201239138 六、發明說明： 【發明所屬之技術領域】 本發明係有關於—種錄電鑛液、以及使用該錄電鍍液 之錄電鍍方法。特別是有關於-種不含棚酸和m酸系強有 機酸、且具有從弱酸性到中性範圍的溶液pH i之錄電錢 液。 x 【先前技術】 鎳電鍍薄膜係已被廣泛應用於以下等領域：追求裝飾 性的曰用品領域、追求防銹和光澤度機能的工業製品領 域、以及追求導電性和焊錫潤滑性等機能的電子零件領域。 此類鎳電鍍薄膜的形成’ i要是使用了瓦特浴 (Watt’ s bath)、氨基績酸浴等之酸性錄電鑛液。在此 處，該酸性錦電鑛液係使用了能夠抑制被電鍍物的侵㈣ 形成穩定的電㈣膜、且可作為㈣抑制PH變動的仙緩 衝劑之删酸。然而，硼酸已在2(m年7月】日施行的修正 水質污染防治法中被列為限制對象物質。因此，市場遂有 了開發使用有機酸類之技術的情 J 馆况，以作為硼酸的替代物 質。 例如，在專利文獻1 (曰太岡审士 、 本國專利申請：特開 2001-1 07284號公報）中，即揭示 J .以&供不含有造成 排水處理困難的硼酸、不對作章援 戸果¥境造成不良影響之鎳電 鍍浴為目的’而利用了添加有〇 〇1 . 旲耳/升〜〇_5莫耳/ 升的脂肪族二羧酸來取代硼酸之钽 ' 鳏電鍍浴。然後，以脂肪 4 201239138 族二羧酸而言’係以丙二酸、丁二酸、戊二酸、己二酸為 較佳’脂肪族二羧酸並係以預先跟鎳鹽水溶液混合完成者 更佳。 在前述專利文獻1的實施例1中，係先調製出含有硫 酸鎳280克/升、氣化鎳50克/升、丙二酸5.〇克/升及碳 酸鎳2· 0 (/升的溶液之ρΗ4· 8的鎳電鍍浴，再放入以作為 被電鍍物的70x100公釐（mm)的黃銅板當作陰極、使用鎳 板作為陽極之薄膜電池（】丄“⑴寺曹中’於溫度5代、 電流2安培（A)的條件下進行1〇分鐘的鎳電鍍其結果 員π出在被電鍍物上得到了具有光澤的平滑鎳電鍍薄膜， 並且電鍵洛的pH也幾乎沒有變動。 再者在專利文獻2 (曰本國專利申請：特開 20 0 9-62577號公報）中，揭示了以提供電鍍均勻度優良、 不使用硼、電鍍成本也低廉的鎳電鍍浴為目的，而使用了 具有下述特徵之鎮電鍍浴技術：含有以錄離子濃度換算為 克升 20克/升之作為鎳離子源的氣化鎳及/或硫酸 鎳，及含有以檸檬酸.1水和物換算為50克/升〜30〇克/ 升之檸檬酸（Citric acid)，並藉由教將溶液pH調整至 在前述專利文獻2的實施例中，係於水中分別將禪樣 酸1水和物以200克/升，將氯化錄· 6水和物以】〇克/ 升、2°克/升、40克/升、6〇克/升、80克/升、100克/升 :個別量添加人之後’加溫溶解並放冷。接著，使用pH測 邊測定冷液pH ' —邊加入濃氨水，將鎳電鍍液調節 4 201239138 至溶液pH呈8. 〇後，使用該鎳電鍍液實施薄膜電池（Hul j ce 11 )試驗’並利用螢光χ射線膜厚計來測定3個地方之 電鍛薄膜的膜厚。其結果顯示出，專利文獻2的實施例一 方’比起使用了溶液ρΗ4. 〇之含有硼酸的瓦特浴之錄電鍵 而言’在電鍍均勻度方面更為優異。 然而’市場上也有人認為，使用如專利文獻1及專利 文獻2所揭示般的含有丙二酸、檸檬酸等羧酸系強有機酸 之電鑛液’其所得到的電鍍薄膜之品質差異度很大。亦即， 如專利文獻1及專利文獻2所揭示之鎳電鍍液，即令其含 有作為pH緩衝劑之丙二酸、檸檬酸等羧酸系強有機酸，也 無法長時間穩定地抑制電鍍液之pH變動，作為結果來說， 就是很難形成穩定的電鍍薄膜。 &另—方面’當使用如專利文獻丨及專利文獻2所揭示 舣的含有羧酸系強有機酸之鎳電鍍液時，由於所調製出的 錄電鍍液的溶液pH，對於被電鑛物而言、特別是當被電鍛 物疋陶資*素材的情況下，堂合 』h况下 *會發生其表面被侵蝕而產生損 傷的情況。 、 乡示上所述，日t ιβ , '市琢上迫切需要具有能夠長時間穩定 地抑制電鍍液之溶液Η鑤叙 _ " /合液ρΗ變動、以獲得與習知相同的生產率 同等外觀等特性之錄電鍍薄膜’並且也迫切需要不含水 ==法所限制物質之錄電鍛液，以及使用該 锻液之鎳電鍍方法。 【發明内容】 5 201239138 ,有鑑於此，經過本案發明人等銳意研究的結果，遂得 到了藉由使用以下的鎳電鍍液’京尤可在既沒有硼酸、也不 含《系強有機酸的情況下，達到可形成能長時間穩定地 將冷液pH的變動抑制在從弱酸性到中性範圍之間的狀離 之鎳電鍍方式。 ^ 本發明之鎳電鍍液： 本發明之鎳電鍍液係為電鍍用之鎳電鍍液’包括作為 鎳離子供給源白“種以上之鎳鹽以A pH緩衝劑，其特徵在 於.該PH緩衝劑為氨基鏈烷磺酸或其衍生物，且溶液邱 為 4 · 0 〜6. 5 〇 其次’本發明之錦電鐘 化鎳，該鎳鹽與氨基鏈烷磺 如下所示之範圍為較佳： 硫酸錄· 6水和物 風化錄· 6水和物 氨基鏈院項酸或其衍生 又’本發明之鎳電鍍液 中’上述鎳鹽為硫酸鎳及氯 或其衍生物的含有量係以在 :120克/升〜48〇克/升 :15克/升〜70克/升 :30克/升〜100克/升。 ’上述錦鹽也可為氨基確酸 鎳及氣化鎳，該鎳鹽與氨基鏈烷磺酸或其衍生物的含有量 係以在如下所示之範圍為較佳： 氨基磺酸鎳.4水和物 ：200克/升〜6〇〇克/升 氣化錄· 6水和物 氨基鏈烷磺酸或其衍生物 此外，本發明之鎳電鑛液中 1克/升〜6克/升 克/升〜1〇〇克/升。 上述氨基鏈烷磺酸或其 6 201239138 更以包括有應力調整劑較 衍生物係以為氨基乙磺酸較佳 又’本發明之鎳電鍍液中 佳。 ’本發明之鎳電鍍液中，上述應力調整劑係以為 鄰-續基苯甲酸亞胺較佳，㈣鄰^基笨甲酸亞胺的濃度 並以在0·1克/升~ 5克/升為更佳。 本發明之鎳電鍍方法： 本發明之錄電鍍方法，其特徵在於包括下列步驟：可 使用以上所述之任一鎳電鍍液，於液溫下， 以陰極電流密度0·05 A/dm、1〇 A/dm、進行電解而於 被電鍍物的表面上形成鎳電鍍薄膜。 本發明之電鍍製品： 本發明之電錄製品，其特徵在於：係利用以上所述之 鎳電鍍方法來形成鎳電鍍薄膜者。 【實施方式】 1.本發明鎳電鍍液之型態 1-1.本發明鎳電鍍液相關之技術思想 本發明之鎳電鍍液係為電鍍用之鎳電鍍液，包括作為 鎳離子供給源的1種以上之鎳鹽以及pH緩衝劑，其特徵在 於：該pH緩衝劑為氨基鏈烷磺酸或其衍生201239138 VI. Description of the Invention: [Technical Field to Be Invented by the Invention] The present invention relates to a recording liquid ore, and a plating method using the recording plating solution. In particular, there is a recording liquid in which a solution acid having no shed acid and m acid is strong and having a pH of from a weakly acidic to a neutral range. x [Prior Art] Nickel plating film has been widely used in the fields of decorative enamel products, industrial products that pursue rust and gloss functions, and electronics that pursue electrical conductivity and solder lubricity. Parts field. The formation of such a nickel-plated film is to use an acid-recorded ore liquid such as a Watt bath or an amino acid bath. Here, the acid brilliance is used to suppress the intrusion of the object to be plated (4) to form a stable electric (tetra) film, and to use (4) to suppress acid fluctuations. However, boric acid has been listed as a restricted substance in the revised water pollution prevention and control method that was implemented on the 2nd of July (May). Therefore, the market has developed the technology of using organic acids to serve as boric acid. For example, in Patent Document 1 (Ottawa, the national patent application: JP-A-2001-1 07284), it is revealed that J. & does not contain boric acid which causes difficulty in drainage treatment, and does not work. Zhang Ai 戸 ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍 镍Electroplating bath. Then, in the case of fat 4 201239138 dicarboxylic acid, it is preferred to use malonic acid, succinic acid, glutaric acid and adipic acid as the preferred 'aliphatic dicarboxylic acid. In the first embodiment of Patent Document 1, the first embodiment contains 280 g/liter of nickel sulfate, 50 g/liter of nickel vapor, 5. g of malonic acid/liter and nickel carbonate 2 · 0 (/L of the solution of ρ Η 4 · 8 nickel plating bath, and then put it as being electroplated A 70x100 mm (mm) brass plate is used as a cathode, and a nickel plate is used as the anode of the thin film battery (] 丄 "(1) 寺曹中' at a temperature of 5 generations, a current of 2 amps (A) for 1 minute. The result of the nickel plating is that a smooth nickel plating film having a gloss is obtained on the object to be plated, and the pH of the electric bond is hardly changed. Further, Patent Document 2 (曰 National Patent Application: Special Opening 20 09) In the case of the nickel electroplating bath which is excellent in plating uniformity, does not use boron, and has low electroplating cost, it is disclosed that a town electroplating bath technique having the following characteristics is used: in terms of recording ion concentration It is a gasification nickel and/or nickel sulfate which is a nickel ion source of 20 g/L, and a citric acid (Citric acid) of 50 g/L to 30 g/L in terms of citric acid and water. And, by teaching the pH of the solution to be adjusted to the embodiment of the aforementioned Patent Document 2, respectively, the water of the medicinal acid 1 in water is 200 g / liter, respectively. 〇克 / liter, 2 ° g / liter, 40 g / liter, 6 gram / liter, 80 g / liter, 100 g / : After adding a certain amount of people, 'heat and dissolve and let cool. Then, use pH to measure the pH of the cold liquid' - add concentrated ammonia water, adjust the nickel plating solution 4 201239138 until the pH of the solution is 8. 〇, use the nickel The plating solution was subjected to a thin film battery (Hul j ce 11 test), and the film thickness of the wrought film in three places was measured by a fluorescent ray film thickness meter. The results show that the one of the examples of Patent Document 2 is The use of the solution ρΗ4. The recording key of the watt bath containing boric acid is more excellent in terms of plating uniformity. However, it is also considered to be used in the market as disclosed in Patent Document 1 and Patent Document 2 The electro-mineral liquid of a carboxylic acid-based strong organic acid such as diacid or citric acid has a large difference in quality of the obtained electroplated film. In other words, the nickel plating solution disclosed in Patent Document 1 and Patent Document 2 contains a strong carboxylic acid-based organic acid such as malonic acid or citric acid as a pH buffering agent, and it is not possible to stably suppress the plating solution for a long period of time. The pH changes, as a result, it is difficult to form a stable plating film. &Alternatively, when using a nickel plating solution containing a carboxylic acid-based strong organic acid as disclosed in Patent Document 2 and Patent Document 2, the pH of the solution of the prepared plating solution is based on the charged mineral. In other words, especially in the case of electric forgings and pottery materials, there will be cases where the surface is eroded and damaged. As shown in the township, the day t ιβ, 'the market is desperately required to have a solution that can stably suppress the plating solution for a long time, and the liquid mixture is changed to obtain the same productivity as the conventional one. The electroplated film of the same characteristics is also required. There is also an urgent need for a recorded forging liquid which does not contain a water-restricted substance, and a nickel plating method using the forging liquid. SUMMARY OF THE INVENTION 5 201239138 , in view of this, after intensive research by the inventors of the present invention, 遂 obtained by using the following nickel plating solution 'Jingyou can be neither boric acid nor strong organic acid In this case, it is possible to form a nickel plating method capable of stably suppressing fluctuations in the pH of the cold liquid from a weakly acidic to a neutral range for a long period of time. The nickel plating solution of the present invention: the nickel plating solution of the present invention is a nickel plating solution for electroplating, which includes a nickel salt as a nickel ion supply source, and a nickel salt as an A pH buffer, characterized in that the pH buffering agent Is an aminoalkanesulfonic acid or a derivative thereof, and the solution is 4·0 to 6. 5 〇 second, the nickel of the present invention, the nickel salt and the aminoalkanesulfone are preferably as shown below. : sulfuric acid recorded · 6 water and weathering records · 6 water and amino chain hospital acid or its derivative and in the nickel plating solution of the present invention, the above nickel salt is the content of nickel sulfate and chlorine or its derivatives In: 120 g / liter ~ 48 gram / liter: 15 g / liter ~ 70 g / liter: 30 g / liter ~ 100 g / liter. 'The above salt can also be nickel amide and nickel vaporization, the The content of the nickel salt and the aminoalkanesulfonic acid or its derivative is preferably in the range shown below: nickel sulfamate. 4 water and: 200 g / liter to 6 gram / liter gasification Recorded 6 water and amino alkane sulfonic acid or its derivative In addition, the nickel electro-mineral solution of the present invention is 1 g / liter ~ 6 g / liter / liter ~ 1 gram / liter. The sulfonic acid or its 6 201239138 further includes a stress modifier than a derivative, and the amino ethanesulfonic acid is preferably the same as in the nickel plating solution of the present invention. In the nickel plating solution of the present invention, the stress modifier is The ortho-benzoic acid imide is preferably used, and the concentration of (iv) ortho-formic acid imide is more preferably from 0.1 g/liter to 5 g/liter. The nickel plating method of the present invention: Record of the present invention The electroplating method is characterized in that it comprises the following steps: electroplating can be carried out by electrolysis at a liquid temperature of 0.05 A/dm, 1 〇A/dm at a liquid temperature using any of the nickel plating solutions described above. A nickel plating film is formed on the surface of the object. The electroplated article of the present invention: The electrophotographic article of the present invention is characterized in that the nickel electroplating film is formed by the nickel plating method described above. Nickel plating solution type 1-1. The present invention relates to a nickel plating solution. The nickel plating solution of the present invention is a nickel plating solution for electroplating, and includes one or more nickel salts as a nickel ion supply source and a pH buffer. Agent, characterized in that the pH buffering agent is Aminoalkanesulfonic acid or its derivatives
明 JL >谷液pH 為 4 · 0 〜6 · 5 〇 201239138 本發明之銻電錢液，係以使用「氨基鍵燒續酸或其衍 」w作pH緩衝劑來作為共同特徵。氨基鏈烷磺酸及其 行生物係、為在分子内具有陽離子中心與陰離子中心之氨 基續酸類’是溶液pH呈中性範圍時以雙性離子狀態存在之 化合物。然後，等枓雜工# 生離子了糟由在其所處溶液變成酸性時 形成出陰離子、装所片、.六冰丄 、斤處命液艾成鹼性時形成出陽離子，藉 此來發揮對其自身所處溶液之PH的緩衝效果。 「在此處於本發明之錄電鍍液中，關於作為pH緩衝劑 之「氨基鏈燒確酸或其衍生物」的含有量，係如前所述。 在本發明之鍊電鑛液中，氨基鏈料酸或其衍生物的含有 量:以為3G克巧~ 1GG克/升較佳。若4基鏈㈣酸或 二:生物的3有置未達3〇克/升，則當錄電鑛液的溶液邱 設定於6. 〇附折，古4·、I P，!· 4 '會…法充分發揮pH緩衝效果，故較 另方面，右氨基鏈烷磺酸或其衍生物的含有量超 過100克/升時，則溶液pH的緩衝效果就已達到飽和含 有量超過的部分就沒有效果’因此會變成資源的浪費而較 不佳°由此而訂出作為PH緩衝劑之「氨基鏈院石黃酸或其衍 生物」的含有量。 更進-步’本發明之錄電鍍液中，「4基鏈院確酸或 ^丁 ,物」又以使用氨基乙續酸為較佳。此種氨基乙碌酸， 二二ΓΓ酸或其衍生物」之中，於錄電錢液中的 優良、長期維持溶液品質之穩定化能力優異、電鑛 六,Γ中之溶液邱變化小’而能得到良好的鎳電鍍薄膜 之"。又，作為化合物而言’氨基乙績酸也作為人體 8 201239138 口部投藥劑使用，不但沒者主t 有I性，市場上調度也容易，並 且不會加重排水處理的負荷， 具有诸多優點。 再者，本發明之鎳電铲 ^ ^ m ^中，作為鎳離子供給源使用 之鎳孤，並未特別予以限定，+人& 在♦電鑛所形成的錄電錢薄 膜可以滿足所要求特性的情 祕 兄下，可由氰基磺酸鎳、氣化 鎳、硫酸鎳、乙酸鎳等之中單 r早獨擇一或混合使用之。 又’本發明之鎳電鍍 收/合液pH係以為4. 0〜6. 5較 佳。若鎳電鐘液的溶液Η县土、* ^ n P疋未達4. 0的強酸範圍時，由於 :使得繼侵触’故無法使用於晶片零件電锻上，因此 佳另方面，右鎳電鍍液的溶液PH超過65，即會 有一達到鹼性就產生氫氣化 — 虱氧化鎳的情況產生，因而报難得到 洛液穩定性優良的鎳電鍍液，故較不佳。 1 2.本發明錄電錢液之具體組成 如上所述，本發明之錄電鍍液係含有作為PH緩衝劑之 氨基鏈烧確酸或其衍生物，3艮「含有以硫酸錄和氯化鋅作 為鎳鹽之瓦特浴系鎳電鐘液」以及「含有以氨基石黃酸錄和 乳化鎳作為鎳鹽之氨基磺酸浴系鎳電鍍液」有著很大的區 別。以下，乃針對個別的鎳電鍍液來進行詳細的說明。另 外關於作為pH緩衝劑的「氨基鏈烷磺酸或其衍生物之 含有量’無論是針對哪一種鎳電鍍液’前述概念都可二 用。 、 卜2-1.瓦特浴系鎳電鍍液 201239138 瓦特浴系之錄電料，係以含有硫_·6水和物⑽ 480克/升、氣化鎳.6水和物以克/升〜克/ =較佳。於上述範圍内使用瓦特浴系錄電鍍液，從電流 效率、薄膜的特性、县如仅六> 長期保存之溶液穩定性、不易產生污 /尼荨觀點來看，會較佳 # #就硫酸鎳·6水和物及氣化鎳· :和物之間的配合平衡來說，位於上述範圍内的話，就 ㈣有特別的問題。以下，乃針對硫酸錄· 6纟和物及氣 化錄.6水和物之間的含有量限定，說明理由。 f該瓦特浴系之錄電㈣中，#硫_ . 6水和㈣ 含有量未達12G克/升的情況下，為了確保作為電鍍液之適 當的錦濃度，硫酸錄·6水和物的含有比率會變多，造成 氯離子辰度過剩，&内部應力會變高，所得到的鎳電鍍薄 齡明顯有晶格歪斜度變大及變脆之傾向，故較不佳。另 方面’當硫酸錄· 6水和物超過48〇克/升時，溶液pH 在6. 5附近的情況下，由於氮氧化錄會很容易析出溶液 穩定性就變得欠佳，故較不佳。 在該瓦特浴;、之鎳電鍍液中，當氯化鎳· 6水和物的 含有量未達15克/升的情況下，其作為去極化劑之功能就 無法發揮，同時在電鑛操作中會從陽極產生出氣體，使得 溶液PH的變動變得很顯著，因而較不佳。另一方面，當氣 :匕鎳· 6水：物超過7…升時，氯離子濃度會過剩，内 P應力會變同’所得到的錄電鍵薄膜會有晶格歪斜度變大 及變脆之明顯傾向，故較不佳。 10 201239138 1-2-2.氨基確酸浴系鎳電鍍液 氨基確酸浴系之鎳電錢液，係鐘 水和物200克/升〜6()n纟虱基％酸鎳· 4 ^ c G克/升、氯化鎳· 6水和物！弟/ 升〜6克/升為較佳。 克 於上述乾圍内使用氨基磺 電鍍液的話，就會如同前 《馱/合糸鎳 流效率、薄臈的特性、 樣，攸電 長期保存之溶液穩定性、 污泥等觀點來看，皆較伴v 不易產生 物及負仆锃.β 土又，若就氨基磺酸鎳· 4水和 ^ ,、·水和物之間的配合平衡來說，位於上述r 二的話’就不會有特別的問題。…乃針對氨基二 理由。’物及氣化錦.6水和物之間的含有量限定，說明 在氨基石黃酸浴系之錄電鍍液中，當氨基石黃酸錄· *水 :，的含有量未達200克/升的情況下，電流效率會顯著降 二：而難以形成穩定的鎳電鍍薄膜，故較不佳。另一方面， 基續酸錦· 4水和物超過咖克/升時就無法達到提 南電流效率及提升電錢操作穩定性等效果。換言之，電鍍 液的各液點度會上升’附著於被電鑛物上而被帶出的電鍍 液之消耗里會增加，鎳電鍍液中的鎳量之管理會變得繁 雜排水處理之負荷也大增，故較不佳。 、 人在氨基績酸洛系之錄電鑛液中，當氯化錄· 6水和物 :含有量未達1克/升的情況下’其作為去極化劑之功能就 =法發揮’同時在電鑛操作中會從陽極產生出氣體，使得 令液PH的變動變得很顯見，因而較不佳。另一方面，當氯 化鎳· 6水和物超過6克/升時，氣離子濃度會過剩’内部 201239138 應力會變高，所得到的鎳電鍍薄膜會有晶格歪斜度變大及 變脆之明顯傾向，故較不佳。 1-2-3.鎳電鍍液之其他添加劑 一般而言，利用電解電鍍法所得到的電鍍薄膜，會在 其析出結晶的晶格内存在有内部應力。即便是使用本發明 之錄電錄液’於既定電解條件下所得到的鎳電鐘薄膜，其 析出結晶的内部也產生了内部歪斜，此乃有内部應力產生 之結果。此種内部應力，會受到電鍍液的構成成分、液溫、 電解條件等之影響’而成為拉伸應力或壓縮應力。然而， 若從令鎳電鍍薄膜相對於被電鍍物之密合度變得更良好的 觀點來看’該㈣1^薄膜係以存在有零應力~壓縮應力 範圍之内部應力為較佳。 亦即’使用錦電鑛液時，若提高溶液pH &氯離子濃 度’鎳電錄薄膜之内部應力即會有轉變成伸張應力之傾 :用：這種情況下，就本發明之鎳電鍍液而言，係以添加 二二力調整劑較佳。此處所謂的應力調整劑，係指可吸 付於陰極表面，並包入於因 & 一 电解所析出之鎳電鍍薄膜中者 而舌0特別是當使用瓦特浴系 m -h a , ^ 螺電鍍液時，鎳電鍍薄膜之 伸張應力已知會有變大之傾 液來爷，π 1 因此，就瓦特浴系鎳電鍍 液來况添加應力調整劑以對所來Λ沾蚀 岸力it杆π Μ 九 斤形成的鎳電鍍薄膜之内部 應力進仃调整，以達到提高鎳 密合度，係為較佳做法。…膜跟被電鍍物之間的 以上述的應力調整劑而言 可使用 鄰-磺基苯曱酸亞 12 201239138 胺、對甲苯石黃醯胺、笨確酸及蔡三項酸等之含硫有機化合 物。其中，尤以在使用本發明之鎳電鍍液的情形下，係以 使=鄰-績基苯甲酸亞胺來作為應力調整劑為較佳。鄰_續 基苯甲酸亞胺係為上述含硫有機化合物之中，作為納鹽者 取得最容易，對水的溶解性也报良好，同時也是應力調整 效果最大的化合物。 此時的鄰-增基苯f酸亞胺，係於鎳電鍍液中以令其變 成是在ο.1克/升〜5克/升濃度範圍内之方式來進行添 加。當該鄰-績基笨甲酸亞胺的濃度未達0.1克/升時，由 於其對於陰極之吸付量會變少’故而無法發揮作為應力調 正』的效果，而較不佳。另一方面，當鄰—磺基笨甲酸亞胺 :農又超過5克/升時，鎳電鍍薄膜所隱藏之壓縮應力就會 fe慢地變大’而無法充分地提升錄電鑛薄膜跟被電鍵物之 間的密合度。 再者，於本發明之錄電鑛液中，若考量浴組成所給予 錄電鍍薄膜之應力影響，則在「瓦特浴系錦電鍵液」以及 「風基績酸浴系鍊電鑛液」中加入該應力調整劑的適當添 加量範圍就會各不相同。亦即，在瓦特浴系錄電鍵液的情 況下，應力調整劑之濃度係以在…升〜5克，升的範圍 内為較佳。而在氨基石黃酸浴系錄電鍍液的情況下，應力調 整劑之濃度則是以在0·1克/升〜5克/升的範圍内更佳。 本發明鎳電鍍方法之型態 本發明之鎳電鍍方法，係击 1乐便用以上所述之任一鎳電鍍 13 201239138 液，於液溫 4 0 C 〜6 f) y T I'/ ϊϊ^ 4.ΤΓ ^ 〇 C下以陰極電流密度〇.〇5A/dm〜 10 A/dm2來進行電解，而认站带姑 ^ 而於被電鍍物的表面上形成鎳電鍍 薄膜。在本錄電链方沐士 ^ rV. 又不击中’乱基％酸浴系鎳電鍍液係比瓦 特浴系錄電舰更能進行高電流密度之電解。然而，為了 令各個鎳電鍍液的特徵都能充分地發揮，瓦特浴系鎳電鍍 液係以液/皿於4〇C ~ 6〇t下、陰極電流密度為〇 〇5 A/dm2 A/dm來％行電解較佳；而氨基績酸浴系鎖電鍵液則以 液溫於40°C〜60。。下、哈抗+ 卜陰極電、"·>也、度為〇. 〇5 A/dm2〜1〇 A/dm2來施行電解更佳。 2.本發明電鍍製品之型態 本發明之錄電鑛液，係依據作為電鍵對象之被電鍍物 的種類來選擇使用 <。故而，可使用於以下各式各樣的鎳 電鍍領域：汽車零件表面裝飾用之鎳電鑛、於印刷電路板 的導體上形成阻抗電路之錄電錢、f子零件之晶片零件表 面之鎳電鍍。因此，本發明之鎳電鍍製品係泛指使用上 述本發明之鎳電鍍液及錄電鍍方法，以形成出鎖電錢薄膜 的全部製品而言。 更進-步’使用本發明之鎳電鍍液時，更具有溶液pH 為4.0〜6.5的中性範圍特徵。因此，並不會因為被電鑛 物之表面材質不同’就對該表面造成損傷。考量到此優點， 本發明之鎳電鍍液非常適合用在：無論是強酸性或強鹼性 的電鑛液下’都很容易受損的含陶究材料電子零件上。亦 即，在對於電子零件領域中容易受到強酸或強鹼損傷之晶 14 201239138 片零件施行電鍍時’就能於導電性部分上形成良好的錄電 鑛薄膜’並對Μ及其保護塗佈層損傷最小。 為了讓讀者能更詳細地理解上述的内容，以下例示出 實施例與比較例’’然而在詳述實施例及比較例之前，先說 明全篇共通之評價方法。鎳電鍍液之評價，係卩「電解前 後之/合液pH變化」、「電鍍所得到的鎳電鍍薄膜之特性 來做評比。具體…乃係針對所得到的錄電鍍薄膜之岸 力、硬度、氣孔hole)及電鍍均句度來進行評價’: 此處’薄膜應力係使用山本鍍金試…股份有限 =叙螺旋應力計來進行敎；薄膜硬度収制明石製 作所（股份有限公司）製土生夕他成ώ J 之微硬度計（型號：MVK-E)來 進1定。此外，氣孔則是針對面積為W5e[n尺寸的鋅 電鑛薄膜進行絲率試驗（Fe咖⑴叫 錄 積lcmxlcm來進行評價；電鍍均 、并面 a 1糸使用山本鍍金 器股份有限公司）製造之薄膜電池槽來進行 =膜的表面則是使用掃描式電子顯微鏡(、: 「SEM」），於傾斜角〇度、放大倍 稱為 察。 千〇〇〇倍下進行觀 [實施例1] 鎳電鍍液的調製： 在實施例1中，係調製出瓦 〆系之鍊電鐘液（TW1 浴）°該瓦特浴系之鎳電錢液（TW1洛），r、 （TW1 水和物濃度為240克/升、翕 ’糸以硫酸鎳· 6 升1化録·6水和物濃度為45克/ 201239138 升作為錄鹽’而作為 Η控 邗马pH緩衝劑之氨基乙磺酸 克/升，並使用炉西*七薪备 又、_i為60 便用硫S久或虱氧化鈉溶液來將溶 4. 50。因此，TW] 、x & 丁人* 從PH调成 岭為不纟應力冑整劑<瓦特 液。茲將TW1浴之知士 ·ί廿 于螺電經 合之組成和其他實施例與比較例所調製出的 鎳電鍍液組成併列如表1所示。 、 鎳電鍍薄膜的作成與評價： 令m浴之液溫為饥’使用金屬錄板作為陽極銅 之薄膜電池（Hullce⑴板作為陰極，以陰極電流密度5 A/cm來進行電解，而形成厚& 2_的錄電鍍薄膜。經過 10分鐘電解後之TW1浴的溶液PH為4.52。又，所得到的 鎮電鑛薄膜之應力為119Pa，硬度為副，氣孔為3.3個 /⑽2 ;電鍵均句度則係1:3時為3 5%，1:5時為5 2 兹將電解後之TW1浴的溶液PH及錄電鍍薄膜特性之評 價結果，以實施例和比較例對照方式彙整表列如表2所 不。此外，錄電鑛薄膜表面< SEM觀察成像則跟比較例丄 中所付到的鎳電鍵薄膜表面< SEM觀察成像並列呈現如 第1 (a)圖所示。 [實施例2 ] 鎳電鑛液的調製： 在實施例2中，係相對應於實施例丨中所調製出的TW1 浴，再令其更包含有作為應力調整劑之鄰-磺基苯曱酸亞胺 的鈉鹽1克/升，而調製出溶液pH為4 5〇之瓦特浴系鎳電 16 201239138 鍍液（TW2浴）。茲將TW9、,、 η 將TW2洽之組成和其他實施例與比較 所調製出的錄電鑛液組成併列如表i所示。 鎳電鍍薄膜的作成與評價： 使用TW2;谷，以跟實施例"目同的方式來施行電解， 而形成厚度2_的錄電鍍薄膜。經過1。分鐘電解後之TW2 浴的溶液pH為4.53。又，將所俨# _ . 將所侍到的鎳電鍍薄膜之應力、 硬度、氣孔及電鍍均白_ ιν — -勻度乂跟貫施例丨相同的方式來進行 測定。所得到的結果是：^ ^ 應力為一94pa，硬度為Hv451，氣 孔為1. Θ個/ cm2 ;電鍍均勺p t ς 士丛 电娀勺勺度則係1 : 3時為4. 2%，1 : :眭5.5%。炫將電解後之m浴的溶液邱及鎳電鍍 膜特性之評價結果彙整表 p 表2所不。此外，亦將鎳電 之表面以跟實施例1相同的方式，完成則觀察。 故將該SEM觀察成像跟比較 而夕㈣η 中所件到的錄電鍍薄膜表 之^觀察成像並列呈現，如第2(a)圖所示。 [實施例3] 鎳電鍍液的調製： 二實施例3中’係相對應於實施例2中所調製出的渭 睡來作Γ:Γ鈉取代原本使用…基苯曱酸亞胺的納 ^鲜詩;^㈣劑’而調f出溶液_4.5()之瓦特浴 液⑽浴）。兹將TW3洛之組成和其他實施例 、Μ所調製出的錦電鐘液組成併列如表i所示。 鎳電鍍薄臈的作成與評價： 17 201239138 使用T W 3浴，以跟音始如 、例1相同的方式來施行電解， 而形成厚度2μπι的舞雷胡：？產胳 . 螺電鍍4臈。經過10分鐘電解後之TW3 洛的溶液pH為4. 53。又，胳於β , 將所仔到的鎳電鍍薄膜之應力' 硬度、氣孔及電錢均勺声以gw 规w度以跟貫施例1相同的方式來進行 測定。所得到的結果是：摩力 疋力為UlPa，硬度為Hv452 ,氣 孔為2. 2個/ cm2 ;電鍍均勻产 屯又J J沒則係1 . 3時為4. 6%，1 : 5時為6. 3%。茲將電解後之Tw TW3冷的〉谷液pH及錄電鍍薄 膜特性之㈣結果彙整表列如表2所示。此外，亦將錄電 ㈣膜之表面以跟實施例1相同的方式，完成SEM觀察。 狄將該SEM觀察成像跟比較例3中所 干又w «j甲所得到的鎳電鍍薄膜表 面之SEM觀察成像並列呈規，如楚、 力王現如第3(a)圖所示。 [貫施例4 ] 鎳電鍍液的調製： 在實轭例4中，係以氨基磺酸鎳· 4水和物為克/ 升、氣化鎳· 6水和物為3克/升作為鎳鹽，而作為pH緩 衝劑之氨基乙績酸則為6()克/升’而調製出溶液pH為4.50 之氨基績酸浴系錄電鍍液（TS4浴）。因此，似浴為不含 應？周整劑之氨基磺酸浴系鎳電鍍液。溶液pH則是使用氨 基美^ '今液或氫氧化鈉溶液來施行調整。茲將TS4浴之組 成U實％例與比較例所調製出的錄電鑛液組成併列如 表1所示。 鎳電鍍薄膜的作成與評價： 使用TS4浴，以跟實施例i相同的方式來施行電解， 201239138 而形成厗度2μιη的鎳電鍍薄膜 〜十 、&過W分鐘電解後之TS4 ，合的洛液PH為4. 53。又，將所, 麻许产 斤件到的鎳電鍍薄膜之應力、 硬度、氣孔及電鍍均勻度以 .a,— 貫轭例1相同的方式來進行 測疋。所得到的結果是：應力 .„ . t 7 马 31.8Pa，硬度為 Hv228， 氣孔為1. 1個/ cm2 ;雷领换6 電鑛均句度則係1··3時為4.4%，1: b枯為7· 1 %。茲將電解後之 S4洽的浴液pH及鎳電鍍 膜特性之評價結果彙整表列如 她一备 表2所不。此外，亦將鎳電 鍍溥犋之表面以跟實施例丨 # 和丨j的方式，完成SEM觀察。 炫將該SEM觀察成像跟比較例 4中所得到的鎳電鍍薄膜表 面之SEM觀察成像並列呈現，如第4u) @所示。 侵姓度的評價： 了評價。關於 (varistor ) ’並藉由將之 在TS4，谷中，對晶片零件之侵餘度進行 評價的對象，係使用了晶片零件之可變電阻 及低溫同時燒結陶瓷（以下稱岑「LTCC」） 浸泡於TS4浴中來評價其被侵蝕的量。 B曰片零件之侵银量，传刺定盆於J h T 诉利疋具於45 c的TS4浴中浸泡 5小時之前後質量變化。呈體炎 具體來5兄就是在攪拌中的液量 100毫升（ml)之TS4恣Φ，a e丨丨收旦， 4〆合中，分別將量秤完成的約1 0克之 可變電阻及L T C C進行5個/丨Ηί· ιίΛ、、夺、rir 延订D個小時的改泡處理。5小時過後， 再分別將晶片零件的全體由TS4浴φ 王祖田i b4洽肀拉起予以水洗，並以 紙巾(paper towel )去昤火份祛，s m ^云除水伤傻再使用循環式烘箱於 6 〇 C下細* 4亍3 0分鐘的乾條卢理。牌私# +丄 刀里刃乾煤處理。將乾燥完成的晶片零件之 質里進行測定，得到以下沾社里.7 _兩 丁』乂 F的結果·可變電阻的質量減少率 19 201239138 為〇. 9%，LTCC的質量減少率則在ο. 1 %以下。針對晶片 零件之侵蝕量，係跟比較例4之評價結果並列如表2中所 示。 [實施例5 ] 鎳電鍍液的調製： 在實施例5中，係相對應於實施例4中所調製出的TS4 冷，再令其更包含有作為應力調整劑之鄰-磺基苯甲酸亞胺 的鈉鹽1克/升，而調製出溶液邱為45〇之氨基磺酸浴系 鎳電鍍液（TS5浴）。茲將TS5浴之組成和其他實施例與 比較例所調製出的鎳電鍍液組成併列如表丨所示。 錦電鑛薄膜的作成與評價： 使用TS5浴，以跟實施例j相同的方式來施行電解， 而形成厚度2Mm的鎳電鍍薄膜。經過1〇分鐘電解後之 洛的溶液pH為4. 53。又’將所得到的鎳f鏟薄膜之應力、 硬度、氣孔及電鍍均句度以跟實施例"目同的方式來進行 測定。所得到的結果是：應力為124Pa，硬度為—Μ，氣 孔為1.1個/ cm2 ;電鍵均勻度則係1: 3時為2 8%，卜 5時為3.7%。兹將電解後之TS5浴的溶液邱及鎳電錄薄 膜特性之評價結果彙整表列如表2所示。此外，亦將鎳電 鑛薄膜之表面以跟實施例1 4目同的方式，完成_觀^ 兹將該SEM觀察成像跟比較例5中所得到的鎳電鑛薄膜表 面之SEM觀察成像並列呈現’如第5(a)圖所示。 20 201239138 [比較例1J 鎳電鍵液的調製： 人之2較例1中，係將實施例1所調製出的ΤΠ浴中所 3作為PH緩衝劑的氨基乙磺酸 券/弁氺而儿 u見7升’改用蝴酸30 克/升來取代之，而調製出溶液 鍍液（ΠΠ、^:彳m 卯為4.50之瓦特浴系鎳電 又履c 冷）。因此，CW1浴為不 4± ^ ^ 3應力調整劑之習知瓦 特冷糸鎳電鍍液。茲將CW1浴 ^ 成和貫施例與其他比軔 歹1斤凋製出的鎳電鍍液組成併列如表i所示。 鎳電鍍薄膜的作成與評價： 使用CW1浴，以跟實施例" 』的方式來把仃電解， 形成厚度的錄電鑛薄膜。 厶過10分鐘電解後之CW1 /合的〉谷液pH為4 57。X，a定從π 57又將所传到的鎳電鍍薄膜之應力、 硬度、氣孔及電鍍均勺声w , 勺句度以跟貫施例1相同的方式來進行 測定。所得到的結果是：庳力Α 疋應刀马114Pa，硬度為Ην227，惫 孔為2· 7個/ cm2 ;電鑛均勺声 士 电緞叼刁度則係！ ： 3時為4_】％，土 ： 5時為4. 5%。茲將雷解祛夕rwi、, 灶肝电解後之CW1冷的溶液pH及鎳電鍍 膜特性之評價結果棄整表列如表2所示。此外，亦 ㈣膜之表面以跟實施例"目同的方式，完成⑽觀察。 拉將6亥SEM觀察成像跟實施例丄中所得到的錄電鑛薄膜表 面之SEM觀察成像並列呈現，如第l(b)圖所示。、 [比較例2] 21 201239138 鎳電鍍液的調製·· 在比較例2中，係相對應於比較例1中所調製出的CW1 浴，再令其更包含有作為應力調整劑之鄰-磺基笨甲酸亞胺 的鈉鹽1克/升，而調製出溶液PH為4.50之瓦特浴系鎳電 鏟液（CW2浴）。这將CW2浴之組成和實施例與其他比較 例所調製出的錦電鍍液組成併列如表i所示。 錄電鐘薄膜的作成與評價： ，使用CW2;谷，以跟實施例1相同的方式來…H 而形成厚度2Mm的鎳電鍍薄膜。經過1〇分鐘電解後之m 浴的溶液PH為4. 55β又，將所得到的鎳電鍍薄膜之應力、 硬度、氣孔及電鍍均勻度以跟實施例"目同的方式來進行 測定。所得到的結果是：應力為_92pa，硬度為，氣 孔為2.4個/ ^ ;電鍍均句度則係1: 3時為4 4%， 5時為7.1%。兹將電解後之CW2浴的溶液ρΗ及鎳電鍍薄 膜特性之評價結果彙整表列如表2所示。此外，亦將錄電 鍍薄膜之表面以跟實施例“目同的方式完成觀察。 茲將該SEM觀察成像跟實施例2中所得到的錄電鍵薄膜表 面之SEM觀察成像並列呈現，如第2 ( b )圖所示。 [比較例3] 鎳電鍍液的調製： 在比較例3中，係將比較例2所調製出的CW2浴令之 鄰-磺基笨曱酸亞胺的鈉鹽，改成以含有萘三磺酸鈉丨克/ 22 201239138 升來取代之’而調絮屮、玄该从 液（CW3浴）。兹將⑵、、谷1為4.50之瓦特浴系鎖電錢 之組成和實施例與其他比較例 所調製出的鎳電鍍液組成併列如表1所示。 鎳電鍍薄膜的作成與評價： 使用叫’以跟實施例1相同的方式來施行電解， ㈣ί厚度錄電㈣膜。經過1G分鐘電解後之CW3 冷的浴液PH為4. 55。又，將所得到的鎳電鍍薄膜之應力、 硬度、氣孔及電鍍均句度以跟實施例"目同的方式來進行 測：。所得到的結果是：應力為u〇Pa，硬度為Hv455,氣 •7個;電鑛均句度則係1:3時為3.8%，1: 5時為6.2% 1將電解後之m浴的溶 膜特性之評價結果囊整表列如表2所 铲壤瞄*主 此外，亦將鎳電 =膜之表面以跟實施例1相同的方式，完成觀察。 ^、該SE^i觀察成像跟實施例3中所得到的錄電錢薄膜表 之SEM觀察成像並列呈現，如第3⑴圖所示。 [比較例4 ] 錄電鍍液的調製： 人在比較例4中’係將實施例4所調製出的TW4浴中所 ::乍為PH緩衝劑的氨基乙續酸6〇克，升，改用蝴酸3。 鲜電二代之，而調製出溶液PH“5°之氨基項酸浴系 比’二S4浴）。兹將CS4浴之組成和實施例與其他 乂 所調製出的鎳電鍍液組成併列如表丨所示。 23 201239138 鎳電鍍薄膜的作成與評價： 使用CS4浴，以跟眚方东办丨！ ·（ α , 貫&例1相同的方式來施行電解， 而形成厚度2μιη的鋅雷妒蓮胺 ]螺電鍍屬膜。經過1〇分鐘電解後之 浴的溶液pH為4 5 5。又，脾撕π _ .旳又，將所得到的鎳電鏟薄膜之應力、 硬度、氣孔及電錢均勻度以跟竇 跟貫轭例1相同的方式來進杆 測定。所得到的結果是··應力為30屬，硬度為_订 乳孔為1.3個/& ;電鐘均勾度則係1:3時為3.伙卜 5時為7. 2 %。茲將電解後之「ς 4、,、^ 电解设之CS4冷的溶液ΡΗ及錄電鍵薄 膜特性之評價結果彙整表列如表 开 ^ 』录2所不。此外，亦將鎳電 鍍薄膜之表面以跟實施例1相同 —』0 作u的方式，完成SEM觀察。 兹將該SEM觀察成像跟實施例4中所得到的錄電鑛薄膜表 面之SEM觀察成像並列呈現’如第4(b)圖所示。 侵钱度的評價： 以跟實施例4相同的方式，藉， 错由TS4浴來評價晶片零 件之侵蝕度。其結果如下：可變雷阳 ^更卩且的質量減少率為6. 6 %，LTCC的質量減少率則為〇. 2%。 針對晶片零件之侵蝕 量’係跟實施例4之評價結果並列如 x衣2中所示。 [比較例5 ] 鎳電鍍液的調製： 在比較例5中’係將實施例5所調製出的TS5浴組成 中所含之作為PH緩衝劑的氨基乙續酸6〇克/升，改用蝴酸 24 201239138 30克/升來取代 n之，而調製出溶液ρίί盔 浴系鎳電鍍液马4· 50之氨基磺酸 (CS5 浴）。茲將 CS5 — 其他比較例所綱制 之！成和貫施例與Ming JL > The pH of the solution is 4 · 0 ～ 6 · 5 〇 201239138 The sputum liquid liquid of the present invention has a common feature by using "amino acid-burning acid or its derivative" w as a pH buffer. The aminoalkanesulfonic acid and its biological system are those in which the amino acid group having a cationic center and an anion center in the molecule is a zwitterionic state when the pH of the solution is in a neutral range. Then, wait for the masher to produce a cation, which forms an cation when the solution is acidic, and forms an anion, a tablet, a hexahydrate, and a sputum. The buffering effect of the pH of the solution in which it is placed. "The content of the "amino chain succinic acid or its derivative" as a pH buffer in the plating solution of the present invention is as described above. In the chain electric ore solution of the present invention, the content of the amino chain acid or its derivative is preferably from 3 g gram to 1 GG g/liter. If the 4 base chain (tetra) acid or the second: the biological 3 is less than 3 gram / liter, then the solution of the recording liquid ore is set at 6. 〇 折, 古 4·, IP, !· 4 'will The method fully exerts the pH buffering effect. Therefore, when the content of the right aminoalkanesulfonic acid or its derivative exceeds 100 g/L, the buffering effect of the solution pH has reached the portion exceeding the saturated content. The effect 'is therefore a waste of resources and is less preferable. Thus, the content of "amino chain resorcin or its derivative" as a pH buffer is determined. Further, in the plating solution of the present invention, it is preferred to use "amino acid" in the "4 base chain". Among such aminoglycolic acid, dinonanoic acid or its derivatives, it is excellent in the recording and liquid-keeping liquid, and has excellent stability in long-term maintenance of solution quality, and the electric ore 6 and the solution in the sputum are small. And can get a good nickel plating film ". Further, as a compound, "amino acid" is also used as a human body in 20123138. It is not only the main one, but also easy to dispose in the market, and does not increase the load of the drainage treatment, and has many advantages. Further, in the nickel electric shovel of the present invention, the nickel orphan used as the nickel ion supply source is not particularly limited, and the human-charged film formed by the ♦ electric mine can satisfy the requirements. Under the circumstance of characteristics, it can be used as a single or a mixture of nickel cyano sulfonate, nickel vaporized, nickel sulfate, nickel acetate, etc.至优选。 Preferably, the preferred embodiment of the present invention. If the solution of the nickel electric clock solution and the *^ n P疋 does not reach the strong acid range of 4.0, it can not be used for the electric forging of the wafer parts because of the intrusion, so the other side, the right nickel plating When the pH of the solution of the liquid exceeds 65, there is a case where hydrogenation occurs due to alkalinity--nickel oxide, and it is difficult to obtain a nickel plating solution excellent in stability of the Lok solution, which is not preferable. 1 2. Specific composition of the recording liquid money of the present invention As described above, the plating liquid of the present invention contains an amino chain succinic acid or a derivative thereof as a pH buffering agent, and 3 艮 "containing zinc sulfate and zinc chloride. There is a big difference between the watt bath-based nickel electric clock liquid as a nickel salt and the sulfamic acid bath-based nickel electroplating liquid containing a fluorescein and emulsified nickel as a nickel salt. The following is a detailed description of individual nickel plating solutions. Further, the above-mentioned concept of "the content of the aminoalkanesulfonic acid or its derivative" as the pH buffering agent can be used for both the nickel plating solution. 卜. 2-1. Watt bath nickel plating solution 201239138 The Watt bath system is charged with sulfur _·6 water and (10) 480 g / liter, vaporized nickel. 6 water and substance in grams / liter ~ gram / = better. Use the Watt bath in the above range Recording of electroplating solution, from the point of view of current efficiency, film characteristics, county, such as only six> long-term preservation of solution stability, and not easy to produce contamination/neutral, it would be better to use nickel sulfate·6 water and Vaporized nickel · : In the balance of the mixture, if it is within the above range, there is a special problem with (4). The following is for the sulfuric acid recorded and the gas and the gasification record. The content of the content is limited, indicating the reason. f The recording of the Watt bath system (4), # sulfur _. 6 water and (4) In the case of less than 12G g / liter, in order to ensure the appropriate concentration of the plating solution, Sulfuric acid recorded · 6 water and the content ratio of the material will increase, resulting in excessive chloride ion, & internal stress will become higher The obtained nickel electroplating thinness obviously has a tendency that the lattice skew becomes large and becomes brittle, so it is not preferable. On the other hand, when the sulfuric acid recorded water and the material exceed 48 gram/liter, the solution pH is 6. In the case of the vicinity of 5, since the nitrogen oxidation is easy to precipitate, the stability of the solution becomes poor, so it is not preferable. In the Watt bath; the nickel plating solution, when the nickel chloride 6 water and the substance When the content is less than 15 g/L, its function as a depolarizing agent cannot be exerted, and at the same time, gas is generated from the anode during the operation of the electric ore, so that the fluctuation of the pH of the solution becomes remarkable, and thus is less On the other hand, when the gas: 匕 nickel · 6 water: the material exceeds 7 ... liters, the chloride ion concentration will be excessive, the internal P stress will become the same as the obtained recording bond film will have a larger lattice tilt and It is a less obvious tendency to become brittle, so it is less. 10 201239138 1-2-2. Amino acid bath nickel plating solution Amino acid bath system of nickel electricity money, system water and matter 200 g / liter ~ 6 ( ) n 纟虱 % % % · · ^ ^ ^ ^ ^ ^ ^ % % % % % % % % % % % % 氯化 弟 弟 弟 弟 弟 弟 弟 弟 弟 弟 弟 弟 弟 弟 弟 弟 弟When using the aminosulfonic acid plating solution, it will be similar to the previous "驮/糸 糸 流 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸 糸And the negative servant. Beta soil, if the balance between the nickel sulfamate and the water, and the balance between water and matter, the above two r will not have a special problem. For the reason of amino 2, 'the content of the substance and gasification jin. 6 water and the content limit, indicating that in the recording solution of the aminophosphoric acid bath system, when the amino-phosphoric acid recorded * water:, contains When the amount is less than 200 g/liter, the current efficiency is significantly reduced by two: it is difficult to form a stable nickel plating film, which is not preferable. On the other hand, when the base acid and the water and the material exceed the calorie/liter, the current efficiency of the current and the stability of the operation of the electricity can not be improved. In other words, the liquid level of the plating solution rises. The consumption of the plating solution that is carried out by the adhering to the charged mineral increases, and the management of the amount of nickel in the nickel plating solution becomes complicated. Increased, it is not good. In the case of human recordings in the alkaline mineral acid system, when the chlorination of 6 water and the substance: the content is less than 1 g / liter, its function as a depolarizer = play At the same time, in the operation of the electric ore, gas is generated from the anode, so that the fluctuation of the pH of the liquid becomes obvious and thus is not preferable. On the other hand, when the nickel chloride·6 water and the substance exceed 6 g/l, the gas ion concentration will be excessive. 'The internal 201239138 stress will become high, and the obtained nickel electroplated film will have a large lattice slack and become brittle. It is obviously inclined, so it is not good. 1-2-3. Other Additives for Nickel Plating Solution In general, a plating film obtained by electrolytic plating has internal stress in a crystal lattice in which crystals are precipitated. Even in the nickel electric clock film obtained by using the electrophotographic recording liquid of the present invention under the predetermined electrolysis conditions, internal cracking occurs in the interior of the precipitated crystal, which is a result of internal stress. Such internal stress is affected by the constituent components of the plating solution, the liquid temperature, the electrolysis conditions, and the like, and becomes a tensile stress or a compressive stress. However, from the viewpoint of making the adhesion of the nickel plating film to the object to be plated more favorable, it is preferable that the film has an internal stress in the range of zero stress to compressive stress. That is, when using Jindian mineral liquid, if the internal stress of the nickel ion recording film is increased, the internal stress of the nickel ion recording film will be converted into the tensile stress: in this case, the nickel plating of the present invention In the case of liquid, it is preferred to add a second force adjuster. The term "stress adjuster" as used herein means that it can be absorbed on the surface of the cathode and entrapped in the nickel electroplated film deposited by & electrolysis, and the tongue 0, especially when using the watt bath system m -ha , ^ snail In the case of electroplating solution, the tensile stress of the nickel electroplated film is known to be increased. The π 1 is therefore added to the stress-adjusting agent of the Watt bath nickel plating solution to corrode the shore force.内部 It is better to adjust the internal stress of the nickel-plated film formed by nine pounds to improve the nickel adhesion. Between the film and the object to be plated, the above-mentioned stress modifier may be used as a sulfur-containing substance such as o-sulfobenzoic acid sub 12 201239138 amine, p-toluene xanthanamine, stupid acid, and triteric acid. Organic compound. Among them, in particular, in the case of using the nickel plating solution of the present invention, it is preferred to use = o-based benzoic acid imide as a stress adjuster. The benzoic acid imide is one of the above-mentioned sulfur-containing organic compounds, and it is the easiest to obtain as a nanosalt, and the solubility in water is also reported to be good, and the compound having the largest stress adjustment effect. The ortho-addition benzene f acid imide at this time is added in a nickel plating solution so as to be changed in a concentration range of ο.1 g/liter to 5 g/liter. When the concentration of the o-based benzoic acid imide is less than 0.1 g/liter, the amount of absorption to the cathode is small, so that it is not effective as a stress adjustment, and it is not preferable. On the other hand, when the o-sulfobenzoic acid imide: more than 5 g / liter, the compressive stress hidden by the nickel electroplated film will become slower and larger, and the recording film can not be sufficiently enhanced. The degree of adhesion between the keys. Furthermore, in the recording fluid of the present invention, if the stress effect of the plating film is given to the plating film, the "Watt bath system key" and the "wind base acid bath chain electric ore" are used. The range of suitable addition amounts to the stress modifier will vary. That is, in the case where the Watt bath is charged with the key liquid, the concentration of the stress modifier is preferably in the range of liters to 5 gram. In the case of the electroplating solution of the aminophosphoric acid bath, the concentration of the stress modifier is preferably in the range of 0.1 g/L to 5 g/L. The nickel electroplating method of the present invention is a nickel electroplating method of the present invention, which is capable of using any of the above-mentioned nickel electroplating 13 201239138 liquid at a liquid temperature of 4 0 C to 6 f) y T I'/ ϊϊ ^ 4. ΤΓ ^ 〇C is electrolyzed at a cathode current density of 〇.5A/dm to 10 A/dm2, and a nickel plating film is formed on the surface of the object to be plated. In this recording electric chain Fang Mushi ^ rV. Also not hit the 'chao-based acid bath nickel plating liquid system than the Watt bath series electric ship can carry out high current density electrolysis. However, in order to fully utilize the characteristics of each nickel plating solution, the Watt bath nickel plating solution is liquid/dish at 4 〇C ~ 6 〇t, and the cathode current density is 〇〇5 A/dm2 A/dm. It is better to carry out the electrolysis of the % line; and the liquid of the amino acid bath is locked at a temperature of 40 ° C to 60 ° C. . Lower, Ha Kang + Bu cathode electricity, "·> also, the degree is 〇. 〇5 A / dm2 ~ 1 〇 A / dm2 to perform electrolysis better. 2. Type of electroplated product of the present invention The electrocaloric liquid of the present invention is selected and used according to the type of electroplated object to be a key object. Therefore, it can be used in the following various nickel plating fields: nickel electro ore for surface decoration of automobile parts, recording electric power for forming an impedance circuit on a conductor of a printed circuit board, and nickel plating for the surface of a wafer part of a f sub-part. . Accordingly, the nickel electroplated article of the present invention generally refers to the use of the above-described nickel electroplating bath and electroplating method of the present invention to form all of the products of the plug-in money film. Further, when the nickel plating solution of the present invention is used, it has a neutral range characteristic of a solution pH of 4.0 to 6.5. Therefore, it is not damaged by the surface material of the charged mineral. In view of this advantage, the nickel plating solution of the present invention is very suitable for use in electronic parts containing ceramic materials which are easily damaged under the presence of strongly acidic or strongly alkaline electric mineral liquids. That is, in the case of electroplating of a crystal 14 201239138 piece which is easily damaged by strong acid or alkali in the field of electronic parts, 'a good recording film can be formed on the conductive portion' and the coating layer and the protective coating layer can be formed. The damage is minimal. In order to allow the reader to understand the above contents in more detail, the following examples and comparative examples will be exemplified. However, before the detailed examples and comparative examples are explained, the evaluation methods common to the entire article will be described. The evaluation of the nickel plating solution is based on the "change in pH before and after electrolysis" and the characteristics of the nickel-plated film obtained by electroplating. Specifically, it is based on the shore force and hardness of the obtained electroplated film. "Pore hole" and plating uniformity to evaluate ': Here's the film stress system using Yamamoto gold-plated test... Share limited = Syria spiral stress gauge for 敎; film hardness acquisition Akashi Manufacturing Co., Ltd. Cheng Hao J's micro hardness tester (model: MVK-E) to enter the first. In addition, the pores are for the area of W5e [n size zinc electromine film for silk rate test (Fe coffee (1) called recording lcmxlcm Evaluation; plating is performed, and the surface of the film is made by using a thin film battery cell manufactured by Yamamoto Gold Co., Ltd.) = the surface of the film is a scanning electron microscope (: "SEM"), and the tilt angle is Magnification is called inspection. Observations at a thousand times [Example 1] Preparation of a nickel plating solution: In Example 1, a corrugated chain bell liquid (TW1 bath) was prepared, and the Watt bath nickel nickel liquid solution was prepared. (TW1 Luo), r, (TW1 water and substance concentration is 240 g / liter, 翕 '糸 with nickel sulfate · 6 liters 1 chemistry · 6 water and the concentration of 45 grams / 201239138 liters as a salt" and as a Η Control the pH of the amino acid sulfonate in liters of the horse's pH buffer, and use the furnace to make a seven-month salary, and the _i is 60 to use the sulfur S long-term or sodium strontium oxide solution to dissolve 4. 50. Therefore, TW], x & Ding * From the PH to the ridge is not the stress tempering agent < watt liquid. I will TW1 bath Zhishi · 廿 螺 螺 螺 螺 螺 螺 螺 螺 螺 螺 调制 调制 调制 调制 调制 调制The composition of the nickel plating solution is shown in Table 1. The preparation and evaluation of the nickel plating film: Let the liquid temperature of the m bath be hungry. Use the metal recording plate as the anode copper thin film battery (Hullce (1) plate as the cathode, the cathode current density Electrolysis was carried out at 5 A/cm to form a plating film of thickness & 2_. The solution pH of the TW1 bath after electrolysis for 10 minutes was 4.52. The stress of the galvanic mine film is 119Pa, the hardness is sub-, the stomata is 3.3/(10)2; the average degree of the electric bond is 3 5% at 1:3, and the TW1 bath after electrolysis at 5:5 The results of the evaluation of the pH of the solution and the characteristics of the electroplated film were summarized in Table 2 in the comparison of the examples and the comparative examples. In addition, the surface of the recorded film was observed and compared with the comparative example. The surface of the nickel bond film < SEM observation image appears side by side as shown in Fig. 1 (a). [Example 2] Modulation of nickel electro-mineral liquid: In Example 2, it was prepared in accordance with Example 丨The TW1 bath is further contained, and the sodium salt of o-sulfobenzoic acid imide as a stress adjuster is further contained in 1 gram/liter, and the pH of the solution is 45 watts of the bath-based nickel battery 16 201239138 Plating solution (TW2 bath). The composition of TW9, 、, η TW2 and other examples and comparisons of the composition of recorded recording liquid ore are shown in Table i. Preparation and evaluation of nickel plating film: Use TW2; Valley, electrolysis was carried out in the same manner as in the example ", and a plating film having a thickness of 2_ was formed. After a minute of electrolysis, the pH of the solution in the TW2 bath is 4.53. In addition, the stress, hardness, pores and plating of the nickel plating film to be applied are white _ ιν - uniformity 乂The measurement was carried out in the same manner. The results obtained were: ^ ^ stress of 94 Pa, hardness of Hv451, stomata of 1. Θ / cm 2 ; plating pt ς 士 丛 娀 娀 勺 1 1 1 : 3 The time is 4. 2%, 1: : 眭 5.5%. Hyun will be the solution of the m bath after electrolysis Qiu and nickel plating film characteristics evaluation results summary table p Table 2 does not. Further, the surface of the nickel electric wire was also observed in the same manner as in the first embodiment. Therefore, the SEM observation image is compared with the observation image of the recorded electroplated film sheet in the (4) η, as shown in Fig. 2(a). [Example 3] Preparation of nickel plating solution: In the second embodiment, 'the system corresponds to the doze produced in the second embodiment as the sputum: the sodium sulphate is replaced by the sodium phthalate imine. Fresh poetry; ^ (four) agent 'and adjust the solution _4.5 () watt bath (10) bath). The composition of the TW3 Luo and other compositions and the composition of the bell powder prepared by the sputum are shown in Table i. Preparation and evaluation of nickel-plated thin crucibles: 17 201239138 Using T W 3 bath, electrolysis was carried out in the same manner as in the first example, and the formation of 2 μπι thickness of the dance Leihu:? Production. Screw plating 4臈.单词。 The pH of the solution of TW3 Luo after the electrolysis was 4. 53. Further, in the case of β, the stress of the nickel plating film, the hardness, the pores, and the electric money were measured in the same manner as in Example 1 by gw. The result is: the force of the force is UlPa, the hardness is Hv452, the stomata is 2. 2 / cm2; the electroplating is evenly produced, and the JJ is not 1. 3. When it is 1. 6%, 1: 5 6. 3%. The results of the (4) results of the Tw TW3 cold > trough liquid pH and the electroplated film characteristics after electrolysis are shown in Table 2. Further, the surface of the film (4) film was also subjected to SEM observation in the same manner as in Example 1. The SEM observation imaging of the SEM observation and the surface of the nickel electroplated film obtained in Comparative Example 3 was carried out in parallel, as shown in Fig. 3(a). [Example 4] Preparation of nickel plating solution: In the solid yoke example 4, nickel sulfamate 4 water and gram/liter, vaporized nickel -6 water and 3 g/liter were used as nickel. The salt was used as the pH buffering agent, and the amino acid was 6 () g / liter' to prepare an aqueous solution of a solution having a pH of 4.50 (TS4 bath). Therefore, the bath is not included? A sulfamic acid bath nickel plating solution for the entire formulation. The pH of the solution is adjusted using ammonia or sodium hydroxide solution. The compositions of the TS4 bath and the composition of the recording fluid prepared by the comparative example are shown in Table 1. Preparation and Evaluation of Nickel Electroplated Film: Using a TS4 bath, electrolysis was carried out in the same manner as in Example i, and a nickel plating film having a twist of 2 μm was formed in 201239138~10, & The liquid PH was 4.53. Further, the stress, the hardness, the pores, and the plating uniformity of the nickel plating film to which the material was supplied were measured in the same manner as in Example 1 of the yoke. The results obtained are: stress. „ . t 7 horse 31.8Pa, hardness Hv228, stomata 1.1 / cm2; Lei collar for 6 electric ore uniformity is 4.4% when 1··3, 1 : b is 7.7%. The evaluation results of the pH of the bath and the characteristics of the nickel plating film after the electrolysis are listed in Table 2 as in Table 2. In addition, the surface of the nickel plating is also applied. The SEM observation was carried out in the same manner as in the examples 丨# and 丨j. The SEM observation and the SEM observation of the surface of the nickel electroplated film obtained in Comparative Example 4 were juxtaposed as shown in Fig. 4u) @. Evaluation of the surname: Evaluation. Regarding (varistor)' and evaluating it in TS4, Valley, the object of the wafer part is the variable resistance of the wafer part and the low temperature simultaneous sintering of the ceramic ( Hereinafter, "LTCC" was immersed in a TS4 bath to evaluate the amount of erosion. The amount of silver intrusion of the B-clamp parts was measured by the mass of the J T 定 疋 疋 浸泡 浸泡 5 5 5 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 The specific body of the body inflammation is the volume of 100 ml (ml) of TS4 恣 Φ, ae 丨丨 丨丨 ,, 4 〆 in the mixing, about 10 grams of variable resistance and LTCC Perform 5 / 丨Η ί ι Λ 、 、 r r r 延 延 延 延 延 延 延 延 延 延 延 延 延 延 延 延 延After 5 hours, the entire wafer parts were pulled up by the TS4 bath φ Wang Zutian i b4, and washed with paper towel. The sm ^ cloud removes the water and uses the circulating oven. At 6 〇C, the fine * 4 亍 30 minutes of dry bar Lu Li.牌私# +丄 Knife blade dry coal treatment. The quality of the dried wafer parts was measured, and the following results were obtained. The mass reduction rate of the variable resistor 19 201239138 was 〇. 9%, and the mass reduction rate of LTCC was ο. 1% or less. The amount of erosion of the wafer parts was shown in Table 2 in conjunction with the evaluation results of Comparative Example 4. [Example 5] Preparation of nickel plating solution: In Example 5, TS4 was prepared in accordance with Example 4, and further contained o-sulfobenzoic acid as a stress adjuster. The sodium salt of the amine was 1 g/liter, and a sulfamic acid bath-based nickel plating solution (TS5 bath) having a solution of 45 Å was prepared. The composition of the TS5 bath and the composition of the nickel plating solution prepared by the other examples and the comparative examples are shown in parallel. Preparation and evaluation of film of galvanic iron ore: Electrolysis was carried out in the same manner as in Example j using a TS5 bath to form a nickel plated film having a thickness of 2 Mm. The pH of the solution after the electrolysis was 1.53. Further, the stress, hardness, pores, and plating uniformity of the obtained nickel-shovel film were measured in the same manner as in the Examples. The results obtained were as follows: stress was 124 Pa, hardness was -Μ, pores were 1.1 / cm2, and signal uniformity was 2 8% at 1:3, and 3.7% at 5:00. The evaluation results of the characteristics of the solution of the TS5 bath after electrolysis and the characteristics of the nickel electro-recording film are shown in Table 2. In addition, the surface of the nickel ore film was also completed in the same manner as in Example 14. The SEM observation and the SEM observation of the surface of the nickel ore film obtained in Comparative Example 5 were carried out in parallel. 'As shown in Figure 5(a). 20 201239138 [Comparative Example 1J Preparation of nickel electro-key solution: In the case of human 2, the aminoethanesulfonic acid coupon of 3 in the bath prepared in Example 1 as a pH buffer was used. See 7 liters 'replaced with 30 grams of citric acid per liter to replace the solution, and prepare the solution plating solution (ΠΠ, ^: 彳m 卯 is 4.50 watt bath nickel battery and c cold). Therefore, the CW1 bath is a conventional Watt cold nickel plating solution which does not have a stress modifier of 4 ± ^ ^ 3 . The composition of the CW1 bath and the other examples are combined with other nickel plating solutions of 1 kg, as shown in Table i. Preparation and Evaluation of Nickel Electroplated Film: Using a CW1 bath, the crucible was electrolyzed in the same manner as in the example " to form a recording film of a thickness. The pH of the CW1 / combined solution was calculated to be 4 57 after 10 minutes of electrolysis. X, a is determined from π 57 and the stress, hardness, pores and plating of the nickel electroplated film are transferred, and the scoring degree is measured in the same manner as in the first embodiment. The result obtained is: 庳力Α 疋 刀 knife 114Pa, hardness Ην227, 惫 hole is 2·7 / cm2; : 3 hours is 4_]%, soil: 5 hours is 4.5%. The evaluation results of the evaluation results of the pH of the CW1 cold solution and the characteristics of the nickel plating film after the liver electrolysis were shown in Table 2. Further, (4) the surface of the film was observed in the same manner as in the example <10>. The SEM observation image of the 6-Hai SEM observation image and the surface of the recorded electro-mineral film obtained in the Example 并 was juxtaposed as shown in Fig. 1(b). [Comparative Example 2] 21 201239138 Preparation of nickel plating solution · In Comparative Example 2, it corresponds to the CW1 bath prepared in Comparative Example 1, and further contains o-sulfonate as a stress adjuster. The sodium salt of the acid imine was 1 g/liter, and a Watt bath nickel electric shovel (CW2 bath) having a solution pH of 4.50 was prepared. This is shown in Table i along the composition and examples of the CW2 bath and the composition of the bismuth plating solution prepared by the other comparative examples. Preparation and Evaluation of Recording Clock Film: Using a CW2; valley, a nickel plating film having a thickness of 2 Mm was formed in the same manner as in Example 1. The pH of the solution of the m bath after electrolysis for 1 minute was 4.55β, and the stress, hardness, pores and plating uniformity of the obtained nickel plating film were measured in the same manner as in the Examples. The results obtained were: stress _92 Pa, hardness, and pores of 2.4/^; electroplating uniformity was 4 4% at 1:3 and 7.1% at 5:00. The results of the evaluation of the results of the solution of the CW2 bath after electrolysis and the characteristics of the nickel electroplated film are shown in Table 2. In addition, the surface of the electroplated film was also recorded in the same manner as in the examples. The SEM observation image was imaged in parallel with the SEM observation of the surface of the electroless magnetic film obtained in Example 2, as shown in the second ( b) Fig. [Comparative Example 3] Preparation of nickel plating solution: In Comparative Example 3, the sodium salt of o-sulfoindole imine of CW2 bath prepared in Comparative Example 2 was changed. It is composed of sodium naphthalene trisulfonate / 22 201239138 liters to replace 'the flocculent sputum, Xuan this liquid (CW3 bath). I will (2), valley 1 is 4.50 watt bath lock money composition The composition of the nickel plating solution prepared in the same manner as in the other comparative examples is shown in Table 1. Preparation and Evaluation of Nickel Electroplated Film: Electrolysis was carried out in the same manner as in Example 1, (4) 厚度 thickness recording (4) The pressure of the CW3 cold bath after electrolysis in 1G minutes is 4.55. Further, the stress, hardness, pores and plating uniformity of the obtained nickel electroplating film are in the same manner as in the example " Test: The result is: stress is u〇Pa, hardness is Hv455, gas • 7; the average degree of electric ore is 3.8% at 1:3, and 6.2% at 1:5. 1 The evaluation results of the film characteristics of the m bath after electrolysis are listed in Table 2 as shown in Table 2 * In addition, the surface of the nickel electric=film was also observed in the same manner as in Example 1. ^, the SE^i observation image was juxtaposed with the SEM observation image of the recorded electric film sheet obtained in Example 3. Presented as shown in Fig. 3 (1). [Comparative Example 4] Preparation of plating solution: Human in Comparative Example 4 'This is the TW4 bath prepared in Example 4: 乍 is the amino acid of pH buffer Continued acid 6 grams, liter, switch to the use of butterfly acid 3. Fresh electricity second generation, and prepare the solution PH "5 ° amino acid bath system than 'two S4 bath." The composition and examples of the CS4 bath are combined with other nickel plating baths prepared as shown in the table. 23 201239138 Preparation and evaluation of nickel plating film: Use CS4 bath to do with Aodong Fangdong! (α, 均和例例1 The same method was used to perform electrolysis, and a zinc sulphate having a thickness of 2 μm was formed). The solution pH of the bath after electrolysis for 1 minute was 4 5 5 . The spleen tear π _ 旳 ,, the obtained nickel shovel film stress, hardness, porosity and electricity uniformity in the same way as the sinus yoke example 1 into the rod. The results are The stress is 30 genus, the hardness is _ ordering the milk hole is 1.3/&; the electric clock is hooked at a ratio of 1:3 to 3. When the bud is 5, it is 7.2%. ,,, ^ Electrolytic design of CS4 cold solution ΡΗ and the results of the evaluation of the characteristics of the film of the recording key are summarized as shown in Table 2. In addition, the surface of the nickel plating film is the same as in the first embodiment - SEM observation was performed in the manner of 0. The SEM observation image was imaged in parallel with the SEM observation of the surface of the recording ore film obtained in Example 4 as shown in Fig. 4(b). Evaluation: In the same manner as in Example 4, the degree of erosion of the wafer parts was evaluated by the TS4 bath. The results are as follows: The mass reduction rate is 6.6 %, and the mass reduction rate of LTCC is 〇. 2%. The amount of erosion for the wafer parts is the same as that of Example 4, as shown in x. 2. [Comparative Example 5 Preparation of Nickel Electroplating Solution: In Comparative Example 5, the amino acid hydrochloride as a pH buffer contained in the composition of the TS5 bath prepared in Example 5 was changed to 6 g/L, and was changed to the butterfly acid 24 201239138 30 g / liter to replace n, and prepare the solution ρίί helmet bath nickel plating solution horse 4 · 50 sulfamic acid (CS5 bath). I will be CS5 - other comparative examples of the system! versus
AES :氨基乙續酸 BA ··硼酸 0SI :鄰-磺基苯甲酸亞胺鈉鹽 j^TS :萘三磺酸鈉 J_ 战併列如表1所示。表 比較例5 NiS〇4:硫酸 NiCh :氣化鎳6水和物 NST:氨基項酸鎮4水和物 鎳電鍍薄膜的作成與評價： 使用CS5浴，、 而形 '，以跟實施例1相同的方式來施行電解， ^ 、旱度2_的鎳電鍍薄膜。經過1〇分鐘 浴的溶液pH為 右也 .4。又，將所得到的鎳電鍍薄膜之應力、 硬又、氣孔及電鑛 鐵均勻度以跟實施例1相同的方式來進行 測疋。所得到的社 、 、、、D果疋.應力為99. 2Pa，硬度為Ην432， 氣孔為〇 · 9個/ 2 ’ Cm ;電鍍均勻度則係1 : 3時為2. 9%，1 : 5 時為 3. 2 y。# • 0 °錄將電解後之CS5浴的溶液pH及鎳電鑛薄 25 201239138 膜特性之評價結果彙整表列如 鍍薄膜之表面以跟實施例1相 茲將該SEM觀察成像跟實施例 面之SEM觀察成像並列呈現， 表2AES: aminoethyl acid BA ··boric acid 0SI: o-sulfobenzoic acid imide sodium salt j^TS: sodium naphthalene trisulfonate J_ The war is shown in Table 1. Table Comparative Example 5 NiS〇4: Sulfuric Acid NiCh: Vaporized Nickel 6 Water and Material NST: Preparation and Evaluation of Amino-Acid Acid 4 Water and Nickel Electroplated Film: Using CS5 Bath, and Form ', with Example 1 In the same way, a nickel-plated film of electrolysis, ^, and drought 2_ was applied. The pH of the solution after 1 minute of bathing is also right. Further, the stress, hardness, porosity, and electric iron uniformity of the obtained nickel plating film were measured in the same manner as in Example 1. The 9%, 1 : 9%, 1 : 9%, 1 : 5 hours is 3. 2 y. # • 0 ° Record the pH of the solution of the CS5 bath after electrolysis and the nickel ore thinning 25 201239138 The evaluation results of the film characteristics are summarized as the surface of the coated film to compare with the example 1 to image the SEM observation and the example SEM observation imaging is presented side by side, Table 2
表2所示。此外，亦將鎳電 同的方式，完成SEM觀察。 5中所得到的鎳電鍍薄膜表 如第5 ( b)圖所示。 [實施例與比較例之對比1:電解前後之溶液pH變化] 如表2所示，電解後之錄電銀液的溶液pH，在實施例 中上升了 〇. 02〜〇. 03，在比較例中則上升了 0.04 - 〇.〇7。 此外針對相同浴組成之間溶液pH的上升度進行對比，比 較例比起實施例高 酸或其衍生物作為 了 〇·〇1〜0.05。因此，含有氨基鏈烷磺 pH緩衝劑之鎳電鍍液，在採用相同的電 解條件下，比起使用習知的鎳電鍍液而言，溶液pH變化比 較小。亦即’可推斷得出：含有氨基鏈烷磺酸或其衍生物 26 201239138 …夠維持長―' [實施例與比較例之對比2 :薄膜特性] 首先，參見第1圖〜第5圖，針對實施例中所得到的錄 電鑛薄膜表面的SEM照片（a)跟比較例中所得到的錦電錄 溥膜表面的SEM照片（b) ’進行對比。由第】圖〜第5圖 可看出’使用氨基乙核跟使用顯來作為pH緩衝劑時， 外觀上看不出有很大的不同。此外，如表2所示，薄膜特 性及電錄均勻度也看不出有很大的不同。另一方面，無論 是在瓦特浴系'或是氨基續酸浴系+，薄膜特性受到應力^ 整劑的影響都很大。因此，可推斷. J催®r侍出.即使是以硼酸來 取代氨基鏈料酸或其衍生物作為pH緩衝劑使用，也可以 獲得跟使用習知鎳電鍍液時㈣薄膜特性之鎳電鑛薄膜。 [實施例與比較例之對比3 :侵蝕度] 關於鎳電錢液對於晶片零件之侵触度，係以實施例4 及比較例4的氨基賴浴來進行比較，在含有侧酸 作為PH緩衝劑之比較例4巾，其侵钱量係；可變電阻為 HLTCC為0.2%;相較於此，在含有氨基乙確酸作為 pH緩衝狀實施例4中，其侵触量係；可變電阻為〇 ， LTCC則在〇·ι%以下。田比 因此’右考量到羧酸系的侵蝕力比 棚酸更強這個事實，即可判斷推得：含有氨基鏈炫續酸或 其衍生物作為dH緩衝密丨丨》麻u P泼衝剤之貫施例的鎳電鍍液，能夠跟不含 27 201239138 針對防止晶片 有硼酸時的情況相同 的效果。 零件被侵蝕發揮極大 L發明的效果] 本發明之鎳電鍍液 物質者。並且，本發明之鐘Γ 染防治法所限制 制電鐘液溶液抑之變動f液’係可長時間穩定地抑 ό…玄 並形成具有不輸於習知鎳電铲滿 率、電料觀等諸特性之料㈣臈。、，又 :二本發明之錦電鑛液，其溶液邱為 並且不含,酸及缓酸系強有機酸。因丨 的陶莞部位受到Si之際，也可抑制晶片零件 塗你展 ^钱，亦即對於具有由陶竞所構成的保護 層之晶片零件而言，也可以施予直接錄電鍍。 ▲再者’本發明之錄電鑛方法’比起習知的錄電鍍方法 而’，並不需要進行降低電流密度之操作。藉此，電鍍薄 膜的生產率也變得非常良 又, 口❿便用本發明的鎳電鍍 電鍍方法’對於晶片零件以外其他之對施行錄電鍍 砰耐腐蝕性不穩定的被電鍍物質，也全體適用。 [產業上可利用性] 本發明之鎳電鍍液，係不含有水質污染防治法所限制 物質者。因此’是屬於對環境負；^、排水負荷影響極小之 電鍍液。而且，本發明之鎳電鍍液，由於可以長時間穩定 地抑制電鍍液溶液ρΗ之變動，故能長時間的使用，具有優 28 201239138 異的成本效果。 本發明之鎳電鍍液 鍍之技術領域。故而， 為從弱酸性到中性範圍 之晶片零件的鎳電鍍薄 陶資•部位受到侵姓。 ’可以應用於所有必須使用到鎳電 本發明之錄電鍍液，由於其溶液pH ’因此也可以使用在具有陶瓷部位 膜形成上’亦能夠抑制晶片零件的 又， 備來實施 本發明之鎳電鍍方法， ，不需要投資新的設備 由於可利用習知之既有設 故能有效利用既有設備。 【圖式簡單說明】 第 1 圖（... ^ 、b)係表示實施例1及比較例1所得到 的鎳電鍍薄膜之播> 二、 、 掃私式電子顯微鏡觀察成像圖（放大 10, 000 倍）。 第 2 圖（. ^ 、〈b)係表示實施例2及比較例2所得到 的錄電鑛薄膜 ' ~私式電子顯微鏡觀察成像圖（玫大 10,000 倍）。 第 3 圖（"gj 、 Q b)係表示實施例3及比較例3所得到 的錄電鍍薄膜 1Λ ' 式電子顯微鏡觀察成像圖（放大 1〇,〇〇0 倍）。 人 第4圖（a、 n . 〈b)係表示實施例4及比較例4所得到 的錄電链薄腹夕 ~描式電子顯微鏡觀察成像圖（玫大 1 0,000 倍）。 八 第 5 圖（a、 、η、Table 2 shows. In addition, SEM observation was also performed in the same manner as nickel. The nickel electroplated film obtained in 5 is shown in Fig. 5(b). [Comparative Example 1 vs. Comparative Example 1: pH change of solution before and after electrolysis] As shown in Table 2, the pH of the solution of the electroplated silver solution after electrolysis was raised in the examples 02. 02~〇. 03, in comparison In the example, it is increased by 0.04 - 〇.〇7. Further, the degree of rise of the pH of the solution between the same bath compositions was compared, and the comparative example was used as the 高·〇1 to 0.05 as compared with the high acid or its derivative of the examples. Therefore, the nickel plating solution containing the aminoalkanesulfone pH buffer has a smaller pH change ratio of the solution than the conventional nickel plating solution under the same electrolytic conditions. That is, it can be inferred that the amino alkanesulfonic acid or its derivative 26 201239138 ... is long enough to maintain - "Comparative Example 2 vs. Comparative Example 2: Film Properties] First, see Figures 1 to 5, The SEM photograph (a) of the surface of the recorded electric ore film obtained in the examples was compared with the SEM photograph (b) of the surface of the tantalum film obtained in the comparative example. It can be seen from Fig. 5 to Fig. 5 that when the aminoethyl nucleus is used and the use is apparent as a pH buffer, there is no significant difference in appearance. In addition, as shown in Table 2, the film characteristics and the uniformity of the electric recording were not significantly different. On the other hand, whether in the Watt bath system or the amino acid acid bath system, the film properties are greatly affected by the stress agent. Therefore, it can be inferred that J-catalyz® is used. Even if boronic acid is used instead of amino chain acid or its derivative as a pH buffer, it is possible to obtain a nickel-electric ore with the characteristics of a film when using a conventional nickel plating solution. film. [Comparative Example 3 vs. Comparative Example 3: Degree of Erosion] The degree of intrusion of the nickel-electric money liquid on the wafer parts was compared with the amino-based baths of Example 4 and Comparative Example 4, and the side acid was used as the pH buffer. Comparative Example 4, the amount of money invaded; the variable resistance was 0.2% for HLTCC; in contrast, in Example 4 containing amino acid as pH buffer, the amount of intrusion was 〇, LTCC is below ι·ι%. Therefore, the fact that the ratio of the carboxylic acid system is stronger than that of the arsenic acid can be judged by the fact that the amino acid chain acid or its derivative is used as a dH buffer. The nickel plating solution of the example can be used in the same manner as in the case of preventing the presence of boric acid on the wafer in 2012. The parts are eroded to the effect of the invention. The nickel plating solution of the present invention. Moreover, the clock dyeing control method of the present invention limits the variation of the electric clock solution to the f liquid, which can stably suppress the sputum for a long time... and the formation of the shovel is not lost to the conventional nickel shovel full rate, the electric material view Wait for the characteristics of the material (four) 臈. And, again: two of the invention's Jindian mineral liquid, the solution is Qiu and does not contain, acid and acid retardant strong organic acid. Since the ceramic part of the enamel is subjected to Si, it is also possible to suppress the wafer parts from being coated with money, that is, for wafer parts having a protective layer composed of Tao Jing, direct recording plating can also be applied. ▲ Further, the method of recording the present invention of the present invention does not require an operation for reducing the current density as compared with the conventional electroplating method. As a result, the productivity of the electroplated film is also very good, and the nickel electroplating method of the present invention is applied to the electroplated material which is unstable to the electroplated crucible other than the wafer part. . [Industrial Applicability] The nickel plating solution of the present invention does not contain substances restricted by the Water Pollution Prevention and Control Act. Therefore, it is a plating solution that is negative to the environment; ^, which has minimal impact on the drainage load. Further, since the nickel plating solution of the present invention can stably suppress the fluctuation of the plating solution solution for a long period of time, it can be used for a long period of time, and has a cost advantage of excellent. The technical field of nickel plating bath plating of the present invention. Therefore, the nickel plating of the wafer parts from the weakly acidic to the neutral range is invaded. 'Can be applied to all of the electroplating baths of the present invention that must be used in the present invention. Since the pH of the solution can also be used in the formation of a film having a ceramic portion, it is also possible to suppress the wafer parts, and the nickel plating of the present invention can be carried out. In this way, there is no need to invest in new equipment because it can be used to make effective use of existing equipment. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (...^, b) shows the broadcast of the nickel electroplated film obtained in Example 1 and Comparative Example 2; , 000 times). Fig. 2 (.^, <b) shows the recording film of the recording film obtained in Example 2 and Comparative Example 2 - a private electron microscope observation image (10,000 times larger). Fig. 3 ("gj, Qb) shows the image of the electroplated film obtained in Example 3 and Comparative Example 1 by an electron microscope observation (magnification 1 〇, 〇〇 0 times). Fig. 4 (a, n. <b) shows the recording lines of the recording electric wires obtained in Example 4 and Comparative Example 4, and the scanning electron microscope observation image (mag. 1 000,000 times). Eight fifth picture (a, η,
Cb)係表示實施例5及比較例5所得刭 的錄電錢薄膜$ 、（婦私式電子顯微鏡觀察成像圖（故大 29 201239138 1 0，0 0 0 倍）。 【主要元件符號說明】 無 30Cb) shows the recording of the electric film of the crucible obtained in Example 5 and Comparative Example 5, (the image of the private electron microscope observation image (so big 29 201239138 1 0, 0 0 times). [Explanation of main component symbols] 30