201207154 四、指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明：無。 本案若有彳時’ 揭*最能顯*㈣特徵的化學 無。 六、發明說明： 【發明所屬之技術領域】 本發明是關於封孔處理 或銅合金構成的表面的基材 作之構件的封孔處理劑及使 法。 劑’特別是關於用於在具有鋼 上已受到鍍金或鍍金合金的施 用此封孔處理劑的封孔處理方 【先前技術】 在電子零組件業界中，因為導電性高而使用含銅或銅 的°金(*銅合金），作為多數的電子構件（連接器 '開關、印 刷土板等）的基材或線路材料。若要例示用於此用途的銅合 金’可列舉出黃銅、磷青銅、鈦銅、鈹銅等。 「_ : 4樣的銅或銅合金構成的表面之材料（以下稱為201207154 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. If there is a flaw in this case, the chemistry that best shows the characteristics of (4) is not available. [Explanation of the Invention] [Technical Field of the Invention] The present invention relates to a sealing treatment agent and a method for a member of a substrate which is subjected to a sealing treatment or a copper alloy. Agent's especially for sealing treatments for applying this sealing treatment agent on steel with gold plating or gold plating alloy. [Prior Art] In the electronic component industry, copper or copper is used because of high conductivity. ° gold (*copper alloy), as a substrate or circuit material for most electronic components (connectors 'switches, printed soil boards, etc.). The copper alloy used for this purpose is exemplified by brass, phosphor bronze, titanium copper, beryllium copper or the like. "_ : 4 kinds of materials made of copper or copper alloy surface (hereinafter referred to as
銅糸材料」），其内部導電性高’但是會有表面氧化等的 理由導致導電性不㈣H 因此，銅系材料構成的電子構件，一般會在其表面鐘 上金、或耐钱性及導電性與金同樣優異的金屬(例如鍵）、 2 201207154 或上述金屬的合金（在本發明中總稱為「鍍金」）。 為了鍛金’先進行一般的鍍鎳作為底鍍層，接下來使 用鹼浴或酸浴進行預鍍金（strike g〇ld plating)。在如此 而形成的鍍層上，視需求亦有以點鍍（sp〇t plating)(局部 鍍）進行鍍軟銲料的情況。在本發明中，是將以銅系材料為 基材而在其表面施作鍍金的構件稱為鍍金構件。 在受到近年來的電子機器的小型化、高密度化、還有 同可罪度的要求的狀況下，對施作於上述構件的金鍍層亦 有高可靠度的要求。 另一方面，近年來對於電子機器的降低成本的要求強 烈，在上述的金鍍層及底鍍層中，為了降低成本而一直作 出薄化鍍層的膜厚的應對措施。其結果，隨著底鍍層、金 錢層等的膜厚的變薄，逐漸在浮現鍍層皮膜上的針孔以指 數函數增加的現象。 这樣的現象，會發生腐蝕性物質（水分、氯化物、硫化 物、氰化物、氨鹽類等）到達鍍金構件的基材之銅系材料而 使其腐蝕，此腐蝕反應物析出於表面，使接觸電阻上升的 問題。 因此，採用在鍍金構件塗佈封孔處理劑而覆蓋針孔而 抑制耐钱性降低的方法。 有人提出併用苯并三唑（benz〇triaz〇le)與笨并噻唑 硫醇（mercapt0benzothlazole)作為上述封孔處理劑的技 術（專利文獻1、2)。 【先行技術文獻】 3 201207154 【專利文獻】 【專利文獻1】特開平8-2601 93號公報 【專利文獻2】特開2003-129257號公報 【發明内容】 【發明所欲解決的問題】 然而’這樣的封孔處理劑在苯并噻唑硫醇的pKa高達 7 ~ 8 ’若p Η值實質上不在9以上則無法使用。這樣的封孔 處理劑的pH值的調整’一般是藉由NaOH、Κ0Η、醇胺 (alcohol amine)等來進行’此時上述成分會殘留在鍍金構 件的表面’而會有腐蝕（例如若殘留NaOH則與曝露的金屬 Cu反應而形成CuOH)作為基材的銅系材料之虞。在封孔處 理劑成為腐姓來源的情況’就喪失作封孔處理的意義。 有鑑於這樣的現狀，本發明的目的是提供一種封孔處 理劑及使用此封孔處理劑之鍍金構件的封孔處理方法上 述封孔處理劑是即使液體組成為中性〜酸性都能充分作用。 【用以解決問題的手段】 為了解决上述問題而提供的本發明，在其一樣態中， 是由含緩蝕劑（inhibitor)的酸性或中性水系液狀組成物 所構成的封孔處理劑，上述緩蝕劑包含苯并三唑 (benzotriazole)及2-羧基甲基硫代笨并噻唑（2 —carb〇xy methyl thiobenzothiazole)。 上述封孔處理劑較好為pH值為3. 〇以上。 上述封孔處理劑較好為：苯并三唑的含量為1 〇以 201207154 上、l〇〇〇pPm以下，且2_綾基 1。卿以上、mo卿以τ。 “…的含量為 .本發明是提供-種封孔處理方法作為另-樣態，其是 在具有鋼或銅合金構成的表、 ^ ^ ^ J 土孖上已文到鍍金或鍍金 田的施作之構件的封孔處理方法，其包含下列步驟··使 =⑴至⑶項任一項所述之封孔處理劑，而 件作電解處理。 馎 【發明功效】 若藉由本發明，由於本質上迴避在鍛金構件的表面殘 留驗性的腐姓材料’而可以穩定地獲得耐钱性優異的镀金 構件。由這樣的鐘金構件構成的電子零組件，不容易經過 長時間而發生接觸電阻的上升。 【實施方式】 【用以實施發明的最佳形態】 1 ·鍍金構件 本發明相關的封孔處理劑之對象構件是鍍金構件。鍍 金構件由於最近的降低生產成本的需求，不可避免地會具 有針孔。因此鍍金處理後的鍍金構件會從其針孔曝露出基 材之銅系材料。以下，將此曝露部分的鋼系材料稱為曝露 銅系材料。 2.封孔處理劑 (1)笨并三。坐（benzotriazole) 本發明相關的封孔處理劑是具有笨并三β坐來作為線 201207154 劑（inhibitor)、也就是藉由吸附鍍金構件中 料而抑制其腐蝕的成分。 厂丁、柯 苯并三唾的含量只要能達成作為緩钱劑的功能，則益 特別限定。若其含量…。卿’視金鍍層的針孔面積而 疋，會有難以覆蓋全體曝露銅系材料的情況；若含量超過 lOOOppm，則視封孔處理劑的處理條件（特別是溫度）、其他 成分的含量等而定’會有產生未溶解成分而使產品外觀劣 化之虞。若亦考慮到產能等，苯并三。坐的含量較好為50卿 以上、5〇〇Ppro以下，更好為7〇1)卯以上、3〇〇ppm以下。 (2) 2-缓基甲基硫代苯并嗔唾（2,咖 thiobenzothiazole) 本發明相關的封孔處理劑’是具有2,基甲基硫代笨 并嗟唾（以下簡稱為「ABT」）來作為緩敍劑。由於ΑΒτ的 pKa低至4· 62 ’即使封孔處理劑是從中性到酸性，仍穩定 地溶解。 ABT的含量只要能達成作為緩蝕劑的功能，則無特別 限定。若其含量不$ 10卿’視金鍍層的針孔面積而定， 會有難以覆蓋全體曝露銅系材料的情況；若含量超過 lOOOppm，則視封孔處理劑的處理條件（特別是溫度）、其他 成分的含量等而定，會有產生未溶解成分而使產品外觀劣 化之虞。若亦考慮到產能等’ ABT的含量較好為5〇卿以 上、500PPm以下，更好為70ppm以上、3〇〇ppm以下。若含 量為1 OOppm以上’就可以穩定地遂行其功能。 (3) pH 值 6 201207154 本發明相關的封孔處理劑由於含有上述的緩钱劑，液 體性質為中性或酸，wThe copper beryllium material) has high internal conductivity, but the surface is oxidized or the like, and the conductivity is not (four) H. Therefore, an electronic component made of a copper-based material generally has gold on its surface, or is resistant to money and conductive. A metal (e.g., a bond) having the same properties as gold, 2 201207154, or an alloy of the above metal (collectively referred to as "gold plating" in the present invention). In order to forge gold, the general nickel plating is first performed as the underplating layer, followed by pre-gold plating using an alkali bath or an acid bath. On the plating layer thus formed, there is also a case where soft solder is applied by spot plating (partial plating) as needed. In the present invention, a member in which a copper-based material is used as a substrate and gold plating is applied to the surface thereof is referred to as a gold-plated member. In the case of the miniaturization, high density, and guilty demands of electronic devices in recent years, there is a demand for high reliability in the gold plating applied to the above members. On the other hand, in recent years, there has been a strong demand for cost reduction of electronic equipment, and in the above-mentioned gold plating layer and underlying plating layer, measures for reducing the film thickness of the thin plating layer have been made in order to reduce the cost. As a result, as the film thickness of the underplating layer, the money layer, and the like is thinned, the pinhole on the plating film gradually increases as a function of an index. Such a phenomenon causes corrosive substances (moisture, chloride, sulfide, cyanide, ammonia salts, etc.) to reach the copper-based material of the substrate of the gold-plated member to cause corrosion, and the corrosion reactant is deposited on the surface. The problem of raising the contact resistance. Therefore, a method of applying a sealing treatment agent to a gold plating member to cover the pinhole and suppressing a decrease in the durability is employed. A technique of using benzotriazole (benz〇triaz〇le) and mercapt0 benzothlazole as the above-mentioned sealing treatment agent has been proposed (Patent Documents 1 and 2). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2003-129257 (Patent Document 2). Such a plugging treatment agent has a pKa of 7 to 8 ' in benzothiazole thiol, and if the p Η value is not substantially 9 or more, it cannot be used. The adjustment of the pH of such a sealing treatment agent is generally performed by NaOH, Κ0Η, alcohol amine or the like, and the above-mentioned components may remain on the surface of the gold-plated member and may be corroded (for example, if residual The NaOH reacts with the exposed metal Cu to form CuOH) as a base material for the copper-based material. In the case where the sealing agent becomes the source of the rot, the meaning of the sealing treatment is lost. In view of the current state of the art, an object of the present invention is to provide a sealing treatment agent and a sealing treatment method for a gold-plated member using the same. The sealing treatment agent can sufficiently function even if the liquid composition is neutral to acidic. . [Means for Solving the Problem] The present invention provided to solve the above problems is, in the same state, a sealing treatment agent composed of an acidic or neutral aqueous liquid composition containing an inhibitor. The above corrosion inhibitor comprises benzotriazole and 2-carbo-methyl thiobenzothiazole. The above sealing treatment agent preferably has a pH of 3. 〇 or more. The above-mentioned sealing treatment agent preferably has a content of benzotriazole of 1 〇 at 201207154, less than 10 〇〇〇pPm, and 2 绫 绫 1 . Qing above, Mo Qing to τ. The content of "... is a method for providing a sealing treatment as another form, which is applied to a watch having a steel or a copper alloy, a ^ ^ ^ J soil, to a gold-plated or gold-plated field. A sealing treatment method for a member comprising the following steps: the sealing treatment agent according to any one of the items (1) to (3), and the member is subjected to electrolytic treatment. 馎 [Effect of the invention] By the present invention, due to the essence It is possible to stably obtain a gold-plated member excellent in the durability of the powder on the surface of the forged gold member. The electronic component composed of such a gold member is not easily subjected to contact resistance over a long period of time. [Embodiment] [Best Mode for Carrying Out the Invention] 1 . Gold-plated member The object member of the plugging treatment agent according to the present invention is a gold-plated member. The gold-plated member inevitably comes due to the recent demand for lowering the production cost. There is a pinhole. Therefore, the gold-plated member after the gold plating treatment exposes the copper-based material of the substrate from the pinhole. Hereinafter, the steel material of the exposed portion is referred to as an exposed copper-based material. The pore treating agent (1) is benzotriazole. The sealing treatment agent according to the present invention has a stupid and three beta sitting as a line 201207154 inhibitor, that is, by adsorbing a gold-plated member. Corrosive ingredients. As long as the content of the diced ketone, ketone and trisal is able to achieve the function as a slow-money agent, the benefits are particularly limited. If the content is... 卿 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视When the content of the copper-based material is exposed to the whole, if the content exceeds 100 ppm, depending on the processing conditions (especially temperature) of the sealing treatment agent, the content of other components, etc., the undissolved component may be generated to deteriorate the appearance of the product. If the productivity is also considered, the content of benzotriene is preferably 50 qing or more and 5 〇〇 Ppro or less, more preferably 7 〇 1) 卯 or more and 3 〇〇 ppm or less. (2) 2- Slow basis Methylthiobenzopyrazole (2, thiobenzothiazole) The sealing treatment agent of the present invention is a stimulating agent having 2, ylmethylthio benzopyrene (hereinafter referred to as "ABT"). Since the pKa of ΑΒτ is as low as 4·62 ′, even if the sealing treatment agent is neutral to acidic, it is stably dissolved. The content of ABT is not particularly limited as long as it can function as a corrosion inhibitor. If the content is not 10 Å, depending on the pinhole area of the gold plating, it may be difficult to cover the entire exposed copper-based material; if the content exceeds 1000 ppm, depending on the processing conditions (especially temperature) of the sealing treatment agent, Depending on the content of other components, etc., the undissolved component may be produced to deteriorate the appearance of the product. If the capacity is also considered, the content of ABT is preferably less than 5 〇 、, 500 ppm or less, more preferably 70 ppm or more, and 3 〇〇 ppm or less. If the content is more than 100 ppm, it can be stably performed. (3) pH value 6 201207154 The sealing treatment agent according to the present invention contains the above-mentioned volatility agent, and the liquid property is neutral or acid, w
或酸t生、也就是PH值為7以下。較佳的pH /、/，右在此範圍㈣可以使緩#_定地吸附於曝 露銅系材料。f妨1 & c P , ' pH值為5〜7。另外，pH值不滿3亦可， 仁pH值過低的情況中，鐘金構林太身合士 - 鍍金構件本身會有受到酸的侵犯之 虞。 (4)其他成分 本發明相關的封孔處理劑，其緩姓劑是由上述成分構 成，只要液體性質滿足上述的要件，亦可含有其他任何成 分。如專利文獻2的記載’可含有界面活性劑及，或胺化合 物。 然而，在更包含2-苯并嗟嗤硫醇—般的難以在中性、 酸性中溶解的物質的情況中，由於此成分會有殘留於產品 表面而成為外觀不良的原因之虞，故不樂見。另外，含有 含氯、氟等的南素的物質(齒素系化合物)、含有高濃：的 酒精等的物質的情況’由於會使作業環境變差、提高排水 負荷等，亦不樂見。 另外，在含有乳膠（enmlsi〇n)成分的情況中，若封口 處理後未充分洗淨’會有殘留於鍍金構件的乳膠成分所含 的界面活性劑將造成腐㈣物f浸透至針孔底部的情況。 在此情況中’造成腐餘的物質到達曝露銅系材料而使1腐 蝕。另-方面’過度的洗淨會有成為以上述的笨并三:坐及 m彼覆曝露銅系材料的阻害要因的可能。因此，在本發 明的封孔處理劑含有乳膠成分的情況，有必要對封孔處理 201207154 的洗淨步驟進行最佳化。 3 ·封孔處理方法 藉由將上述的封孔處理劑與鍍金構件接觸’在位於鍍 金構件的曝露銅系材料會有緩飯劑吸附，而進行封孔處理。 此封孔處理劑的接SS -jb* '4- i- W的接冑方法並無特別⑯定，彳舉出一血 是將鍍金構件浸潰於封孔處理劑之浴的浸潰處 2’八他例示有使鍍金構件接觸含封孔處理劑的流體之喷 k (spray)、使鑛金構件技 牛接觸已3浸封孔處理劑的海綿 (sponge)等的處理等等。 可進行以封孔處理劑為電解液、與鍍金構件通電接觸 的電解處理。電解圖形為任意，且 使用直電、交流雷皆 可，但較佳為直流電解。 甘且丨L電解的情況中，從摇古 蝕劑的吸附效率的觀點， 巧鉍 ^ ^ φ , 較好為以鍍金構件鍍金構件為陽 極的陽極電解。此時，電解條件未特別限定，但電壓較好 為0.001〜5.0V、更好為0 M q ην 电&孝乂好 文好為0.05〜3· 0V ,另外電流密度較 10〜40roA/dm2、更好Α η qn 2 又毕又好為 好。 為15〜3〇mA/dm、若25〜3—則特別 、封孔處財的封孔處料的溫度、鍍金構件與封 理液的接觸時間等，是考慮電解的有無、鑛金構件的針 的程度、鍍金構件的材質·形狀等來作適當設 -例，則為50t下5秒。 右舉出 與封孔處理液接觸後的鍵金構件，視需求進 通㊉疋進行水洗。緩蝕劑的含量$ 1〇〇〇_以下 中’由於即使未進行洗淨仍不會成為鑛金構件的汗染^兄 201207154 面中的緩蝕 ’故較佳。 則不作洗淨。在此情況中，由於鐘金構件的夺 劑可以充分地進行與曝露銅系材料的相互作用 【實施例】 準備以下所示的材質及形狀的基材。 材質：磷青銅（C5210) 形狀.寬 20mmx長 25mmx厚 〇. 25mm 對上述的基材以下列步驟施以底層鍍與上舞 鍍金構件。 、e鍍’成為 (1) 錄的底層鑛 鍍浴.確胺類（su 1 f am i ne )鑛浴 膜厚：1 μπι (2) 金的上層鍍 鍍浴：酸性浴 膜厚.0. 1 μιη (3) Ni-P(]的底層鍍 錄浴：氨浴 膜厚：1 μιη (4) Au-Co的上層鍍 鍍洛：酸性浴 膜厚：〇. Ιμπι (5) Rh的上層鍍 鍍浴：酸性浴 膜厚： 製作示於表1的組成的封孔處理劑。 201207154 【表1】 試驗 No. 鍍 封孔處理劑 電解條件 niA/dm2 封孔處理 後的水洗 底層 上層 組成 菇果 1 2 3 A Ni Au Au-Co 溶解性 耐餘性 5 木τ L處理 1，2, 3-笨并三°坐：lOOppm 9 +25 1 3 1 +25 無 1 3 5 fi 1，2, 3-笨并三。圭：lOOppm ABT : lOOpprn 7 +25 無 1 1 3 9 +25 無 1 0 7 0 1，2, 3-苯并三°坐：lOOppm 2-笨并β塞。坐硫醇：lOOppm JO 7 +25 無 1 3 由於未溶解而 無法作封孔處理 無 2 Ο 9 in 1, 2, 3-苯并三。坐：l〇〇ppm ABT : lOOppm 乳膠 7 +25 無 — 2 7 +25 有 一 4 1，2, 3-笨并三σ坐：lOOppm ABT : lOOppm 3 11 +25 無 1 1 1? +25 無 1 1 — 13 14 8 +25 無 1 1 1U +25 無 1 _ 一 3 7 +15 無 1 5 Ifi t 僅浸潰 無 1 4 17 7 +25 無 1 1 18 t +25 無 1 1 19 Ni-Pd 7 +25 無 1 1 20 Ni Rh 7 7 +25 +25 無 無 1 1 1 — 1 另外，表1中的乳膠的組成是：流動石蠟Uiquid Paraffm): 0.04質量％以及非離子系（n〇ni〇nic)界面活性 Μ .微里。另外，各封孔處理劑的pH值是以K〇H來調整。 使用上述的鍍金構件及封孔處理劑，以示於表丨的條 件進行封孔處理。另外’附在位於表丨的顯示電解條件的 攔位的數值之前的「+」，是意指已以鍍金構件為陽極進 行電解處理（處理時間均為5秒）的情況。處理後的鍍金構 件視需求進行水洗（在25t的水洗浴浸潰1〇秒）並乾燥（在 6(TC—30%RH下風乾）’其他則在封孔處理後未作水洗並進 行同樣的乾燥。 10 201207154 對於封孔處理劑及乾燥後的鍵金構件，進行以下的評 〇 (1 )溶解性 以目視觀察調製的封孔處理劑，針對混濁、沉殿等的 有無’以下列基準作評量。以判定為丨的封孔處理劑為合 格。 1 :透明且無混濁也無白濁；以及 2 ·確遇有混濁或沉殿。 (2)耐颠性 以JIS C5444-01為根據，將鍍金構件在4(Γ(： — 8⑽μ —lOppm的S〇2的氣氛放置96小時。以目葙勘玆s⑥ 町 M曰視觀察曝露試驗 後的鍍金構件，以下列的判定基準來評量。以判定為1及 2的鑛金構件為合格。 1 :評量對象面的各處均未找到腐蝕生成物； 2 ’在評量對象面找到腐钱生成物的痕跡； 3 :在評量對象面散見腐蝕生成物； 4 :在評量對象面的一半以上的區域中找到點狀的腐蝕 生成物； 5 .在評量對象面的全部區域中找到點狀的腐蝕生成 物。 另外’在試驗No. 1之未實施封孔處理的鍍金構件中， 在試驗前後的接觸電阻值的變化為1 0mΩ以上。 【圖式簡單說明】 11 201207154 無。 【主要元件符號說明】 益 。 <*»> 12Or acid t, that is, the pH is below 7. The preferred pH /, /, right in this range (four) can be used to adsorb the exposed copper-based material. f 1 1 & c P , 'pH is 5~7. In addition, if the pH value is less than 3, the pH of the kernel is too low, and the gold-plated structure is too close to the body - the gold-plated member itself may be invaded by acid. (4) Other components The sealing agent according to the present invention is composed of the above-mentioned components as long as the liquid property satisfies the above requirements, and may contain any other components. The description of Patent Document 2 may contain a surfactant and an amine compound. However, in the case of a substance containing 2-benzoxyl mercaptan which is difficult to dissolve in neutral or acidic, since this component may remain on the surface of the product and cause a poor appearance, it is not Happy to see. In addition, when a substance containing a substance such as chlorine or fluorine (a dentate-based compound) or a substance containing a high concentration of alcohol is used, it is unpleasant because the working environment is deteriorated and the drainage load is increased. In addition, in the case of containing a latex (enmlsi〇n) component, if it is not sufficiently washed after the sealing treatment, the surfactant contained in the latex component remaining in the gold plating member will cause the rot (four) substance f to penetrate into the bottom of the pinhole. Case. In this case, the material causing the decay reaches the exposed copper-based material to cause corrosion. On the other hand, 'excessive cleaning' may become the cause of the above-mentioned stupidity: sitting and m covering the copper-based materials. Therefore, in the case where the sealing treatment agent of the present invention contains a latex component, it is necessary to optimize the cleaning step of the sealing treatment 201207154. 3. Sealing treatment method The above-mentioned sealing treatment agent is brought into contact with a gold-plated member. The exposed copper-based material located on the gold-plated member is adsorbed by a slow-acting agent, and is subjected to a sealing treatment. The sealing method of the SS-jb* '4-i-W of the sealing treatment agent is not particularly limited, and one blood is a dipping point in which the gold-plated member is immersed in the bath of the sealing treatment agent 2 'Eight' is exemplified by a process of bringing a gold-plated member into contact with a fluid containing a sealing agent, a sponge for bringing a gold-bearing member into contact with a sponge, and the like. An electrolytic treatment in which the sealing treatment agent is used as an electrolytic solution and is electrically contacted with the gold plating member can be performed. The electrolysis pattern is arbitrary, and it is possible to use direct current or alternating current, but it is preferably direct current electrolysis. In the case of the electrolysis of the lanthanum lanthanum L, from the viewpoint of the adsorption efficiency of the etchant, it is preferable that the anodic electrolysis of the gold-plated member of the gold-plated member is an anode. In this case, the electrolysis conditions are not particularly limited, but the voltage is preferably 0.001 to 5.0 V, more preferably 0 M q ην electric & filial filth is preferably 0.05 to 3·0 V, and the current density is 10 to 40 roA/dm2. Better Α η qn 2 is good and good. It is 15~3〇mA/dm, if 25~3—the temperature of the sealing material at the sealing hole, the contact time between the gold plating member and the sealing liquid, etc., considering the presence or absence of electrolysis, and the gold component The degree of the needle, the material and shape of the gold-plated member, and the like are set as appropriate, and it is 5 seconds at 50 t. The key member after contact with the sealing solution is lifted to the right, and the water is washed as needed. The content of the corrosion inhibitor is less than or equal to or less than 5% of the corrosion resistance of the mineral gold component. Then do not wash. In this case, the interaction with the exposed copper-based material can be sufficiently performed by the agent of the bell gold member. [Examples] A substrate of the material and shape shown below was prepared. Material: Phosphor Bronze (C5210) Shape. Width 20mmx Length 25mmx Thick 〇. 25mm For the above substrate, the underlying plating and the upper-plated gold-plated member are applied in the following steps. , e plating 'become (1) recorded underlying mineral plating bath. Determination of amines (su 1 f am i ne ) ore bath thickness: 1 μπι (2) gold upper plating bath: acidic bath film thickness. 0. 1 μιη (3) Ni-P(] bottom plating bath: ammonia bath thickness: 1 μηη (4) Au-Co upper plating plating: acidic bath film thickness: 〇. Ιμπι (5) Rh upper plating Plating Bath: Acid bath film thickness: The sealing agent for the composition shown in Table 1 was prepared. 201207154 [Table 1] Test No. Electroplating hole treatment agent Electrolysis condition niA/dm2 Water-washing underlayer after sealing treatment Composition of mushroom 1 2 3 A Ni Au Au-Co Solubility tolerance 5 wood τ L treatment 1, 2, 3- stupid and three-degree sitting: lOOppm 9 +25 1 3 1 +25 no 1 3 5 fi 1,2, 3 - Stupid and three. Gui: lOOppm ABT: lOOpprn 7 +25 No 1 1 3 9 +25 No 1 0 7 0 1,2, 3-Benzyl three-degree sitting: lOOppm 2-stup and β-plug. lOOppm JO 7 +25 No 1 3 Cannot be sealed because it is not dissolved. 2 Ο 9 in 1, 2, 3-benzotriene. Sit: l〇〇ppm ABT : lOOppm Latex 7 +25 No - 2 7 + 25 There are 4 1, 2, 3- stupid and three sigma sitting: lOOppm ABT : lOOppm 3 11 +25 no 1 1 1? +25 no 1 1 — 13 14 8 +25 no 1 1 1U +25 no 1 _ a 3 7 +15 no 1 5 Ifi t only dip without 1 4 17 7 +25 no 1 1 18 t +25 no 1 1 19 Ni-Pd 7 +25 no 1 1 20 Ni Rh 7 7 +25 +25 no no 1 1 1 — 1 In addition, the composition of the latex in Table 1 is: Mobile Paraffin (Uiquid Paraffm): 0.04% by mass and nonionic (n〇ni〇nic) interfacial activity 微. Further, the pH of each of the plugging treatment agents was adjusted by K 〇 H. The gold plating member and the sealing treatment agent described above were used for sealing treatment under the conditions shown in the surface. Further, "+" attached to the value of the stopper indicating the electrolysis condition in the surface of the watch means that the gold plating member has been subjected to electrolytic treatment for the anode (the processing time is 5 seconds). The gold-plated component after the treatment is washed with water as needed (immersed in a 25-ton water bath for 1 sec.) and dried (air-dried at 6 (TC-30% RH)', and the other is not washed after the sealing treatment and the same is performed. 10 201207154 The sealing evaluation agent and the key member after the drying are evaluated as follows: (1) Solubility, the prepared sealing treatment agent is visually observed, and the presence or absence of turbidity, sag, etc. Evaluation: The sealing treatment agent with the determination of 丨 is qualified. 1 : Transparent and no turbidity and no white turbidity; and 2 · True turbidity or sinking. (2) Resistance to subversion is based on JIS C5444-01. The gold-plated member was placed in an atmosphere of 4 Γ (: 8 (10) μ - 10 ppm of S 〇 2 for 96 hours. The gold-plated member after the exposure test was observed by spectroscopy, and the evaluation was based on the following criteria. The gold ore members judged to be 1 and 2 are qualified. 1 : No corrosion products were found in all parts of the surface of the evaluation object; 2 'The trace of the money-making product was found on the surface of the evaluation object; 3: The object of measurement See the corrosion product on the surface; 4: In the area above half of the surface of the assessment object A point-like corrosion product was found; 5. A point-like corrosion product was found in all areas of the surface of the evaluation object. In addition, in the gold-plated member of the test No. 1 which was not subjected to the sealing treatment, before and after the test The change in contact resistance value is 10 mΩ or more. [Simple description of the diagram] 11 201207154 No. [Description of main component symbols] Benefits. <*»> 12