溶液，鈀-錫觸媒，可自 Shipley公司購得，ConductronDP-H濃縮活化劑，鈀-錫觸 媒，可自LeaRonal Japan公司購得，皆可使用，但不限於 此。如果使用該鈀-錫觸媒，鈀對錫之比率爲，鈀：錫 = 1 : 1 至 1 : 100，更佳爲 1 : 1 至 1 : 10。 本發明之無電鍍銅方法中，首先該祀或-錫觸媒係沈 積於樹脂基材上。至於沈積觸媒之方法，任何可將觸媒沈 積於樹脂基材上之方法皆可使用，例如，將該樹脂基材浸 沒於該觸媒溶液中，或將該觸媒溶液噴灑在該樹脂基材上 ，但不限於此。另外，如果有需要的話，在觸媒與樹脂基 材接觸之前，可對該樹脂基材施以調節處理及蝕刻處理， 例如，藉由將該樹脂基材浸沒於該觸媒溶液中；或藉由將 (請先閲讀背面之注意事 蜱 項再填· 裝-- :寫本頁) 、11 % :中國國家標準（CNS ) A4規格（210X297公釐） -14- 經濟部智慧財產局員工消費合作社印製 583339 A7 B7 五、發明説明（12 ) 該觸媒溶液噴灑至該樹脂基材，使鈀或-錫觸媒易沈積於 該樹脂基材上。 用於本發明之觸媒溶液之觸媒濃度以鈀濃度而言爲 30毫克/升至5 00毫克/升，較佳爲70毫克/升至2 00毫克/ 升。該鈀之濃度太低時，將無法自含還原劑之銅溶液獲得 充分的銅沈積。該鈀之濃度太高時，鈀觸媒之吸附變得過 量，因此，會降低該觸媒之黏著性並且提高成本。 如上述，該樹脂基材上之沈積處理藉由該該樹脂基材 浸沒於該觸媒溶液或藉由將該觸媒溶液噴灑在該樹脂基材 上而進行。在垂直處理的情況中，沈積所需之時間普通爲 3至10分鐘，較佳爲5至8分鐘；沈積所需之處理溫度 通常爲25至50°C，較佳爲35至45°C。在水平處理的情 況中，沈積所需之時間普通爲15秒至3分鐘，較佳爲30 秒至2分鐘；沈積所需之處理溫度通常爲25至5 (TC，較 佳爲35至45t：。 接著，在本發明之無電鍍銅方法中，利用本發明之無 電鍍銅溶液處理由上述處理所獲得表面上含觸媒之樹脂基 材而不需進行任何習知技藝中進行之加速處理。在使用甲 醛之習知無電鍍銅方法中，錫係於授與該觸媒之後的加速 步驟期間自鈀-錫觸媒移除。事實上係由於對甲醛具有高 觸媒活性之鈀在該觸媒進行加速處理之前並未暴露出來。 因此，比起觸媒已經經過加速處理之情況，引發該無電鍍 銅反應要耗費極長的時間。如果所使用爲未經加速處理之 觸媒，自觸媒所分解之材料衍生之不純物將會摻入該液體 0231S2_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ ------r--1^"-裝----：---訂-----•線 (請先閱讀背面之注意事項再填寫本頁) 583339 A7 _ B7 五、發明説明（13 ) 溶液，使該無電鍍銅溶液變得不安定，並且提高分解的風 險。 (請先閲讀背面之注意事項再填寫本頁) 本發明中「未進行觸媒之加速處理」該段表示並未進 行增強觸媒活性之處理；要不然就是在該未活化觸媒沈積 在該樹脂上之步驟及隨後以該無電鍍銅溶液處理之步驟之 間的獨立步驟。如果以本發明之無電鍍銅溶液處理的時該 無電鍍銅溶液包含具有高反應性之還原劑，該觸媒將會在 該無電鍍銅溶液中活化，同時，該無電鍍銅反應將會進行 。在此例子中，該觸媒的活性係增強了。然而，此活化不 會在單一獨立步驟中進行。因此，即使該觸媒之活性以無 電鍍銅溶液處理而達到，此等增強作用仍就包含於本說明 書之「未進行觸媒之加速處理」所述之範圍內。 因爲本發明之無電鍍銅溶液包含銅離子及還原劑，所 以該無電鍍銅溶液會在該樹脂基材上形成銅薄膜並且產生 該銅-樹脂複合材料。本發明之無電鍍銅方法中，因爲該 樹脂基材係於該觸媒沈積在該樹脂基材上之後才以該無電 鍍銅溶液處理，所以鈀或-錫觸媒將以金屬形式存在於該 銅-樹脂複合材料之銅薄層中。 經濟部智慧財產局員工消費合作社印製 本發明中，如果使經沈積觸媒於其上之基材與本發明 之無電鍍銅溶液接觸，銅將會迅速地沈積，直到該觸媒的 整個表面都被覆著銅時反應就會結束。儘管該沈積反應完 成時該銅薄層之厚度可藉由轉變成不同的條件而調整，該 厚度通常爲0.01至0.2微米，較佳爲0.03至0.1微米。 但無論如何，尙比0.2至0.5微米更薄，該厚度係包括以 583339 A7 B7 五、發明説明（14 ) 無電鍍銅步驟進行加速處理步驟，該無電鍍銅溶液包含甲 醛並且使用相同觸媒及樹脂基材之方法所獲得之銅薄層的 一般厚度。 本發明之銅層的沈積速率係定義爲本發明之無電鍍銅 溶液與該基材接觸1分鐘之後之銅層厚度。惟該銅層之沈 積在1分鐘內結束時，適當地將測量之時間設定爲完成該 銅層沈積所耗費的時間。 如果所用爲含甲醛之無電鍍銅溶液時，因爲所沈積之 銅具有自身催化的作用，所以不會發生如本發明之銅層沈 積結束。即使在此情況下，該銅之沈積速率係定義爲該無 電鑛銅溶液與該樹脂接觸1分鐘之後的銅層厚度。如果該 無電鍍銅溶液與該基材接觸1分鐘之後仍未觀察到銅之沈 積時，沈積速率將表示爲0微米/分鐘。在本發明之無電 鍍銅方法中，該沈積速率較佳爲0.02微米/分或更高，更 佳爲0.05微米/分或更尚。 經 濟 部 智 慧 財 產 局 消 費 合 社 印 製 以本發明之無電鍍銅溶液處理係藉由將該樹脂基材浸 沒於該無電鍍銅溶液中，或藉由將該無電鍍銅溶液噴灑在 該樹脂基材上。在垂直處理中，浴液處理時間通常爲1至 5分鐘，較佳爲1至2分鐘；該浴液處理期間之溫度通常 爲30至70°C，較佳爲50至60t。在水平處理中，浴液 處理時間通常爲15秒至2分鐘，較佳爲30秒至1分鐘； 該浴液處理期間之溫度通常爲3 0至7 0 °C，較佳爲5 0至 6〇°C。本發明之較佳具體實施例中，比起習知技藝中使用 含甲醛之無電鍍銅溶液並且使用相同觸媒及樹脂基材進行 17- (請先閱讀背面之注意事項再填寫本頁) 用中國國家標準（CNS ) A4規格（210X297公釐） 583339 A7 B7 五、發明説明（15 ) 無電鍍銅方法’沈積時間係縮短並且整個系統所需之處理 時間也會縮短。 藉由本發明之無電鍍銅方法所獲得之銅-樹脂複合材 料可用於該無電鍍銅處理俾於該複合材料之銅薄層上形成 另外的銅層。至於上述之無電鍍銅方法，本技藝中習知之 任何無電鍍銅方法，例如硫酸銅鍍覆、氰化銅鍍覆及焦磷 酸銅鍍覆，皆可使用。 實施例 以下之實施例中，除非另加指定，各實施例及比較實 施例之各種方法係於使用市面上可購得並且通常用於此方 法之化學藥劑實現。 使用以下方法之無電鎪銅溶液的處理時間係直到銅之 沈積幾乎完成時的時間。該銅層之沈積速率係藉由測量沈 積期間所沈積之鍍銅層之厚度計算，直到本發明之無電鍍 銅溶液與該基材接觸1分鐘之後爲止。在該情況中，如果 該沈積在1分鐘內完成，測量該沈積幾乎完成之前的適當 點處的沈積速率。 用於測量該銅層之沈積速率的方法如下：1)以精準的 天平測量經充分地乾燥之玻璃-環氧基材；2)在該基材上 進行無電鍍銅；3)藉由測量乾燥處理之後的重量以測定重 量平衡時的增量；4)由該重量增量及該基材之表面積計算 該沈積厚度。 (請先閲讀背面之注意事項再填寫本頁) •裝· 、11 經濟部智慧財產局員工消費合作社印製 本紙國家標準（CNS ) A4規格（210X297公釐） -18- 583339 經濟部智慧財產局員X消費合作社印製 五、發明説明（16 ) 實施例1至8及比較實施例1 比較藉由本發明之無電鍍銅方法及電解銅電鍍方法製 得的銅-樹脂複合材料與藉由習知無電鍍銅方法製得的銅_ 樹脂複合材料。 薄片厚度爲1.6毫米並且包括玻璃纖維及雙酚a型環 氧樹脂（FR-4)之銅包四層積板（由Hitachi有限公司製造）係 用作樹脂基材。垂直處理係運用於實施例1至6、10及 1 1，以及比較實施例1。水平處理係運用於實施例7、8 及實施例9。對於實施例8，測量該沈積銅層厚度隨時間 之變化。 實施例1 [表1] 步驟 處理溫度 處理時間 調節 60°C 5分鐘 鈾刻 25〇C 1分鐘 鈀-錫觸媒授與 43〇C 5分鐘 不含甲醛之無電鍍銅溶液* 60°C 5分鐘 電解銅電鍍 25〇C 40分鐘 :不含甲醛之無電鍍銅溶液 023166 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -19- — J-L---1---裝-- (請先閲讀背面之注意事項再填寫本頁) 、11 .•線 583339 A7 B7 五、發明説明 17 五水合硫酸銅 15克/升 EDTA 45克/升 硼氫化鈉 1克/升 2,2’-聯吡啶 10毫克/升 pH 12.5 如果以上述之方法處理時，由開始處理至完成無電鍍 銅處理所需之時間爲1 6分鐘；並且無電鍍銅處理所需之 處理爲5分鐘。獲得厚度爲〇· 〇5微米之銅層。該銅層之 沈積速率爲0.01微米/分。觀察100個直徑爲〇·3毫米的 洞孔發現未形成銅層處之電解銅電鍍層具有26%孔隙發生 率。所製備之無電鍍銅溶液在試驗之後立即分解。 實施例2 (請先閱讀背面之注意事 #1 .項再填· 裝-- :寫本頁) 訂 經濟部智慧財產局員工消費合作社印製583339 A7 _____B7 V. Description of the invention (1) Scope of the invention (please read the precautions on the back before filling out this page) The present invention relates to the use of an electroless copper solution containing copper ions and reducing agents but no formaldehyde. Copper plating method. The present invention also relates to an electroless copper plating solution used in the above method and a copper-resin composite material prepared by the method. BACKGROUND OF THE INVENTION When preparing a printed circuit board, a conductive copper layer in a through hole of a non-conductive plastic substrate is used by an electroless copper plating method using an electroless copper plating solution. Then, electrolytic copper plating is performed on the conductive copper layer of the through hole. The problem to be solved by the invention A significant problem inherent in the prior art method is formaldehyde used in electroless copper solution. Formaldehyde is associated with teratogenicity, mutagenicity and carcinogenicity. Therefore, some formaldehyde-free electroless copper solutions have been developed. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Furthermore, in the prior art electroless copper method using an electroless copper solution containing formaldehyde, a problem will be encountered. Unless a catalyst is used, the time required to deposit copper is Lengthy. Due to its high reactivity, most conventional electroless copper solutions without formaldehyde have poor stability and will decompose quickly when used. Therefore, what is desired is a non-formaldehyde-free electroless copper solution with high bath stability, and the electroless copper solution can be used to quickly complete the electroless copper process. The object of the present invention is to provide an electroless copper plating method that does not require the use of formaldehyde, by eliminating the environmental impact associated with the use of the chemical. Formaldehyde and carcinogenicity 023151 This paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) 77 ^ ^ 583339 A7 B7 5. Description of the invention (2) Malformation, mutagenicity and carcinogenicity are related. Another object of the present invention is to provide an electroless copper plating solution that does not contain formaldehyde. The solution can quickly deposit copper; and another object of the present invention is to provide a formaldehyde-free, fast-reacting solution with high bath stability. Electroless copper solution. A method for solving these problems The present invention provides a method for electroless copper plating, comprising the steps of: depositing a palladium or palladium-tin catalyst on a resin substrate; and using a method that includes copper ions and a reducing agent but does not contain The substrate is treated with an electroless copper plating solution of formaldehyde. The invention also relates to a wake-free electroless copper plating solution for use in the claimed method, as well as composite materials prepared according to the method. The present invention further relates to a method for electrolytic copper plating on a composite material prepared according to the method, and a composite material prepared according to the method. Preferred embodiments In the present invention, "electroless copper plating" means a chemical method whereby a conductive copper layer is formed on a resin substrate. This deposition is carried out before the subsequent plating treatment 'such as copper sulfate plating. In the present invention, a thin layer of highly conductive copper is rapidly formed on the surface of a resin substrate to which a palladium or palladium-tin catalyst is applied. A formaldehyde-free electroless copper bath is prepared in the present invention for use in the method. The bath contains copper ions and reducing agents, and can use palladium or palladium-tin catalysts to form a thin copper layer on the surface of the resin substrate. Among them, for the fine Jing — _ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) jl · 1——Bulled II (Please read the precautions on the back before filling this page) Order-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of Fengfeng Ministry of Economy 583339 A7 ____B7_ V. Description of Invention (3) ( Please read the notes on the back before filling this page.) The accelerated processing of this catalyst has been performed in advance. In the present invention, the "electroless copper plating solution" means a bath solution capable of forming a thin copper layer on the substrate by contacting the substrate, wherein the palladium or palladium-tin is not performed on the surface of the substrate Accelerated processing of catalysts. The use of the catalyst on the surface of the substrate can eliminate the need for accelerated processing. The copper ions present in the solution can be derived from any suitable source. For example, copper compounds that can generate copper ions when dissolved in the bath can be used. Alternatively, it is soluble in water to form a compound containing copper ions which is then applied to the bath. Copper compounds useful as sources of copper include those that are water soluble; those that contain copper ions; and those that are conventionally used in the art. Preferably, the compounds include: copper sulfate; copper nitrate; copper chloride; copper hydroxide; copper sulfamate; cuprous carbonate; copper oxide and the like. More preferred are copper sulfate and copper chloride. Suitable copper compounds can be used alone or in combination. The copper ion concentration in the solution is usually 0.5 to 5 g / l, preferably 1 to 2 g / l, calculated on the basis of copper metal. However, if the electroless copper plating solution of the present invention contains a complexing agent and the concentration of the complexing agent is high, the concentration of copper ions may be 2 g / liter or more. For example, the concentration of copper ions can be as high as 10 g / l or more. The reducing agent printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for use in the electroless copper plating solution of the present invention is water-soluble and can reduce copper ions to the resin. Copper metal is deposited on the substrate. In addition to formaldehyde, any reducing agent can be used. Examples of preferred reducing agents include, but are not limited to: sodium borohydride; potassium borohydride; dimethylaminoborane; trimethylaminoborane; hydrazine; and derivatives thereof. Also more suitable as reducing agents are sodium borohydride and potassium borohydride; the most preferred is sodium borohydride. The above reducing agent can be 023153. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 7r _ 583339 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4) Exclusive use or combination倂 Use. The concentration of the reducing agent in the electroless copper plating solution of the present invention is usually 0.1 to 10 g / L, preferably 0.5 to 2 g / L. When the concentration exceeds 10 g / L, the bath liquid becomes unstable and the reducing agent tends to be exhausted. The electroless copper plating solution of the present invention may optionally include a complexing agent. The complexing agent used must be compatible with copper ions. Examples include, but are not limited to: polyamines and their salts; aminocarboxylic acids and their salts; oxycarboxylic acids and their salts; alcohol amines and their salts, and the like. In the present invention, a single complex agent or a combination of a plurality of agents can be used. Polyamines and their salts include, for example, ethylenediamine, diethylenetriamine, diethylenetetramine, triethylenetetramine, and the like, as well as hydrochlorides, sulfates, and the like, but are not limited thereto. The polyamine and its salts in the electroless copper plating solution are usually used at a concentration of 1 to 100 g / l, preferably 5 to 50 g / l. Aminocarboxylic acids and their salts include, but are not limited to: iminodiacetic acid and its sodium salts; nitriletriacetic acid and its sodium salts; and, hydroxyethylethylenediaminetriacetic acid; tetrahydroxyethylenediamineacetic acid ; Dimethylol ethylenediamine diacetic acid; Ethylenediamine tetraacetic acid; Cyclohexane-1,2-diaminetetraacetic acid; Ethylene glycol diethyl ether diamine tetraacetic acid; Ethylenediamine tetrapropionic acid; Ν, Ν , N ', N'-(2-hydroxypropyl) ethylenediamine, etc., and its sodium and potassium salts. The alcohol amine compound preferably includes, but is not limited to, mono-, di-, and triethanolamine. The alcohol amine compound is usually used in the electroless copper plating solution at a concentration of 5 to 200 ml / liter, preferably 50 to 100 g / liter. Examples of oxycarboxylic acids include: tartaric acid; citric acid; and gulonic acid 023i54 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) IJ " " Packing and ordering (please read first Note on the back page, please fill out this page) 583339 A7 B7 V. Description of the invention (5) (Please read the note on the back page, and then fill out this page). Examples of oxycarboxylates include sodium tartrate; potassium tartrate, tartrate Sodium potassium; sodium citrate; potassium citrate; ammonium citrate; sodium gulose; and potassium gulose; but is not limited thereto. The above compounds are usually used in the present invention at a concentration of 100 to 100 g / liter In the electroless copper plating solution, it is preferably 5 to 50 g / liter. The electroless copper electroplating solution of the present invention may optionally include: a water-soluble europium compound; a water-soluble europium compound; and / or a water-soluble sulfide. The inclusion of a water-soluble rhenium compound, a water-soluble rhenium compound, and / or a water-soluble sulfide in the electroless copper plating solution can significantly improve the stability of the bath. The water-soluble rhenium compound and / or the water-soluble rhenium compound are most preferred. Ren Any water-soluble rhenium or rhenium compound can be used in the electroless copper plating solution of the present invention. As for the water-soluble sulfide, any solution-soluble compound can be used, and the compound contains sulfur as a sulfide. The water-soluble compound The cerium compound or sulfide may include a compound containing any one of sulphur element in the form of thorium element, element or sulfide; or may include a compound containing a plurality of elements in sulfur in the form of thorium, sharp and sulfide. In addition, this The compounds can be used alone or in combination. The water-soluble hydrazone compound printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs' The water-soluble hydrazone compound and / or the water-soluble sulfide can be directly dissolved in the electroless copper solution It can be all dissolved in water at one time; the final solution can then be added to the bath. Water-soluble hydrazone compounds useful in the present invention include, for example, hydrazone acetate, nitric acid, sulfuric acid, desertification; carbonic acid; chlorination Sisters; osmium chloride; salts such as osmium oxalate and their hydrates; but is not limited thereto. Water-soluble osmium compounds that can be used in the present invention include, for example, Rhenium chloride; Rhenium formate; Nitric acid; Oxygen Q2JL55_ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) One ~ -'One ~ --- 583339 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (6) Samarium; Samarium sulfate; Samarium acetate and the like, or hydrates thereof, but are not limited thereto. The sulfides useful in the present invention include sulfides of alkali metals or alkaline earth metals, but It is not limited to this. The water-soluble sulfide preferably contains sodium sulfide; sodium hydrogen sulfide; potassium sulfide; potassium hydrogen sulfide; barium sulfide; barium hydrogen sulfide; magnesium sulfide; The amount of the water-soluble rhenium compound, water-soluble rhenium compound, and / or water-soluble sulfide contained in the electroless copper plating solution may be sufficient to make the electroless copper plating solution Stabilizing dosage. The amount of the water-soluble hydrazone compound is usually 1 mg / L to 1000 mg / L, preferably 5 mg / L to 30 mg / L, and the amount of the water-soluble sulfide is usually 1 mg / L to 100. 0 mg / liter, preferably 5 mg / liter to 20 mg / liter. The electroless copper plating solution of the present invention may optionally contain iodine and / or a water-soluble iodine compound. The electroless copper plating solution of the present invention preferably contains iodine and / or a water-soluble iodine compound. If iodine or an iodine compound is contained in the electroless copper plating solution, the stability of the electroless copper bath will be increased and the copper deposition rate will be enhanced. The advantage obtained by including iodine in the electroless copper plating solution is that it can improve the stability of the electroless copper plating bath and the deposition rate of copper. These effects can be achieved in the method of the present invention under normal conditions. If the electroless copper plating solution contains iodine or a water-soluble iodine compound, another advantage is obtained by which the deposited copper is densified and the obtained copper layer has gloss and metallic copper hue. In the electroless copper plating method of the present invention, if the electroless copper plating solution does not contain iodine ions, the deposited copper layer will have a matte opposite metal appearance. In the field of electroless copper plating, the appearance of the deposited copper layer is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -9- IJ1L --- ^ --- installation ---- ^ --- order- ----- · Wire (please read the precautions on the back before filling this page) 583339 A7 B7 V. Description of the invention (7) Important, therefore, a shiny metallic surface copper layer is particularly required. (Please read the precautions on the back before filling this page) Any compound containing iodine in its molecule and soluble in the electroless copper plating solution can be used as the water-soluble iodine compound of the present invention, but it is not particularly limited thereto. For the water-soluble iodine compound, iodine may be present in any form, for example, 'in the form of an iodide ion salt, such as potassium iodide, ammonium iodide, thallium iodide; -Dichloro-4-iodobenzene, 8-hydroxy-7-iodo-5-quinolinesulfonic acid and iodine benzoate. The water-soluble iodine compounds contained in the present invention can be used alone or in combination. The water-soluble iodine compound may simultaneously contain another component useful in the present invention, such as europium iodide. Iodine and / or the water-soluble iodine compound may be directly dissolved in the electroless copper solution or may be dissolved in water all at once, and then the resulting solution is added to the bath. In the electroless copper plating solution of the present invention, the iodine element may exist in the form of iodine ions or constitute a part of a molecule, for example, a compound composed of an iodine-based covalent bond to the above-mentioned organic compound. The electroless copper plating solution of the present invention preferably contains an iodine compound. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, it is speculated that iodine will accelerate the copper deposition reaction during the electroless copper treatment. With the mechanism of adsorbing iodine on palladium catalyst or palladium-tin catalyst, these catalysts Used to speed up processing. Since iodine has the above-mentioned effects both in the ionic state and in the state of being covalently bonded to the compound, it is speculated that the iodine element itself will also act on the palladium catalyst or the palladium-tin catalyst. If the amount used is too small, the iodine and / or water-soluble iodine compound contained in the electroless copper plating solution of the present invention does not have the effect of accelerating the copper deposition. 297 mm) _ '〇583339 A7 B7 V. Description of the invention (8) When used in excess, these compounds will cause the palladium catalyst or the palladium-tin catalyst to be inactive. Therefore, the amount of iodine and / or water-soluble compound is based on the weight of iodine, usually 1 mg / L to 1000 mg / L, preferably 5 mg / L to 30 mg / L and more preferably 10 mg / L To 20 mg / L. The electroless copper plating solution of the present invention may optionally include hydantoin and / or a hydantoin derivative. If the electroless copper solution contains hydantoin and / or hydantoin derivatives, the copper deposition rate will be accelerated. The electroless copper plating solution of the present invention preferably contains a derivative of hydantoin. As a specific example of the hydantoin derivative contained in the electroless copper plating solution of the present invention, any compound having a hydantoin structure can be used. Another embodiment of the present invention includes a compound obtained by cleavage of a hydantoin ring of a compound having a hydantoin structure such as ureidoacetic acid. These hydantoin derivatives may contain any compound suitable for use in the electroless copper solution. These hydantoin and / or hydantoin derivatives can be used alone or in combination. Hydantoin and / or hydantoin derivatives useful in the present invention include hydantoin, ureidoacetic acid, 1-methyl-hydantoin, 5,5'-diphenylhydantoin , 5,5'-dimethylhydantoin, ι, 5,5-trimethylhydantoin and its derivatives, but not limited thereto. Preferred are 5,5'-dimethylhydantoin and 5,5'-diphenylhydantoin. The hydantoin and / or hydantoin derivative in the electroless copper plating solution of the present invention can be used usually at a concentration of 1 to 100 g / l, preferably 5 to 50 g / l. Various additives can be incorporated into the electroless copper plating solution of the present invention. These additives include, for example, pH adjusters, layer modifiers, but are not limited to this IJ.L --- r ——, 0_ 装 — 丨 (Please read the precautions on the back before filling this page), ^ 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Π This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -11 583339 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 9) The pH adjusting agent keeps the electroless copper plating solution of the present invention at a better temperature and accelerates the reduction reaction of copper ion deposition to copper. These pH adjusting agents include, but are not limited to, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and hydroxides such as sodium hydroxide and potassium hydroxide. The pH adjusting agent can be added to adjust the amount of the electroless copper plating solution. The pH of the electroless copper solution used in the electroless copper method of the present invention is preferably 10 or higher, more preferably 13 or higher. This layer of modifier is added to achieve the purpose of modifying the properties of the copper thin layer produced by the method of the present invention, such as brittleness, tensile strength, hardness, internal stress, etc .; or to achieve the purpose of depositing refined copper particles. These layer modifiers include, for example, sulfur compounds containing thio compounds, 2,2 bipyridine, 1,1-morpholine, potassium ferricyanide, ethylene oxide type surfactants, polyethylene glycol, and the like. Compounds, but are not limited thereto. These additives can be used alone or in combination. The amount of these additives added to the electroless copper plating solution of the present invention is conventionally set so that each additive has a desired effect. For example, the concentration of the thio compound is usually 1 to 100 mg / L, preferably 5 to 10 mg / L; the concentration of the bipyridine compound is usually 1 to 50 mg / L, preferably 5 to 15 mg / L The concentration of the surfactant is usually 1 to 500 mg / L, preferably 10 to 20 mg / L. As for the resin substrate of the present invention, any substrate having properties suitable for the purpose of the application, such as strength and corrosion resistance, may be used; the resin substrate may be in any form without particular limitation. The resin substrate that can be used in the present invention is not particularly limited to resin moldings, but may include reinforcing materials, such as (please read the precautions on the back, fill in the items and then fill in-: write this page) using Chinese national standards (CNS) A4 specification (210X297 mm) -12- 583339 A7 B7 V. Description of the invention (1Q) Glass fiber doped with this resin, composite materials; or various materials, such as ceramics, glass, metals, etc., with resin Layer of composite material. (Please read the notes on the back before filling out this page) Any resin printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be used as a resin substrate, such as polyolefin resin, for example, polyethylene resin, such as the density of the office Polyethylene; medium density polyethylene; branched low density polyethylene; linear low density polyethylene; ultra high molecular weight polyethylene; polypropylene resin; polybutadiene resin; polybutene resin; polystyrene resin, etc. . Halogen-containing resins such as polyvinyl chloride; polyvinylidene chloride; polyvinylidene chloride-vinyl chloride copolymer resins; chlorinated polyethylene; chlorinated polypropylene; tetrafluoroethylene and the like can also be used. In addition, AS resins; ABS resins; M BS resins; polyvinyl alcohol resins; polyacrylate resins such as polymethyl acrylate; polymethacrylate resins such as polymethyl methacrylate; methyl methacrylate -Styrene copolymer resin; maleic anhydride-styrene copolymer resin; polyvinyl acetate resin; cellulose resins such as cellulose propionate resin, cellulose acetate resin; epoxy resin; polyimide resin Polyamine resins, such as Nylon; Polyamine imine resins; Polyacrylic resins; Polyetherimine resins; Polyether-etherketone resins; Polyethylene oxide resins; Various polyester resins, such as PET resins; Polycarbonate resin; Polyester resin; Polyvinyl ether resin; Polyvinyl butyral; Polyethylene ether resin, such as polyphenylene ether; Polyphenylene sulfide resin; Polybutylene terephthalate resin; Polymethylpentene Resins; polyacetal resins; vinyl chloride-vinyl acetate copolymer resins; ethylene-vinyl acetate copolymers; ethylene-vinyl chloride copolymers; and thermoplastic resins, such as copolymers and blends thereof Thermosetting resins, such as epoxy resins; xylene resins; guanoamine resins; dipropylene phthalate resins; vinyl ester resins; phenol resins; unsaturated f Chinese National Standard (CNS) A4 specifications (210x297 mm) 583339 Printed by A7 ____B7, Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) Polyester resin; Furan resin; Polyimide resin; Polyurethane resin; Maleic resin; Melamine resin; Urea resin And the like, and blends thereof, but are not limited thereto. Preferred resins include epoxy resins, polyimide resins, vinyl resins, phenol resins, nylon resins, polyphenylene ether resins, polypropylene resins, fluorine resins, and ABS resins. More preferred resins include epoxy resins. Resins, polyimide resins, polyphenylene ether resins, fluorine resins and ABS resins, and more preferably epoxy resins and polyimide resins. The resin substrate may be composed of a single resin or a plurality of resins. Other composite materials containing coated resin or laminated resin on the substrate can be used. As for the palladium or -tin catalyst used in the present invention, any commercially available palladium or -tin catalyst can be used. The catalyst used is a liquid catalyst former, wherein the palladium or -tin catalyst contained in the medium is colloidal. For example, Crimson Activator-5300 water-diluted solution, palladium-tin catalyst, can be purchased from Shipley Company, ConductronDP-H concentrated activator, palladium-tin catalyst, can be purchased from LeaRonal Japan company, can be used , But not limited to this. If this palladium-tin catalyst is used, the ratio of palladium to tin is: palladium: tin = 1: 1 to 1: 100, and more preferably 1: 1 to 1:10. In the electroless copper plating method of the present invention, first, the catalyst or tin catalyst is deposited on a resin substrate. As for the method of depositing the catalyst, any method that can deposit the catalyst on a resin substrate can be used, for example, immersing the resin substrate in the catalyst solution, or spraying the catalyst solution on the resin substrate Material, but not limited to this. In addition, if necessary, the resin substrate may be adjusted and etched before the catalyst contacts the resin substrate, for example, by immersing the resin substrate in the catalyst solution; or By (please read the notes on the back of the tick and then fill and install-: write this page), 11%: China National Standard (CNS) A4 specification (210X297 mm) -14- Consumption by the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative 583339 A7 B7 V. Description of the invention (12) The catalyst solution was sprayed onto the resin substrate, so that the palladium or -tin catalyst was easily deposited on the resin substrate. The catalyst concentration of the catalyst solution used in the present invention is 30 mg / L to 500 mg / L, preferably 70 mg / L to 200 mg / L in terms of palladium concentration. When the palladium concentration is too low, sufficient copper deposition cannot be obtained from a copper solution containing a reducing agent. When the concentration of the palladium is too high, the adsorption of the palladium catalyst becomes excessive, and therefore, the adhesiveness of the catalyst is reduced and the cost is increased. As described above, the deposition treatment on the resin substrate is performed by immersing the resin substrate in the catalyst solution or by spraying the catalyst solution on the resin substrate. In the case of vertical processing, the time required for deposition is generally 3 to 10 minutes, preferably 5 to 8 minutes; the processing temperature required for deposition is usually 25 to 50 ° C, preferably 35 to 45 ° C. In the case of horizontal processing, the time required for deposition is generally 15 seconds to 3 minutes, preferably 30 seconds to 2 minutes; the processing temperature required for deposition is usually 25 to 5 (TC, preferably 35 to 45 t: Next, in the electroless copper electroplating method of the present invention, the resin substrate containing the catalyst on the surface obtained by the above treatment is treated with the electroless copper electroplating solution of the present invention without performing any accelerated processing performed in a conventional technique. In the conventional electroless copper method using formaldehyde, tin is removed from the palladium-tin catalyst during an accelerated step after the catalyst is given. In fact, palladium has high catalytic activity against formaldehyde at the catalyst. The medium was not exposed before the accelerated treatment. Therefore, it takes a very long time to initiate the electroless copper reaction compared to the case where the catalyst has been accelerated. If the catalyst is used without acceleration treatment, Impurities derived from the materials decomposed by the media will be incorporated into the liquid 0231S2_ This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) _ ------ r--1 ^ " -pack-- -: --- Order ----- • Line (Please read first Note on the back page, please fill in this page) 583339 A7 _ B7 V. Description of the invention (13) The solution will make the electroless copper solution unstable and increase the risk of decomposition. (Please read the note on the back page before filling in this (Page) The paragraph of the present invention, "accelerated treatment without catalyst" indicates that no treatment to enhance catalyst activity has been performed; otherwise, the step of depositing the unactivated catalyst on the resin and the subsequent electroless copper plating A separate step between the steps of solution treatment. If the electroless copper plating solution contains a highly reactive reducing agent when treated with the electroless copper plating solution of the present invention, the catalyst will be activated in the electroless copper plating solution, At the same time, the electroless copper reaction will proceed. In this example, the activity of the catalyst is enhanced. However, this activation will not occur in a single independent step. Therefore, even if the activity of the catalyst is electroless copper It is achieved by solution treatment, and these enhancement effects are still included in the range described in the "accelerated treatment without catalyst" in this specification. Because the electroless copper plating solution of the present invention contains Ions and reducing agents, so the electroless copper solution will form a copper film on the resin substrate and produce the copper-resin composite. In the electroless copper plating method of the present invention, the resin substrate is deposited on the catalyst After the resin substrate is treated with the electroless copper plating solution, palladium or -tin catalyst will exist in the form of metal in the copper thin layer of the copper-resin composite material. Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs In the present invention, if the substrate on which the deposited catalyst is placed is brought into contact with the electroless copper plating solution of the present invention, copper will be rapidly deposited until the entire surface of the catalyst is covered with copper, and the reaction will end. Although the thickness of the copper thin layer can be adjusted by changing to different conditions when the deposition reaction is completed, the thickness is usually 0.01 to 0.2 micrometers, preferably 0.03 to 0.1 micrometers. But in any case, thorium is thinner than 0.2 to 0.5 micrometers. The thickness includes 583339 A7 B7. V. Description of the invention (14) The electroless copper plating step is an accelerated processing step. The electroless copper plating solution contains formaldehyde and uses the same catalyst and Typical thickness of a thin copper layer obtained by a resin substrate method. The deposition rate of the copper layer of the present invention is defined as the thickness of the copper layer after the electroless copper plating solution of the present invention is in contact with the substrate for 1 minute. However, when the deposition of the copper layer ends within 1 minute, the measurement time is appropriately set to the time taken to complete the deposition of the copper layer. If an electroless copper plating solution containing formaldehyde is used, since the deposited copper has an autocatalytic effect, the end of the copper layer deposition as in the present invention does not occur. Even in this case, the copper deposition rate is defined as the thickness of the copper layer after the electroless copper solution is in contact with the resin for 1 minute. If no deposition of copper is observed after the electroless copper plating solution has been in contact with the substrate for 1 minute, the deposition rate will be expressed as 0 m / min. In the electroless copper plating method of the present invention, the deposition rate is preferably 0.02 m / min or more, more preferably 0.05 m / min or more. The Consumer Co., Ltd., Bureau of Intellectual Property, Ministry of Economic Affairs, printed the electroless copper solution treatment of the present invention by immersing the resin substrate in the electroless copper solution or by spraying the electroless copper solution on the resin base Wood. In the vertical treatment, the bath treatment time is usually 1 to 5 minutes, preferably 1 to 2 minutes; the temperature during the bath treatment is usually 30 to 70 ° C, preferably 50 to 60 t. In horizontal processing, the bath treatment time is usually 15 seconds to 2 minutes, preferably 30 seconds to 1 minute; the temperature during the bath treatment is usually 30 to 70 ° C, preferably 50 to 6 0 ° C. In the preferred embodiment of the present invention, compared with the conventional technique using an electroless copper solution containing formaldehyde and using the same catalyst and resin substrate, 17- (Please read the precautions on the back before filling this page) Use Chinese National Standard (CNS) A4 specification (210X297 mm) 583339 A7 B7 V. Description of the invention (15) Electroless copper plating method 'The deposition time is shortened and the processing time required for the entire system is also reduced. The copper-resin composite material obtained by the electroless copper plating method of the present invention can be used in the electroless copper treatment to form an additional copper layer on the copper thin layer of the composite material. As for the above electroless copper plating method, any electroless copper plating method known in the art, such as copper sulfate plating, copper cyanide plating, and copper pyrophosphate plating, can be used. EXAMPLES In the following examples, unless otherwise specified, the various methods of the examples and comparative examples were achieved using commercially available chemicals that are commonly used in this method. The treatment time of the electroless copper solution using the following method is the time until the copper deposition is almost completed. The deposition rate of the copper layer was calculated by measuring the thickness of the copper plating layer deposited during the deposition, until the electroless copper plating solution of the present invention was in contact with the substrate for 1 minute. In this case, if the deposition is completed within 1 minute, the deposition rate is measured at an appropriate point before the deposition is almost completed. The method for measuring the deposition rate of the copper layer is as follows: 1) a sufficiently dried glass-epoxy substrate is measured with an accurate balance; 2) electroless copper plating is performed on the substrate; 3) drying is measured by measurement The weight after treatment is determined by the increase in weight balance; 4) The deposition thickness is calculated from the weight increase and the surface area of the substrate. (Please read the precautions on the back before filling out this page) • Equipment · 11 National Standard (CNS) A4 Specification (210X297 mm) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -18- 583339 Member of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by X Consumer Cooperatives 5. Description of the Invention (16) Examples 1 to 8 and Comparative Example 1 Compare the copper-resin composite material made by the electroless copper method and electrolytic copper electroplating method of the present invention with the conventional Copper_resin composite made by electroplating copper. A copper-clad four-layer laminate (manufactured by Hitachi Co., Ltd.) having a thickness of 1.6 mm and including glass fiber and bisphenol a type epoxy resin (FR-4) was used as a resin substrate. Vertical processing is applied to Examples 1 to 6, 10, and 11, and Comparative Example 1. Horizontal processing is applied to Examples 7, 8 and 9. For Example 8, the change in thickness of the deposited copper layer over time was measured. Example 1 [Table 1] Step processing temperature processing time adjustment 60 ° C 5 minutes uranium etch 25 ° C 1 minute palladium-tin catalyst grant 43 ° C 5 minutes formaldehyde-free electroless copper solution * 60 ° C 5 Min. Electrolytic copper plating at 25 ° C for 40 minutes: non-formaldehyde-free electroless copper solution 023166 This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) -19- — JL --- 1 --- pack- -(Please read the precautions on the back before filling out this page), 11. • Wire 583339 A7 B7 V. Description of the invention 17 Copper sulfate pentahydrate 15 g / L EDTA 45 g / L sodium borohydride 1 g / L 2,2 '-Bipyridine 10 mg / L pH 12.5 If the above method is used, the time from the start of the process to the completion of the electroless copper treatment is 16 minutes; and the time required for the electroless copper treatment is 5 minutes. A copper layer having a thickness of 0.05 μm was obtained. The copper layer was deposited at a rate of 0.01 m / min. Observing 100 holes having a diameter of 0.3 mm, it was found that the electrolytic copper plating layer where the copper layer was not formed had a porosity rate of 26%. The prepared electroless copper solution was decomposed immediately after the test. Example 2 (Please read the note on the back # 1. Fill in the item and fill in-: Write this page) Order Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
_線 本^&^^?國國家標準（〇奶）八4規格（210乂297公釐) 583339 A7 B7 及、發明説明（18 ) 五水合硫酸銅 15克/升 EDTA 45克/升 硼氫化鈉 1克/升 2,2’-聯吡啶 10毫克/升 硫酸鉈 14毫克/升 pH 12.5 經濟部智慧財產局員工消費合作社印製 如果以上述之方法處理時，由開始處理至完成無電鍍 銅處理所需之時間爲1 6分鐘；並且無電鍍銅處理所需之 處理爲5分鐘。獲得厚度爲〇.〇5微米之銅層。該銅層之 沈積速率爲0.01微米/分。 在效能評比方面，觀察100個直徑爲0.3毫米的洞孔 發現未形成銅層處之電解銅電鍍層具有1 6 %孔隙發生率。 然而，未見到該無電鍍銅溶液分解。 比較實施例1及實施例2，儘管無電鍍銅所用的處理 時間相同，但實施例2之孔隙發生率較低。由此結果來看 ，顯然實施例2之銅層的沈積性質已獲得改善。再者，證 明藉由添加鉈至該無電鍍銅溶液，能抑制該無電鍍銅溶液 分解。 實施例3 (請先閱讀背面之注意事項再填寫本頁) A4規格（210X297公釐） -21 - 583339 A7 B7 五、發明説明（19 [表3] 步驟 處理溫度 處理時間 調節 60°C 5分鐘 蝕刻 25〇C 1分鐘 鈀-錫觸媒授與 43〇C 5分鐘 不含甲醛之無電鍍銅溶液* 60°C 2分鐘 電解銅電鍍 25〇C 40分鐘 不含甲醛之無電鍍銅溶液 五水合硫酸銅 15克/升 二甲基乙內醯脲 30克/升 硼氫化鈉 0.5克/升 2,2’-聯吡啶 10毫克/升 硫酸鉈 14毫克/升 pH 13-0 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 如果以上述之方法處理時，由開始處理至完成無電鍍 銅處理所需之時間爲1 3分鐘；並且無電鍍銅處理所需之 處理爲2分鐘。獲得厚度爲〇.〇8微米之銅層。該銅層之 沈積速率爲〇.〇4微米/分。 在效能評比方面，即使是進行100回（260°C油/10秒 ’ 2 5 °C甲醇/1 0秒）之耐熱試驗的例子中，該內部銅箔層及 硫酸銅鍍覆層之間也沒有剝落。觀察1 〇〇個直徑爲0.3毫 米的洞孔發現沒有孔隙，此表示爲良好的結果。再者，未 中國國家標準（CNS )Α4規格（210X297公釐） 〇? 583339 A7 B7 五、發明説明（2(3 ) 觀察到該無電鍍銅溶液分解。 例 施 表 步驟 處理溫度 處理時間 調節 60°C 5分鐘 蝕刻 25〇C 1分鐘 鈀-錫觸媒授與 43〇C 5分鐘 不含甲醛之無電鍍銅溶液* 60°C 2分鐘 電解銅電鍍 25〇C 40分鐘 :不含甲醛之無電鍍銅溶液 五水合硫酸銅 15克/升 二甲基乙內醯脲 30克/升 硼氫化鈉 0.5克/升 1，10-啡啉 10毫克/升 硫酸鉈 14毫克/升 pH 13.0 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 線 經濟部智慧財產局員工消費合作社 3 bh 如果以上述之方法處理時，由開始處理至完成無電鍍 銅處理所需之時間爲 1 3分鐘；並且無電鍍銅處理所需之 處理爲2分鐘。獲得厚度爲〇·〇8微米之銅層。該銅層之 沈積速率爲0.04微米/分。 170 •在效能評比方面，即使是進行1 〇 〇回（2 6 0 °C油/1 0秒 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） »23- 583339_Linebook ^ & ^^ National standard (0 milk) 8 4 specifications (210 乂 297 mm) 583339 A7 B7 and invention description (18) Copper sulfate pentahydrate 15 g / l EDTA 45 g / l boron Sodium hydride 1 g / L 2,2'-bipyridine 10 mg / L Hafnium sulfate 14 mg / L pH 12.5 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. If processed in the above-mentioned way, from the beginning of processing to the completion of electroless plating The time required for the copper treatment is 16 minutes; and the time required for the electroless copper treatment is 5 minutes. A copper layer having a thickness of 0.05 micron was obtained. The copper layer was deposited at a rate of 0.01 m / min. In terms of performance evaluation, observing 100 holes with a diameter of 0.3 mm, it was found that the electrolytic copper plating layer where the copper layer was not formed had a porosity of 16%. However, decomposition of the electroless copper plating solution was not seen. Comparing Example 1 and Example 2, although the treatment time used for the electroless copper plating was the same, the porosity occurrence rate of Example 2 was low. From this result, it is apparent that the deposition property of the copper layer of Example 2 has been improved. Furthermore, it was proved that by adding gadolinium to the electroless copper plating solution, decomposition of the electroless copper plating solution can be suppressed. Example 3 (Please read the precautions on the back before filling this page) A4 specifications (210X297 mm) -21-583339 A7 B7 V. Description of the invention (19 [Table 3] Step processing temperature processing time adjustment 60 ° C 5 minutes Etching at 25 ° C for 1 minute, palladium-tin catalyst imparted at 43 ° C, 5 minutes without formaldehyde-free electroless copper solution * 60 ° C, 2 minutes electrolytic copper plating, 25 ° C, 40 minutes, formaldehyde-free electroless copper solution, pentahydrate Copper sulfate 15 g / L dimethylhydantoin 30 g / L sodium borohydride 0.5 g / L 2,2'-bipyridine 10 mg / L Europium sulfate 14 mg / L pH 13-0 (Please read the back first Note: Please fill in this page again.) If printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, if the above method is used, the time from the start of processing to the completion of electroless copper treatment is 13 minutes; The required treatment is 2 minutes. A copper layer with a thickness of 0.08 micrometers is obtained. The deposition rate of the copper layer is 0.04 micrometers / min. In terms of performance evaluation, even 100 times (260 ° C oil / 10 seconds' 2 5 ° C methanol / 1 10 seconds) in the heat resistance test example There was no peeling between the inner copper foil layer and the copper sulfate plating layer. One hundred holes with a diameter of 0.3 mm were observed and no pores were found, which is a good result. Furthermore, the Chinese National Standard (CNS) Α4 specification (210X297 mm) 〇 583339 A7 B7 V. Description of the invention (2 (3) The decomposition of the electroless copper solution was observed. Example Application Step Processing Temperature Adjustment Time 60 ° C 5 minutes Etching 25 ° C 1 minute Palladium-tin catalyst was given at 43 ° C for 5 minutes without formaldehyde-free electroless copper solution * 60 ° C 2 minutes for electrolytic copper plating at 25 ° C for 40 minutes: formaldehyde-free non-plated copper solution 15 grams of copper sulfate pentahydrate / L dimethylhydantoin 30 g / L sodium borohydride 0.5 g / L 1,10-morpholine 10 mg / L Rhenium sulfate 14 mg / L pH 13.0 (Please read the notes on the back before filling this page) Assembling and routing staff consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 bh If the above method is used, the time from the start of processing to the completion of electroless copper processing is 13 minutes; and the processing required for electroless copper processing is 2 minutes. Get thickness 0.08 micron copper layer. The deposition rate of the copper layer is 0.04 micron / minute. 170 • In terms of performance evaluation, even if it is performed 100 times (260 ° C oil / 10 seconds) This paper size is applicable China National Standard (CNS) A4 (210X297 mm) »23- 583339
7 7 A B 五、發明説明（21 ) ’ 25°C甲醇/10秒）之耐熱試驗的例子中，該內部銅箔層及 硫酸銅鍍覆層之間也沒有剝落。觀察100個直徑爲0.3毫 米的洞孔發現沒有孔隙，此表示爲良好的結果。再者，未 觀察到該無電鍍銅溶液分解。 由實施例2及3之結果，發現無論使用各種類型層改 質劑皆能獲得本發明之功效。 實施例5 H H 屢」·· It ........ -二· ϋ (請先聞讀背面之注意事項再填寫本頁) 訂 [表5] 步驟 處理溫度 處理時間 調節 60°C 5分鐘 蝕刻 25〇C 1分鐘 鈀-錫觸媒授與 43〇C 5分鐘 不含甲醛之.無電鍍銅溶液* 60°C 1分鐘 電解銅電鑛 25〇C 40分鐘 * :不含甲醛之無電鍍銅溶液 _線卜 經濟部智慧財產局員工消費合作社印製 五水合硫酸銅 4克/升 二甲基乙內醯脲 30克/升 硼氫化鈉 0.5克/升 2,2’-聯吡啶 10毫克/升 醋酸鈽 15毫克/升 碘化鉀 10毫克/升 pH 12.5 本‘皮適用+國國家標準（CNS ) A4規格（210X297公釐） -24 - 583339 A7 B7 ___ 五、發明説明（22 ) 如果以上述之方法處理時，由開始處理至完成無電鑛 銅處理所需之時間爲1 2分鐘；並且無電鑛銅處理所需之 處理爲1分鐘。獲得厚度爲〇· 微米之銅層。該銅層之 沈積速率爲0.06微米/分。 在效能評比方面，即使是進行100回（260°C油/10秒 ，2 5 °C甲醇/1 0秒）之耐熱試驗的例子中，該內部銅箔層及 硫酸銅鍍覆層之間也沒有剝落。觀察丨〇〇個直徑爲0.3毫 米的洞孔發現沒有孔隙，此表示爲良好的結果。再者，未 觀察到該無電鍍銅溶液分解。 實施例ό (請先閲讀背面之注意事項再填寫本頁) -裝· 訂 經濟部智慧財產局員工消費合作社印製 [表6] 步驟 處理溫度 處理時間 調節 60°C 5分鐘 蝕刻 25〇C 1分鐘 鈀-錫觸媒授與 43〇C 5分鐘 不含甲醛之無電鍍銅溶液* 60°C 1分鐘 電解銅電鍍 25t 40分鐘 * :不含甲醛之無電鍍銅溶液 _線 023172_ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 583339 A7 B7 -、發明説明（23 ) 五水合硫酸銅 4克/升 二甲基乙內醯脲 30克/升 硼氫化鈉 0.5克/升 鐵氰化鉀 10毫克/升 醋酸鈽 15毫克/升 碘化鉀 10毫克/升 pH 12.5 (請先閲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 如果以上述之方法處理時，由 銅處理所需之時間爲12分鐘；並 處理爲1分鐘。獲得厚度爲〇·06 沈積速率爲〇·〇6微米/分。 在效能評比方面，即使是進行 ，2 5 °C甲醇/1 〇秒）之耐熱試驗的例 硫酸銅鍍覆層之間也沒有剝落。觀 米的洞孔發現沒有孔隙，此表示爲 觀察到該無電鍍銅溶液分解。 由實施例5及6之結果，發現 質劑皆能獲得本發明之功效。 比較實施例2至6時，在實施 完成時間係5分鐘，在實施例3及 5及6中1分鐘。實施例3及4中 •實施例5及6中使用二甲基乙內醯 峰+求中國國家標準（CNS ) A4規格（210X297公釐） 開始處理至完成無電鍍 且無電鍍銅處理所需之 微米之銅層。該銅層之 100 回（260°C 油 /10 秒 子中，該內部銅箔層及 察100個直徑爲0.3毫 良好的結果。再者，未 無論使用各種類型層改 例2中無電鍍銅處理之 4中2分鐘’在實施例 使用二甲基乙內醯脲， 脲及碘化鉀。由此，發 、11 -26- 583339 A7 B7 五、發明説明（24 ) 現乙內醯脲化合物及碘元素會增進本發明之無電鍍銅方法 中銅之沈積速率。 步驟 處理溫度 處理時間 調節 60°C 15秒 鈾刻 25〇C 15秒 鈀-錫觸媒授與 43〇C 30秒 不含甲醛之無電鍍銅溶液* 60°C 30秒 電解銅電鍍 25〇C 40分 *:不含曱醛之無電鍍銅溶液 —^ ^ Αντί Ί (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 五水合硫酸銅 4克/升 二甲基乙內醯脲 30克/升 硼氫化鈉 0.5克/升 三乙醇胺 4克/升 2，2 ’ -聯D比D定 10毫克/升 醋酸鈽 15毫克/升 8-羥基-7-碘基-5-喹啉 10毫克/升 磺酸 pH 13.0 如果以上述之方法處理時，由開始處理至完成無電鍍 丨訂-----^線 27- G用中國國家標準（CNS ) A4規格（210X297公釐) 583339 A7 B7 五、發明説明（25 ) 銅處理所需之時間爲1分鐘又30秒；並且無電鍍銅處理 所需之處理爲3 0秒。獲得厚度爲0. 〇 5微米之銅層。該銅 層之沈積速率爲〇·1微米/分。 在效能評比方面，即使是進行100回（260°C油/10秒 ，25 °C甲醇/1 〇秒）之耐熱試驗的例子中，該內部銅箔層及 硫酸銅鍍覆層之間也沒有剝落。觀察100個直徑爲0.3毫 米的洞孔發現沒有孔隙，此表示爲良好的結果。再者，未 觀察到該無電鍍銅溶液分解。 由實施例7的結果，發現添加碘元素會增進銅之沈積 速率，即使碘係以碘化合物的形式存在。 實施例8 -^ϋ· m !r_ I j 1---- I 1 HI — j -..... -- -1 m - ------ \ V ^ 、v" (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 [表8] 步驟 處理溫度 處理時間 調節 60°C 15秒 鈾刻 25〇C 15秒 鈀-錫觸媒授與 43〇C 30秒 不含甲醛之無電鍍銅溶液* 60°C 30秒 電解銅電鍍 25〇C 40分 *:不含甲醛之無電鍍銅溶液 523175 ·線 -28- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583339 A7 _ _ B7 五、發明説明（26 ) 五水合硫酸銅 4克/升 二甲基乙內醯脲 30克/升 硼氫化鈉 0.5克/升 三乙醇胺 4毫克/升 硫酸鈉 10毫克/升 醋酸鈽 15毫克/升 8-羥基-7-碘基-5-口奎啉 10毫克/升 磺酸 pH 13.0 (請先閱讀背面之注意事項再填寫本頁) 如果以上述之方法處理時，由開始處理至完成無電鍍 銅處理所需之時間爲1分鐘又30秒；並且無電鍍銅處理 所需之處理爲30秒。獲得厚度爲〇.〇5微米之銅層。該銅 層之沈積速率爲0.1微米/分。 經濟部智慧財產局員工消費合作杜印製 在效能評比方面，即使是進行1〇〇回（260°C油/10秒 ，25 °C甲醇/10秒）之耐熱試驗的例子中，該內部銅箔層及 硫酸銅鍍覆層之間也沒有剝落。觀察1〇〇個直徑爲0.3毫 米的洞孔發現沒有孔隙，此表示爲良好的結果。再者，未 觀察到該無電鍍銅溶液分解。 由實施例8的結果，發現能獲得本發明之功效，即使 硫化物與鈽化合物一起使用也是一樣。 使用含實施例8之組成的無電鍍銅溶液測量藉由垂直 處理沈積之銅層厚度隨著時間的變化。該實驗係於以下條 本紙參尽寿適風私國國家標準（CNS ) A4規格（210X297公釐1 ^9 _ '^ 583339 A7 B7 五、發明説明（27 ) 件下進行：調節步驟，60°C，5分鐘；蝕刻步驟，25。〇， 1分分；鈀-錫觸媒授與步驟，4 3 °C，5分鐘。不含甲醒之 無電鍍銅溶液之處理步驟係於60°C時進行2〇分鐘，並且 (請先閲讀背面之注意事項再填寫本頁) 測量沈積之銅層厚度隨著時間的變化。結果顯示於表1中 〇 比較實施例1 [表9] 步驟 處埋溫度 處理時間 調節 6〇°C 5分鐘 鈾刻 25〇C 1分鐘 把-錫觸媒授與 43它 5分鐘 無電鍍銅溶液* 60°C 1分鐘 電解銅電鍍 25〇C 40分 * :無電鍍銅溶液 五水合硫酸銅 4克/升 EDTA 45克/升 甲醛 20克/升 2,2’-聯吡啶 10毫克/升 pH 12.5 經濟部智慧財產局員工消費合作社印製 以比較實施例1之無電鍍銅處理所需之時間爲1分鐘 ;與實施例5及6相同。然而，未觀察到銅之沈積。也就 -30 - 本紙國家標準（CNS ) A4^格（210X297公釐) 583339 A7 B7 五、發明説明（28 ) 是說，關於電解銅電鍍層之被覆性質，觀察100個直徑爲 (請先閲讀背面之注意事項再填寫本頁) 0.3毫米的洞孔發現其被覆性質有100%孔隙發生率，所以 並未確認以該無電鍍銅溶液之銅沈積。未觀察到該無電鍍 銅溶液分解。 在比較實施例1中，進一步持續進行該無電鍍銅處理 以沈積達到可用於電解銅電鍍處理程度之層厚度的銅層。 測量該沈積銅之層厚度隨著時間的變化。沈積0.1微米之 銅層耗費20分鐘。沈積銅層之厚度隨著時間的變化係顯 示於第1圖。 由第1圖顯然可見，以該無電鍍銅溶液處理之後並無 法立即觀察到隨著含甲醛之習知無電鍍銅溶液的銅沈積。 另一方面，在實施例8中，也就是本發明之無電鍍銅溶液 ，在該無電鍍銅處理之後立即就可觀察到銅沈積。該層厚 度幾乎呈線性地增加直到該處理開始之後1分鐘，並且該 銅層之沈積速率爲0.06微米/分。該沈_反應幾乎在該處 理之初之後2分鐘內完成。 經濟部智慧財產局員工消費合作社印製 如上述，如果沒有進行觸媒加速處理，利用含甲醛之 無電鍍銅溶液沈積銅會大幅地延遲。然而，由實施例1至 8的結果顯然可見，本發明之無電鍍銅溶液可大幅地增進 銅之沈積速率，即使觸媒未進行加速處理也是一樣。再者 ，如實施例1至8所75，藉由本發明之無電鍍銅方法形成 之層上進行電解銅電鍍而獲得之複合材料具有優良的耐熱 性及黏著性。另外，該複合材料之孔隙發生率會降低。因 此，證明本發明之無電鍍銅方法可於短時間內形成適用於 023179_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） _ 31 _ 583339 Α7 Β7 五、發明説明（29 ) 電解銅電鍍之銅層。 步驟 處理溫度 處理時間 調節 60°C 15秒 蝕刻 25〇C 15秒 鈀-錫觸媒授與 4 3〇C 30秒 不含甲醛之無電鍍銅溶液* 60°C 30秒 電解銅電鍍 25〇C 40分 *:不含甲醛之無電鍍銅溶液 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 五水合硫酸銅 4克/升 二甲基乙內醯脲 30克/升 硼氫化鈉 0.5克/升 三乙醇胺 4毫克/升 硫酸鈉 10毫克/升 醋酸铈 15毫克/升 pH 13.0 如果以上述之方法處理時，由開始處理至完成無電鍍 銅處理所需之時間爲1分鐘又30秒；並且無電鍍銅處理 所需之處理爲30秒。獲得厚度爲0.03微米之銅層。該銅 層之沈積速率爲0.06微米/分。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -32- 經濟部智慧財產局員工消費合作社印製 583339 A7 B7____ 五、發明説明（30 ) 在效能評比方面，即使是進行1 〇 〇回（2 6 0 °c油/1 〇秒 ，25 °C甲醇/1 0秒）之耐熱試驗的例子中，該內部銅箔層及 硫酸銅鍍覆層之間也沒有剝落。觀察1 00個直徑爲〇. 3毫 米的洞孔發現沒有孔隙，此表示爲良好的結果。再者，未 觀察到該無電鍍銅溶液分解。 比較實施例9及實施例8的結果，實施例9之沈積速 率，其中並不包含碘元素，係0.06微米/分，然而實施例 8之沈積速率，其中包含碘元素，係0.10微米/分。因此 ，暸解添加碘會增進該沈積速率。 實施例10 [表 11] 步驟 處理溫度 處理時間 調節 60°C 5分鐘 蝕刻 25〇C 1分鐘 鈀-錫觸媒授與 43〇C 5分鐘 不含甲醛之無電鍍銅溶液* 60°C 1分鐘 電解銅電鍍 25〇C 40分 :不含甲醛之無電鍍銅溶液 . w * u ^ ^ ^ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ——L---r---φ-裝------r——^訂--------·線 (請先閲讀背面之注意事項再填寫本頁) 583339 A7 B7 五、發明説明（31 ) 五水合硫酸銅 4克/升 硼氫化鈉 0.5克/升 三乙醇胺 4克/升 氯化鉈 15毫克/升 碘化鈉 10毫克/升 pH 13.0 (請先閱讀背面之注意事項再填寫本頁) 如果以上述之方法處理時，由開始處理至完成無電鑛 銅處理所需之時間爲12分鐘；並且無電鍍銅處理所需之 處理爲1分鐘。獲得厚度爲〇.〇6微米之銅層。該銅層之 沈積速率爲0.06微米/分。 在效能評比方面，即使是進行1〇〇回（260°c油/10秒 ，2 5 °C甲醇/1 〇秒）之耐熱試驗的例子中，該內部銅箔層及 硫酸銅鍍覆層之間也沒有剝落。觀察1 〇〇個直徑爲〇. 3毫 米的洞孔發現沒有孔隙，此表示爲良好的結果。再者，未 觀察到該無電鍍銅溶液分解。 經濟部智慧財產局員工消費合作社印製 比較實施例10及實施例2的結果，實施例2之沈積 速率，其中並不包含碘元素，係0.01微米/分，然而實施 例10之沈積速率，其中包含碘元素，係0.06微米/分。 因此，暸解添加碘會大幅地增進該沈積速率。 實施例11 023182 -34 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 583339 A7 B7 五、發明説明（ Γ 圭 1 ο 1 -------~~-1 ^ J 步驟 處理溫度 處理時間 調節 60°C 5分鐘 蝕刻 25〇C 1分鐘 鈀-錫觸媒授與 43〇C 5分鐘 不含甲醛之無電鍍銅溶液* 60°C 1分鐘 電解銅電鍍 25〇C 40分 :不含甲醛之無電鍍銅溶液 五水合硫酸銅 4克/升 硼氫化鈉 〇·5克/升 三乙醇胺 4毫克/升 8-羥基-7-碘基-5-喹啉 10毫克/升 磺酸 pH 13.0 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 如果以上述之方法處理時，由開始處理至完成無電鍍 銅處理所需之時間爲1 2分鐘；並且無電鍍銅處理所需之 處理爲1分鐘。獲得厚度爲〇.〇6微米之銅層。該銅層之 沈積速率爲0.06微米/分。 在效能評比方面，即使是進行100回（260°C油/10秒 ，25°C甲醇/10秒）之耐熱試驗的例子中，該內部銅箔層及 硫酸銅鍍覆層之間也沒有剝落。觀察1 〇〇個直徑爲〇· 3毫 米的洞孔發現沒有孔隙，此表示爲良好的結果。再者，未 本 .度 ;尺 準 標 家 國 國. 210X297公釐） -35- 583339 A7 B7 五、發明説明（33 ) 崔見察到該無電鑛銅丨谷液分解。 比較實施例1 1及實施例1的結果，實施例1之沈積 速率，其中並不包含碘元素，係0.01微米/分，然而實施 例11之沈積速率，其中包含碘元素，係0.06微米/分。 因此，瞭解添加碘會大幅地增進該沈積速率。同時，觀察 到實施例1之無電鍍銅溶液之分解。然而，實施例1 1中 未觀察到該分解。 由此發現碘元素同時會增進沈積速率及無電鍍銅溶液 之安定性。 實施例1至1 1之沈積銅層外觀皆係經由目視檢查。 實施例5至8、10及1 1之外觀，其中各無電鍍銅溶液皆 包含碘元素，皆散發出金屬色調的光澤。另一方面，實施 例2至4及實施例9，其中各無電鍍銅溶液不含碘元素， 並無光亮外觀或金屬色調。因此，發現添加碘元素將提供 光亮的外觀及金屬色調之鍍覆金屬銅。 實施例1至11及比較實施例1之結果總結如以下。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 中國國家標準（CNS ) A4規格（210X297公釐） 36 5833397 7 A B 5. In the example of the heat resistance test of (21) '25 ° C methanol / 10 sec), there was no peeling between the inner copper foil layer and the copper sulfate plating layer. Observation of 100 holes having a diameter of 0.3 mm revealed no pores, which indicates good results. Furthermore, no decomposition of the electroless copper plating solution was observed. From the results of Examples 2 and 3, it was found that the effects of the present invention can be obtained regardless of the use of various types of layer modifiers. Example 5 HH repeated "... It .........-Two ... ϋ (Please read the precautions on the back before filling out this page) Order [Table 5] Step processing temperature processing time adjustment 60 ° C 5 Etching at 25 ° C for 1 minute, palladium-tin catalyst given at 43 ° C for 5 minutes, no formaldehyde. Electroless copper solution * 60 ° C, 1 minute electrolytic copper ore at 25 ° C, 40 minutes *: No formaldehyde Copper plating solution_printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China printed copper sulfate pentahydrate 4 g / L dimethylhydantoin 30 g / L sodium borohydride 0.5 g / L 2,2'-bipyridine 10 Mg / L acetic acid 15 mg / L potassium iodide 10 mg / L pH 12.5 This' skin is applicable + National Standard (CNS) A4 specification (210X297 mm) -24-583339 A7 B7 ___ V. Description of the invention (22) In the above-mentioned method, the time required from the start of the process to the completion of the electroless copper processing is 12 minutes; and the process required for the electroless copper processing is 1 minute. A copper layer having a thickness of 0 μm was obtained. The copper layer was deposited at a rate of 0.06 m / min. In terms of performance evaluation, even when the heat resistance test is performed 100 times (260 ° C oil / 10 seconds, 25 ° C methanol / 10 seconds), the inner copper foil layer and the copper sulfate plating layer are also between No peeling. Observation of the pores having a diameter of 0.3 mm revealed no pores, which indicates good results. Furthermore, no decomposition of the electroless copper plating solution was observed. Example (Please read the notes on the back before filling this page)-Binding and printing Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 6] Step Processing Temperature Processing Time Adjustment 60 ° C 5 minutes Etching 25 ° C 1 Min. Palladium-tin catalyst grants 43 ° C. 5 minutes. Formaldehyde-free electroless copper solution * 60 ° C. 1 minute electrolytic copper plating 25t 40 minutes *: Formaldehyde-free electroless copper solution._Line 023172_ This paper size is applicable Chinese National Standard (CNS) A4 specification (210 × 297 mm) 583339 A7 B7-, Description of the invention (23) Copper sulfate pentahydrate 4 g / L dimethylhydantoin 30 g / L sodium borohydride 0.5 g / L iron Potassium cyanide 10 mg / L 钸 Acetate 15 mg / L Potassium iodide 10 mg / L pH 12.5 (Please read the precautions on the back before filling out this page}-Packed · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs When the method is processed, the time required for copper processing is 12 minutes; and the processing is 1 minute. The thickness is obtained. The deposition rate is 0.06 micrometers / min. In terms of performance evaluation, even if it is performed, 2 5 ° C methanol / 1 (0 seconds) Example of heat resistance test There was no peeling between the copper sulfate plating layers. No holes were observed in the observation holes, which was expressed as the decomposition of the electroless copper solution observed. From the results of Examples 5 and 6, it was found that the agents can obtain the efficacy of the present invention. In Comparative Examples 2 to 6, the implementation completion time was 5 minutes, and in Examples 3 and 5 and 6, it was 1 minute. In Examples 3 and 4 • The use of dimethyl ethyl hydrazone peak in Examples 5 and 6 + Chinese National Standard (CNS) A4 specification (210X297 mm) Start processing to complete the electroless and electroless copper treatment Micron copper layer. 100 times of the copper layer (260 ° C oil / 10 seconds), the inner copper foil layer and 100 samples with a diameter of 0.3 millimeters were good results. Furthermore, no electroplated copper was used in Modification 2 regardless of the use of various types of layers. 2 minutes of the 4th treatment 'used dimethylhydantoin, urea and potassium iodide in the examples. Thus, the hair, 11 -26-583339 A7 B7 V. Description of the invention (24) present hydantoin urea compound and iodine Elements will increase the copper deposition rate in the electroless copper electroplating method of the present invention. Step processing temperature treatment time adjustment 60 ° C 15 seconds uranium engraving 25 ° C 15 seconds palladium-tin catalyst grant 43 ° C 30 seconds without formaldehyde Electroless copper solution * 60 ° C 30 seconds electrolytic copper plating 25 ° C 40 minutes *: electroless copper solution without formaldehyde— ^ ^ Αντί Ί (Please read the precautions on the back before filling this page) Wisdom of the Ministry of Economy Printing of copper sulfate pentahydrate 4 g / L dimethylhydantoin 30 g / L sodium borohydride 0.5 g / L triethanolamine 4 g / L 2,2 '-Link D ratio D fixed 10 Mg / L osmium acetate 15 mg / L 8-hydroxy-7-iodo-5-quinoline 10 mg / L sulfonic acid pH 13 .0 If it is processed in the above way, from the beginning of processing to the completion of electroless plating Order ----- ^ Line 27- G Chinese National Standard (CNS) A4 specification (210X297 mm) 583339 A7 B7 V. Description of the invention (25) The time required for the copper treatment is 1 minute and 30 seconds; and the processing required for the electroless copper treatment is 30 seconds. A copper layer having a thickness of 0.05 micron is obtained. The deposition rate of the copper layer is 〇 · 1 micron / minute. In the performance evaluation, even if the heat resistance test is performed 100 times (260 ° C oil / 10 seconds, 25 ° C methanol / 10 seconds), the inner copper foil layer and copper sulfate plating There was no peeling between the cladding layers. The observation of 100 holes with a diameter of 0.3 mm showed no pores, which is a good result. Furthermore, no decomposition of the electroless copper plating solution was observed. From the results of Example 7, it was found Addition of iodine element will increase the deposition rate of copper, even if iodine exists as an iodine compound. Example 8-^ ϋ · m! R_ I j 1 ---- I 1 HI — j -.....- -1 m------- \ V ^, v " (Please read the notes on the back before filling this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Fei Cooperative [Table 8] Step processing temperature processing time adjustment 60 ° C 15 seconds uranium etch 25 ° C 15 seconds palladium-tin catalyst grant 43 ° C 30 seconds formaldehyde-free electroless copper solution * 60 ° C 30 seconds electrolytic copper electroplating at 25 ° C 40 minutes *: electroless copper plating solution without formaldehyde 523175 · wire-28- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 583339 A7 _ _ B7 V. Description of the invention (26) Copper sulfate pentahydrate 4 g / L dimethylhydantoin 30 g / L sodium borohydride 0.5 g / L triethanolamine 4 mg / L sodium sulfate 10 mg / L Acetic acid 15 mg / L 8 -Hydroxy-7-iodo-5-quinoline 10 mg / l sulfonic acid pH 13.0 (Please read the precautions on the back before filling this page) If you use the above method, from the beginning of processing to the completion of electroless copper plating The time required for the treatment is 1 minute and 30 seconds; and the time required for the electroless copper treatment is 30 seconds. A copper layer having a thickness of 0.05 micron was obtained. The copper layer was deposited at a rate of 0.1 m / min. In terms of efficiency evaluation, even if it is a heat resistance test for 100 times (260 ° C oil / 10 seconds, 25 ° C methanol / 10 seconds), the internal copper There was no peeling between the foil layer and the copper sulfate plating layer. Observation of 100 holes having a diameter of 0.3 mm revealed no pores, which indicates good results. Furthermore, no decomposition of the electroless copper plating solution was observed. From the results of Example 8, it was found that the effects of the present invention can be obtained even when a sulfide is used together with a sulfonium compound. The change in the thickness of the copper layer deposited by the vertical treatment with time was measured using an electroless copper solution containing the composition of Example 8. The experiment was carried out under the following papers: National Standards for Endurance and Private Life (CNS) A4 specifications (210X297 mm 1 ^ 9 _ '^ 583339 A7 B7) 5. Description of the invention (27): Adjustment steps, 60 ° C, 5 minutes; etching step, 25.0, 1 minute; palladium-tin catalyst granting step, 4 3 ° C, 5 minutes. The processing step of the electroless copper plating solution without carbohydrate is at 60 ° C It takes 20 minutes at a time, and (please read the precautions on the back before filling this page) to measure the thickness change of the deposited copper layer over time. The results are shown in Table 1. Comparative Example 1 [Table 9] Step buried Temperature processing time adjustment 60 ° C 5 minutes uranium etch 25 ° C 1 minute Give -tin catalyst 43 minutes 5 minutes electroless copper solution * 60 ° C 1 minute electrolytic copper plating 25 ° C 40 minutes *: electroless Copper solution copper sulfate pentahydrate 4 g / litre EDTA 45 g / litre formaldehyde 20 g / litre 2,2'-bipyridine 10 mg / litre pH 12.5 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to compare the absence of Example 1 The time required for the copper plating treatment was 1 minute; the same as in Examples 5 and 6. However, no sinking of copper was observed. -30-National Standard for Paper (CNS) A4 ^ (210X297 mm) 583339 A7 B7 V. Description of Invention (28) It means that regarding the coating properties of electrolytic copper plating layer, observe 100 diameters (please Read the precautions on the back before filling in this page.) The 0.3mm hole was found to have a 100% porosity in the coating properties, so no copper deposition with the electroless copper solution was confirmed. No decomposition of the electroless copper solution was observed. In Comparative Example 1, the electroless copper treatment was further continuously performed to deposit a copper layer to a thickness that can be used for electrolytic copper plating. The thickness of the deposited copper layer was measured over time. 0.1 micron copper was deposited The layer took 20 minutes. The change of the thickness of the deposited copper layer with time is shown in Figure 1. From Figure 1, it can be clearly seen that after treatment with the electroless copper solution, it is not immediately possible to observe the presence of formaldehyde. Copper deposition of electroplated copper solution. On the other hand, in Example 8, which is also the electroless copper electroplating solution of the present invention, copper deposition can be observed immediately after the electroless copper electroplating treatment. This layer is thick It increased almost linearly until 1 minute after the start of the process, and the deposition rate of the copper layer was 0.06 micrometers / minute. The sinking reaction was completed almost 2 minutes after the beginning of the process. Employee Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs As described above, if the catalyst is not accelerated, the deposition of copper using the electroless copper plating solution containing formaldehyde will be greatly delayed. However, it is obvious from the results of Examples 1 to 8 that the electroless copper plating solution of the present invention can greatly To increase the copper deposition rate even if the catalyst is not accelerated. Furthermore, as in Examples 1 to 8, the composite material obtained by electrolytic copper plating on the layer formed by the electroless copper plating method of the present invention has excellent heat resistance and adhesion. In addition, the porosity of the composite material is reduced. Therefore, it is proved that the electroless copper plating method of the present invention can be formed in a short period of time applicable to 023179_ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) _ 31 _ 583339 Α7 Β7 V. Description of the invention (29) Copper layer for electrolytic copper plating. Step Processing Temperature Processing time adjustment 60 ° C 15 seconds etching 25 ° C 15 seconds palladium-tin catalyst grant 4 30 ° C 30 seconds formaldehyde-free electroless copper solution * 60 ° C 30 seconds electrolytic copper plating 25 ° C 40 points *: Non-formaldehyde-free electroless copper solution (please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, copper sulfate pentahydrate 4 g / L dimethylhyperuronium 30 g / l sodium borohydride 0.5 g / l triethanolamine 4 mg / l sodium sulfate 10 mg / l cerium acetate 15 mg / l pH 13.0 If it is processed in the above-mentioned method, it is required from the beginning of the process to the completion of electroless copper plating The time is 1 minute and 30 seconds; and the processing required for the electroless copper treatment is 30 seconds. A copper layer was obtained with a thickness of 0.03 microns. The copper layer was deposited at a rate of 0.06 m / min. This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -32- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 583339 A7 B7____ V. Description of the invention (30) In terms of performance evaluation, even if it is 1 〇 In the heat resistance test example of 260 times (260 ° C oil / 10 sec, 25 ° C methanol / 10 sec), there was no peeling between the inner copper foil layer and the copper sulfate plating layer. Observation of 100 holes having a diameter of 0.3 mm revealed no pores, which indicates good results. Furthermore, no decomposition of the electroless copper plating solution was observed. Comparing the results of Example 9 and Example 8, the deposition rate of Example 9 does not include the iodine element and is 0.06 micrometers / min. However, the deposition rate of Example 8 includes the iodine element and is 0.10 micrometers / min. Therefore, it is understood that the addition of iodine will increase this deposition rate. Example 10 [Table 11] Step processing temperature processing time adjustment 60 ° C 5 minutes etching 25 ° C 1 minute palladium-tin catalyst grant 43 ° C 5 minutes formaldehyde-free electroless copper solution * 60 ° C 1 minute Electrolytic copper plating 25 ℃ 40 minutes: electroless copper solution without formaldehyde. W * u ^ ^ ^ This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) ---- L --- r-- -φ-pack ------ r —— ^ order -------- · line (please read the notes on the back before filling this page) 583339 A7 B7 V. Description of the invention (31) Pentahydrate Copper sulfate 4 g / L sodium borohydride 0.5 g / L triethanolamine 4 g / L Tritium chloride 15 mg / L Sodium iodide 10 mg / L pH 13.0 (Please read the precautions on the back before filling this page) In the above method, the time required from the start of the process to the completion of the electroless copper treatment is 12 minutes; and the process required for the electroless copper treatment is 1 minute. A copper layer having a thickness of 0.06 μm was obtained. The copper layer was deposited at a rate of 0.06 m / min. In terms of performance evaluation, even if the heat resistance test is performed 100 times (260 ° C oil / 10 seconds, 25 ° C methanol / 10 seconds), the internal copper foil layer and the copper sulfate plating layer There was no flaking. Observation of 100 holes having a diameter of 0.3 mm revealed no pores, which indicates good results. Furthermore, no decomposition of the electroless copper plating solution was observed. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed and compared the results of Example 10 and Example 2. The deposition rate of Example 2 does not include the iodine element, which is 0.01 micrometers / min. Contains iodine, 0.06 microns / minute. Therefore, it is understood that the addition of iodine will greatly enhance this deposition rate. Example 11 023182 -34-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 583339 A7 B7 V. Description of the invention (Γ Gui 1 ο 1 ------- ~~ -1 ^ J Step processing temperature processing time adjustment 60 ° C 5 minutes etching 25 ° C 1 minute palladium-tin catalyst grant 43 ° C 5 minutes formaldehyde-free electroless copper solution * 60 ° C 1 minute electrolytic copper plating 25 ° C 40 points: electroless copper solution without formaldehyde, copper sulfate pentahydrate 4 g / l sodium borohydride 0.5 g / l triethanolamine 4 mg / l 8-hydroxy-7-iodo-5-quinoline 10 mg / l L sulfonic acid pH 13.0 (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs If the above method is used, the time required to start processing to complete the electroless copper treatment is 12 minutes; and the treatment required for electroless copper treatment is 1 minute. A copper layer having a thickness of 0.06 micron is obtained. The deposition rate of the copper layer is 0.06 micron / min. In terms of performance evaluation, even 100 (260 ° C oil / 10 seconds, 25 ° C methanol / 10 seconds) In the sample, there was no peeling between the inner copper foil layer and the copper sulfate plating layer. Observation of 1,000 holes with a diameter of 0.3 mm showed no pores, which is a good result. Furthermore, the original Degree; rule standard home country and country. 210X297 mm) -35- 583339 A7 B7 V. Description of the invention (33) Cui Jian observed that the electroless copper ore valley solution was decomposed. Comparing the results of Example 11 and Example 1, the deposition rate of Example 1, which does not include the iodine element, is 0.01 micrometers / minute, but the deposition rate of Example 11, which includes the iodine element, is 0.06 micrometers / minute . Therefore, it is understood that the addition of iodine will greatly enhance this deposition rate. At the same time, decomposition of the electroless copper plating solution of Example 1 was observed. However, this decomposition was not observed in Example 11. It was found that the iodine element also enhanced the deposition rate and the stability of the electroless copper solution. The appearances of the deposited copper layers of Examples 1 to 11 were visually inspected. The appearances of Examples 5 to 8, 10, and 1 1 in which each of the electroless copper plating solutions contained an iodine element, all of which gave off a metallic-tone gloss. On the other hand, in Examples 2 to 4 and Example 9, each of the electroless copper plating solutions does not contain iodine element, and has no bright appearance or metallic hue. Therefore, it was found that the addition of iodine would provide a bright appearance and metallic tint of plated metal copper. The results of Examples 1 to 11 and Comparative Example 1 are summarized as follows. (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 China National Standard (CNS) A4 Specification (210X297 mm) 36 583339
AA
7 B 五、發明説明（34 ) [表13之1] 經濟部智慧財產局員工消費合作社印製 實施例1至11及比較實施例1之結果總結 無電鍍銅溶液中包含的組成分 甲醛 甲醛以 外之還 原劑 隹它、姉 或硫化 物 乙內醯 脲 碘 處理方 法 實施例1 + . _ 垂直 實施例2 . + 鉈 _ 蒙 垂直 實施例3 _ + 鉈 + 垂直 實施例4 . + 鉈 + 垂直 實施例5 + 鈽 + + 垂直 實施例6 _ + 鈽 + + 垂直 實施例7 . + 鈽 + + 水平 實施例8 - + 鋪、硫 化物 + + 水平 垂直 實施例9 - + 姉、硫 化物 + - 水平 實施例 - + 鉈 - + 垂直 10 實施例 - + - - + 垂直 11 比較實施 + - - - - 垂直 例1 (請先閱讀背面之注意事 #1 項再填· 裝----Ί :寫本頁) 訂-----^線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -37- 583339 A7 B7 五、發明説明（35 [表13之2] 實施例1至11及比較實施例1之結果總結7 B V. Description of the invention (34) [Table 13-1] Results of Examples 1 to 11 and Comparative Example 1 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Summary of the composition contained in electroless copper solution other than formaldehyde and formaldehyde The reducing agent 隹, sister or sulfide hydantoin urea iodine treatment method Example 1 +. _ Vertical example 2. + 铊 _ Mongolia vertical example 3 _ + 铊 + vertical example 4. + 铊 + vertical implementation Example 5 + 钸 + + vertical example 6 _ + 钸 + + vertical example 7. + 钸 + + horizontal example 8-+ shop, sulfide + + horizontal example 9-+ sister, sulfide +-horizontal Example-+ 铊-+ Vertical 10 Example-+--+ Vertical 11 Comparative Implementation +----Vertical Example 1 (Please read the Note # 1 on the back first and then fill and install ---- Ί: write This page) Order ----- ^ The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -37- 583339 A7 B7 V. Description of the invention (35 [Table 13-2] Examples 1 to Summary of results of 11 and Comparative Example 1
處理 方法 沈積速 率（微米/ 分） 沈積銅 膜厚 (微米） 無電鍍銅 溶液之處 理時間（分） 孔隙度 (%) 銅膜 外觀 實施例1 垂直 0.01 0.05 5 26 X 實施例2 垂直 0.01 0.05 5 16 X 實施例3 垂直 0.04 0.08 2 0 X 實施例4 垂直 0.04 0.08 2 0 X 實施例5 垂直 0.06 0.06 1 0 〇 實施例6 垂直 0.06 0.06 1 0 〇 實施例7 水平 實施例8 水平 0.10 0.05 0.5 0 〇 垂直 0.06 0.075 2 N 〇 實施例9 水平 0.06 0.03 0.5 〇 X 實施例 垂直 0.06 0.06 1 0 〇 10 實施例 垂直 0.06 0.06 1 0 〇 11 比較實施 垂直 0 0 1 100 例1 0.10 20 N 經濟部智慧財產局員工消費合作社印製 註）在上表中，^ -」表示相對應的組成分係排除在外， 而「+」表示包含相對應的組成分。「N」表示未測量。 在表示銅膜外觀之列中，「〇」表示所獲得爲光亮的外觀 及金屬銅色調；而「X」表示相反結果。 38- 分?执:度藏中國國家標準(。奶）八4規格（210父297公釐） 583339 A7 B7 五、發明説明（36 ) 實施例1 2及比較實施例2 藉由水溶性鉈化合物使浴液安定化 製備如以下所示之比較實施例2及實施例12之無電 鑛銅溶液並且以無電鍍銅溶液比較其浴液安定化。 至於評估浴液安定化之方法，將包含350克/升鈀及 1 0克/升錫之觸媒添加至比較實施例2及實施例1 2之無電 鍍銅溶液。比較添加直到浴液分解變得明顯爲止之觸媒用 (請先閲讀背面之注意事 _ ▼項再填· 裝-- :寫本頁) ·訂 ▼線l· 經濟部智慧財產局員工消費合作社印製 ^3187 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -39- 583339 A7 B7 五、發明説明（37 [表 比較實施例2 浴液組成 實施例1 2 浴液組成 五水合硫 15克/升 五水合硫 15克/升 酸銅 酸銅 三乙醇胺 5毫克/升 三乙醇胺 5毫克/升 硼氫化鈉 0.5克/升 硼氫化鈉 0.5克/升 2,2’-聯吼 10毫克/ 2,2’-聯吡 10毫克/ D定 升 n定 升 硫酸銳 14毫克/ 升 pH 13.0 pH 13.0 溫度 60°C 溫度 6(TC 浴液安 浴液經添加2毫 浴液安 浴液經添加20 定性 升/升鈀溶液而 定性 毫升/升鈀溶液 分解 而分解 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 上述試驗結果發現，本發明中含水溶性鉈化合物之無 電鍍銅溶液具有1 0倍於不含水溶性鉈化合物及甲醛之無 電鍍銅溶液之浴液安定性。 實施例1 3及比較實施例3 藉由水溶性鈽化合物使浴液安定化 以比較實施例2及實施例1 2之相似方法，製備如以 準 標 家 國 國. (〇叫八4規格（210父297公釐） -40- 583339 A7 ___B7_ 五、發明説明（38 ) 下所示之比較實施例3及實施例1 3之無電鍍銅溶液。接 著以無電鍍銅溶液比較其浴液安定化。 (請先閲讀背面之注意事項再填寫本頁) 至於評估浴液安定化之方法，將包含2 0 0克/升鈀及 1 〇克/升錫之觸媒添加至比較實施例3及實施例1 3之無電 鍍銅溶液。比較添加直到浴液分解變得明顯爲止之觸媒用 [表 15] 比較實施例3 實施例13 浴液組成 浴液組成 五水合硫酸銅 15克/升 五水合硫酸銅 15克/升 三乙醇胺 5毫克/升 三乙醇胺 5毫克/升 硼氣化鈉 0.5克/升 硼氫化鈉 0.5克/升 2,2 ’ -聯吼口定 10毫克/升 2,2’-聯吡啶 10毫克/升 硫酸鈽 14毫克/升 pH 13.0 pH 13.0 溫度 60°C 溫度 60°C 浴液安定性 浴液經添加 浴液安定性 浴液經添加1 4 2毫升/升鈀 毫升/升鈀溶液 溶液而分解 而分解 經濟部智慧財產局員工消費合作社印製 由上述試驗結果發現，本發明中含水溶性鈽化合物之 無電鍍銅溶液具有7倍於不含水溶性鈽化合物之無電鍍銅 溶液之浴液安定性。 -41 · (-#〇^^用中國國家標準（匚奶）八4規格（21〇/297公釐） 583339 A7 __B7_ 五、發明説明（39 ) 實施例14及比較實施例4 藉由水溶性鈽化合物使浴液安定化 以比較實施例3及實施例1 3之相似方法，製備如以 下所示之比較實施例4及實施例1 4之無電鍍銅溶液。接 著以無電鍍銅溶液比較其浴液安定化。 至於評估浴液安定化之方法，將包含200克/升鈀及 10克/升錫之觸媒添加至比較實施例4及實施例14之無電 鍍銅溶液。比較添加直到浴液分解變得明顯爲止之觸媒用 (請先閲讀背面之注意事項再填寫本頁) #1 項再填. 裝· 丨If 經濟部智慧財產局員工消費合作社印製 汾氏張子参缚$中國國家標準（CNS ) A4規格（210X297公釐） -42- 583339 A7 B7 五、發明説明（ 40 [表 16] 比較實施例4 實施例1 4 浴液組成 浴液組成 五水合硫酸銅 15克/升 五水合硫酸銅 15克/升 三乙醇胺 5毫克/升 三乙醇胺 5毫克/升 硼氫化鈉 0.5克/升 硼氫化鈉 0.5克/升 鐵氰化鉀 10毫克/升 鐵氰化鉀 10毫克/升 硫酸姉 14毫克/升 pH 13.0 pH 13.0 溫度 60°C 溫度 60°C 浴液安定性 浴液經添加 浴液安定性 浴液經添加 2毫升/升 14毫升/升鈀 鈀溶液而分 溶液而分解 解 由上述試驗結果發現，本發明中含水溶性鈽化合物之 無電鎪銅溶液具有7倍於不含水溶性鈽化合物之無電鍍銅 溶液之浴液安定性。 同時又發現無論層改質劑類型，例如鐵氰化鉀、2,2’-聯吡啶，皆可獲得抑制本發明浴液之分解的功效。 本發明的功效 截至目前爲止所解釋的，本發明之無電鍍銅方法可使 用含銅離子及還原劑但不含甲醛之無電鍍銅溶液在該樹脂 0^3104 L紙張元ίΚ中國國家標準(CNS ) Α4規格（210Χ 297公釐） ϋϋ i^n I ml I m 士flm —^ϋ (請先閱讀背面之注意事項再填寫本頁) --Ί.--訂------^線 經濟部智慧·財產局員工消費合作社印製 43Treatment method Deposition rate (micron / minute) Thickness of deposited copper film (micron) Processing time of electroless copper solution (minutes) Porosity (%) Appearance of copper film Example 1 Vertical 0.01 0.05 5 26 X Example 2 Vertical 0.01 0.05 5 16 X Example 3 Vertical 0.04 0.08 2 0 X Example 4 Vertical 0.04 0.08 2 0 X Example 5 Vertical 0.06 0.06 1 0 〇 Example 6 Vertical 0.06 0.06 1 0 〇 Example 7 Horizontal Example 8 Horizontal 0.10 0.05 0.5 0 〇Vertical 0.06 0.075 2 N 〇Example 9 Horizontal 0.06 0.03 0.5 〇X Example Vertical 0.06 0.06 1 0 〇10 Example Vertical 0.06 0.06 1 0 〇11Comparative Implementation Vertical 0 0 1 100 Example 1 0.10 20 N Ministry of Economic Affairs Intellectual Property Printed by the Bureau's Consumer Cooperatives Note) In the above table, ^-"indicates that the corresponding composition is excluded, and" + "indicates that the corresponding composition is included. "N" means not measured. In the column indicating the appearance of the copper film, "0" indicates the appearance obtained as bright and metallic copper hue; and "X" indicates the opposite result. 38- Separate execution: Chinese national standard (.milk) 8 4 specifications (210 mm 297 mm) 583339 A7 B7 5. Description of the invention (36) Example 1 2 and Comparative Example 2 The bath solution was stabilized. The electroless copper solutions of Comparative Examples 2 and 12 as shown below were prepared and the bath solutions were compared with the electroless copper solution. As for the method for evaluating the stabilization of the bath, a catalyst containing 350 g / L of palladium and 10 g / L of tin was added to the electroless copper plating solutions of Comparative Examples 2 and 12. Comparison of catalysts added until the bath decomposition becomes obvious (please read the precautions on the back _ ▼ items and then fill out-: write this page) · order ▼ line l · Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative Printed ^ 3187 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) -39- 583339 A7 B7 V. Description of the invention (37 [Table Comparative Example 2 Bath composition example 1 2 Bath solution Composition Sulfur Pentahydrate 15g / L Sulfur Pentahydrate 15g / L Copper Copper Ethyl Triethanolamine 5mg / L Triethanolamine 5mg / L Sodium Borohydride 0.5g / L Sodium Borohydride 0.5g / L 2,2'- Lianhua 10mg / 2,2'-bipyridine 10mg / D fixed liter n fixed liter sulfate sulfate 14mg / liter pH 13.0 pH 13.0 temperature 60 ° C temperature 6 (TC bath solution bath solution by adding 2 milliliter bath solution The ampoules were decomposed and decomposed by adding 20 qualitative liters per liter of palladium solution and qualitative milliliter per liter of palladium solution was decomposed and decomposed (please read the precautions on the back before filling out this page). Water-soluble tritium compound in the present invention The electroless copper plating solution has 10 times the bath stability of the electroless copper solution containing no water-soluble europium compound and formaldehyde. Example 13 and Comparative Example 3 The bath was stabilized by the water-soluble europium compound for comparison Example 2 and Example 12 are similar to the method, and are prepared as the standard of the home country. (〇 called eight 4 specifications (210 father 297 mm) -40-583339 A7 ___B7_ V. Description of the invention (38) Compare the electroless copper plating solutions of Example 3 and Example 13. Then compare the bath stabilization with the electroless copper plating solution. (Please read the precautions on the back before filling this page) As for the method of evaluating the bath stabilization A catalyst containing 200 g / L of palladium and 10 g / L of tin was added to the electroless copper plating solution of Comparative Examples 3 and 13. The catalysts were added until the bath decomposition became apparent. [Table 15] Comparative Example 3 Example 13 Bath composition Bath composition 15 g copper sulfate pentahydrate / l copper sulfate pentahydrate 15 g / liter triethanolamine 5 mg / liter triethanolamine 5 mg / liter sodium boron gasification 0.5 g / l sodium borohydride 0.5 g / l 2,2 '-coupling Houkouding 10mg / L 2,2'-bipyridine 10mg / L Rhenium Sulfate 14mg / L pH 13.0 pH 13.0 Temperature 60 ° C Temperature 60 ° C Bath Stability Bath Addition Bath Stability Bath It was decomposed and decomposed by adding 142 ml / liter of palladium / liter of palladium solution and decomposed by printing. It was found by the above-mentioned test results that the electroless copper solution containing water-soluble europium compounds in the present invention has 7 times Bath stability in an electroless copper plating solution containing no water-soluble europium compounds. -41 · (-# 〇 ^^ In accordance with Chinese National Standard (匚 奶) 八 4 size (21〇 / 297 mm) 583339 A7 __B7_ V. Description of the invention (39) Example 14 and Comparative Example 4 The hydrazone compound stabilized the bath to compare Example 3 and Example 13 in a similar manner, and prepared the electroless copper plating solutions of Comparative Example 4 and Example 14 shown below. Then, the electroless copper plating solutions were compared. Bath solution stabilization. As a method for evaluating bath solution stabilization, a catalyst containing 200 g / L of palladium and 10 g / L of tin was added to the electroless copper plating solutions of Comparative Examples 4 and 14. The addition was continued until the bath For catalysts until the liquid decomposition becomes obvious (please read the precautions on the back before filling out this page) # 1 then fill in. Packing 丨 If printed by Fen's Zhang Zi Participant Co-operation of the Intellectual Property Bureau of the Ministry of Economic Affairs $ 中国National Standard (CNS) A4 specification (210X297 mm) -42- 583339 A7 B7 V. Description of the invention (40 [Table 16] Comparative Example 4 Example 1 4 Bath composition Bath composition 15 g copper sulfate pentahydrate Copper sulfate pentahydrate 15 g / l triethanolamine 5 mg / l trihydrate Alcoholamine 5 mg / L sodium borohydride 0.5 g / L sodium borohydride 0.5 g / L potassium ferricyanide 10 mg / L potassium ferricyanide 10 mg / L sulfuric acid 14 mg / L pH 13.0 pH 13.0 Temperature 60 ° C Temperature 60 ° C. Stability bath solution. Addition of bath solution. Stability bath solution is decomposed and decomposed by adding 2ml / l 14ml / l palladium and palladium solution. It was found from the above test results that the present invention contains a water-soluble europium compound. The electroless copper solution is 7 times more stable than the electroless copper solution without water-soluble europium compounds. It is also found that regardless of the type of layer modifier, such as potassium ferricyanide, 2,2'-bipyridine, The effect of suppressing the decomposition of the bath liquid of the present invention can be obtained. The effect of the present invention has been explained so far. The electroless copper electroplating method of the present invention can use an electroless copper electroplating solution containing copper ions and a reducing agent but no formaldehyde in the resin. 0 ^ 3104 L Paper Yuan ί Chinese National Standard (CNS) Α4 size (210 × 297 mm) ϋϋ i ^ n I ml I m 士 flm — ^ ϋ (Please read the precautions on the back before filling this page) --Ί .-- Order ------ ^ Wisdom of Ministry of Economy Property Office employees consumer cooperatives printed 43