200831716 九、發明說明： 【發明所屬之技術領域】 關於一種用 本發明是有關於一種電鍍液，且特別是有 於高速電鍵之錫電鍍液配方。 【先前技術】 為了增加物體表面之光澤或保護，因此 打錯-錫電鍍製程。然而，由於以往 ；°口夕、 中，所含的重金屬錯會對土壤與地下水造成嚴重污;% 此，目賴使用的電鍍液，係朝向無錯的錫電錢液發展。 卞為了改善電鐘品質，傳統錫電鑛液中常加入各^添加 劑，但由於各添加劑的消耗速率（consumpti〇n叫不一， 於進打高速電鍍時，電鍍液中各添加劑含量無法 比例，造成所形成的鍍膜層粗㈣淡，電鍍品質不佳。故 =了使電鑛品質維持在最佳條件，除了必須於電鑛過程 中，持續監控各添加劑消耗量外，有時還需停止電鑛程序， 關閉電鐘槽，以更換電鑛液，耗費大量時間與成本。此外， -般傳統錫電鐘液所適用的電流密度範圍（贿ent d⑽办 _ge)相當窄’僅能於狹小的電流密度範圍下，才能產生較 ^鑛膜層的效果，無法應用於大_的電流密度，尤其 疋商產量所需的高電流密度。 據此仍待發展出一種錫電鑛液，除了可適用於較大 的電流密度範圍外，在進行高速電鑛時，可保有良好的電 鍍品質。 【發明内容】 5 200831716 因此本發明目的之一就是在提供一種錫電鍍液之配 方，可於高速電鍍時達到良好的電鍍效果，並適用於廣泛 的電流密度範圍。 根據本發明之上述目的’提出一種錫電鐘液之配方’ 此配方至少包含電鍍空白液、潤濕劑、第一光澤劑與第二 光澤劑。其中電鍍空白液包含甲基磺酸錫（Sn(CH3S03)2 ’ tin methanesulfonate)與甲基績酸（CH3S03H，methanesulfonic acid)，潤濕劑係為 ethyleneoxide/propyloxide copolymer (EO/PO copolymer)，而第一光澤劑係為丙烯酸（acrylic acid)，第二光澤劑則為苯酮（benzylidene acetone)。 依照本發明之一實施例，電鍍空白液中曱基磺酸錫含 量為30-45 g/L，而所使用的甲基磺酸濃度為70 wt %，其 含量為100-150 ml/L。潤濕劑中的乙烷/丙烷共聚物 (ethyleneoxide/propyloxide copolymer，EO/PO copolymer) 之分子量係為15000-2000，含量為5-20 g/L。第一光澤劑 中的丙烯酸係為甲基丙烯酸，其含量為0.01-0.12 g/L。第 二光澤劑中的苯酮之含量為0.01 _0.1 g/L。 依照本發明之另一實施例，更可於電鑛液中，加入高 電流促進劑，以於高速電鍍時，進一步加強鍍膜層之平整 度與光澤。而所使用的高電流促進劑可為戊二醛，其含量 為0.1-1.3 g/L。而為了防止該電鐘空白液中的二價錫離子 氧化，可於電鍍液中加入抗氧化劑，所使用的抗氧化劑係 選自由對苯二酚、鄰苯二酚、1，3,5-苯三酚以及上述任意組 合所組成之一族群，抗氧化劑之含量為0· 1 -1 ·2 g/L。此外， 為了使鍍膜層於中低速電鍍時，仍具有均勻的色澤，因此 200831716 可於電鍍液中加入中低電流促進劑。所使用的中低電流促 進劑例如可為肉桂酸，其含量為〇 〇5-〇15 。 由上述可知，本發明電鑛液之配方，無論是進行高速 弘鍍或中低速電鍍，皆可達到良好的電鍍效果，且所適用 的電流密度範圍亦較寬廣。 【實施方式】 • 於下文中，首先提出本發明錫電鍍液配方之一實施 例接著進行電鍍測試，以驗證本發明錫電鍵液配方是否 有較佳之電鍍效果。 實施例一 於此實施例中，電鍍液之配方主要包含電鍍空白液、 潤濕刎第一光澤劑以及第二光澤劑四種。首先，電鐘空 白液係用以提供鍍錫時所需之二價錫離子，其成份包含了 30-45 g/L的甲基磺酸錫，與重量量百分率7〇%的曱基磺酸 藝 1 〇〇 150 ml/L。至於，潤濕劑則是用以降低電鍍時所產生的 氣體與電鍍液間的表面張力，降低氣泡的形成，並促進氣 體的析出，以免氣體與金屬沈積並列進行，進而減小鍍膜 層凹凸不平的情形，使鑛膜層表面平整光滑。潤濕劑之主 要成份為乙烷/丙烷共聚物（E0/P〇 c〇p〇lymer)，其分子式可 以（E〇)m(P〇)n表不，分子量約為15〇〇〇-2〇〇〇，含量為5-2〇 g/L。而第一光澤劑則能夠減小鍍膜層微觀凹凸不平幅度， 使鏡層表面平整光滑。第一光澤劑係為甲基丙稀酸，其含 里為0·01-0·12 g/L。而第二光澤劑係用以增進鍍膜層之光 澤度，其成份係為苯酮，含量為l yL。 200831716 M 施例中’為了改善電鑛效果於 液中加人南電流促㈣與抗氧 、電，又 速電鍍下，進一步加強铲腹M 门电仇促進劑可於高 乂加強鍍膜層之平整度與光 進劑係為戊二醛，其含量為〇· …促 v u g/JL。另外，兔了田 防止該電鑛空白液中的價 ' 貝踢料乳化，亦於電錢亦中加 —仏乳化刮，抗氧化劑可為對苯二紛、鄰苯二盼或⑻· 2齡，其含量為0.M.2 g/L。為了使鍵膜層於中低速電 ，.又守，仍具有均句的色澤，因此可於電鑛液中加中低電 流促進劑。所使用的中低電流促進劑係為肉桂酸—a· acnd)，其含量為 0 〇5-〇15 g/L。 MMMMl200831716 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a plating solution, and more particularly to a tin plating solution formulation having a high speed key. [Prior Art] In order to increase the gloss or protection of the surface of the object, the wrong-tin plating process is performed. However, due to the past, the heavy metal contained in the mouth and the middle of the mouth caused serious pollution to the soil and groundwater;%, the plating solution used depends on the development of the error-free tin battery. In order to improve the quality of electric clocks, various tin additives are often added to the tin-based mineral liquids. However, due to the consumption rate of each additive (consumpti〇n is not called, when the high-speed electroplating is carried out, the content of each additive in the plating solution cannot be proportional, resulting in The formed coating layer is coarse (four) light and the plating quality is not good. Therefore, the quality of the electric ore is maintained at the optimum condition. In addition to the continuous monitoring of the consumption of each additive in the process of electric ore, it is sometimes necessary to stop the electric ore. The procedure, closing the electric clock slot to replace the electric mineral liquid, takes a lot of time and cost. In addition, the current density range (the bribe ent d (10) _ge) is generally narrow in the traditional tin battery. In the current density range, the effect of the film layer can be produced, and it cannot be applied to the current density of large _, especially the high current density required for the quotient. Therefore, a tin-electric slag is still to be developed, except that it can be applied. In the case of large current density range, good electroplating quality can be maintained during high-speed electric ore mining. [Invention] 5 200831716 Therefore, one of the objects of the present invention is to provide a tin battery. The formulation of the liquid can achieve a good electroplating effect at high speed electroplating and is suitable for a wide range of current densities. According to the above object of the present invention, a formulation of a tin bell solution is proposed, which contains at least a plating blank and is wetted. a first brightener and a second brightener, wherein the plating blank comprises tin methanesulfonate (Sn(CH3S03)2' tin methanesulfonate) and methyl acid (CH3S03H, methanesulfonic acid), and the wetting agent is ethyleneoxide / propyloxide copolymer (EO/PO copolymer), the first brightener is acrylic acid, and the second brightener is benzylidene acetone. According to an embodiment of the present invention, the ruthenium base in the plating blank The tin sulfonate content is 30-45 g/L, and the methanesulfonic acid concentration used is 70 wt%, and its content is 100-150 ml/L. Ethane/propane copolymer in the wetting agent (ethyleneoxide/ The propyloxide copolymer, EO/PO copolymer) has a molecular weight of 15000-2000 and a content of 5-20 g/L. The acrylic acid in the first brightener is methacrylic acid, and the content thereof is 0.01-0.12 g/L. Benzene in gloss The content is 0.01 _0.1 g / L. According to another embodiment of the present invention, a high current promoter can be added to the electro-mineral liquid to further enhance the flatness and gloss of the coating layer during high-speed electroplating. The high current promoter used may be glutaraldehyde in an amount of 0.1-1.3 g/L. In order to prevent oxidation of the divalent tin ions in the blank of the electric clock, an antioxidant may be added to the plating solution. The antioxidant used is selected from the group consisting of hydroquinone, catechol, 1,3,5-benzenetriol, and any combination thereof, and the antioxidant content is 0·1 -1 ·2 g/ L. In addition, in order to make the coating layer have a uniform color when it is plated at medium and low speeds, the medium and low current promoters can be added to the plating solution in 200831716. The medium-low current promoter used may, for example, be cinnamic acid in an amount of 〇5-〇15. From the above, it can be seen that the formulation of the electromineral liquid of the present invention can achieve a good electroplating effect regardless of whether it is subjected to high speed electroplating or medium or low speed electroplating, and the applicable current density range is also wide. [Embodiment] In the following, an embodiment of the tin plating solution of the present invention was first proposed and then subjected to an electroplating test to verify whether the tin electro-key solution of the present invention has a better plating effect. Embodiment 1 In this embodiment, the formulation of the plating solution mainly comprises four kinds of electroplating blank liquid, wet 刎 first brightener and second brightener. First, the electric clock blank liquid is used to provide the divalent tin ions required for tin plating, and the composition thereof comprises 30-45 g/L of tin methanesulfonate, and the mass percentage of 7〇% of mercaptosulfonic acid Art 1 〇〇 150 ml / L. As for the wetting agent, it is used to reduce the surface tension between the gas generated during electroplating and the plating solution, reduce the formation of bubbles, and promote the precipitation of gas, so as to prevent gas and metal deposition from juxtaposed, thereby reducing the unevenness of the coating layer. The situation makes the surface of the mineral film smooth and smooth. The main component of the wetting agent is ethane/propane copolymer (E0/P〇c〇p〇lymer), and its molecular formula can be expressed by (E〇)m(P〇)n, and the molecular weight is about 15〇〇〇-2. 〇〇〇, the content is 5-2〇g/L. The first brightener can reduce the micro unevenness of the coating layer and make the surface of the mirror layer smooth and smooth. The first brightening agent is methyl acrylic acid, which is 0.01-0.12 g/L. The second gloss agent is used to enhance the gloss of the coating layer, and its composition is benzophenone, and the content is l yL. 200831716 M In the example, in order to improve the effect of electric ore in the liquid, add the south current (4) and anti-oxidation, electricity, and speed plating, further strengthen the shovel M door electric enemies to strengthen the coating layer in the sorghum The degree and the light-injecting agent are glutaraldehyde, and the content thereof is 〇· Promoting vug/JL. In addition, the rabbit field prevents the price of the electro-mineral blank from emulsification, and it is also added to the electric money. The antioxidant can be benzodiazepine, ortho-benzene or (8)· 2 , its content is 0.M.2 g / L. In order to make the bond film layer in the middle and low-speed electricity, and keep it, it still has the color of the uniform sentence, so the medium and low current promoter can be added to the electric ore liquid. The medium and low current promoter used is cinnamic acid-a· acnd) in an amount of 0 〇5-〇15 g/L. MMMMl
為了測試於高速電鍍時，以上述方法所配製之電鍍 液，是否具有較佳的電鍍效果，因此於電鍍空白液中分別 加入不同比例之添加劑，以配製成四種不同電鐘液。而此 四種電鍍液配方係如表一所示。 表一各電鍍液之配方 添加劑成份與比例 濕潤劑 第二光 澤劑 第一光澤劑 南電流促進 劑 樣品一 300 1 N/A N/A 才羨品二 300 2 N/A N/A 樣品二 300 2 4 N/A 樣品四 300 2 4 15 200831716 甲基磺 實施例 <註>樣品-至樣品四之電鍍空白液成份係為4〇机 酸錫與120ml/L甲基磺酸（7〇wt%)，而夂 ’而各添加劑之成份則如 一戶斤示0In order to test whether the electroplating solution prepared by the above method has a better electroplating effect during high-speed electroplating, different proportions of additives are separately added to the electroplating blank to prepare four different electric clock liquids. The four plating solution formulations are shown in Table 1. Table 1 Formulation Additives and Proportioning Wetting Agents for Each Electroplating Solution Second Luminant First Luster South Current Accelerator Sample 300 1 N/AN/A Only Product 2 300 2 N/AN/A Sample 2 300 2 4 N/A Sample 4 300 2 4 15 200831716 Methylsulfonate Example <Note> Sample-to sample 4 The plating blank is composed of 4 lanthanum acid and 120 ml/L methanesulfonic acid (7 〇 wt%) ), and 夂' and the ingredients of each additive are as shown in one
首先，於樣品-中，僅添加了濕潤劑與第二光澤 兩者之比例分別為卜而樣品二則把第二光澤劑轉 加比例提高，使濕潤劑與第二光澤劑比例為3〇〇: 2。至於 樣品三’㉟了濕潤劑與第二光澤劑外，還多加了第、、果 劑’使濕潤劑、第二光澤劑與第—光澤劑之添加比例為 300 : 2 : 最後，於樣品四中，再加入高電流促進劑，使 二光澤劑、第—光澤劑與高電流促進劑之添加 :為3〇〇:2:4:15。當配製好樣品後，再利用哈氏片_ )，於15-20〇c下以5安培1分鐘之電流量進行電 鍍測試。 疋仃电 第1-4目分別為樣品一至樣品四之測試結果。由1 圖與第2圖可知，若提高第二光澤劑的添加比例，哈氏片 右側邊緣之光澤亦隨改善。若於電鍍液中加入第一光澤劑 的話^結果如第3顧示，哈氏片左側的光澤大為改/。 而於弟、4圖中，則是加了高電流促進劑，明顯地整片哈氏 片之光澤與平整度大幅提升。若將第1·4目中的哈氏片電 鍍結果，對照哈氏片上的刻度可知，上述實施例之電鍍液 於電鍍時所適用冑流密度範目，約4 5安培/平方公寸 (Ampere Sq職e %_加，ASD)至25asd，甚至是碰奶。 由上述可知，本發明電鍍液之配方，不僅可於 後度耗圍下’達到良好的電鍍效果，於進行高速電鐘時， 更可保有良好的電鏡品質。 200831716 雖然本發明已以一實施例揭露如上，然其並非用以限 定本發明，任何熟習此技藝者，在不脫離本發明之精神和 範圍内，當可作各種之更動與潤飾，因此本發明之保護範 圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 為讓本發明之上述和其他目的、特徵、優點與實施例 能更明顧易懂，所附圖式之詳細說明如下： 第1-4圖是本發明一實施例之哈氏片電鍍測試圖。 【主要元件符號說明】First, in the sample--, only the ratio of the humectant to the second gloss is added, and the sample 2 is used to increase the ratio of the second gloss agent to a ratio of the humectant to the second gloss agent. : 2. As for the sample three '35 humectant and the second gloss agent, the addition of the first, fruit agent 'the humectant, the second gloss agent and the first gloss agent are added in the ratio of 300 : 2 : Finally, in the sample four In addition, a high-current accelerator is added to add the two-gloss agent, the first-gloss agent and the high-current accelerator: 3〇〇: 2:4:15. After the sample was prepared, the electroplating test was carried out using a Hastelloy sheet _) at a current of 5 amps for 1 minute at 15-20 〇c.第 Electricity No. 1-4 is the test result of sample one to sample four, respectively. It can be seen from Fig. 1 and Fig. 2 that if the addition ratio of the second brightener is increased, the gloss of the right edge of the Hastelloy sheet is also improved. If the first brightener is added to the plating solution, the result is as shown in the third note, and the gloss on the left side of the Hastelloy sheet is greatly changed. In the case of Yu Di and 4, a high current accelerator was added, and the gloss and flatness of the whole piece of Hastelloy were significantly improved. If the Hastelloy plating result in the first and fourth orders is compared with the scale on the Hastelloy sheet, the plating solution of the above embodiment is applied to the turbulent density range at the time of electroplating, about 45 amps/cm 2 (Ampere). Sq job e %_plus, ASD) to 25asd, even touching milk. As can be seen from the above, the formulation of the plating solution of the present invention not only achieves a good electroplating effect after the subsequent consumption, but also maintains a good electron microscope quality when a high-speed electric clock is used. The present invention has been disclosed in an embodiment of the present invention, and is not intended to limit the present invention, and the present invention can be modified and retouched without departing from the spirit and scope of the present invention. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; Harrington sheet plating test chart. [Main component symbol description]