201223357 六、發明說明： 【發明所屬之技術領域】 【先前技術】 近年來在印刷電路板的配線高密度：:：：刷電路板: 板和組裝技術的印刷電路板應用又中、：、：例如在薄 化，為了避免絕緣性不佳的問題路的微細 縫度較小之㈣，但使用粗化 ^使用減面的粗 基材料熱壓合後，有點八 、把X小的銅箔與樹脂 佳，則在製造過程中和做問題’如果黏合力不 板、剝離或漂料脫層的㈣電路會出現爆 面會預先進行粗二:喊使電路板用㈣之表 到較高的黏合、接荖❹"層豐於樹脂基材料後可得 露一種銅落表面粗化處^的^日=公昭54·38〇53揭 一定量的選自下列的至小―在酸性鑛銅浴中加入 並在大於極限電流密；：種：屬:砷、銻、鉍、硒及碲’ 中加入，、錦、叙、：:：：電鑛：文中提出於物谷 在上述的方法中使 :°㈣成細小的凸出物，但 應用在印刷電路拓 鉍、硒或碲等毒性的物質 重的環境問題 〃廢棄蝕刻液、鍍液等會引起嚴 3/22 201223357 【發明内容】 本發明之貫施例提供一種經粗化處理的銅箔，包含： 一銅箔，其具有一被接著面；以及一設於該被接著面上的 複合金屬層，其中該複合金屬層係具有以下所示之組份 (A )、組份（b )與組份（c )形成之微細粗化粒子，其 中’組份（A):銅；組份（B):由第瓜八族元素及碟所組 成之群組中所選出的至少一種元素；以及組份（C):由鐵、 鉻、鈷、釩、鎳、鋅、鎢、錫、鋇及錳所組成之群組中所 選出的至少一種金屬元素。 本發明實施例更提供一種經粗化處王里的銅落的冑造® 方法’包含以下步驟：提供—銅笛，其具有—被接著面； 將該銅箔浸入一電鍍浴中，該電鍍浴具有以下組成： (j ):銅離子，其濃度為1〇至15〇克/升；（π ):由第冚 Α族元素及磷所組成之群組所選出的至 其濃度為…⑽鹏；⑻：由鐵 鋅、錫、鎢、鋇及錳所組成之群組所選出的至少一種金屬 元素離子，其漢度為1至簡鹏；以及進行—電鍍步驟， 使該被接著面上成型有一複合金屬層，其中該複合金屬層 係具有以下所示之組份⑷、組份⑻與組份（C)开^ 成之微細粗化粒子，其中，組份（A)··銅；組份（B):由> 第ΠΙΑ族το素及磷所組成之群組中所選出的至少—種_ 素；以及組份（C):由鐵、鉻、銘、妞、錄、鋅、鶴、錫兀 鋇及錳所組成之群組中所選出的至少一種金屬元素。 元辛ί發二!Γ有益的效果:本發明採用較為環保的 兀素進仃銅浴的表面改質，經過實驗後，可獲致一種環保 4/22 201223357 二化處理方法及經粗化處理的鋼箱，進而得到粗面形狀 二粗T的銅羯’應用於印刷電路㈤㈤*」 =_ B〇=)、賴覆晶封裝（Chip 〇η η6χ)、軟 (FlexPnntClrcuit)等領域具有良好之黏合力。 板 為使能更進-步瞭解本發明之特徵二 =以下有關本發明之詳細說明與附圖，然而下述之發= 明以及所附圖式僅提供參考盥 加以限制者。 ’I非㈣對本發明 【實施方式】 本發明利用組份（A):銅；組 磷的至少其中之一.纟日^ r r）.苐m a奴το素、 n Wc)鐵、鉻、鈷、釩、鎳、鋅、 鎢、錫、鋇、錳的至少苴一 ”、 毒性的m 性的元素取代具有 而可得到粗面形狀均勻且粗丁銅箱之粗化處理， 可應用於印刷電路板，以製造糊 而解決傳統利用坤、録、级等：：f:要求’進 行銅落粗化處理，卻次蹄寺“有母性的元素進 本發明所提出㊃污㈣問題。 括以下步驟： 、，工粗化處理的銅羯的製造方法可包 本發明箱，其具有-被接著面(s-)。 箱（又稱原料銅=陰極’以進行後述的電鑛步驟，而銅 係使用電解銅落:行電解銅落、壓延銅羯等，本發明 接著’將該鋼^入:電链浴中，以利用電鍵方式在 5/22 201223357 ·,，， 銅箔之被接著面上成型複合金屬層。請參考表―，其為本 元 素含量 銅 (g/l) 硫 酸 (g/l) 姻 (ppm) 碌 (ppm) 鐵 (PPm) 絡 (ppm) 姑 (PPm) 鎢 (ppm) 蜾 (PPm) 石申 (ppm) 電鍍 浴溫 度rc) 電流密 度 (A/dm2) 處理 時間 (sec.) 電鍍浴 A 2U.i 9b 1200 5 40 30 3 電鍍浴 B 2ϋ.ί> 9b 150 5 40 30 3 電鏟浴 C 20.5 95 1200 150 5 40 30 3 電鍍浴 D 20.5 9b 500 600 5 40 30 3 冤鍍浴 E 20.5 9b 1200 50 40 30 3 電錄 >谷 F 20.5 95 150 50 40 30 3 電鍍浴 G 20.5 9b 500 600 1000 40 30 Λ 電鍍浴 Η 20.5 9i) 500 600 450 40 30 3 表一201223357 VI. Description of the invention: [Technical field to which the invention pertains] [Prior Art] In recent years, the wiring density of printed circuit boards has been high: :::: brush circuit board: printed circuit board application of board and assembly technology, and: For example, in the case of thinning, in order to avoid the problem of poor insulation, the fineness of the road is small (4), but after roughing and using the rough-based material of the reduced surface, it is a little eight, and the copper foil with a small X is Resin is good, in the manufacturing process and do the problem 'If the adhesion is not plate, peeling or bleaching delamination (four) circuit will appear the explosion surface will be pre-roughed two: shouting the board with the (four) table to a higher bond接 荖❹ quot 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层 层Add and add in the limit current density;: species: genus: arsenic, antimony, bismuth, selenium and strontium', jin, sui, :::: electric ore: proposed in the article in the above method: ° (d) into small protrusions, but applied to printed circuit topography, selenium or Environmental problems of toxic substances such as hydrazine, etched etching liquid, plating solution, etc. may cause severeness. 3/22 201223357 SUMMARY OF THE INVENTION The present invention provides a roughened copper foil comprising: a copper foil, And having a composite metal layer disposed on the surface to be bonded, wherein the composite metal layer has the composition (A), component (b) and component (c) shown below Finely roughened particles, wherein 'component (A): copper; component (B): at least one element selected from the group consisting of a group of elements and dishes; and component (C): At least one metal element selected from the group consisting of iron, chromium, cobalt, vanadium, nickel, zinc, tungsten, tin, antimony, and manganese. The embodiment of the present invention further provides a method for manufacturing a copper drop in a roughened portion, comprising the steps of: providing a copper flute having a surface to be bonded; immersing the copper foil in a plating bath, the plating The bath has the following composition: (j): copper ion at a concentration of 1 〇 to 15 gram per liter; (π): selected from a group consisting of a steroidal element and phosphorus to a concentration of (10) Peng; (8): at least one metal element ion selected from the group consisting of iron, zinc, tin, tungsten, niobium and manganese, the degree of which is from 1 to Jianpeng; and the electroplating step to make the surface Forming a composite metal layer, wherein the composite metal layer has finely roughened particles of the composition (4), the component (8) and the component (C) shown below, wherein the component (A)·· copper; Component (B): at least one selected from the group consisting of > ΠΙΑ τ τ 及 and phosphorus; and component (C): from iron, chrome, Ming, Niu, Lu, Zinc At least one metal element selected from the group consisting of: crane, tin bismuth and manganese. Yuan Xin Li Fa 2! ΓBeneficial effect: The invention adopts a relatively environmentally friendly surface modification of the bismuth copper bath, and after the experiment, an environmental protection 4/22 201223357 dimerization treatment method and roughening treatment can be obtained. The steel box, and then the matte shape of the rough-faced two-thick T is applied to the printed circuit (5) (5) *" =_ B〇 =), the laminated chip package (Chip 〇η η6χ), soft (FlexPnntClrcuit) and other fields have good adhesion. force. The present invention is described in detail with reference to the accompanying drawings in which: FIG. 'I non (four) to the present invention [Embodiment] The present invention utilizes component (A): copper; at least one of the group phosphorus. 纟 ^ ^ rr). 苐ma slave το, n Wc) iron, chromium, cobalt, Vanadium, nickel, zinc, tungsten, tin, antimony, manganese, at least one", and a toxic m-type element substitution can be obtained to obtain a rough surface shape and roughening of a thick copper box, which can be applied to a printed circuit board. To solve the traditional use of Kun, record, grade, etc.::f: requires 'to carry out copper roughening treatment, but the second hoof temple "the mother of the elements into the four dirty (four) problems raised by the invention. The method includes the following steps: The manufacturing method of the copper ruthenium for roughening treatment may include a box of the present invention having a suffix (s-). a box (also referred to as raw material copper = cathode) to perform an electric ore step to be described later, and a copper system using electrolytic copper falling: electrolysis copper falling, rolling copper crucible, etc., and the present invention then 'incorporates the steel into the electric chain bath, The composite metal layer is formed on the bonded surface of the copper foil by means of a key switch on 5/22 201223357 ·,,, please refer to the table, which is the content of copper (g/l) sulfuric acid (g/l). ) (ppm) Iron (PPm) Complex (ppm) Amount (PPm) Tungsten (ppm) 蜾 (PPm) Shishen (ppm) Electroplating bath temperature rc) Current density (A/dm2) Processing time (sec.) Electroplating bath A 2U.i 9b 1200 5 40 30 3 Electroplating bath B 2ϋ.ί> 9b 150 5 40 30 3 Electric shovel bath C 20.5 95 1200 150 5 40 30 3 Electroplating bath D 20.5 9b 500 600 5 40 30 3 冤 plating bath E 20.5 9b 1200 50 40 30 3 Electrologue> Valley F 20.5 95 150 50 40 30 3 Electroplating bath G 20.5 9b 500 600 1000 40 30 Λ Electroplating bath Η 20.5 9i) 500 600 450 40 30 3 Table 1
Rza (β m) 黏合強度a (Ib/in) 殘餘鋼 粉末脫落 實施例1 5.33 7.9 無 無 實施例2 5.57 8.2 益 «««\ 無 ^ If'J 5 5.43 8.6 無 —— 無 貫施例4 5.25 7.6 無 無 實施例5 5.35 7.7 無 無 實知例6 5.67 8.1 無 無 貫把例7 6.41 7.2 7個直徑約 20-50個直徑約 10 # m顆粒 2-10 // m 顆粒 比較例1 6.30 8.5 益 無 表二 註：a表示測試5次之數值平均值 以下將洋細說明表一所述之實驗例： 實驗例1 6/22 201223357 (1)原料鋼羯（厚度 • 10%硫酸溶液20秒。 m)於粗化處理前先酸浸於 ’浸於清洗乾淨後，將原料鋼羯 理’電鑛浴組成以及；::=^糙面的粗化處 浸於清洗乾淨後，將原料㈣ 粗化粒子之複輔助電錢浴中將㈣上之微細 •較佳是10幻5〇1古 以覆蓋’其中銅離子濃度 2〇〇g/卜此牛㈣曰升)’而硫酸濃度較佳是30至 粗化層或：層= 結構斷裂造成於 σ至屬層上’使其避免複合金屬層 免短現象，制於PCB中可避 程。㈣生或姓刻不全的問題發生，其可為—必要製 >，=)依順序重複進行步驟2以及步驟3 —次、兩次或多 •二::：的在於提升包覆層的表面微細粗化粒子的電著量 .層均句=2 ’以及加強微細粗化粒子之複合金屬層被包覆 曰二復盍，以有效地抑制剝離現象（落粉）的發生。 (5)❹絲子水將粗域理後的㈣清洗乾淨後 t處理後的㈣在室溫、PH=3.75的16g/1重鉻酸納二 水3物水溶液中浸泡10秒，以形成防銹層。 5斤（6)進行殘銅和粉末脫落試驗以及黏合強度的測定：將 鋼謂的f合表面對著相應於FR-4的玻纖-環氧樹脂浸潰基 f進仃鍾’製造覆鋪疊物，將覆銅層疊物裁切出鋼落 見度為Imm的試片。根據JIS 6481，在室溫下測定該試片 7/22 201223357 =箱和樹脂基材之間的黏合強度，試驗結果如表二所 實驗例2 (υ原料銅箱（厚度18 職硫酸溶液20秒。㈣）於粗化處^先酸浸於 ⑺使用去離子水將原料銅 浸於粗化處理的電鑛㈣ 料銅泪 電鑛浴組成《及電鍍條件如純面㈣化處理， 去離子轉原料銅料洗乾淨後， fe化妆w人成助㈣浴中將㈣上之微細 :交佳二〇 Γ:广屬層的表面加以覆蓋，其中銅離子濃度 7 〇 g/I (克/升），而硫酸濃度較佳是30至 〇 =。此步驟的目的係、在於成型包覆層（又稱保護層、 t盖囊層）於複合金屬層上，使其避免複合金屬層 、·，。構斷裂造成粉落現象以及_現象，應用於PCB中可避 〇 免紐路的發生或蝕刻不全的問題發生，其可為一必要製 程。 ^ (4)依順序重複進行步驟2以及步驟3 __次、兩次或多 、其目的在於提升包覆層的表面微細粗化粒子的電著量 以及均勻，’以及加強微細粗化粒子之複合金屬層被包覆 層均勻覆蓋，以有效地抑制剝離現象（落粉）的發生。 / (5)使用去離子水將粗化處理後的銅箔清洗乾淨 後將粗化處理後的銅羯在室溫、ρΗ=3·75 # ^重絡 酸納二水合物水溶液中浸10秒形成防銹層。 ⑹進行殘銅和粉末n試驗以及黏合強度的測定，將 8/22 201223357 銅箔的黏合表面對著相應於FR_4的玻纖_環氧樹脂浸潰基 ^進行叠壓，製造覆銅層疊物，將覆銅層疊物裁切出銅箱 見度為lmm的試片。根據JIS 6481，在室溫下測定該試片 的銅治和樹脂基材之間的黏合強度，試驗結果如表二所 示。 X驗例 (1)原料銅咱（厚度18/zm)於粗化處理前先酸浸於 10%硫酸溶液20秒。 、 ⑺使用去離子水將原料_清洗乾淨後，將原料銅笔 浸於粗化處理的電鑛W中進行銅落粗綠面的粗化處理， 電鑛洛組成以及電鍍條件如表一所示： ^理 (^)使用去離子水將原料㈣清洗乾淨後，將原料 =、及硫酸組成的辅助電祕中將㈣上之微細 二圭:金屬層的表面加以覆蓋，其中鋼離子濃度 孕乂佳疋10至150 〇71丨、 g/ι。此步驟的二^：=硫酸漠度較佳是30至 、’r、在於成型包覆層（又稱伴 粗化層或膠囊層）於複合 ％保邊層、 結構斷裂造成粉落頊意 曰上’使“避免複合金屬層 免短路的發生或蝕刻不全 、中可避 程。 +王的問通發生’其可為一必要製 ⑷依順序重複進行步驟2以 —a ^ 次，其目的在於提升包覆 —人、兩-人或多 以及均勻性，以及Λ故 表面微細粗化粒子的電著量 層均勻覆蓋，以==化粒子之複合金屬層被包覆 欠將粗化處理後的鋼箱清洗乾淨 9/22 201223357 後，將粗化處理後的銅箔在室溫、ρΗ=3·75的丄6 / 酸鈉一水合物水溶液中浸1 〇秒形成防銹層。 絡 (6)進行殘銅和粉末脫落試驗以及黏合強度的 . 銅镇，合表面對著相應於F R _ 4的玻纖·環“：产= 材進行豐壓，製造覆銅層疊物，將覆銅層4物裁切出^ 寬度為lmm的試片。根據JIS 6481，在室溫下 = 的銅箱和樹脂基材之間的黏合強度，試驗結果如表二 示0 τ 實驗例4 ⑴原料銅箱（厚度…m)於粗化處理前先酸浸於 10%硫酸溶液20秒。 、 ，⑺使用去離子水將原料㈣清洗乾淨將原料銅落 浸於粗化處理的電鍍浴D中進行銅箔粗糙面的粗化 理，電鍍浴組成以及電鍍條件如表一所示。 * (3)使用去離子水將原料銅落清洗乾淨後，將原料銅荡 :叉於由銅以及硫酸組成的輔助電鍍浴中將銅箔上之微细 粗化粒子之複合金屬層的表面加以覆蓋产 較佳是…。卿升)，而硫酸漠度較佳是= 2〇〇g/l。此步驟的目的係在於成型包覆層（又稱保護層、 粗化層或職層）於複合金屬層上，使其避免複合金屬層 結構斷裂造成㈣現象以及轴縣，應㈣PCB中可避 免紐路的發生或蝕刻不全的問題發生，其可為一必要製 程。 A (4)依順序重複進行步驟2以及步驟3 —次、兩次或多 人其目的在於提升包覆層的表面微細粗化粒子的電著量 10/22 201223357 = 以及加強微細粗化粒子之複合金屬層被包覆 曰句勻覆盍，以有效地抑制剝離現象（落粉）的發生。 (5)使用去離子水將粗化處理後的銅 將粗化處理後的銅羯在官〜Η_，月冼乾乎後 一 此， 白在至，皿、PH—3·75的].6 g/丨重鉻酸鈉 一水5物水溶液中浸泡1〇秒，以形成防銹層。 ⑹進行殘銅和粉末脫落試驗以及黏合 =的=表:對著相應於…的玻纖·環氧樹脂浸潰基 &造覆銅層疊物’將覆銅層疊物裁切出銅箱 見又為1mm的試片。根據JIS 6481，在室溫 的㈣和樹脂基材之間的黏合強度，試驗結果如表二^ 不 ° 實驗例5 ⑴原料㈣（厚度…m)於粗化處 ]〇%硫酸溶液20秒。 & ^d ^使用去離子水將原料㈣清洗乾淨後，將原料銅绪 π於粗化處理的電鍍浴E中進行銅落粗糙面的粗化處理， 私鍍浴組成以及電鍍條件如表一所示。 ，於去離子水將原料㈣清洗乾淨後，將原料銅箱 ===:組成的輔助電_將㈣上之微細 、’、 複α i屬層的表面加以覆蓋，其中銅離子濃 較佳是10至150 Γ古/也、 卞，辰度 g (克/升），而硫酸濃度較佳是30至 g此步驟的目的係在於成型包覆層（又稱保 ⑽層或膠囊層）於複合金屬層上，使 ； 結構斷裂造成料縣以及_縣，應⑽咖中^ 免短路的發生或㈣不全的問題發生，其可為—必要製 11/22 201223357 程。 (4)依順序重複進行步驟2以及步驟3 一次、兩次或多 次’其目的在於提升包覆層的表面微細粗化粒子的電著量 以及均勻性，以及加強微細粗化粒子之複合金屬層被包覆 層均勻覆蓋’以有效地抑制剝離現象（㈣）的發生。 (5)使用去離子水將粗化處理後的銅箔清洗乾淨後， 將粗化處理後的㈣在室溫、pH=3 75的16g/l重鉻酸納 二水合物水溶液中浸泡1〇秒，以形成防銹層。 ⑹進行殘銅和粉末脫落試驗以及黏合強度的測定：將 銅落的黏合表面對著相應於FR_4的玻纖_環氧樹脂浸潰基 材進行疊壓，製造覆銅層疊物，將覆銅層叠物裁切出銅箱 寬度為1mm的試片。根據JIS 6481，在室溫下測定該試片 的銅箱和樹絲材之間的黏合·，試驗結果如表二所 示。 實驗例6 18/^m)於粗化處理前先酸浸於 (1)原料銅箔（厚度 10%硫酸溶液20秒。 ❶ (2)使帛去離子水將射4㈣清洗乾淨後，將原料鋼令 浸於粗化處理的電祕F t進行銅絲糙面的粗化處理/ 電鑛/谷組成以及電錢條件如表一所示。 、（3)使用去離子水將原料㈣清洗乾淨後，將原料鋼《 浸於由銅以及硫酸組成的辅助電鑛浴中將銅箱上之微; 粗化粒子之複合金屬層的表面加以覆蓋，其中鋼離子 車乂佳疋1〇至150 g/1 (克/升）’而硫酸濃度較佳是3〇 " 2聲此步驟的目的係在於成型包覆層（又稱保護層 12/22 201223357 囊層i於複合金屬層上，使其避免複合金屬層 '° ;造成粉落現象以及殘銅現象，應用於PCB中可避 免短路的發生或I虫刻不全的問題發生，其可為—必要製 程0 a (甘4)依順序重複進行步驟2以及步驟3 -次、兩次或多 、’、目的在於提升包覆層的表面微細粗化粒子的電著量 屏生’以及加強微細粗化粒子之複合金屬層被包覆 曰二勻復盍，以有效地抑制剝離現象（落粉）的發生。 將相使用去離子水將粗化處理後的㈣清洗乾淨後， 將後的銅箱在室溫、pH=3 75的_重絡酸納 -水3物水溶液中浸泡]()秒，以形成防錄層。 銅銅和粉末脫落試驗以及黏合強度的測定··將 材進^二表面對著相應於FR_4的玻纖·環氧樹脂浸潰基 :广製造覆銅層疊物，將覆銅層疊物裁切出銅羯 =m:的試片。根據JIS 6481，在室溫下測定該試片 ;銅泊和樹脂基材之間的黏合強度，試驗結果如表二所 實驗例7 (厚4 18_)於粗化處理前先酸浸於 iU/❶‘酸溶液20秒。 浸於切補㈣清洗乾淨後’將原料銅箱 理，G中進行銅絲链面的粗化處 电鍍洽組成以及電鍍條件如表一所示。 浸於====原料㈣清洗乾淨後，將原料㈣ ”文組成的輔助電鍍浴中將銅箔上之微細 13/22 201223357 粗化粒子之複合金屬層的表面加以覆蓋，其中銅離子濃度 較佳是10至150 g/丨（克/升），而硫酸濃度較佳是30至 200g/l。此步驟的目的係在於成型包覆層（又稱保護層、 粗化層或膠囊層）於複合金屬層上，使其避免複合金屬層 結構斷裂造成粉落現象以及殘銅現象，應用於pCB中可避 免短路的發生或蝕刻不全的問題發生，其可為一必要製 程。 (4)依順序重複進行步驟2以及步驟3 一次、兩次或多 -人其目的在於提升包覆層的表面微細粗化粒子的電著量❶ 以及均勻性，以及加強微細粗化粒子之複合金屬層被包覆 層均勻覆蓋，以有效地抑制剝離現象（落粉）的發生。 (5)使用去離子水將粗化處理後的銅箔清洗乾淨後， 將粗化處理後的㈣在室溫、pH=3 75的丨㈣重絡酸納 二水合物水溶液中浸泡10秒，以形成防銹層。 ^(6)進行殘銅和粉末脫落試驗以及黏合強度的測定：將 銅羯的，合表面對著相應於FR_4的玻纖_環氧樹脂浸潰基 ^進行豐壓，製造覆銅層疊物，將覆銅層叠物裁切出銅羯❶ 寬度為1mm的試片。根據JIS 6481，在室溫下測定該試片 的銅落和樹脂基材之間的黏合強度，試驗結果如表二所 示。 比較例1 (1) 原料銅泊（厚度於粗化處理前先酸浸於 10%硫酸溶液20秒。 ' (2) 使用去離子水將原料銅箱清洗乾淨後，將原料銅羯 浸於粗化處判電翁Η巾進㈣絲㈣的粗化處 14/22 201223357 理，電鍍浴組相及_條件如表—所干。 浸於===:銅_乾淨後’將原料㈣ 粗化粒子之複合金屬層的表:加 =;中= =…(克/升)，二度 相二：驟的目的係在於成型包覆層（又稱保護層、 =;囊層)於複合金屬層上，使其避免複合金屬層 、，，°構斷放造成粉落現象以及殘銅現象，應用於PCB中可避 :短路的發生或蝕刻不全的問題發生，其可為一必要製 ^⑷依順序重複進行步驟2以及步驟3 -次咱次或多 -人，其目的在於提升包覆層的表面微細粗化粒子的電著量 以及均勻性’以及加強微細粗化粒子之複合金屬層被包覆 層均勻覆蓋，以有效地抑制剝離現象（落粉）的發生。 (5)使用去離子水將粗化處理後的銅羯清洗乾淨後， 將粗化處理後的銅箱在室溫、pH=3 75的l 6g/l重鉻酸納 二水合物水溶液中浸泡10秒，以形成防銹層。 (6)進行殘銅和粉末脫落試驗以及黏合強度的測定：將 鋼箔的黏合表面對著相應於FR_4的玻纖_環氧樹脂浸潰基 材進行豐壓，製造覆銅層疊物，將覆銅層疊物裁切出銅箔 寬度為lmm的試片。根據JIS 6481，在室溫下測定該試片 的銅磘和樹脂基材之間的黏合強度’試驗結果如表二所 不 。 請配合表一及表二，其申根據十點平均粗度（RZ)分 析’由表二中貫施例1、2及實施例5、6可知添加填元素 15/22 201223357 進行粗化處理所得到之銅箔的平均粗度略高，由掃描型電 子顯彳政4兄照像圖發現利用鱗（P )元素進行粗化處理所得 到之銅箔之被接著面（Matte side)結構，於波峰有較細 長的樹枝狀結構生成；而利用第]ΠΑ族元素之銦（In)元 素進行粗化處理所得到之銅箔之被接著面結構，可有效的 抑制波峰的樹枝狀結構生成，且於波谷有較多的微細粗化 粒子生成。 實施例4以鐵（Fe)、鉻（Cr)以及鎢（w)三種金屬 元素進行粗化處理可得到較低的平均粗度（約5.25以爪），❸ 但其黏合強度（約7.6Ib/in);實施例M及實施例5_6其 平均粗度（5.33//m至5.67 ym)相較於比較例】之平均 粗度（約6.3/zm)有明顯較低，而且上述實驗例所製作之 銅箔與FR-4熱壓板後也具有良好的黏合強度（約7.7 Ib/in 至 8.6 Ib/in)。 根據黏合強度之分析，由表二之實施例丨_2及實施例 5-6發現添加鱗⑺元素進行粗化處理所得到之銅箱對於 FR-4樹脂有較高的黏合強度，此為添加鱗（p)元素進行❶ 粗化處理所得到之銅结之被接著面結構，於波峰有較細長 ，樹枝狀結構生成’而此樹枝狀結構有增強銅落與叩_4 树月曰黏合強度的效果’藉由碌元素之濃度以及電錢條件的 控制可於銅落之被接著面結構的波峰得到適當高度的樹 枝狀結構’應用於印刷電路板可有效避免細現象的發 生。 實施例3利用銦（In)、鱗（P)及鶴（w)進行粗化 處理’相較於實施例2利用磷⑴及鎢（w)進行粗化 16/22 201223357 处里貝把例3之黏合強度較南，由掃描型電子顯微鏡照 像圖發現，添加銦（In)元素進行粗化處理所得到之銅箔 之被接著面結構，於波谷有較多的微細粗化粒子生成，可 有效提高銅箔與FR-4樹脂的表面接觸面積，相對也提高 銅箔與FR-4樹脂黏合強度。Rza (β m) Bonding strength a (Ib/in) Residual steel powder shedding Example 1 5.33 7.9 None Example 2 5.57 8.2 Yi «««\ No ^ If'J 5 5.43 8.6 None - No application 4 5.25 7.6 None Example 5 5.35 7.7 Nothing to Know Example 6 5.67 8.1 Nothing to pass Example 7 6.41 7.2 7 diameters about 20-50 diameters about 10 # m particles 2-10 // m Particles Comparative Example 1 6.30 8.5 Benefits No Note 2: a indicates the numerical average of the test 5 times. The following is an example of the experiment described in Table 1: Experimental Example 1 6/22 201223357 (1) Raw material steel 羯 (thickness • 10% sulfuric acid solution 20 Second. m) before the roughening treatment, first acid immersion in the 'immersion in the clean, the raw material steel 羯理' electric ore bath composition and;::=^ rough surface of the roughened area is immersed in the clean, the raw materials (4) The coarsening of the particles in the auxiliary electric money bath will be fine on (4) • It is preferably 10 illusion 5〇1 ancient to cover 'the concentration of copper ions is 2〇〇g/Bu this cow (four) soaring)' and the concentration of sulfuric acid is higher. Good is 30 to the rough layer or: layer = structural fracture caused by σ to the genus layer 'to avoid the composite metal layer to avoid short phenomenon, made in the PCB can be avoided . (4) The problem of incompleteness of birth or surname occurs, which may be - necessary system >, =) Repeat steps 2 and 3 in sequence - once, twice or more • 2::: to raise the surface of the cladding The electric quantity of the finely roughened particles. The layer average sentence = 2 ' and the composite metal layer reinforcing the finely roughened particles are coated with the second retanning to effectively suppress the occurrence of the peeling phenomenon (falling powder). (5) After removing the coarse-grained water from the coarse-grained soil, (4) after the t-treatment, (4) soaking in a 16g/1 aqueous solution of sodium dichromate dihydrate at room temperature and pH=3.75 for 10 seconds to form an anti- Rust layer. 5 kg (6) for residual copper and powder shedding test and determination of adhesive strength: the steel f-surface is made to face the glass fiber-epoxy impregnating base corresponding to FR-4 The laminate was cut into a test piece having a steel drop visibility of 1 mm. According to JIS 6481, the test piece 7/22 201223357 = bonding strength between the box and the resin substrate was measured at room temperature, and the test results are as shown in Table 2 of the experimental example 2 (the raw material copper box (thickness 18 working sulfuric acid solution for 20 seconds) (4)) in the roughening area, first acid leaching (7) using deionized water to immerse the raw material copper in the roughened electric ore (4) material copper tear electric mine bath composition and plating conditions such as pure surface (four) treatment, deionization After the raw material copper material is cleaned, the fe makeup w is made into a helper. (4) The bath is fined on the (4): Jiaojia Erqi: The surface of the wide layer is covered, and the copper ion concentration is 7 〇g/I (g/L). The concentration of sulfuric acid is preferably from 30 to 〇 =. The purpose of this step is to form a coating layer (also called a protective layer, a capping layer) on the composite metal layer to avoid the composite metal layer. The phenomenon of powder breakage and _ phenomenon caused by the fracture of the structure is applied to the PCB to avoid the occurrence of the nucleus or the incomplete etching, which may be a necessary process. ^ (4) Repeat steps 2 and 3 in sequence. _ times, twice or more, the purpose of which is to increase the electric power of the finely roughened particles on the surface of the coating layer The amount and uniformity, and the composite metal layer reinforcing the finely roughened particles are uniformly covered by the coating layer to effectively suppress the occurrence of peeling phenomenon (falling powder). / (5) Using deionized water to roughen the treated After the copper foil is cleaned, the roughened copper crucible is immersed in an aqueous solution of ρΗ=3·75 # ^ hydroxyaluminate dihydrate for 10 seconds to form a rustproof layer. (6) Performing residual copper and powder n test and The bonding strength was measured by laminating the bonding surface of 8/22 201223357 copper foil against the glass fiber _ epoxy resin impregnation base corresponding to FR_4 to produce a copper clad laminate, and cutting the copper clad laminate to copper. A test piece having a box visibility of 1 mm. The bonding strength between the copper rule and the resin substrate of the test piece was measured at room temperature according to JIS 6481, and the test results are shown in Table 2. X Test Example (1) Raw material copper咱 (thickness 18/zm) is acid immersed in 10% sulfuric acid solution for 20 seconds before roughening treatment. (7) After cleaning the raw material with deionized water, the raw material copper pen is immersed in the roughened electric ore W. The coarsening treatment of the copper-thick green surface, the composition of the electro-mine and the plating conditions are shown in Table 1: (^) After using the deionized water to clean the raw materials (4), the raw materials = and the auxiliary components of the sulfuric acid composition (4) on the surface of the metal layer: the metal ion concentration is good. 10 to 150 〇71丨, g/ι. The sulphuric acidity of this step is preferably 30 to, 'r, in the molding coating (also known as the coarse layer or the capsule layer) in the composite % The edge layer and the structural fracture cause the powder to fall on the ' 使 使 使 使 避免 避免 避免 避免 避免 避免 避免 避免 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合 复合Step 2 is -a ^ times, the purpose of which is to improve the coating - human, two - person or more and uniformity, and even the surface of the finely roughened particles of the surface of the fine-grained particles are evenly covered, to == composite particles of the composite metal After the layer is covered, the roughened steel box is cleaned 9/22 201223357, and the roughened copper foil is immersed in a 丄6/sodium monohydrate aqueous solution at room temperature and ρΗ=3·75. 1 〇 second to form a rust-proof layer. (6) Residual copper and powder shedding test and adhesion strength. Copper town, the surface of the glass fiber ring corresponding to FR _ 4: production = material for abundance, copper laminate, will be covered The copper layer 4 was cut out to have a test piece having a width of 1 mm. According to JIS 6481, the bonding strength between the copper box and the resin substrate at room temperature was as shown in Table 2. 0 τ Experimental Example 4 (1) Raw material The copper box (thickness...m) is acid immersed in a 10% sulfuric acid solution for 20 seconds before the roughening treatment., (7) The raw material (4) is cleaned with deionized water, and the raw material copper is immersed in the roughened electroplating bath D. The roughening of the rough surface of the copper foil, the composition of the plating bath and the plating conditions are shown in Table 1. * (3) After the raw material copper is cleaned by using deionized water, the raw material is copper: the fork is composed of copper and sulfuric acid. In the auxiliary plating bath, it is preferred to cover the surface of the composite metal layer of the finely roughened particles on the copper foil, and the sulfuric acid is preferably 2 〇〇g/l. The purpose of this step is It is formed on a composite metal layer by forming a coating layer (also called a protective layer, a roughening layer or a job layer) The phenomenon of (4) cracking caused by the failure of the composite metal layer structure and the problem of the occurrence of incomplete etching or incomplete etching in the PCB may be a necessary process. A (4) Repeat steps 2 and 3 in sequence. The secondary, secondary or multi-person purpose is to increase the electrical flux of the surface of the coating layer to finely coarsen the particles 10/22 201223357 = and to strengthen the finely roughened particles of the composite metal layer is coated with 曰 匀 盍 盍Inhibition of the occurrence of peeling phenomenon (falling powder). (5) Using deionized water to roughen the copper after the roughening treatment of the copper enamel in the official ~ Η _, the moon 冼 后 一 , , , , Soak the dish for 1 〇 〇 〇 〇 PH PH PH PH PH PH PH PH PH PH PH 〇 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 ( ( ( ( ( ( ( ( 水溶液 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The glass-coated epoxy resin impregnated base & copper-clad laminate corresponding to ... was cut out of the copper-clad laminate and the test piece was again 1 mm. According to JIS 6481, at room temperature (4) The bonding strength between the resin and the resin substrate, the test results are shown in Table 2. No. Experimental Example 5 (1) Raw materials (4) Thickness...m) at the roughing point] 〇% sulfuric acid solution for 20 seconds. & ^d ^ After cleaning the raw material (4) with deionized water, the raw material copper π is roughened in the plating bath E for rough copper The roughening treatment of the surface, the composition of the private plating bath and the plating conditions are shown in Table 1. After the raw material (4) is cleaned in deionized water, the raw material copper box ===: the auxiliary electric _ composed of (4) ', the surface of the complex α i layer is covered, wherein the copper ion concentration is preferably 10 to 150 Γ ancient / also, 卞, 度 g (g / liter), and the sulfuric acid concentration is preferably 30 to g of this step The purpose is to form a coating layer (also known as a protective layer (10) layer or a capsule layer) on the composite metal layer, so that the structural fracture causes the county and the county to be (10) the occurrence of a short circuit or (4) incomplete problems. It can be - the necessary system 11/22 201223357. (4) Repeat steps 2 and 3 in sequence, once, twice or more. The purpose is to increase the electrical quantity and uniformity of the surface roughened particles of the coating layer, and to strengthen the composite metal of the finely roughened particles. The layer is uniformly covered by the coating layer to effectively suppress the occurrence of the peeling phenomenon ((4)). (5) After the roughened copper foil is cleaned with deionized water, the roughened (4) is immersed in a 16 g/l aqueous solution of sodium dichromate dihydrate at room temperature and pH=3 75. Seconds to form a rustproof layer. (6) Performing residual copper and powder shedding test and measuring the bonding strength: laminating the bonding surface of the copper falling surface against the glass fiber-epoxy impregnated substrate corresponding to FR_4 to produce a copper clad laminate, and laminating the copper clad A test piece with a copper box width of 1 mm was cut out. According to JIS 6481, the adhesion between the copper box and the tree material of the test piece was measured at room temperature, and the test results are shown in Table 2. Experimental Example 6 18/^m) Acid immersion in (1) raw material copper foil (thickness 10% sulfuric acid solution for 20 seconds) before roughening treatment. ❶ (2) After deionized water was sprayed 4 (four), the raw materials were removed. The steel is immersed in the roughened electric fissure F t to roughen the rough surface of the copper wire / the composition of the electric ore / valley and the electricity and money conditions are shown in Table 1. (3) The raw material (4) is cleaned with deionized water. After that, the raw material steel is immersed in an auxiliary electric ore bath composed of copper and sulfuric acid to cover the surface of the composite metal layer of the roughened particles; wherein the steel ion 乂 乂 疋 1〇 to 150 g /1 (g/L) and the concentration of sulfuric acid is preferably 3〇" 2 The purpose of this step is to form a coating layer (also known as protective layer 12/22 201223357 capsule layer i on the composite metal layer, Avoid the composite metal layer '°; cause powder drop phenomenon and residual copper phenomenon, can be avoided in the PCB to avoid the occurrence of short circuit or I insect insufficiency, which can be - necessary process 0 a (Gan 4) repeat in order Step 2 and Step 3 - times, twice or more, ', the purpose is to increase the surface of the coating layer The composite screen of the amount of screen and the finely roughened particles are coated and entangled to effectively suppress the occurrence of peeling (falling powder). The phase is cleaned by deionized water after the roughening treatment. After cleaning, the copper box was immersed in an aqueous solution of sodium hydride/water 3 at room temperature and pH=3 75 for () seconds to form an anti-recording layer. Copper-copper and powder shedding test and adhesion strength Measurement·· The surface of the material was placed against the glass fiber/epoxy resin impregnation group corresponding to FR_4: a copper-clad laminate was widely produced, and the copper-clad laminate was cut out to have a test piece of copper 羯=m: JIS 6481, the test piece was measured at room temperature; the bond strength between the copper poise and the resin substrate, and the test results were as shown in Table 2, Experimental Example 7 (thickness 4 18 _), before the roughening treatment, acid immersion in iU/❶ 'Acid solution for 20 seconds. Immersion in the cut-off (four) after cleaning, 'the raw material copper box, G in the copper wire chain surface roughening plating composition and plating conditions as shown in Table 1. Immersion ==== After the raw material (4) is cleaned, the fine material of the copper foil is 13/22 201223357 roughened particles in the auxiliary plating bath composed of the raw materials (4) The surface of the composite metal layer is covered, wherein the copper ion concentration is preferably 10 to 150 g/丨 (g/L), and the sulfuric acid concentration is preferably 30 to 200 g/l. The purpose of this step is to form a coating layer ( Also referred to as a protective layer, a rough layer or a capsule layer on the composite metal layer, so as to avoid the phenomenon of powder falling and copper residue caused by the fracture of the composite metal layer structure, and the problem of occurrence of short circuit or incomplete etching can be avoided in pCB. , which can be a necessary process. (4) Repeat steps 2 and 3 in sequence, once, twice or more - the purpose is to increase the electrical quantity 均匀 and uniformity of the surface roughened particles of the coating layer. And the composite metal layer reinforcing the finely roughened particles is uniformly covered by the coating layer to effectively suppress the occurrence of peeling phenomenon (falling powder). (5) After the roughened copper foil is cleaned with deionized water, the roughened (iv) is immersed in a solution of cerium (tetra) aqueous solution of dibasic acid dihydrate at room temperature for 3 seconds at room temperature for 10 seconds. To form a rustproof layer. ^(6) Performing the residual copper and powder shedding test and the determination of the adhesive strength: the copper-clad, the surface of the matte is condensed against the glass fiber-epoxy resin impregnating base corresponding to FR_4 to produce a copper-clad laminate. The copper clad laminate was cut out to have a test piece having a copper crucible having a width of 1 mm. The bond strength between the copper drop of the test piece and the resin substrate was measured at room temperature according to JIS 6481, and the test results are shown in Table 2. Comparative Example 1 (1) Copper boride of the raw material (thickness was first immersed in a 10% sulfuric acid solution for 20 seconds before the roughening treatment. ' (2) After cleaning the raw material copper box with deionized water, the raw material copper crucible was immersed in the coarse The chemical section of the electrician Η 进 进 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 The table of the composite metal layer of the particles: plus =; medium = = ... (g / liter), second phase two: the purpose of the step is to form a coating layer (also known as a protective layer, =; capsule layer) in the composite metal layer On the other hand, it avoids the phenomenon of powder metal falling and the phenomenon of residual copper caused by the composite metal layer, and is applied to the PCB to avoid: the occurrence of short circuit or incomplete etching occurs, which can be a necessary system (4) Step 2 and step 3 are repeated in sequence, the purpose of which is to increase the electric quantity and uniformity of the surface of the coating layer and to refine the composite metal layer of the finely roughened particles. The coating is evenly covered to effectively suppress the occurrence of peeling (falling powder). (5) Using deionized water to roughen After the copper crucible was cleaned, the roughened copper box was immersed in an aqueous solution of 16 g/l sodium dichromate dihydrate at room temperature and pH=3 75 for 10 seconds to form a rustproof layer. Residual copper and powder shedding test and determination of adhesive strength: the adhesive surface of the steel foil is subjected to ablation under the glass fiber-epoxy impregnated substrate corresponding to FR_4 to produce a copper clad laminate, and the copper clad laminate A test piece having a copper foil width of 1 mm was cut out. According to JIS 6481, the adhesion strength between the copper ruthenium and the resin substrate of the test piece was measured at room temperature. The test results are shown in Table 2. Please refer to Table 1 and Table 2, the application is based on the ten-point average roughness (RZ) analysis. The average of the copper foil obtained by the roughening treatment by adding the filling element 15/22 201223357 is known from the examples 1, 2 and 5 and 6 in Table 2. The thickness is slightly higher, and the surface of the copper foil obtained by the roughening treatment using the scale (P) element is found by the scanning electron show, and the slender branches are formed in the peak. The formation of a structure; and the use of the indium (In) element of the cerium element for roughening The bonded surface structure of the copper foil can effectively suppress the formation of the dendritic structure of the peak, and there are many fine coarsened particles in the trough. Example 4 is iron (Fe), chromium (Cr), and tungsten (Example 4). w) The roughening of the three metal elements gives a lower average roughness (about 5.25 centimeters), but its bond strength (about 7.6 Ib/in); the average thickness of Example M and Example 5_6 (5.33) //m to 5.67 ym) is significantly lower than the average thickness of the comparative example (about 6.3/zm), and the copper foil produced in the above experimental example has good adhesion to the FR-4 hot plate. Strength (about 7.7 Ib/in to 8.6 Ib/in). According to the analysis of the adhesive strength, the copper box obtained by the addition of the scale (7) element for roughening treatment from the examples 丨_2 and the examples 5-6 of Table 2 has a higher adhesive strength for the FR-4 resin, which is added. The squall (p) element is subjected to ❶ roughening treatment to obtain the continuum structure of the copper junction, which is relatively slender in the peak, and the dendritic structure is formed, and the dendritic structure has the adhesion strength of the copper drop and the 叩_4 tree 曰The effect of 'the density of the lumps and the control of the electricity money conditions can be obtained at the appropriate height of the dendritic structure of the copper to the peak of the junction surface structure' can be applied to the printed circuit board to avoid the occurrence of fine phenomena. Example 3: Roughening treatment using indium (In), scale (P), and crane (w) 'Compared with phosphorus (1) and tungsten (w) in Example 2, 16/22 201223357 The adhesion strength is relatively south. It is found by the scanning electron microscope photographic image that the copper foil obtained by the indium (In) element is subjected to the roughening treatment, and the surface of the copper foil is formed in the trough, and more coarse coarse particles are generated. Effectively increase the surface contact area between the copper foil and the FR-4 resin, and relatively increase the bonding strength between the copper foil and the FR-4 resin.
由表二發現未添加銦（In)或磷（P)元素進行微細粗 化粒子複合金屬的粗化處理，例如：實施例4及實施例7， 所得到的經粗化處理銅箔與FR_4熱壓板後，其黏合強度 (7.6 Ib/in、7.2 Ib/in)相較於有添加銦（In)或磷（p) 之實施例】-3及實施例5_6(7.7Ib/in至86ib/in)為低。It is found from Table 2 that the indium (In) or phosphorus (P) element is not added to carry out the roughening treatment of the finely roughened particle composite metal. For example, in Example 4 and Example 7, the obtained roughened copper foil and FR_4 heat are obtained. After pressing, the bond strength (7.6 Ib/in, 7.2 Ib/in) is compared to the example with added indium (In) or phosphorus (p) -3 and Example 5_6 (7.7 Ib/in to 86ib/ In) is low.
、/根據上述實驗例的結果，本發明將銅箔浸入電鍍浴中 進仃電鍍，以生成複合金屬層’而該電鍍浴具有以下組 成：（I ):銅離子，其濃度為10至15〇克/升，較佳為2〇·5 克/升·’（ n )··由銦及磷所組成之群組所選出的至少一種元 素離子’其濃度為1至15〇0ppm，較佳為15〇至135〇卯爪· ⑻：由鐵、鉻、钻、釩、鎳、鋅、錫、嫣、鋇及錳所 =成之群組所選出的至少-種金屬元素離子，其濃度為i 至2500卯111;較佳為5至21〇〇卯111。 再者，進行電錢的步驟中，電锻之電鍍浴溫度為 至65C ’例如為4(TC ;電流密度為！至％安 二广例如為3。安培/平方公寸（a/ 。 間為1至30秒、，例如為3#。 更錢 金屬層之電鐘步驟之後更可包括成型 該鋼箱與該複合金屬層浸入輔助電 冷中’⑽成鋼質的包覆層，所述的輔助電鑛浴具^ 17/22 201223357 .， 為】0至150克/升之銅離子及濃度為30至2〇〇克/升之硫 酸，該辅助電鍍浴溫度為10至65t：，電流密度為i至5〇 安培/平方公寸（A/dm2)，電鍍時間為1至30秒；且成型 複合金屬層的步驟與成型包覆層的步驟係重覆依序進行 電鍍一次或者兩次以上，以形成交錯重覆設置的該複合金 屬層與該包覆層，進而提高黏合強度，以解決落粉、剝離 的現象。 絲上所述，本發明依據上述具體實施例的方法，製作 出-種經粗化處理的銅㉖，其包含：_及成型於該銅落 之被接著面上的複合金屬層；該複合金屬層係具有以下所 示之組份⑷、組份⑻與組份（c)形成之微細粗化 粒子，其中，組份⑷：銅；組份⑻：由第财族元素 及磷所組成之群組中所選出的至少一種元素，直中第瓜八 族元素係包括蝴⑻、銘㈤、鎵（Ga)、銦（in)、銘 (T1);以及組份（C):由鐵、絡、錄、鈒、錄、鋅、鶴、 錫、鋇及益所組成之群組中所選出的至少一種金屬元素。 而以第料素之銦與及刺組成之群組中所選出的至 ^一種 分析，該複合金屬層之組份 ^〇〇〇〇,g/d^ 選㈣至少-種元素所組成的該複 =金屬層之（B)的附著量係介於 g/dm，該複合金屬層之纟 至謂心/仏而該包覆=):附著量係介於約10 50000至35_0 _m2。 ^者里係"於約 化處理之原料銅箱的掃描 ^^圖1 ’其為未經粗 子.4U鏡（SEM)照片；而 18/22 201223357 '貝2:驗例3所得的經粗化處理之銅箔的粗化處理面 μ著面）之掃插型電子顯微鏡照片。 、二IS處=明=:細上述之複合金屬層 防銹層m展 τ根據產品品要’在包覆層上形成 :^ s、偶合劑處理層及/或抗熱層等等，其中 ::丄抗氧化層以及抗熱層可以為銅鋅合金層、鎳鋅銦 曰鋅5金層、鉻酸鹽層或者鎳鈷鉬層等等。 鲁本發明」Γ/堇為本發明之較佳可行實施例，非因此词限 所為二 故舉凡運用本發明說明書及圖示内容 寻指錢化，均包含於本發明之範圍内。 【圖式簡單說明】 =為未經粗化處理之原料銅㈣掃描型電子顯微鏡照 之經粗化處理之銅箱的粗化處理面之掃描 1玉子顯微鏡照片。 【主要元件符號說明】 無 19/22According to the results of the above experimental examples, the present invention immerses the copper foil in an electroplating bath to form a composite metal layer, and the electroplating bath has the following composition: (I): copper ions, the concentration of which is 10 to 15 〇克 / liter, preferably 2 〇 · 5 g / liter · '( n ) · at least one elemental ion selected from the group consisting of indium and phosphorus' has a concentration of 1 to 15 〇 0 ppm, preferably 15〇至135〇卯爪·(8): At least one metal element ion selected from the group consisting of iron, chromium, diamond, vanadium, nickel, zinc, tin, antimony, bismuth and manganese, the concentration of which is i Up to 2500 卯 111; preferably 5 to 21 〇〇卯 111. Furthermore, in the step of performing the electric money, the electroplating bath temperature of the electric forging is up to 65 C ', for example, 4 (TC; current density is from ! to % An Erguang, for example, 3. Amperes per square inch (a/. 1 to 30 seconds, for example, 3#. The electric clock step of the metal layer may further comprise molding the steel box and the composite metal layer immersed in the auxiliary electric cooling '(10) into a steel coating layer, Auxiliary electric bath bath ^ 17/22 201223357 ., is 0 to 150 g / liter of copper ions and a concentration of 30 to 2 g / l of sulfuric acid, the auxiliary plating bath temperature is 10 to 65t:, current density For i to 5 amps per square inch (A/dm2), the plating time is 1 to 30 seconds; and the step of molding the composite metal layer and the step of forming the cladding layer are sequentially plated one or more times. The composite metal layer and the coating layer are formed in a staggered manner to improve the bonding strength to solve the phenomenon of falling powder and peeling. According to the method of the above specific embodiment, the present invention produces - a roughened copper 26 comprising: _ and a complex formed on the surface of the copper drop a metal layer; the composite metal layer having finely roughened particles formed by the component (4), the component (8) and the component (c) shown below, wherein the component (4): copper; the component (8): the element of the fiscal class And at least one element selected from the group consisting of phosphorus, and the elements of the group of the third group include the butterfly (8), the inscription (5), the gallium (Ga), the indium (in), the inscription (T1); and the component (C) ): at least one metal element selected from the group consisting of iron, complex, recorded, sputum, recorded, zinc, crane, tin, antimony, and beneficial, and the group consisting of indium and thorn of the first element In the analysis selected from the above, the composition of the composite metal layer, g/d^ (4) at least one element of the complex metal layer (B) g/dm, the composite metal layer is 谓 to pre-heart/仏 and the coating =): the adhesion amount is between about 10 50000 and 35_0 _m2. ^^Fig. 1 'It is not a rough. 4U mirror (SEM) photograph; and 18/22 201223357 'Bei 2: the roughened surface of the roughened copper foil obtained in Test Example 3 is facing the surface) Sweep type Micrograph. , 2 IS = Ming =: fine above the composite metal layer anti-rust layer m τ according to the product product to be formed on the cladding layer: ^ s, coupling agent treatment layer and / or heat resistant layer, etc., where: The antimony oxide layer and the heat resistant layer may be a copper-zinc alloy layer, a nickel zinc indium antimony zinc 5 gold layer, a chromate layer or a nickel cobalt molybdenum layer or the like. The present invention is a preferred embodiment of the present invention, and is not intended to be a limitation of the present invention. [Simple description of the drawing] = Scanning of the roughened surface of the roughened copper box for the copper material which has not been roughened (4) Scanning electron microscope 1 Jade microscope photo. [Main component symbol description] None 19/22