201139757 六、發明說明： 【發明所屬之技術領域】 本發明係有關於光澤鎳電鍍 , 鍍材枓、使用光澤鎳電鍍材 科的電子零件及光澤鎳電鑛材料的製造方法。 【先前技術】 其材連接器等之電子零件或金屬裝飾品等的金屬 ^澤鎳電料材料。於製造光㈣電鐘之 示斤產生的問題，可舉出雷 举出電鍍外觀會受到電鍍材料之表面 特性的影響。嬖如，在普卸^ Γ ΟΛ 。 ’、銅（Cu-30%Zn)條狀上進行光澤 '、’又日、’若黃銅材料為燒鈍材料的話’則於電錢後外觀 看不出良好的光澤，甚至有時候會出現類似模糊或光澤 ，、模糊混合之外觀。另外 乃外在磷青銅（Cu-8%Sn-P)條狀 上進行光澤錄電鍍時，也可確認會產生相同問題點。 為了要解決如此之問題點，譬如於專利文獻1揭示有 又生佳之銅合金的製造方法。且其中記載著若藉由此技 術特徵的話’將可縮小銅合金表面之加工變質層的厚度， 特別是可形成良好的電鍍銀或電鍍銅。 [先前技術文獻] [專利文獻特開2007-39804號公報 【發明内容】 【發明所欲解決之問題】 然而’上述之銅合金，雖然可良好適用於電鍍銀或電 3 201139757 鍍銅，但於光澤鎳電鍍上卻很難獲得良好 ^ ,,, 尤澤’仍有很 二本發明之課題將提供―種具有良好外觀 之先澤錄電鐘材料，使用光㈣電鍍㈣的電 澤鎳電鍍材料的製造方法。 . 【用以解決問題之手段】 本發明者們，認真檢討之結果， 進仃有電鍍處理之 金屬基材表面上利用形成有加工變質 . 1員層即可獲得外觀良 好之光澤錄電鑛。a出與專利文獻i相反的事實。 以上述的知識為基礎所完成之本發明，於本實施形態 中為光澤鎳電鍍材料，係包括： 金屬基材，表面加工變質層厚度為大於等於〇; 及 鎳電鍍層，形成於該金屬基材之表面上。 本發明之光澤錄電鍍材料’進一步於另一實施形態 中，加工變質層厚度為0. 25至3. 0 /Ζ 本發明之光澤鎳電鍍材料’進一步於另—實施形態 中’加工變質層厚度為0.3至2.Oym。 本發明之光澤鎳電鍍材料，進一步於另一實施形態 中’構成鎳電錄層之鎳結晶粒子直徑為小於〇. 3 " m。 本發月之光澤鎳電鍍材料，進一步於另一實施形態 中，構成該鎳電鍍層之鎳結晶粒子直徑為〇.〇1至〇 3"。 本發月之光澤鎳電鍍材料，進一步於另一實施形態 中，金屬基材係以不鏽鋼、銅或銅合金所形成。 本發明於另一實施形態，係使用光澤鎳電鍍材料的電 4 201139757 子零件。 本發明進一 的製造方法，準 之金屬基材，且 步於另一實施形態中 係光澤鎳電鍍材料 備表面加工變質層厚度為大於等於 於該表面上形成有錄電錢層。 0 . 2 // m 於本發明之光澤鎳電鍍材料的製造方法之其中一實施 形態中，構成鎳電鍍層之鎳結晶粒子直徑為小於 ： 0 · 3 e m 〇 * 【發明效果】 若藉由本發明，將可提供一種具 、另民好外觀之光澤鎳 電鐘材料，使用光澤鎳⑽材料的電子零件及光澤錄電鐘 材料的製造方法。 【實施方式】 (金屬基材） 雖無限制用於本發明之金屬基材的型態，但可舉出譬 如不鏽鋼、銅或銅合金。其中可使用麻田散鐵 Uartensite)、亞鐵鹽（ferrite)，沃斯田鐵⑷ 等材料來作為不鏽鋼。另外，雖以用於連接器或端子等電 子零件的基材作為銅或銅合金，習知任意的銅或銅合金也 可以’但若考慮用於電氣’電子機器之連接端子等：則最 好係使用電㈣料較高者（⑽（Internati〇nai201139757 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a glossy nickel plating, a plating material, an electronic component using a gloss nickel plating material, and a glossy nickel electric ore material. [Prior Art] A metal material such as an electronic component such as a material connector or a metal ornament such as a metal ornament. The problem caused by the manufacture of the light (four) electric clock is that the appearance of the plating is affected by the surface characteristics of the plating material. For example, in general unloading ^ Γ ΟΛ. ', copper (Cu-30% Zn) strips on the gloss ', 'again, 'if the brass material is a blunt material', then the appearance of the money after the money does not see a good luster, and sometimes even appear Similar to blur or luster, the appearance of fuzzy blending. In addition, when the gloss recording was performed on the outer strip of phosphor bronze (Cu-8% Sn-P), it was confirmed that the same problem occurred. In order to solve such a problem, for example, Patent Document 1 discloses a method for producing a copper alloy which is excellent in life. Further, it is described that if the technical characteristics are used, the thickness of the work-affected layer on the surface of the copper alloy can be reduced, and in particular, good electroplated silver or electroplated copper can be formed. [Prior Art Document] [Patent Document No. 2007-39804 [Invention] [Problems to be Solved by the Invention] However, the above-mentioned copper alloy can be suitably applied to electroplating silver or electricity 3 201139757 copper plating, but Glossy nickel plating is difficult to obtain good ^,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Manufacturing method. [Means for Solving the Problem] As a result of careful review, the inventors have carefully processed the surface of the metal substrate which has been subjected to electroplating treatment to form a process of deterioration. a out of the facts contrary to patent document i. The present invention, which is based on the above knowledge, is a glossy nickel plating material in the present embodiment, comprising: a metal substrate having a surface-treated metamorphic layer having a thickness of 大于 or more; and a nickel plating layer formed on the metal base On the surface of the material. The gloss recording plating material of the present invention is further processed in another embodiment. The thickness of the modified layer is 0.25 to 3. 0 / Ζ The gloss nickel plating material of the present invention is further processed in another embodiment. It is 0.3 to 2.Oym. Further, in another embodiment, the gloss nickel plating material of the present invention has a nickel crystal particle diameter of less than 〇. 3 " m. Further, in another embodiment, the nickel-plated particles constituting the nickel plating layer have a diameter of 〇.〇1 to 〇3". In another embodiment, the metallic nickel substrate is formed of stainless steel, copper or a copper alloy. In another embodiment of the invention, an electric 4 201139757 sub-part of a glossy nickel plating material is used. The manufacturing method of the present invention is a metal substrate, and in another embodiment, the gloss nickel plating material has a thickness of the surface-treated metamorphic layer equal to or greater than that formed on the surface. 0. 2 // m In one embodiment of the method for producing a glossy nickel plating material according to the present invention, the diameter of the nickel crystal particles constituting the nickel plating layer is less than: 0 · 3 em 〇 * [effect of the invention] It will provide a method for manufacturing a glossy nickel electric clock material with a good appearance, an electronic component using a glossy nickel (10) material, and a glossy recording electric clock material. [Embodiment] (Metal substrate) Although it is not limited to the type of the metal substrate of the present invention, it may be, for example, stainless steel, copper or a copper alloy. Among them, materials such as Uartensite, Ferrite, and Vostian Iron (4) can be used as the stainless steel. Further, although a base material for an electronic component such as a connector or a terminal is used as a copper or a copper alloy, any conventional copper or copper alloy may be used. However, it is preferable to use a connection terminal for an electric 'electronic device: Use the electricity (four) material higher ((10) (Internati〇nai
Annealed CopperStandard:國際標準軟銅之導電率為ι〇〇 時的數值）為15至80% )，譬如可舉出Cu_Sn_p (譬如磷 青銅）、Cu-Zn(譬如黃銅、紅銅）、Cu_Ni_Zn(譬如洋白 201139757Annealed CopperStandard: the value of the international standard soft copper is 15 to 80%), such as Cu_Sn_p (such as phosphor bronze), Cu-Zn (such as brass, copper), Cu_Ni_Zn (such as White white 201139757
Cu-Ni-Si (銅鎳硅合金）、Cu-Fe-P合金等。另外，無特 定限制金屬基材之形狀，即使板狀，條狀及壓擠品也可。 於進行有錄電錄層之金屬基材表面上，具有加工變質 層為大於等於〇.2"m的厚度。若加工變質層為小於 m，則形成於該表面之鎳電鍍所有組織或局部會變粗大，無 法獲得-良好外觀之電鍍。所謂加工變質層乃藉由輾壓二 工或拋光輪研磨等產生於金屬表面之結晶流細微層。加工 變質層的厚度最好為0.25至3.0以m，0.3至2.0#m為更 佳。 …、 另外，於製造光澤鎳電鍍材料時，雖使用含有光澤劑 之電鍍於金屬基材上來形成電鍍保護膜，但如上述所言， 依據金屬基材表面的狀態有時候鎳電鍍的外觀不會很光 澤。那是因為錄電锻具有容易受到基材的金屬結晶影響之 特（·生4如，若金屬基材的結晶粒較為粗大，則電鍍的結 晶粒也會變大’結果電鑛表面的凹凸也變大。&，電鑛外 觀就變為不光澤。另外，若金屬基材的結晶粒較為細微， 電鍍組織也變為細m，則電鍍表面就變為平滑。故，電鍍 的外觀就變為光澤。 (光澤鎳電錄） 本發明之光澤鎳電鍍材料，係於上述之加工過之金屬 基材表面形成'鎳電鍍層。此鎳電制係利用具有對應於 金屬基材表面之金屬結晶粒大小的結晶粒直徑（小於〇 3 “)所構成。此鎳電鍍層’如上述所言由於結晶粒直徑較 :’、、 '故八有良好的光澤。另外，構成鎳電鍍層之鎳的 6 201139757 結晶粒直徑最好為。.〇1至〇3 一 雖鎳電鍍層係以鎳所構0 _ 機光澤劑成分。此e 生 〜、中也含有極微1之有 被滲入到保護臈。疋澤劑成分在電鍍步驟上有微量 另外’本發明之端子，、4 口。 ^ ^ Φ 連接盗等電子零件，係以上述 先澤鎳電鍍材料所構成。 4 (光澤鎳電鍍材料的製造方法） 其二先：準：―以不鏽鋼，鋼或銅合金等所形成之金屬 基材其二人，再利 拋光輪研磨、刷研廢& 先軋機（skinpass)輾壓、 届 土材表面形成一加工變質 層。加工的條件譬如調整輾壓加 力亦B本鬥，4 度抛先輪研磨時之壓 力次時間讓加工變質層厚度為大 a ,. ^ ^ 、寺於〇 · 2 /z m。加工變質 層的銳察係利用FIB(Fc>cused 3買 ., 1 〇n Beam .聚焦離子戾）央 進行剖面觀察再確認加工成功與否。 束）來 其次’準備_光澤鎳電鍍浴槽。用於光澤錦電鑛浴槽 的光澤料鍍液，具有水溶 趟 ^ '、PH緩衝劑，亦、、罢杰j 於此，水溶性鎳鹽譬如 ， 。 等添加總計咖至350g/L。出硫酸錄、氯化錄等，此 PH緩衝劑可舉出譬如硼酸 35至45g/L。 讀^專’此等添加總計 光澤劑，可舉出譬如糖精、w 丁 (l，4-butynedi〇1)，此等添加總計〇1至心。、-醇 光澤錄電鍍液為水溶液，pH值最好調g ° 整到3. 8至4. 2為更佳。 ’’’’至5 ’調 201139757 另外’光澤錄電鐘液最好使用浴槽溫度為μ m 45至50°C為更佳。 若光澤錄電鑛液的pH值及浴槽溫度不在上述範圍，則 會有電錄速度變慢或容易產生外觀不良等問題。 其次，將上述表面加工過的金屈 、w隻屬基材既定時間浸潰於 光澤電鍍浴槽内，即可獲得一且右 〃有先澤的光澤鎳電鍍基 材。此時，於金屬基材表面，社日 两！仞衣囬、，口日曰粒子直徑最好小於i “ m， 且由於會形成厚度為〇 〇1至〇 ? ^ 111的加工變質層，因此 形成於該表面之之電鍍層的金屬 甸、〇日日粒子直杈也會變為較 為細緻。故’所形成之電鑛層表 尽衣甶也會較為平滑而可獲得 良好的光澤。 【實施例】 以下為本發明之實施例’但此等實施例乃為更佳清楚 明白本發明而提供，並非用以限制本發明。 (範例1 :實施例1至10 ) 準備-厚度為0·65_的黃銅板來作為金屬基材。於黃 銅板表面藉由拋光輪研磨來形成如表！所示厚度之加工變 質層。此變質層的厚度乃使用FIB來觀看。 另外，藉由FIB來觀看構成金屬基材之加工變質層的 金屬結晶粒子直徑。 接著，準備-含有以下成分之光澤電鍵液的光澤電鑛 浴槽。Cu-Ni-Si (copper-nickel-silicon alloy), Cu-Fe-P alloy, and the like. Further, the shape of the metal substrate is not particularly limited, and it may be a plate shape, a strip shape or a compressed product. The surface of the metal substrate on which the recorded recording layer is formed has a thickness of the working metamorphic layer of 大于.2 " m. If the affected metamorphic layer is less than m, all the microstructure or localization of the nickel plating formed on the surface becomes coarse, and plating of a good appearance cannot be obtained. The so-called process metamorphic layer is a fine layer of crystal flow generated on the surface of the metal by rolling or polishing. The thickness of the processed metamorphic layer is preferably 0.25 to 3.0 m, and more preferably 0.3 to 2.0 #m. In addition, in the production of a glossy nickel plating material, a plating resist is formed by plating on a metal substrate using a glossing agent, but as described above, depending on the state of the surface of the metal substrate, the appearance of nickel plating sometimes does not occur. Very shiny. That is because the electric forging is particularly susceptible to the influence of the metal crystallization of the substrate. (If the crystal grains of the metal substrate are coarser, the crystal grains of the plating will become larger. When the metal substrate has fine crystal grains and the plating structure becomes fine m, the plating surface becomes smooth. Therefore, the appearance of the plating becomes smooth. Glossy. (Glossy nickel electro-recording) The glossy nickel electroplating material of the present invention forms a 'nickel plating layer' on the surface of the above-mentioned processed metal substrate. The nickel electroforming system utilizes metal crystals corresponding to the surface of the metal substrate. The particle size of the crystal grain is smaller than 〇3". The nickel plated layer has a good luster as compared with the following: since the crystal grain diameter is as follows: ', ', and the nickel is formed by the nickel plating layer. 6 201139757 The crystal grain diameter is preferably .。1 to 〇3. Although the nickel plating layer is made of nickel, it has a composition of 0 _ machine luster. This e-~, and also contains a very small one, which is infiltrated into the protective 臈. The bismuth agent component has a plating step A small amount of the terminal of the present invention, 4 ports. ^ ^ Φ The electronic parts such as the thief are connected by the above-mentioned Zeozhuang nickel plating material. 4 (Manufacturing method of the gloss nickel plating material) The second is: The metal substrate formed by stainless steel, steel or copper alloy, and the like, the polishing wheel grinding, brushing and scraping & the first rolling machine (skinpass) rolling, the surface of the soil material forms a processing metamorphic layer. Adjusting the rolling force and the force is also B. The pressure of the 4 degree throwing first wheel grinding time makes the thickness of the processing metamorphic layer large a, . ^ ^, and the temple is 〇· 2 /zm. The use of the sharpening system for processing the metamorphic layer FIB (Fc > cused 3 buy., 1 〇n Beam. Focused ion 戾) Central section observation to confirm the success of the processing. Bundle) followed by 'preparation _ gloss nickel plating bath. For the luster of the shiny gold mine bath Material plating solution, with water-soluble ' ^, PH buffer, also,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The buffer may be, for example, 35 to 45 g/L of boric acid. Adding a total gloss agent, for example, saccharin, w, (l, 4-butynedi〇1), these additions total 〇1 to the heart., - the alcohol luster plating solution is an aqueous solution, the pH value is preferably adjusted to ° ° It is better to 3. 8 to 4.2. '''' to 5' adjustment 201139757 In addition, it is better to use a bath temperature of μ m 45 to 50 ° C for luster recording. It is better for luster recording. When the pH of the liquid and the bath temperature are out of the above range, there is a problem that the electro-recording speed is slow or the appearance is liable to be defective. Next, the surface-treated gold and w substrates are immersed in the gloss plating for a predetermined period of time. In the bath, you can get a glossy nickel-plated substrate with a right-handed front. At this time, on the surface of the metal substrate, the social day two! The 直径 回 back, the diameter of the 曰 曰 最好 particles is preferably less than i “m, and since a thickness of 加工1 to 〇? ^ 111 is formed, the metal layer formed on the surface of the metal layer, 〇 The daily particle enthalpy will also become more detailed. Therefore, the formed electric ore layer will be smoother and obtain a good gloss. [Embodiment] The following is an embodiment of the present invention' The examples are provided to better understand the present invention and are not intended to limit the present invention. (Example 1: Examples 1 to 10) A brass plate having a thickness of 0·65_ was prepared as a metal substrate. The surface of the copper plate is polished by a polishing wheel to form a work-affected layer having a thickness as shown in Table! The thickness of the altered layer is observed using FIB. In addition, the metal crystal crystallization of the processed metamorphic layer constituting the metal substrate is observed by FIB. Particle diameter Next, a gloss electric ore bath containing a glossy key liquid of the following composition was prepared.
NiS〇4 · 6H2O 250g/l NiC12 · 6H2O 50g/1 8 201139757 硼酸40糖精2g/l 1-4 丁 炔二醇 〇. 2g/ 1 其次’將表面加工過的黃銅板經過脫脂、酸洗後，浸 潰到電鍍浴槽再以電流密度為5A/dm2來形成電鍍層。光澤 電鍍浴槽設定pH值為4.0’溫度為45°C。 第1圖為表示實施例3之黃銅基材、 加工變質層級錄 電鍍層的放大剖面圖。 (範例2 :比較例1至5 ) 比較例1至5，首先準備一與實施例相同的銅箔。其 次’準備與實施例相同的電鍍浴槽，於此不對該黃銅板表 面進行加工，或輕輕地以刷研磨等之輕微加工來進行電 鐘。電鍍電流及浴槽溫度也設定成與實施例相同。 (評估） 利用FIB來觀察構成鎳電鍍層之鎳結晶粒子直徑的剖 面。 對鎳電鍍層的光澤進行外觀觀察。使用光澤度計（日 本電色工業製反射濃度計ND-1 )來進行外觀評估，若剛定 值超過1 · 8就評估為〇’若測定值位於1. 6至丨.8， . 只J厅尤 評估為△，若測定值低於1. 6就評估為x。 表1為表示範例1及範例2的結果 【表1】NiS〇4 · 6H2O 250g/l NiC12 · 6H2O 50g/1 8 201139757 Boric acid 40 saccharin 2g/l 1-4 butynediol 〇. 2g/ 1 Next 'The surface processed brass plate is degreased and pickled The plating layer was formed by dipping into an electroplating bath and then having a current density of 5 A/dm 2 . The gloss plating bath was set to a pH of 4.0' at a temperature of 45 °C. Fig. 1 is an enlarged cross-sectional view showing a brass base material and a work-affected layer-level plating layer of Example 3. (Example 2: Comparative Examples 1 to 5) In Comparative Examples 1 to 5, first, a copper foil similar to that of the examples was prepared. Next, the same electroplating bath as in the embodiment is prepared, and the surface of the brass plate is not processed here, or the electric clock is gently processed by brushing or the like. The plating current and bath temperature were also set to be the same as in the examples. (Evaluation) The FIB was used to observe the cross-section of the diameter of the nickel crystal particles constituting the nickel plating layer. The appearance of the nickel plating layer was observed. The appearance was evaluated using a gloss meter (Nippon Denshoku Industrial Reflective Densitometer ND-1). If the value is more than 1.8, it is evaluated as 〇' if the measured value is at 1.6 to 丨.8, . The hall is evaluated as △, and if the measured value is lower than 1.6, it is evaluated as x. Table 1 shows the results of Example 1 and Example 2 [Table 1]
金屬基材 加工變質 層的厚度 (#m) 加工變質層表面 之結晶粒子直徑 (/zm) -------- 錄電錢層的 子直徑 (/zm) ---1 外觀 實施例1 黃銅（C2600) 0.20 0.12 0.06 ----J 201139757Thickness of the metal substrate processing metamorphic layer (#m) The crystal particle diameter (/zm) of the surface of the processing metamorphic layer -------- Sub-diameter (/zm) of the recording money layer ---1 Appearance example 1 Brass (C2600) 0.20 0.12 0.06 ----J 201139757
實施例2 黃銅（C2600) 0.25 0.10 0. 05 〇 實施例3 黃銅（C2600) 0.30 0.09 0. 04 〇 實施例4 精煉銅（C1100) 0.30 0.11 0. 05 〇 實施例5 磷青銅（C5210) 0.30 0.13 0. 07 〇 實施例6 銅鎳硅（C7025) 0.30 • 0.12 0.05 〇 實施例7 洋白（C7701 ) 0. 30 0.11 0.06 〇 實施例8 不鏽鋼（SUS301) 0. 30 0.10 0.05 〇 實施例9 不鏽鋼（SUS304) 0.30 0.14 0.06 〇 實施例10 不鏽鋼（SUS430) 0.30 0.12 0.06 〇 比較例1 黃銅（C2600) 0.00 4. 90 0.58 X 比較例2 黃銅（C2600) 0.10 0.22 0. 32 Δ 比較例3 不鏽鋼（SUS301) 0.00 6. 60 0.55 X 比較例4 不鏽鋼（SUS304) 0.00 5. 40 0.47 X 比較例5 不鏽鋼（SUS430) 0.00 4. 20 0.41 X 【圖式簡單說明】 第1圖為表示實施例3之黃銅基材、加工變質層及鎳 電鍍層的放大剖面圖。 【主要元件符號說明】 Μ 10Example 2 Brass (C2600) 0.25 0.10 0. 05 〇 Example 3 Brass (C2600) 0.30 0.09 0. 04 〇 Example 4 Refined Copper (C1100) 0.30 0.11 0. 05 〇 Example 5 Phosphor Bronze (C5210) 0.30 0.13 0. 07 〇 Example 6 Copper nickel silicon (C7025) 0.30 • 0.12 0.05 〇 Example 7 Ocean (C7701) 0. 30 0.11 0.06 〇 Example 8 Stainless steel (SUS301) 0. 30 0.10 0.05 〇 Example 9 Stainless steel (SUS304) 0.30 0.14 0.06 〇 Example 10 Stainless steel (SUS430) 0.30 0.12 0.06 〇Comparative example 1 Brass (C2600) 0.00 4. 90 0.58 X Comparative Example 2 Brass (C2600) 0.10 0.22 0. 32 Δ Comparative Example 3 Stainless steel (SUS301) 0.00 6. 60 0.55 X Comparative Example 4 Stainless steel (SUS304) 0.00 5. 40 0.47 X Comparative Example 5 Stainless steel (SUS430) 0.00 4. 20 0.41 X [Simplified description of the drawings] Fig. 1 shows the example 3 An enlarged cross-sectional view of the brass substrate, the processed altered layer, and the nickel plated layer. [Main component symbol description] Μ 10