經濟部智慧財產局員工消費合作社印製 A7 --— B7 *--------- - •五、發明說明（l ) [發明之詳細說明] [發明所屬技術領域] 本發明有關電錢方法，特別是有關無鉛之電錢且能連 續形成可焊接特性良好的金屬材料之電錢膜的電鍍方法。 [以往之技術] 使用Sn(錫）單體或Sii合金之電鍍層被覆如銅）單 >體或Cu含金或Fe-Ni(鐵-鎳）合金的導電元件之表面的導線 Oeed)材，係具有Cu單體或Cu合金所具備的優異的導電 性與機械性強度，且亦併有Sn單體或以合金所具備的气 蝕性及良好的可焊接性的高性能導體，而多用在如各種端 子、連接器（connector)、導線的電氣、電子器具領域或電 力電纜之領域。 又’如將半導體晶片裝載於電路基板的情形，一般採 用於半導體晶片之外導線部施予使用Sll合金的熔融電鍍 |或電鍍，以改善該外導線部之可焊接性。如此的Sll合金 之代表性例為焊劑（s〇lder)(Sn-Pb(錫-鉛）合金），而由於可 焊接性、耐餘性等良好之故，廣用為連接器或導線架（lead frame)等的電氣、電子工業用零件之工業用電鍍。 然而，由於軟焊條所使用的pb對人體有害之故其有 害性受人重視，而有世界性規範Pb之使用的趨勢。如例 如被廢棄在屋外的電子機械類等被酸性雨淋曬時，則從機 械内部所使用的軟焊條（Sn_Pb合金）或電子零件之表面所 施的錫焊電鍍流出Pb，由此原因，地下水或河川被污染。 為防止環境污染，最好的方法係使用不含Pb的Sn合金。 丨 —1! — · I i — — — — — — β — 蘿 -----I ·線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公嫠） 1 312338 A7 ----~-----B7 _ 五、發明說明（2 ) 因此，逐漸有替代以往的Sn-Pb電鍍液而不含Pb的新電 鍛之開發。並且已有不含Pb而以Sn為主成分的電鍍液， 例如仏-出（錫_鉍）系、Sn-Ag(錫-銀）系、Sn_Cu系之電鍍液 之開發並正在被替代中。 第3圖係表不導線材之基本構成的剖面圖。例如，導 屯兀件21係由以Cu、Cu為主成分的&系合金，或者以 Fe-Ni為主成分的Fe_Ni系合金所構成。並且，在此導電元 件21之表面實施有相異的金屬材料之2層電鍍膜。例如按 Sn之第1電鍍膜22及Sn_Bi之第2電鍍膜23之順序所形 成^在此，如設第1電鍍膜22之厚度為、、第2電鍍膜 23之厚度為h時，如設定、為約3至15 # m、、為約i至 5从m、q/q為約（^至〇5時，在成本之層面，錫焊焊接、 耐熱眭方面，再者錫焊之接合強度或與鋁線等之熔接部之 熔接強度之面均有良好的特性，由於可獲得作為導線材的 性犯改善之故，一般認為好用。 第4圖係自動電鍍裝置整體之佈置圖。首先，於鹼電 解清洗浴槽31中，進行阻礙導電元件21之表面的錫焊電 鍍被膜之密著性或可焊接性的油脂等之有機性污染物質之 去除。接著，在水洗用浴槽32内經清洗後在化學蝕刻浴槽 33内進行化學蝕刻處理（基本上為利用氧化_還元反應的處 理），將因粒塊或混雜物等的存在而成為不均勻的表面的導 電元件21表面使之均勻化。 接著，在水洗用浴槽34經清洗後，在酸活性化浴槽 35内將去除在水洗用浴槽34所附著的氧化膜。接著，在 本紙張尺度適用中關家標準（CNS)A4規格（21G >c 297公爱）--- 2 312338 -----------_·裝 (請先閱讀背面之注意事項再填寫本頁) ----訂ί # 經濟部智慧財產局員工消費合作社印製 506100 經濟部智慧財產局員工消費合作社印製 3 A7 五、發明說明（3 ) 水洗用浴槽36經清洗後，在焊劑電鍍（s〇lder phating)裝置 37施予電鍍。由於焊劑電鍍液係強酸性之故，電鍍後之表 面已成為酸性。在如此的表面，隨著時間之經過而被膜將 變色，可焊接性將劣化。因此，在水洗用浴槽38、中和處 理浴槽39中，中和電鍍表面所殘留的酸並去除所吸著的有 機物。其後，在水洗用浴槽40、溫水洗用浴槽41中進行 _清洗，並在乾燥裝置中進行經電鍍的導電元件之乾燥。 第5圖係在以往之電鍍裝置37中施行電鍍的部分之詳 細的佈置圖。在此電鍍方法中，係在預潰（predip)浴槽371 中浸潰導電元件21以去除表面之氫氧化膜，並浸潰在第i 電鍍浴槽372之電鍍液中施予第}電鍍膜22後，將導電元 件浸潰於第1電鍍浴槽372之電鍍液與第2電鍍浴槽374 之電鐘液之間所設置的水洗用浴槽373之純水中以去除電 鍍液，接著，將導電元件21浸潰於第2電鍍浴槽374之電 丨鍍液並施予第2電鍍臈23。最後，在水洗用浴槽375進行 電鍍面之情況。 在上述的電鍍方法中，施予第i電鍍膜22的第丨電鍍 浴槽372之電鍍液，與施予第2電鍍膜23的第2電鍍浴槽 374之電鍍液，如除去構成各別的電鍍液的金屬材料及使 其/合解的酸性溶劑，則並非為同樣的液構成者。例如，如 第1電鍍膜22為由Sn單體而成而第2電鍍膜23為由Sn-Bi 合金而成的情形，第1電鍍浴槽372及第2電鍍浴槽374 之電鍍液之構成，關於有機酸、溶劑以及純水而言，係使 用同樣的液構成的材料。但，關於添加劑而言，前者一般 [紙張尺度適用中關家標準（CNS)A4規格（210 X 297公釐） 312338 I------------^--------^------- Ί ·線 (請先閱讀背面之注意事項再填寫本頁) 506100 經濟部智慧財產局員工消費合作社印製 A7 -------- B7 _ 五、發明說明（4 ) ^ — 使用焊劑電鍍液用之添加劑’而後者一般使用sn_Bi電錢 液用之添加劑。 又，第1電鍍浴槽372及第2電鍍浴槽374使用同樣 形狀的情形較多。 如此的電鏡方法，經已於曰本專利公開特開平1〇_22 9152镜公報中所說明。 [發明擬解決的課題] 首先，如上所述，施予第1電鍍膜22的第〗電鍍浴槽 372之電鍍液，與施予第2電鍍臈23的第2電鍍浴槽374 之電鍍液，如除去構成各別的電鍍液的金屬材料及使其溶 解的酸性溶劑，則並非為同樣的液構成者σ因此，按能防 止將導電元件21所附著的第1電鍍浴槽372之電鏡液直接 帶至第2電鍍浴槽374之電鍍液内之方式，在第1電鍍浴 槽372之電鍍液與第2電鍍浴槽3 74之電鍍液之間設置有 水洗用浴槽。而且，不得不使用此水洗用浴槽373之純水 以除去第1電鍍浴槽372之電鍍液。因而，在以往之電鍍 方法中水洗用浴槽373係不可或缺者，而有需要多餘的過 程的問題。 又，於施予第2電鍍膜23的第2電鍍浴槽374之電鍍 液中，經施予第1電鍍膜22的導電元件21，在水洗用浴 槽373經清洗後，將浸潰於第2電鍍浴槽374之電鍍液。 此時，由於水洗用浴槽373之純水會混入第2電鍍浴槽374 之電鍍液内之故，第2電鍍浴槽3 74之電鍍液將被稀釋。 因而亦有一定需要第2電鍍浴槽374之電鍍液之構成管理 « n n n n n n n n n I 8 n n 8 n n I I I # (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 4 312338 506100 A7 •五、發明說明（5 ) 以及濃度管理，而工程管理方面較為複雜的問題。 再者，第1電鍍浴槽372之電鍍液及第2電鍍浴槽374 之電鍍液内所含的金屬材料，除將被電鍍於導電元件上之 外，亦會被取代析出於陽極（anode)上。但，由於構成第2 電鑛液的叫叙）、Ag以及Cu將顯著被取代析出於陽極之 故，補充其等的量亦將大幅增多。另―方面，&於金屬材 料(特別是Bl、Ag以及Cu)為高價之故，亦有成為成本高 昂的原因的問題。 [為解決課題的方法] 訂 本發明係馨於上述的以往的問題而開發I，係在導電 元件之表面施予相異的金屬材料或者雖然為同—金屬材料 但金屬材料之組成比率㈣的2層之電鍍膜的帛ι電鍍膜 及第2電鐘膜的電鑛方法，而以提供—種能縮短作該 程、簡易化濃度管理的電鍍方法為目的。 經濟部智慧財產局員工消費合作社印製 為達成上述之目的’本發明之特徵為：將第工電錢液 及第2電鍍液所包含的組成作成經去除金屬材料以及溶解 其金屬材料的酸性溶劑以外的其餘為相同的溶液组成者。 具體而言’將經去除第」電鍍液及第2電鍍液所包含的金 屬材料以及溶解其金屬材料的酸性溶劑以外的其餘有機 酸、溶劑、添加劑以及純水作成為實質上同樣的溶液組成 者。 [發明之實施形態] 第1圖，係表示為實施本發明的電鏡方法之用的自動 電鏡裝置中施予電鍵的部分的佈置圖，相當於第4圖所示 ^紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐；τ 5 312338 5〇61〇〇 經濟部智慧財產局員工消費合作社印製 6 A7 五、發明說明（6 ) 的全體電鍍裝置之焊劑電鍍裝置37者众 第1圖中’自動電鍍裝置係由預潰浴槽1、第1電鍍 冷槽2、第2浴槽3以及水洗用浴槽4所構成。在預潰浴 槽1中，去除在先前之水洗用浴槽36(參見第4圖）中清洗 之際在導電元件21(參見第3圖）所附著的氧化膜，並使導 電元件21之表面為活性狀態。第j電鍍浴槽2中，對導電 元件21施予第！電鍍膜22,然後，在第2電鍍浴槽3中， 則對導電元件21施予第2電鍍膜23。在此，電鍍膜厚按 以往之方式設第1電鍍膜22之厚度為q、前述第2電鍍膜 23之厚度為q時，施予電鍍為％為約3至i5#瓜、q為约 1至為约Ο·1至〇·5。另外，由於導線材之構造 為第3圖相同之故，將符號作成為共通者。 本發明中，係將第i電鍍浴槽2之電鍍液及第2電鍍 浴槽3之電鏡液所包含㈣！及第2金屬材料以及溶解其 金屬材料的酸性溶劑的溶液作成為相同的溶液組成者。由 此具有將導電元件21浸潰於P電鍍浴槽2之電鍍液中施 予第1電鍍膜22之後，連續能浸潰於第2電鍍浴槽3之電 鍍液中施予第2電鍍膜23的特徵。 亦即’第1電鍍浴槽2之電鑛液之組成，係將全部或 殆全部的第i金屬材料作成Sn，並去除此等金屬材料以及 溶解此等金屬材料的酸性溶劑的溶液係由有機酸、溶劑、 添加劑以及純水所構成者。例如，有機酸可包含甲續酸或 丙醇續酸、溶劑可包会1 匕各異丙醇。而且，第2電鍍浴槽3之 電鍍液之組成，係以由、Ae以；r >丄 _ Ag以及Cu之中所選擇的至少 本紙張尺度_ T國國冢標準（cns;；A4規格⑽Χ 297 312338Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 --- B7 * ----------• V. Description of the Invention (l) [Detailed Description of the Invention] [Technical Field to which the Invention belongs] Money methods, especially electroplating methods that are related to lead-free electricity money and capable of continuously forming a metal material film with good solderability characteristics. [Previous technology] The plating layer of Sn (tin) monomer or Sii alloy is used to cover copper (e.g., copper) single body or a conductive wire Oeed on the surface of a conductive element containing Cu or gold-containing or Fe-Ni (iron-nickel) alloy. It is a high-performance conductor that has the excellent conductivity and mechanical strength of Cu monomer or Cu alloy, and also has the cavitation properties and good weldability of Sn monomer or alloy. In the fields of electrical and electronic appliances such as various terminals, connectors, wires, and power cables. As for the case where a semiconductor wafer is mounted on a circuit board, it is generally used to apply molten plating or electroplating using an Sll alloy to a lead portion other than the semiconductor wafer to improve the solderability of the outer lead portion. A typical example of such an Sll alloy is a solder (Sn-Pb (tin-lead) alloy), and because of good solderability and residual resistance, it is widely used as a connector or lead frame ( Industrial plating of electrical and electronic parts such as lead frames. However, because the pb used in soft electrodes is harmful to the human body, its harmfulness is valued, and there is a tendency to regulate the use of Pb worldwide. For example, when the electronic machinery and equipment abandoned outside are exposed to acid rain, Pb flows out from the soldering electrode (Sn_Pb alloy) used on the inside of the machine or the surface of the electronic parts. Or rivers are polluted. To prevent environmental pollution, the best method is to use Sn alloys without Pb.丨 —1! — · I i — — — — — — — β — Lo ----- I · Line (Please read the precautions on the back before filling out this page) This paper size applies to Chinese national standards (CNS > A4 specifications (210 X 297 males) 1 312338 A7 ---- ~ ----- B7 _ V. Description of the invention (2) Therefore, there are gradually new electric forgings that replace the previous Sn-Pb plating bath without Pb. Developed. And there are Pb-free and Sn-based electroplating baths, such as thorium-out (tin-bismuth) -based, Sn-Ag (tin-silver) -based, and Sn-Cu-based plating solutions. The figure 3 is a cross-sectional view showing the basic structure of the wire. For example, the guide member 21 is made of Cu and Cu-based & series alloy, or Fe-Ni-based Fe_Ni series. It is made of an alloy. On the surface of the conductive element 21, a two-layer plating film of a different metallic material is implemented. For example, it is formed in the order of the first plating film 22 of Sn and the second plating film 23 of Sn_Bi ^ here For example, if the thickness of the first plating film 22 is, and the thickness of the second plating film 23 is h, if it is set, it is about 3 to 15 # m, for about i to 5, from m, and q / q is about ( ^ To At 5 o'clock, in terms of cost, in terms of soldering and heat resistance, in addition, the bonding strength of soldering or the strength of welding with aluminum wires and other welding parts have good characteristics. It is generally considered to be useful for improvement. Figure 4 is the overall layout of the automatic plating device. First, in the alkaline electrolytic cleaning bath 31, the adhesion of the solder plating film on the surface of the conductive element 21 may be blocked. Removal of organic pollutants such as weldable grease. Then, after washing in the water-washing bath 32, chemical etching treatment (basically a treatment using oxidation_reduction reaction) is performed in the chemical etching bath 33, and the particles The surface of the conductive element 21 which becomes a non-uniform surface due to the presence of a block or a foreign matter is uniformized. Then, after washing in the water washing bath 34, the acid activation bath 35 will be removed and attached to the water washing bath 34 Next, apply the Zhongguanjia Standard (CNS) A4 specification (21G > c 297) in this paper standard --- 2 312338 -----------_ install (please Read the notes on the back first (Fill in this page) ---- 定 ί # Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 506100 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 A7 V. Description of the invention (3) After washing 36, Solder phating device 37 applies electroplating. Because the flux plating solution is strongly acidic, the surface after electroplating has become acidic. On such a surface, the film will change color with time and weldability Will deteriorate. Therefore, in the water-washing bath 38 and the neutralization treatment bath 39, the acid remaining on the plated surface is neutralized and the adsorbed organic matter is removed. Thereafter, washing is performed in the water bath 40 and the warm water bath 41, and the electroplated conductive element is dried in a drying device. Fig. 5 is a detailed layout diagram of a portion where plating is performed in the conventional plating apparatus 37. In this electroplating method, the conductive element 21 is immersed in a predip bath 371 to remove the hydroxide film on the surface, and is immersed in the plating solution of the i-th plating bath 372 and the second plating film 22 is applied. The electroconductive element is immersed in pure water in a water washing bath 373 provided between the electroplating solution of the first electroplating bath 372 and the electric clock liquid of the second electroplating bath 374 to remove the electroplating solution. Then, the electroconductive element 21 is immersed The electroplating solution that has collapsed in the second plating bath 374 is applied to the second plating bath 23. Finally, in the case of a water-washing bath 375, the surface is plated. In the above-mentioned electroplating method, the plating solution of the first plating bath 372 applied to the i-th plating film 22 and the plating solution of the second plating bath 374 applied to the second plating film 23 are removed. Metal materials and acidic solvents that dissolve / dissolve them are not the same liquid constituents. For example, if the first plating film 22 is made of Sn alone and the second plating film 23 is made of Sn-Bi alloy, the constitution of the plating solution of the first plating bath 372 and the second plating bath 374 is as follows. Organic acids, solvents, and pure water are made of the same liquid. However, with regard to additives, the former is generally [paper size applies to Zhongguanjia Standard (CNS) A4 specification (210 X 297 mm) 312338 I ------------ ^ ------ -^ ------- 线 · Line (Please read the notes on the back before filling out this page) 506100 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 -------- B7 _ V. Description of the Invention (4) ^ — Use of additives for flux plating solution ', and the latter generally uses additives for sn_Bi electrolyte solution. The first plating bath 372 and the second plating bath 374 often use the same shape. Such an electron microscope method has been described in Japanese Patent Laid-Open Publication No. Hei 10-22 22152. [Problems to be Solved by the Invention] First, as described above, the plating solution of the first plating bath 372 applied to the first plating film 22 and the plating solution of the second plating bath 374 applied to the second plating bath 23 are removed. The metal materials constituting the respective plating baths and the acidic solvents that dissolve them are not the same bath composition σ. Therefore, it is possible to prevent the electron microscope liquid of the first plating bath 372 to which the conductive element 21 is attached from being brought directly to the first bath. In the plating solution in the 2 plating bath 374, a bath for washing is provided between the plating solution in the first plating bath 372 and the plating solution in the second plating bath 3 74. Further, pure water in the water washing bath 373 has to be used to remove the plating solution in the first plating bath 372. Therefore, in the conventional electroplating method, the bath 373 for water washing is indispensable, and there is a problem that an unnecessary process is required. Furthermore, in the plating solution of the second plating bath 374 to which the second plating film 23 is applied, the conductive element 21 to which the first plating film 22 is applied is washed in the bath 373 for washing, and then immersed in the second plating Bath 374 plating solution. At this time, since the pure water in the water washing bath 373 is mixed into the plating solution in the second plating bath 374, the plating solution in the second plating bath 3 74 is diluted. Therefore, there must be a need for the composition management of the plating solution in the second plating bath 374. «nnnnnnnnn I 8 nn 8 nn III # (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 4 312338 506100 A7 • Fifth, the description of the invention (5) and concentration management, but the project management is more complicated. In addition, the metal material contained in the plating solution of the first plating bath 372 and the plating solution of the second plating bath 374 will not only be electroplated on the conductive element but also be deposited on the anode. However, due to the composition of the second electric mineral fluid), Ag and Cu will be significantly replaced and precipitated in the anode, and the amount of supplementation will also increase significantly. On the other hand, the & price of metal materials (especially Bl, Ag, and Cu) is also a cause of high cost. [Methods for solving problems] The present invention was developed based on the above-mentioned conventional problems. The present invention is based on the application of different metallic materials on the surface of conductive elements or the same metal composition but the composition ratio of metallic materials. The two-layer electroplating film and the electroplating method of the second electric clock film are intended to provide a plating method that can shorten the process and simplify the concentration management. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to achieve the above-mentioned purpose. The present invention is characterized in that the composition contained in the second industrial liquid and the second plating solution is made into an acidic solvent by removing metal materials and dissolving the metal materials. The rest are the same solution composition. Specifically, the remaining organic acids, solvents, additives, and pure water other than the metal materials included in the first and second plating solutions and the acidic solvent in which the metal materials are dissolved are made into substantially the same solution composition. . [Embodiment of the Invention] FIG. 1 is a layout diagram of a part to which an electric key is applied in an automatic electron microscope device for implementing the electron microscope method of the present invention, which is equivalent to that shown in FIG. 4 CNS) A4 specification (210 X 297 mm; τ 5 312 338 5 6 61 00; printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 A7 V. Invention description (6) of the entire electroplating device of the solder plating device 37 people The automatic plating device in the figure 1 is composed of a pre-collapsed bath 1, a first electroplating cold bath 2, a second bath 3, and a water bath 4. In the pre-bath bath 1, the previous water bath 36 (see FIG. (Figure 4), the oxide film attached to the conductive element 21 (see Figure 3) during cleaning, and the surface of the conductive element 21 is made active. In the jth plating bath 2, the conductive element 21 is given the first! The plating film 22 is then applied to the conductive element 21 in the second plating bath 3. The second plating film 23 is applied to the conductive element 21. Here, the thickness of the plating film is set to the thickness of the first plating film 22 in the conventional manner, and the first 2 When the thickness of the plating film 23 is q, the applied plating is about 3%. i5 # melon, q is about 1 to about 0. 1 to 0. 5. In addition, since the structure of the wire is the same as that in FIG. 3, the symbols are used in common. In the present invention, the i-th plating is used. The plating solution in bath 2 and the electron microscope solution in second plating bath 3 contain 3! And the solution of the second metal material and the acidic solvent in which the metal material is dissolved to make the same solution composition. Thus, the conductive element 21 is impregnated After applying the first plating film 22 to the plating solution of the P plating bath 2, it can be continuously immersed in the plating solution of the second plating bath 3 to apply the second plating film 23. That is, the first plating bath 2 The composition of the electric mineral liquid is to make all or all of the i-th metal material into Sn, and remove the metal material and the acidic solvent that dissolves the metal material. The solution is composed of organic acids, solvents, additives and pure water. For example, the organic acid may include formic acid or propanol, and the solvent may contain 1 isopropyl alcohol. In addition, the composition of the plating solution in the second plating bath 3 is based on Ae and r; r > 丄 _ At least the paper size selected among Ag and Cu_ T country national grave standard (cns ;; A4 specification ⑽ 297 312338
Aw I ^ I — 層 1 I — I t---I ---I I (請先閱讀背面之注意事項再填寫本頁) 506100 A7Aw I ^ I — layer 1 I — I t --- I --- I I (Please read the precautions on the back before filling this page) 506100 A7
五、發明說明（7 ) 1種類之第2金屬材料及包含有帛！金屬材料的Sn者作為 金屬材料，而去除此等金屬材料以及溶解此等金屬材料的 酸性溶劑的溶液係以有機酸、溶劑、禾^如 合和添加劑以及純水所組 成。例如’與第1電鍍浴槽2同樣’有機酸中包含有甲磺 酸或丙醇績酸、溶劑中包含有異丙醇。 因此，於此電鍍方法中，即使導電元件21上附著有第 _1電鍍浴槽2之電鍍液，而被帶至第2電鍍浴槽3之電鍍 液内而混有2種電鍍液而言，由於去除第1及第2金屬材 料以及溶解其等金屬材料的酸性溶劑的其餘者作成相同的 液組成之故，第2電鍍浴槽3之電鍍液之組成不致於被攪 亂0 一般，當構成電鍍液時，金屬材料係溶解於酸性溶劑 中使用之。但，由於酸性溶劑係較電鍍液之量為極少量之 故，縱然多少被包含而言，仍不致於影響其電鍍液之組成。 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) _ 因而，將導電元件21浸潰於第1電鍍浴槽2之電鍍液 而施予第1電鍍膜22之後，即能連續將導電元件2 1浸潰 於第2電鍍浴槽3之電錢液並施予第2電鍍膜23。因此， 可省略以往的施予第1電鍍膜22之後之使用水洗用浴槽的 .洗淨，而達成作業過程以及作業時間之短縮。 接著，關於第2電鍍浴槽3之電鍍液而言，於如上所 說在本電鍍作業過程中，第1電鍍浴槽2之電鍍液將附著 於導電元件21而混入第2電鑛浴槽3之電鐘液中〇此時， 在第2電鍍浴槽3之電鍍液中，附著於導電元件21而將被 帶入第1金屬材料的Sn。但，在Bi、Ag以及Cu之中所 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公嫠） 7 312338 A7 A7 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 五、發明說明（8 ) 使用的第2金屬材料則不被帶入。再者，在Bi、Ag以及 之中所使用的第2金屬材料將作為與sn的合金而被析 岀於導電元件21之外，亦太胳技从沿、 听 足外，亦在陽極被取代析出0又，加之， 由於在其等m、Ag以及Cu之中所使用的第2金屬材料將 附著於導電元件21而姑卷屮夕从 .. 而被常出之故，比較第1金屬材料的V. Description of the invention (7) The second kind of metal material of 1 kind and contains 帛! The Sn of the metal material is regarded as the metal material, and the solution for removing the metal material and the acidic solvent in which the metal material is dissolved is composed of an organic acid, a solvent, an organic additive, and pure water. For example, "same as the first plating bath 2", the organic acid contains methanesulfonic acid or propanol, and the solvent contains isopropanol. Therefore, in this electroplating method, even if the electroplating solution of the _1 electroplating bath 2 is attached to the conductive element 21, the electroplating solution is brought into the electroplating bath of the second electroplating bath 3 and mixed with the two electroplating solutions. Because the rest of the first and second metal materials and the acidic solvent in which the metal materials are dissolved have the same liquid composition, the composition of the plating solution in the second plating bath 3 is not disturbed. Generally, when the plating solution is formed, Metal materials are used by dissolving in an acidic solvent. However, since the amount of the acidic solvent is extremely small compared with the amount of the plating solution, it does not affect the composition of the plating solution even if it is included to some extent. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) _ Therefore, the conductive element 21 is immersed in the plating solution of the first plating bath 2 and the first plating film 22 is applied That is, the conductive element 21 can be continuously immersed in the electric liquid of the second plating bath 3 and applied to the second plating film 23. Therefore, conventional washing using a bath for washing with water after the application of the first plating film 22 can be omitted, and the work process and work time can be shortened. Next, regarding the electroplating solution of the second electroplating bath 3, as mentioned above, during the electroplating operation, the electroplating solution of the first electroplating bath 2 will adhere to the conductive element 21 and be mixed into the electric clock of the second electroplating bath 3. At this time, in the plating solution of the second plating bath 3, the conductive element 21 is adhered and Sn is brought into the first metal material. However, the paper standards used in Bi, Ag, and Cu are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 gigabytes) 7 312338 A7 A7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, the paper standards are applicable to Chinese countries Standard (CNS) A4 specification (210 X 297 mm) 5. Description of the invention (8) The second metal material used is not brought in. In addition, the second metal material used in Bi, Ag, and the like will be separated from the conductive element 21 as an alloy with sn. It will also be replaced by the edge, the leg, and the anode. Precipitation of 0, in addition, because the second metal material used in the m, Ag, and Cu will adhere to the conductive element 21, and it is often rolled out .., so it is compared with the first metal material of
Sn時，其減少之情況特別顯著。 另方面，於一般的電鍍中，由於電鍍膜之厚度以及 電鍍膜组成係被電流密度、電鍍時間以及電缠液濃度所控 制之故，藉由保持電流密度、電鍍時間以及電鍍濃度為一 定，而可崎電鍍膜厚錢電鍍膜組成之管理。由此，可 管理電鍍膜上所析出的電屬材料之量或電鍍液濃度，如有 因析出而有金屬材料之減少的情形時，則予以補充即可。 第1電鍍浴槽2及第2電鍍浴槽3之電鍍液之金屬材料， 如上所述，亦有因陽極上的取代析出以及被導電元件21 被出所引起的減少。但，由於第i電鍍浴槽2及第2電鍍 浴槽3之陽極係由例如純度99.9%以上之S]Q所形成之故， 電鍍液之第1金屬材料的Sn除主要因陽極之溶解而被補 充之外，將由定期性的分析而視需要進行溶液補充。 例如，如進行Sn為100(重量％)之電鍍液之濃度管理 的情形，各別的液濃度係按能保持Sn+2濃度為30至60(克 /公升）、游離酸濃度為120至160(克/公升）、添加劑濃度 為20至50(克/公升）之間的電鍍液之濃度之方式進行§11之 管理。但，如上所述，在第1電鍍浴槽2之管理中，由於 有Sn的陽極溶解之故，不需要如第2電鍍浴槽3的頻繁 312338 n n n n n ϋ n n« n I I · n n n n n n n 一 ：0¾ β I i Is Bi «8 II ϋ I (請先閱讀背面之注意事項再填寫本頁) 五、發明說明（9 ) 的管理。 ς在第2電鍵浴槽3之電鑛液中，由於第i金屬材料的 Sn’將如前述，被因陽極之溶解而補充之故，主In the case of Sn, the decrease is particularly significant. On the other hand, in general electroplating, since the thickness of the electroplated film and the composition of the electroplated film are controlled by the current density, the electroplating time, and the concentration of the entangled liquid, by keeping the current density, electroplating time, and electroplating concentration constant, The management of Kizaki plated film thick money plated film composition. Thereby, the amount of the electric metal material deposited on the plating film or the concentration of the plating solution can be managed, and if there is a decrease in the metal material due to the precipitation, it can be supplemented. As described above, the metal materials of the plating solution in the first plating bath 2 and the second plating bath 3 also have a reduction caused by the substitution precipitation on the anode and the extraction by the conductive element 21. However, since the anodes of the i-th plating bath 2 and the second plating bath 3 are formed of, for example, S] Q having a purity of 99.9% or more, the Sn of the first metal material of the plating solution is mainly supplemented by the dissolution of the anode. In addition, solution replenishment will be performed as needed by periodic analysis. For example, if the concentration management of a plating solution with Sn of 100 (wt%) is performed, the respective solution concentrations are such that the Sn + 2 concentration can be maintained at 30 to 60 (g / liter) and the free acid concentration is 120 to 160. (G / L), and the concentration of the plating solution with an additive concentration of 20 to 50 (g / L) is subject to §11. However, as described above, in the management of the first plating bath 2, since the anode of Sn is dissolved, it is not necessary as frequently as the second plating bath 3 312338 nnnnn ϋ nn «n II · nnnnnnn 1: 0¾ β I i Is Bi «8 II ϋ I (Please read the precautions on the back before filling out this page) V. Management of invention description (9). In the electric mineral liquid of the second key bath 3, since the Sn ′ of the i-th metal material will be replenished due to the dissolution of the anode as described above, the main
Sn顯著曲較少的*Bl、Ag以及Cu之中所選擇的第2金屬乂 材料之濃度進行管理即可。 例如，如進行U，重量％):3(重量％)之電錢液 >之濃度官理的情形，各別的濃度係按能保持農度為 至州克/公升）、ΒΓ3濃度為3·〇至4 2(克/公升）、游離酸 濃度為120至160(克/公升）、添加劑濃度為⑽至叫毫升/ 公升）之間的電鍍液之方式進行⑴之管理。 經濟部智慧財產局員工消費合作社印製 如上述之方式，由於可依流水線作業的作業速度之一 定化，且將第1電鍍浴槽2及第2電鍵浴槽3中的電流密 度為一定之故，第2電鐘浴槽3之第2金屬材料的 以及Cu之濃度管理亦變成容易。亦即，在第2電鍍浴槽3 中，藉由Bi、Ag以及Cu之第2金屬材料之定期性補充而 將可簡單地進行濃度管理》結果，可保持第2電鍍浴槽3 之電鍍液之金屬材料濃度為一定而使第2電鍍膜23之膜厚 以及電鍍膜組成為均勻。 ” 亦即，於此電鍍方法中，藉由第1電鍍浴槽2及第2 電鐘浴槽3中的電流密度設定為最適電流密度，而可達成 金屬析出粒徑之均勻化及抑制2層的膜厚比率之偏差乂由 此，在依流水線作業的作業速度之一定化且在一定電流密 度下的電鍍方法中，如電鍍膜厚tl、t2能滿足之關係 時，設導電元件21移動第1電鍍液内的距離為Dl、導電 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 312338 506100 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（10 ) 元件2 1移動第2電鍍液内的距離為時，則Di、d2能成 立Di>D2之關係，係自明之理。 再者，第2圖係表示第1電鍍浴槽2與第2電鍍浴槽 3之關係^如上述，當電鍍膜厚q、匕能滿足之關孫 時，設第1電鍍浴槽之作業方向之長度為心、第2電鍍浴 槽之作業方向之長度為Z2時，如斷面積（Χγ γι=Χ2Χ γ2)相 同時，則Ζ〗、Ζ2可成立Zi>Z2之關係。因此，由第2圖吁 知，如設第1電鍍液之液量、第2電鍍 液之液篁為V2(=X2x Υ2χΖ2)時，則、v2能成立之 關係，係自明之理β 換言之，在第2電鍍浴槽3之電鍍液之液量中，可使 第2電鍍浴槽〇之電鑛液之液量大幅度減少。換言之，第 2電鍍浴槽3之電鍍液内，較第1金屬材料的311為高價的 Bi、Ag以及Cxi之中所使用的第2金屬材料之使用量亦能 大幅度減少而可實現成本之降低& 再者’就本發明之其他實施形態如下說明之。 本發明中’在第1電鍍浴槽2之電鍍液以及第2電鍍 浴槽3之電鍍液，各別之金屬材料之組成比率雖異，惟液 構成則相同。因此，具有將導電元件21浸潰於第1電鍍浴 槽2之電鍍液以施予第i電鍍臈22之後，可連續浸潰於第 2電鍍浴槽3之電鍍液以施予第2電鍍膜23的特徵。而， 實施形態方面，係與上述的方法相同。 例如’本發明中有Sn-Bi液。在此，第1電鍍浴槽^ 之電鍍液中，包含有數％程度之Bi。由此，第1電錢棋^ 1 本紙張尺度$用中國國家標準（CNS)A4規格（210 X 297公爱)_ 10 312338 I I I I I I 1 · I I--— — It--I--I--1 I (請先閱讀背面之注意事項再填寫本頁) A7 A7 經濟部智慧財產局員Η消費合作社印製 11 五、發明說明（11 ) 之表面，將可j|g ! 又，此電㈣之^Ρ制晶鬚（WlHS㈣(針狀結晶）之成長。 行則之管理辰度管理方法，係與前述的方法同樣，進 程度Si ;:第！電鑛浴槽2之電鍍液中，包含有數％ 又 電鍍浴槽3之電鍍液中所使用的sn以外之 =r’Bl、Ag以及Cu之中所選擇的至少1種類之金 1屬材料。因此’可顯著抑制第1電鍍膜22之表面之晶鬚(針 狀結晶）之成長。 [發明之效果] 由上述之說明可知，本發明之電鍍方法具有如下的效 果。 第1為第1電鍍液及第2電鍍液之組成，係去除構成 各別的電鍍液的第i及第2金屬材料以及溶解其金屬材料 的酸性/谷劑時，其餘為相同的溶液組成。因此，即使第1 I電鍍液混入第2電鍍液内仍不會攪亂溶液組成，而可於導 電元件上連續施予相異的金屬材料或雖為同一金屬材料但 金屬材料之組成比率相異的2層電鍍膜^結果，可省略第 1電鍍膜與第2電鍍膜之間的作業的依水洗用浴槽的清 洗’而可達成作業過程及作業時間之縮短。 第2為第1電鍍液及第2電鍍液内所包含的第1及第 2金屬材料之管理中，首先第丨電鍍液及第2電鍍液之溶 液構成’係去除構成各別的電鍍液的第1及第2金屬材料 以及溶解其金屬材料的酸性溶劑時，其餘為相同的溶液組 成者。各別之電鍍液之第1金屬材料的Sn，係主要可依陽 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 312338 — II — III— . —II--^ ----I I I Ί I (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 ^υοιυυ A7 B7__ 五、發明說明（I2 ) 麵 一^ ^、〜 、解而可進行濃度之調整。因此，在第2電鍍液中將 定期性進行Bi，以及〜之中所使用的第2金屬材料之 /農度管理即可，而電鍍液之濃度管理將變為容易。 第3為由於使用自動電鍍裝置的作業速度之一定化， 電流密度之一定化以及將去除第1電鍍液及第2電鍍液的 第1及第2金屬材料以及溶解其金屬材料的酸性溶劑的溶 液作成為相同的溶液構成。因此，由於第2電鍍膜較第1 電鍍膜為大幅度單薄之故，可縮短導電元件浸潰於第2電 鍍液中的時間％結果，可大幅度減少第2電鍍浴槽之液量。 因此，亦可大幅度減少第2電鍍液所用的第2金屬材料的 Bi、Ag以及Cu之使用量，結果，可實現成本減低之結果。 第4為在第！電鍍浴槽之電鍍液中，除第2電鍍浴槽 之電鍍液所使用的第1金屬材料之Sn以外，尚包含數％程 度的由Bi、Ag以及Cii之中所選擇的至少j種第2金屬材 料。因此，可顯著抑制第〗電鍍膜之表面之晶鬚（針狀結 晶}。 第5為在使用以上之電鍍方法的導線或半導體裝置 中，由於所使用的電鍍液不包含鉛之故，不會對人體或環 境有害。加之，由於將去除第i電鍍液及第2電鍍液的金 屬材料以及溶解其金屬材料的酸性溶劑的溶液作成相同的 溶液構成以及第1電鍍液與第2電鍍液的金屬材料之组成 雖異’惟由於將金屬材料作成為相同，而可實現電鍍品質 之提升° [圖面之簡單說明] I ----I ^-------訂·------I I f請先閱讀背面之注意事項再填寫本頁} 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚） 12 312338 A7 A7 的圖 B7 Ί、發明說明（13 ) 第1圖說明本發明之電鍍方法所用的焊劑電鍍裝置的 圖。 第2圖說明本發明之電鍍方法所用的第1電鍍浴槽及 第2浴槽的圖。 第3圖說明本發明及以在之施予2層電鍰的導電元件 第4圖說明本發明及以往之自動電鍍裝置全體之佈置 的_。 第5圖說明以往之焊劑電鍍裝置部分之佈置的圖。 [元件符號說明] ϋ n n ϋ n n n n n f— n I · ϋ n n n n 1« flu )：eJI ϋ n n n n n n I (請先閱讀背面之注意事項再填寫本頁) 經 濟 部 智 慧 財 產 局 1、371 預潰浴槽 2 ^ 372 第1電鍍浴槽 3、374 第2電鍍浴槽 4、32、 34 、 36 〜38 、 40 、 373 - 375 水洗用浴槽 21 導電元件 22 第1電鍍膜 ·23 第2電鍍膜 31 驗電解清洗浴槽 33 化學蝕刻浴槽 35 酸活性化浴槽 37 焊劑電鍍裝置 39 中和處理浴槽 41 溫水洗用浴槽 42 乾燥裝置 消 費 合 η 社 印 製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚） 13 312338The concentration of the second metal rhenium material selected from among * Bl, Ag, and Cu, which has a small amount of significant Sn, may be managed. For example, if U, wt%): 3 (wt%) of the concentration of the electric money solution > is regulated, the respective concentrations are based on the ability to maintain the agricultural degree to the state g / liter), and the concentration of βΓ3 is 3 ⑴ The management of ⑴ is performed in a plating solution between 0 to 42 (g / L), a free acid concentration of 120 to 160 (g / L), and an additive concentration of ⑽ to a milliliter / liter. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed the above-mentioned method. Since the operating speed of the assembly line can be fixed and the current density in the first electroplating bath 2 and the second key bath 3 is constant, the first It is also easy to manage the concentration of the second metal material of the second electric bath 3 and the concentration of Cu. That is, in the second plating bath 3, the concentration of the second metal material such as Bi, Ag, and Cu can be periodically replenished to simplify the concentration management. As a result, the metal of the plating solution in the second plating bath 3 can be maintained. The material concentration is constant so that the film thickness of the second plated film 23 and the composition of the plated film are uniform. That is, in this plating method, by setting the current density in the first plating bath 2 and the second electric bell bath 3 to the optimum current density, it is possible to achieve uniformity of the metal precipitation particle size and to suppress the two-layer film. The deviation of the thickness ratio. Therefore, in the plating method in which the working speed of the assembly line is constant and the current density is constant, if the plating film thickness t1 and t2 can satisfy the relationship, the conductive element 21 is moved to the first plating. The distance in the liquid is Dl, the size of the conductive paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 312338 506100 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (10) Element 2 1 When the distance in the second plating solution is moved, the relationship between Di and d2 can be established as Di & D2, which is self-evident. Moreover, the second figure shows the relationship between the first plating bath 2 and the second plating bath 3 ^ As mentioned above, when the thickness of the plating film q and the dagger can be satisfied, let the length of the working direction of the first electroplating bath be the center and the length of the working direction of the second electroplating bath be Z2, such as the cross-sectional area (× γ γ = When χ2Χ γ2) is the same, then Z , Z2 can establish the relationship of Zi > Z2. Therefore, as shown in the second figure, if the liquid volume of the first plating solution and the liquid volume of the second plating solution are V2 (= X2x Υ2χZ2), then v2 can be established. The relationship is self-explanatory. In other words, the amount of electroplating liquid in the second electroplating bath 0 can be greatly reduced in the amount of electroplating liquid in the second electroplating bath 3. In other words, the amount of the electroplating liquid in the second electroplating bath 3 can be greatly reduced. In the plating solution, the amount of the second metal material used in Bi, Ag, and Cxi, which is more expensive than the 311 of the first metal material, can also be greatly reduced, and the cost can be reduced & Other embodiments are described below. In the present invention, although the composition ratios of the respective metal materials in the plating solution of the first plating bath 2 and the plating solution of the second plating bath 3 are different, the composition of the liquid is the same. Therefore, After the conductive element 21 is immersed in the plating solution of the first plating bath 2 to apply the i-th plating bath 22, it can be continuously immersed in the plating solution of the second plating bath 3 to apply the second plating film 23. The embodiment is the same as the method described above. For example, '本 发There is Sn-Bi solution. Here, the plating solution of the first electroplating bath ^ contains Bi in a percentage of several percent. Therefore, the first electronic money is ^ 1 This paper size uses the Chinese National Standard (CNS) A4 specification (210 X 297 public love) _ 10 312338 IIIIII 1 · I I --- — It--I--I--1 I (Please read the precautions on the back before filling this page) A7 A7 Member of Intellectual Property Bureau, Ministry of Economic Affairs ΗPrinted by the Consumer Cooperative 11 V. The surface of the invention description (11) will be j | g! Also, this electric whisker (WlHS) (needle crystal) will grow. The management method of the rules is the same as the previous method, the degree of Si ;: No.! The electroplating bath of the electric ore bath 2 contains several% of at least one type of gold selected from the group consisting of r = B ', Ag, and Cu other than sn used in the electroplating bath of the electroplating bath 3, and is a metal. Therefore, the growth of whiskers (acicular crystals) on the surface of the first plating film 22 is significantly suppressed. [Effects of the Invention] As can be seen from the above description, the plating method of the present invention has the following effects. The first is the composition of the first plating solution and the second plating solution. When the i-th and second metal materials constituting the respective plating solutions and the acid / cereal agent dissolving the metal materials are removed, the rest have the same solution composition. Therefore, even if the first I plating solution is mixed into the second plating solution, the composition of the solution is not disturbed, and different metallic materials can be continuously applied to the conductive element or the composition ratios of the metallic materials are different even though they are the same metallic material. As a result of the two-layer electroplated film, it is possible to omit the cleaning of the bath for washing with water according to the operation between the first electroplated film and the second electroplated film, and to shorten the working process and working time. The second is the management of the first and second metal materials included in the first plating solution and the second plating solution. First, the solution composition of the first plating solution and the second plating solution is to remove the components that constitute the respective plating solutions. In the case of the first and second metal materials and the acidic solvent in which the metal materials are dissolved, the rest are the same solution composition. The Sn of the first metal material of each plating solution is mainly applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) according to the paper size. 312338 — II — III —. —II-^- --- III Ί I (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ υοιυυ A7 B7__ V. Description of the Invention (I2) One ^, ^, ~, solution Adjust the density. Therefore, in the second plating solution, it is only necessary to periodically perform Bi and the management of the second metal material used in the method, and the concentration control of the plating solution becomes easy. The third is a solution in which the working speed of the automatic plating device is constant, the current density is constant, and the first and second metal materials of the first and second plating solutions are removed, and a solution of an acidic solvent that dissolves the metal materials. Made into the same solution composition. Therefore, since the second plating film is considerably thinner than the first plating film, it is possible to shorten the time% that the conductive element is immersed in the second plating solution. As a result, the amount of liquid in the second plating bath can be greatly reduced. Therefore, the amount of Bi, Ag, and Cu used in the second metal material used in the second plating solution can be significantly reduced. As a result, the cost can be reduced. No. 4 is at No.! In addition to the Sn of the first metal material used in the plating solution of the second plating bath, the plating bath of the plating bath also contains at least j kinds of second metal materials selected from Bi, Ag, and Cii to a degree of several percent. . Therefore, whiskers (acicular crystals) on the surface of the plated film can be significantly suppressed. The fifth is that the lead or semiconductor device using the above plating method does not contain lead because the plating solution does not contain lead. It is harmful to the human body or the environment. In addition, the solution of the metal material of the i-th plating solution and the second plating solution and the acidic solvent that dissolves the metal materials are made into the same solution composition, and the metals of the first plating solution and the second plating solution are the same. Although the composition of the materials is different, but the metal materials are made the same, which can improve the quality of electroplating ° [Simplified description of the drawing] I ---- I ^ ------- Order · ---- --II f Please read the notes on the back before filling out this page} This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 cm) 12 312338 A7 A7 Figure B7 Ί, Description of Invention (13) 1 is a diagram illustrating a flux plating apparatus used in the electroplating method of the present invention. FIG. 2 is a diagram illustrating a first plating bath and a second bath used in the electroplating method of the present invention. FIG. 3 is a diagram illustrating the present invention and its application. Figure 4 shows the conductive element of a two-layer electric cell. The layout of the present invention and the conventional automatic electroplating device. Figure 5 illustrates the layout of the conventional flux electroplating device. [Description of component symbols] ϋ nn ϋ nnnnnf— n I · ϋ nnnn 1 «flu): eJI ϋ nnnnnn I (Please read the precautions on the back before filling out this page) Intellectual Property Bureau of the Ministry of Economic Affairs 1, 371 Pre-collapse bath 2 ^ 372 1st plating bath 3, 374 2nd plating bath 4, 32, 34, 36 ~ 38 , 40, 373-375 Bath for water washing 21 Conductive element 22 First plating film · 23 Second plating film 31 Electrolytic cleaning bath 33 Chemical etching bath 35 Acid activation bath 37 Solder plating device 39 Neutralization treatment bath 41 Warm water washing Bath tub 42 Drying device consumer printing company Printed paper size Applicable to China National Standard (CNS) A4 (210 X 297 cm) 13 312338