201002870 六、發明說明： 【發明所屬之技術領域】 本發明係關於適於電子機器構件之電鍍之部份鍍敷用 鍍液。詳述之，本發明係關於適於廣泛被用於攜帶用行動 機窃、攜帶電5舌等之資訊機器之連接器相關構件之電接點 之鑛敷等之含有金之部份鍍敷用鍍液。 【先前技術】 作爲用於電子機器之連接器之素材，例如，有以碟青 銅爲代表之銅合金之類，富彈性之金屬材料。於連接器之 電接點部份之素材表面’以提高電傳導性、或附於耐於重 複使用之耐久性爲目的，施以鍍金或金合鍍金。 近年’貴金屬價格高漲，並隨著要求電子機器、尤其 是攜帶用行動機器之本身價格降價，對鍍金步驟亦被要求 降低成本。 以往’以降低材料費爲目的，用於電子機器之連接器 自身之小型化，同時附與接點構件等之電傳導性僅進行部 份鍍金之部份鍍敷普及。具體言之’連接器等之接點部份 之鍍金範圍，限定於數mm以下。 作爲部份鍍敷之一例，例如，製造攜帶電話之連接器 時’於連接器之鍍金’採用捲軸式（reel-t0_reel)等稱爲 連續鍍敷之方法。此方法中，各連接器，形成連續之帶狀 。經形成此帶狀的連接器，被捲軸捲繞的同時，以搬運之 狀態經部份鍍敷。部份鍍敷，係自形成噴嘴狀的陽極電極 -5- 201002870 ，朝爲陰極之被鍍敷素材進行噴射鍍液。 陽極電極和陰極電極之間的間隔，或完全不存於此等 形狀，得比較性均勻的鍍敷於廣大面積之鍍液（均鍍性良 好的鍍液）時，被鍍敷物，和鑛液接觸之部份全面被鍍敷 。其結果，使捲軸式之類的鍍液自陽極電極的噴嘴噴射鎪 敷方法，因鍍液黏著於廣大範圍，必要以上之廣大範圍被 鍍敷。此時，鍍敷後，必須藉蝕刻將不須部份之鍍金皮膜 剝離之步驟，或預先將不須部份施以遮罩步驟。但，如此 步驟的追加因隨著製造費用之提高，以降低成本之觀點來 看是不適合的。再者，若進行必要以上之廣大範圍鍍敷時 ，隨著鍍敷材料費之提高。因此等理由，因而期望開發， 可以高精度，僅於狹小範圍可準確地鍍金之技術。 [先行技術文獻] [專利文獻1]特開2008-45 1 94號公報（發明申請專利 範圍） 【發明內容】 [發明槪要] [發明所欲解決之課題] 以往之金鍍液，作爲傳導鹽成分係使用檸檬酸鹽、磷 酸鹽或銨鹽。此等鹽所含之以往之鍍液之電傳導性，係超 過5 0,000 // S之高値。此鍍液之鍍敷均鍍性良好。因此， 以往的鍍液，不適合用於鍍敷微細之區域之部份鍍金之用 -6- 201002870 途。 反之，藉減少鍍液中此等成分濃度可能降低電傳導性 。但傳導鹽之含量若少，恐損及金鹽的穩定性。其結果， 金鹽之分解物浮游於鍍液中，無法形成連續且穩定的鍍金 皮膜。 本發明者們，爲解決上述問題進行各種檢討。其結果 ，係嘗試將作爲添加劑，莫耳傳導度顯示1 〇〇 /z s以下之 値之脂肪族α -胺基酸類，和規定之傳導鹽成分，於規定 之濃度範圍加以組合。於是，無損及鍍液中之金鹽的穩定 性，得到作爲金鍍液顯示50,000 //S以下之電傳導度之鍍 液。得知此鍍液，係於3 00mA電解時之電解電壓爲5V以 上，因鍍液之均鍍性低，僅於侷限狹小範圍得以高精度進 行鍍敷。本發明，係以上述見解作爲基礎以至完成。 因此，本發明之目的，係提供適於電子機器之連接器 等之微細部份之鍍敷的金鍍液。 [用於解決課題之手段] 達成上述目的的本發明，係記載如下。 [1 ] 一種含有金之部份鍍敷用鍍液，係由氰化金鹽和 傳導鹽及添加劑所成之含有金之部份鍍敷用鍍液，其特徵 爲鍍液之電傳導度以溫度25 °C測定時爲20,0 0 0-5 0,0 00 // S 〇 [2]如[1]所記載之含有金之部份鍍敷用鍍液，其中鍍 液之pH爲3.5〜6.0之範圍。 201002870 [3 ] —種含有金之部份鍍敷用鍍液，其特徵係含有使 氰化金鹽作爲金含有量之1.0〜1 5 g/ 1 ，和作爲添加劑之脂 肪族α-胺基酸10〜100g/l’和傳導鹽10~l〇〇g/i之。 [4] 如[3]所記載之含有金之部份鍍敷用鍍液，其中含 有銘鹽0 . 1〜1 g/Ι。 [5] 如[4]所記載之含有金之部份鍍敷用鍍液，其中鈷 鹽，係硫酸鈷、氯化鈷、碳酸鈷、氨基磺酸鈷、磷酸鈷、 檸檬酸鈷、或葡糖酸鈷。 [6] 如[3]所記載之含有金之部份鍍敷用鍍液，其中脂 肪族α -胺基酸，係甘胺酸或丙胺酸。 [7 ] —種部份鍍敷方法’其特徵爲將[1 ]或[3 ]所記載之 含有金之部份鍍敷用鍍液，自形成噴嘴狀之陽極電極朝作 爲陰極電極之被鍍敷素材噴射。 [發明效果] 本發明之鍍液’係將脂肪族CC -胺基酸類之添加劑， 和傳導鹽成分以規定之濃度範圔加以組合，進行鍍敷時， 得無損及鍍液中之金鹽的穩定性，使金鍍液的電傳導度爲 5 〇，0 0 0 " S以下。其結果，鍍液的均鍍性降低，於侷限狹 小範圍可進行高精度鍍敷。本發明之鍍液，係自帶鋼鍍敷 、捲軸連續鍍敷等之噴嘴噴射鍍液，爲適合部份鍍敷之鍍 液。 本發明之鍍液’適合於電子機器之電接點之形成。具 體性可舉出’攜帶電話之充電接點等。 -8 - 201002870 [用以實施發明之最佳型態] [金鍍液] 添加於本發明之金鍍液之金離子源，係氰化金鉀、氰 化金鈉等之氰化金鹽。 鍍液中之氰化金鹽的濃度，係作爲金元素之添加量之 1〜15g/l ’以1〜10g/l爲宜，較佳爲4~8g/l 。金添加量 若未達1 g/ 1 ，鍍敷速度變慢。金添加量若超過1 5g/ 1 ， 鍍敷的均鍍性變佳，其結果，致使不適於部份鍍敷。再者 ’製造成本提高，以經濟面觀點並不宜。 本發明之金鍍液中，作爲添加劑，係摻合甘胺酸、丙 胺酸、L-胱氨酸、D-天冬氨酸等之脂肪族α -胺基酸。藉 摻合脂肪族α -胺基酸作爲添加劑，增加鏟液之電阻値。 自噴嘴狀之陽極噴射此鍍液，噴塗於平面狀之陰極（平面 狀之鍍敷對象物），使陰極和陽極之間的間隔爲最小，使 電流選擇性地流通和陽極面對之陰極的部份。反之，自陰 極面之陽極遠離的部份，電解電流很難流通。其結果，致 難形成鍍敷皮膜。 脂肪族α -胺基酸之添加量，係 1〇〜l〇〇g/l，以 2 0~6 0g/l爲宜。添加量若未達2 0g/l，無法完全降低鍍液 的電傳導度。若超過60g/l，即使增加添加量亦無特別優 點故不利於經濟面。 作爲添加於金鍍液之傳導化合物，例舉，檸檬酸、磷 酸、脯氨酸鉀、甲酸、及此等之鹼金屬鹽等。 金鍍液，以調整pH爲目的通常可於電解鍍液添加氫 -9- 201002870 氧化鉀、氫氧化鈉等之鹼金屬氫氧化物。其添加量，以 3 0g/l以下爲宜，較佳爲25g/l以下。脂肪族α -胺基酸以 外之各種成分之添加量若增多’鍍液之電傳導度上升。其 結果，係鍍液的均鍍性增加’因被鍍敷範圍變大，易形成 不適部份鍍敷的鍍液。 本發明之金鍍液’作爲ρ Η緩衝劑，以添加琥珀酸、 苯—甲酸、酒石酸、檸檬酸、磷酸、亞硫酸、或此等之鹼 金屬鹽爲宜。ρ Η緩衝劑的添加量若可達到本發明之效果 的範圍內即無制限，通常爲20〜6〇g/ 1 ，以30〜40g/l爲 宜。 鍍液的pH値’以PH3.5〜6.0的範圍爲宜。鍍液的pH 若未達3 · 5，金鹽變得易於分解，產生不溶性之金鹽浮游 於鍍液中。再者，所得之金皮膜的外觀易產生不勻。pH 若超6 · 0 ’電傳導性提高之結果，均鍍性變高，得不到精 度高的部份鍍敷。再者，鍍敷皮膜的光澤性變差，外觀不 佳。pH値的調整，藉加入pH緩衝劑調整濃度，或添加少 量的酸或鹼進行之。 [金-鈷合金鍍液] 金-鈷合金鍍液，於上述之金鍍液，進而作爲鈷離子 源得摻合鈷鹽。作爲鈷鹽，以硫酸鈷、氯化鈷、碳酸鈷、 氨基磺酸鈷、磷酸鈷、檸檬酸鈷、葡糖酸鈷等爲宜。金-鈷合金鍍液中之鈷鹽的濃度，作爲鈷含有量爲1 g/ι以下 ，以0.1〜lg/Ι爲宜，較佳爲0.2〜0.5g/l。 -10- 201002870 以附與鍍敷皮膜充分的耐久性之觀點，金··鈷合金鍍 液中之鈷鹽的濃度作爲鈷含有量以0· 1 g/l以上爲宜。鈷含 有量若超過1 g/1，析出皮膜中的鈷量若增加，接觸電阻値 變高。 本發明之鍍液的電傳導度，以20,000〜5 0,000 # S爲 宜，較佳爲 25,000〜40，〇〇〇// S，更佳爲 30,000~35,000 //8，最佳爲32,000〜3 5,000//8。使電傳導度的範圍設定 於上述範圍内，形成適於部份鍍敷的鍍液。電傳導度的調 整，得藉調整脂肪族α -胺基酸之添加量進行。藉增加脂 肪族α -胺基酸的添加量，使電傳導度縮小。 使用本發明之鍍液進行電解電鍍時，鍍液的溫度以 30〜7〇°C爲宜，較佳爲40〜60 °C。鍍液的溫度，若未達30 °C ’鍍液的溫度控制不易，再者因鍍敷的析出效率降低， 不適於操作。若超過701：，析出鍍敷變無光澤。再者， 均鍍性變好’無法作出高精度的部份鍍敷。進而，操作中 鍍液的蒸發大使鍍敷容量減少，產生須變更鍍液中之各成 分濃度的問題。201002870 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a plating solution for a part of plating suitable for electroplating of electronic machine components. In detail, the present invention relates to a gold-containing portion plating which is suitable for use in mineral deposits such as electrical contacts of connector-related members of an information machine for carrying mobile hacking, carrying electric tongues and the like. Plating solution. [Prior Art] As a material for a connector for an electronic device, for example, there is a copper alloy such as a copper bronze, which is an elastic metal material. The surface of the material of the electrical contact portion of the connector is plated with gold or gold for the purpose of improving electrical conductivity or for durability against repeated use. In recent years, the price of precious metals has risen, and as the price of electronic machines, especially portable mobile machines, has been reduced, the cost of gold plating has also been required to reduce costs. In the past, in order to reduce the material cost, the connector for an electronic device has been miniaturized, and the electrical conductivity of the contact member and the like has only been partially plated with a part of gold plating. Specifically, the gold plating range of the contact portion of the connector or the like is limited to a few mm or less. As an example of the partial plating, for example, when the connector for a mobile phone is manufactured, the "gold plating on the connector" is a method called continuous plating by a reel-t0_reel or the like. In this method, each connector forms a continuous strip. The ribbon-formed connector is partially plated while being conveyed by the spool while being wound. Part of the plating is from the nozzle-shaped anode electrode -5 - 201002870, and the plating solution is applied to the plated material for the cathode. The spacing between the anode electrode and the cathode electrode, or the shape of the cathode electrode at all, is relatively uniform, and is plated on a large area of the plating solution (plating solution having good plating properties), the plated material, and the mineral liquid. The part of the contact is fully plated. As a result, a plating solution such as a reel type is sprayed from the nozzle of the anode electrode, and the plating solution is adhered to a wide range, and is required to be plated in a wide range. At this time, after the plating, the step of peeling off the gold plating film is not required by etching, or the masking step is not required in advance. However, the addition of such a step is not suitable from the viewpoint of cost reduction as the manufacturing cost is increased. Furthermore, when plating over a wide range of necessary or more, the cost of the plating material increases. Therefore, for the same reason, it is desired to develop a technology that can accurately plate gold only in a narrow range. [Provisional Technical Document] [Patent Document 1] JP-A-2008-45 1 94 (Invention Patent Application) [Disclosure of the Invention] [Problems to be Solved by the Invention] Conventional gold plating solution is used as a conduction The salt component is a citrate, phosphate or ammonium salt. The electrical conductivity of the conventional plating bath contained in these salts is more than 50,000 // s. The plating of this plating solution is excellent in plating. Therefore, the conventional plating solution is not suitable for the plating of a part of the fine plating area -6- 201002870. Conversely, reducing the concentration of these components in the bath may reduce electrical conductivity. However, if the content of the conductive salt is small, the loss of the salt and the stability of the gold salt. As a result, the decomposition product of the gold salt floated in the plating solution, and a continuous and stable gold plating film could not be formed. The present inventors conducted various reviews to solve the above problems. As a result, it is attempted to combine an aliphatic α-amino acid having a molar conductivity of 1 〇〇 /z s or less as an additive and a predetermined conductive salt component in a predetermined concentration range. Thus, the stability of the gold salt in the plating solution is not impaired, and a plating solution exhibiting electrical conductivity of 50,000 //S or less as a gold plating solution is obtained. It was found that the plating solution was electrolyzed at a voltage of 5 V or more at 300 mA electrolysis, and the plating solution was low in plating efficiency, and plating was performed with high precision only in a narrow range. The present invention has been completed on the basis of the above findings. Accordingly, it is an object of the present invention to provide a gold plating solution suitable for plating of a fine portion of a connector or the like of an electronic device. [Means for Solving the Problems] The present invention for achieving the above object is described below. [1] A plating solution for gold plating, which is a gold plating-containing plating solution made of a gold cyanide salt and a conductive salt and an additive, and is characterized in that the conductivity of the plating solution is When the temperature is measured at 25 °C, it is 20,0 0 0-5 0,0 00 // S 〇 [2] The plating solution containing gold as described in [1], wherein the pH of the plating solution is 3.5. ~6.0 range. 201002870 [3] A plating solution containing a part of gold plating, characterized in that it contains a gold cyanide salt as a gold content of 1.0 to 15 g/1, and an aliphatic α-amino acid as an additive. 10~100g/l' and conductive salt 10~l〇〇g/i. [4] The plating solution for gold plating, as described in [3], containing the salt of 0. 1~1 g/Ι. [5] The plating solution for gold plating according to [4], wherein the cobalt salt is cobalt sulfate, cobalt chloride, cobalt carbonate, cobalt sulfamate, cobalt phosphate, cobalt citrate, or hydrochloric acid. Cobalt saccharate. [6] The gold plating-containing plating solution according to [3], wherein the aliphatic α-amino acid is glycine or alanine. [7] A partial plating method characterized in that the gold-containing portion plating solution described in [1] or [3] is plated from the nozzle-shaped anode electrode toward the cathode electrode. Apply material spray. [Effect of the Invention] The plating solution of the present invention combines an aliphatic CC-amino acid additive and a conductive salt component in a predetermined concentration range, and when deposited, it is non-destructive and the gold salt in the plating solution is obtained. Stability, the electrical conductivity of the gold plating solution is 5 〇, 0 0 0 " S or less. As a result, the plating efficiency of the plating solution is lowered, and high-precision plating can be performed in a narrow range. The plating solution of the present invention is a nozzle spray plating solution for strip plating or continuous plating of a reel, and is a plating solution suitable for partial plating. The plating solution of the present invention is suitable for the formation of electrical contacts of an electronic machine. Specifically, a charging contact for a mobile phone or the like can be cited. -8 - 201002870 [Best type for carrying out the invention] [Gold plating bath] The gold ion source added to the gold plating solution of the present invention is a gold cyanide gold salt such as potassium cyanide or gold cyanide. The concentration of the gold cyanide salt in the plating solution is preferably 1 to 10 g/l as the amount of the gold element added, preferably 1 to 10 g/l, more preferably 4 to 8 g/l. The amount of gold added is less than 1 g / 1, and the plating speed is slow. If the amount of gold added exceeds 15 g/1, the plating resistance of the plating becomes good, and as a result, it is unsuitable for partial plating. Furthermore, the increase in manufacturing costs is not economical. In the gold plating solution of the present invention, as the additive, an aliphatic ?-amino acid such as glycine, alanine, L-cystine or D-aspartic acid is blended. By blending an aliphatic α-amino acid as an additive, the resistance enthalpy of the shovel is increased. This plating solution is sprayed from a nozzle-shaped anode and sprayed on a planar cathode (planar plating object) to minimize the interval between the cathode and the anode, allowing current to selectively flow and the anode facing the cathode. Part. On the contrary, the electrolysis current is hard to circulate from the portion where the anode of the cathode is far away. As a result, it is difficult to form a plating film. The amount of the aliphatic α-amino acid added is 1〇~l〇〇g/l, and preferably 20 to 60g/l. If the amount added is less than 20 g/l, the electrical conductivity of the plating solution cannot be completely reduced. If it exceeds 60 g/l, there is no particular advantage even if the amount of addition is increased, which is disadvantageous to the economic side. The conductive compound to be added to the gold plating solution is exemplified by citric acid, phosphoric acid, potassium citrate, formic acid, and the like. Gold plating solution is usually added to the electrolytic plating solution for the purpose of pH adjustment. Hydrogen -9-201002870 Alkali metal hydroxide such as potassium oxide or sodium hydroxide. The amount of addition is preferably 30 g/l or less, preferably 25 g/l or less. When the amount of the various components other than the aliphatic α-amino acid is increased, the electrical conductivity of the plating solution increases. As a result, the plating efficiency of the plating solution is increased. ‘Because the plating range is increased, it is easy to form a plating solution which is not partially plated. The gold plating solution of the present invention is preferably used as a ρ Η buffer to add succinic acid, benzene-formic acid, tartaric acid, citric acid, phosphoric acid, sulfurous acid, or the like. The amount of the ρ Η buffering agent to be added is not limited to the range of the effect of the present invention, and is usually 20 to 6 〇g / 1 and preferably 30 to 40 g / l. The pH 値' of the plating solution is preferably in the range of pH 3.5 to 6.0. If the pH of the plating solution is less than 3.5, the gold salt becomes easily decomposed, and an insoluble gold salt is floated in the plating solution. Furthermore, the appearance of the obtained gold film is liable to cause unevenness. As a result of an increase in the electrical conductivity of the pH of 6·0', the uniform plating property is high, and partial plating with high precision cannot be obtained. Further, the gloss of the plating film is deteriorated, and the appearance is not good. The adjustment of pH , is carried out by adding a pH buffer to adjust the concentration or adding a small amount of acid or base. [Gold-Cobalt Alloy Plating Bath] A gold-cobalt alloy plating bath is blended with a cobalt salt in the above gold plating bath, and further as a cobalt ion source. As the cobalt salt, cobalt sulfate, cobalt chloride, cobalt carbonate, cobalt sulfamate, cobalt phosphate, cobalt citrate, cobalt gluconate or the like is preferred. The concentration of the cobalt salt in the gold-cobalt alloy plating bath is preferably 1 g/m or less, preferably 0.1 to lg/cm, and preferably 0.2 to 0.5 g/l. -10-201002870 The concentration of the cobalt salt in the gold-cobalt alloy plating solution is preferably 0.1 g/l or more in terms of cobalt content in view of sufficient durability of the plating film. When the amount of cobalt exceeds 1 g/1, the amount of cobalt in the precipitated film increases, and the contact resistance 値 becomes high. The conductivity of the plating solution of the present invention is preferably 20,000 to 5,000 #s, preferably 25,000 to 40, 〇〇〇//s, more preferably 30,000 to 35,000 //8, and most preferably 32,000 to 3 5,000//8. The range of electrical conductivity is set within the above range to form a plating solution suitable for partial plating. The adjustment of the electrical conductivity can be carried out by adjusting the amount of addition of the aliphatic ?-amino acid. By increasing the amount of the aliphatic α-amino acid added, the electrical conductivity is reduced. When electrolytic plating is carried out using the plating solution of the present invention, the temperature of the plating solution is preferably 30 to 7 ° C, preferably 40 to 60 ° C. If the temperature of the plating solution is less than 30 °C, the temperature control of the plating solution is not easy, and the deposition efficiency of the plating is lowered, which is not suitable for operation. If it exceeds 701:, the precipitation plating becomes dull. Furthermore, the uniform plating property is improved, and it is impossible to perform high-precision partial plating. Further, the evaporation of the plating solution during the operation greatly reduces the plating capacity, which causes a problem that the concentration of each component in the plating solution needs to be changed.
鍍敷時的電流密度以1〜5 0A/dm2爲宜，較佳爲 10~40A/dm2。此電流密度範圍中，藉適當選擇鍍液之pH 値、液溫、金濃度、添加劑及傳導鹽濃度等，可形成優良 的鍍敷皮膜。 藉本發明之鍍液經鍍敷之被鍍敷素材，並無特別限定 ’例舉如作爲電機器之電接點用構件之用的連接器、開關 、繼電器等。作爲素材的材質，可適用磷青銅或鈹青銅、 -11 - 201002870 黃銅、銅、鐵鎳合金、鐵等。此等之素材，藉常法進行鎳 電鍍後’使用本發明之鍍液進行鍍敷爲宜。 作爲對被鍍敷素材進行鍍敷之方法，可採用公知之方 法’本發明之鑛液，最適合作爲帶鋼（hoop )鍍敷、捲軸 連續（reel-to-reel )鍍敷等部份鍍敷用之鍍液。此等鍍敷 方中，係以被鍍敷物作爲陰極，使配合部份鍍敷形狀所形 成之鍍液噴出噴嘴作爲陽極使用。使由作爲陽極機能之噴 嘴，對作爲陰極機能之被鍍敷物噴射鍍液，於其狀態藉陽 極-陰極間施加電壓，進行部份鍍敷。 本發明之部份鍍敷用鍍液因電傳導度小，電解電流很 難流通於陽極-陰極間的距離長的部份。爲此，僅於由陽 極的距離短的部份集中電解電流，遂可於陰極表面，僅限 於接近陽極之範圍進行鍍敷。根據後述之鍍敷均鍍性測試 的結果，均鍍範圍係1 0 m m〜2 0 m m程度之範圍。 藉本發明之鍍液所形成之鍍敷皮膜之膜厚得藉調節電 解時間、電解電流等形成所期的厚度。對電接點構件進行 鍍敷時，鍍敷皮膜的厚度通常爲 〇.〇5~1·Ομιη，以 0_ 1 〜0·5μιη 爲宜。 【實施方式】 [實施例] 實施例1、2及比較例1、2 以下組成之基本鍍液，係如表1所載之添加劑調製 金-鈷合金鍍液。其次，使用氫氧化鉀調整ΡΗ爲4.3。又 -12- 201002870 ’爲用以調整pH之氫氧化鉀的量依各鍍液有所不同，金 鹽、鈷鹽、傳導鹽 '添加劑的莫耳數則所有的鍍液皆相同 〇 使用調製之金-鈷合金鍍液，各自的電傳導度、電鍍 中電解電壓、鍍敷均鍍性藉後述的方法測定。所測定的電 傳導度、電解電壓之値示於表1。 (基本鍍液） KAu ( CN ) 2 Au = 7.34 g/1 硫酸銘 2.39g/ 1 檸檬酸 6 0 g/ 1 吡啶甲酸 2.2g/ 1 表1 實施例1 實施例2 比較例1 比較例2 添加劑之種類 甘胺酸 丙胺酸 檸檬酸 甲酸 添加劑之添加量 40g/l 47.5g/l llg/1 24.5g/l 電傳導度US) 34700 32900 70600 72600 電解電壓（V) 5.42 5.51 3.78 3.88 鍍敷均鍍性（mm) 18 18 93 73 Ρ (μηι) 0.176 0.181 0.175 0.140 q (mm) 16 16 81 51 [各鍍液之電傳導度和電解電壓之比較] 將金-鈷合金鍍液500ml注入電解槽’以50°C保溫。 接著，以無攪拌的狀態，於陽極和陰極之間施加電壓，進 -13- 201002870 行60秒鐘的定電流電解（ 300mA)。陰極之鍍敷基板’ 係使用1 · 4 d m2之鑛鎳銅板1張。陽極，係使用鉑-鈦筛孔 〇 如表1所示，實施例1、2之鍍液的電傳導度’係比 較例1、2之鍍液的電傳導度約1 /2。反之’電鍍中的電解 電壓，係實施例1、2均較比較例1、2增加約4成以上。 [鍍敷均鑛測試験] 使用圖i所示之鍍敷均鍍評估裝置，進行鍍敷均鍍性 評估。 一般而言，陰極的形狀若有凹凸，陽極和陰極之間的 距離短的陰極部份之鍍敷厚度’較同距離長的陰極部份的 鍍敷厚度亦變大。圖1之評估裝置，係利用此原理’以評 估陽極和陰極之間的距離對鍍敷厚度影響之程度（鍍敷均 鍍性）爲目的的裝置。 圖1中，1係電解槽，2係陽極板，3係陰極板，4係 遮蔽板。又，遮蔽板4，係全面被覆樹脂。2張的遮蔽板 4和陰極板3係相互平行排列。陰極板3和陽極板2，係 相互垂直排列。陰極板3和遮蔽板4，形成相同尺寸（横 1 〇〇X高度7 0 mm )，相鄰的陰極板3和遮蔽板4之間的間 隔，係5mm。陰極板3之陽極板側的陰極板端部3a，和 陽極板2係各自相離5 0mm。陰極板3，係連接於無圖式 之外部電源的陰極。陽極板2，係連接於外部電源的陽極 。陰極板，其下端側浸於鍍液5之中深度爲2.5 cm。 -14- 201002870 電解後，取出陰極板3，自陰極板下端3 b之上側 20mm的位置，自陰極板端部3a朝陰極板之另一側之端部 3 c自1 mm之位置P朝端部3 c以5 mm間隔測定鍍敷膜厚 。測定膜厚至0.01 μ*η以下止的膜厚’求出膜厚爲〇·〇 km 之位置和位置p之間的距離（q)。膜厚之測定’係使用 螢光X射線膜厚計（SII製SFT-3200)。膜厚Ο.ΟΙμιη， 係用上述膜厚計可測定的鄰界値。設定作爲目的之鍍敷膜 厚爲0.2μιη，於位置Ρ之膜厚設爲（Ρ)時，求出以下記 式（1 )定義的鍍敷均鍍性。 均鍍性（mm) = [〇.2(pm)/p(pm)]xq(mm). ♦ '(1) 對鍍液之電傳導度的均鍍性以圖表示於圖2，對鍍敷 時之電解電壓的均鍍性以圖表示於圖3。 關於各種鍍液的電傳導性和鍍敷均鍍性之間的關係， 由圖2得知若使用比較例1、2之電傳導性高的鍍槽，鍍 敷均鍍性變佳，廣大範圍被鍍敷。 反之，若使用甘胺酸、丙胺酸作爲添加劑的實施例1 、2之低電傳導性鍍槽’鍍敷均鍍性係比較例1、2的 1/4〜1/5。 關於電解電壓和鍍敷的均鍍性之間的關係，示於圖3 。比較例1、2中，得以3.7 V前後的低電解電壓電解，此 情況’均鍍性佳。實施例1、2中，電解電壓係5 · 5 v前後 ，均鍍性如上述的小。 -15- 201002870 由以上的結果’得知使用甘胺酸、丙胺酸之實施例1 、2的鍍液，電傳導性降低，鍍敷均鍍性變小。實施例1 、2之鍍液因均鍍性低，得良好地進行部份鍍敷。 【圖式簡單說明】 [圖1 ]係表示鍍敷均鍍性評估裝置之構成的槪略立體 圖。 [圖2]係表示鍍敷均鍍性，和鍍液之電傳導度之間之 關係的圖表。 [圖3 ]係表示鍍敷均鍍性，和電解電壓（電池電壓）之 間之關係的圖表。 [主要元件符號說明】 1 :電解槽 2 :陽極板 3 :陰極板 3 a :端部 3 b :陰極板下端 3c :另一側之端部 4 :遮蔽板（全面樹脂被覆） 5 :鍍液 -16-The current density at the time of plating is preferably 1 to 50 A/dm 2 , preferably 10 to 40 A/dm 2 . In this current density range, an excellent plating film can be formed by appropriately selecting the pH 値, liquid temperature, gold concentration, additive, and conductive salt concentration of the plating solution. The plated material to be plated by the plating solution of the present invention is not particularly limited. For example, a connector, a switch, a relay, or the like, which is used as a member for an electric contact of an electric machine, is exemplified. As the material of the material, it can be applied to phosphor bronze or beryllium bronze, -11 - 201002870 brass, copper, iron-nickel alloy, iron, and the like. Such materials are preferably plated by using the plating solution of the present invention after nickel plating by a conventional method. As a method of plating the material to be plated, a well-known method 'the mineral liquid of the present invention can be used, and it is most suitable as a part plating such as hoop plating, reel-to-reel plating, or the like. Apply plating solution. In such a plating method, a plating liquid is used as a cathode, and a plating liquid discharge nozzle formed by a plating portion is used as an anode. The nozzle is used as a function of the anode, and a plating solution is sprayed on the object to be plated as a cathode function, and a voltage is applied between the anode and the cathode in a state thereof to perform partial plating. In the plating solution for plating of the present invention, since the electrical conductivity is small, it is difficult for the electrolysis current to flow through the portion where the distance between the anode and the cathode is long. For this reason, the electrolysis current is concentrated only in the portion where the distance from the anode is short, and the crucible can be plated on the surface of the cathode only in the range close to the anode. According to the results of the plating uniformity test described later, the plating range is in the range of about 10 m 2 to 2 m m . The film thickness of the plating film formed by the plating solution of the present invention is such that the desired thickness is formed by adjusting the electrolysis time, the electrolysis current, and the like. When the electrical contact member is plated, the thickness of the plating film is usually 〇. 5~1·Ομιη, preferably 0_1 to 0·5 μιη. [Embodiment] [Examples] Examples 1, 2 and Comparative Examples 1 and 2 The following basic plating solutions were prepared by adding the additive gold-cobalt alloy plating solution as shown in Table 1. Next, adjust the enthalpy to 4.3 using potassium hydroxide. -12- 201002870 'The amount of potassium hydroxide used to adjust the pH varies depending on the plating solution. The molar amount of the gold salt, cobalt salt, and conductive salt' additive is the same for all the plating solutions. The gold-cobalt alloy plating solution was measured by the method described below for each of electrical conductivity, electrolysis voltage during plating, and plating plating. The measured electrical conductivity and electrolytic voltage are shown in Table 1. (Basic plating solution) KAu (CN) 2 Au = 7.34 g/1 Sulfuric acid, 2.39 g/1 Citric acid 60 g/1 Picolinic acid 2.2 g/1 Table 1 Example 1 Example 2 Comparative Example 1 Comparative Example 2 Additive The amount of glycine acid alanine citrate formic acid additive added 40g / l 47.5g / l llg / 1 24.5g / l electrical conductivity US) 34700 32900 70600 72600 electrolytic voltage (V) 5.42 5.51 3.78 3.88 plating plating Properties (mm) 18 18 93 73 Ρ (μηι) 0.176 0.181 0.175 0.140 q (mm) 16 16 81 51 [Comparison of electrical conductivity and electrolytic voltage of each plating bath] Inject 500 ml of gold-cobalt alloy plating solution into the electrolytic cell' Keep at 50 ° C. Next, a voltage was applied between the anode and the cathode without agitation, and a constant current electrolysis (300 mA) was carried out for -60-201002870 for 60 seconds. The plated substrate of the cathode was one piece of a nickel-copper plate of 1 · 4 d m2. For the anode, a platinum-titanium mesh was used. As shown in Table 1, the electrical conductivity of the plating solutions of Examples 1 and 2 was about 1 /2 in comparison with the plating solutions of Examples 1 and 2. On the other hand, in the electrolysis voltage in electroplating, both of Examples 1 and 2 were increased by about 40% or more compared with Comparative Examples 1 and 2. [Plating ore testing test] The plating plating evaluation device shown in Fig. i was used to evaluate the plating uniformity. In general, if the shape of the cathode is uneven, the plating thickness of the cathode portion having a short distance between the anode and the cathode is larger than the plating thickness of the cathode portion having a long distance. The evaluation apparatus of Fig. 1 uses this principle to evaluate the degree of influence of the distance between the anode and the cathode on the plating thickness (plating uniformity). In Fig. 1, a 1-series electrolytic cell, a 2-series anode plate, a 3-series cathode plate, and a 4-series shielding plate are used. Further, the shielding plate 4 is entirely coated with a resin. The two shielding plates 4 and the cathode plates 3 are arranged in parallel with each other. The cathode plate 3 and the anode plate 2 are arranged perpendicular to each other. The cathode plate 3 and the shielding plate 4 are formed in the same size (horizontal 〇〇X height 70 mm), and the interval between the adjacent cathode plate 3 and the shielding plate 4 is 5 mm. The cathode plate end portion 3a on the anode plate side of the cathode plate 3 and the anode plate 2 are each separated by 50 mm. The cathode plate 3 is connected to a cathode of an external power supply without a pattern. The anode plate 2 is connected to an anode of an external power source. The cathode plate has a lower end side immersed in the plating solution 5 to a depth of 2.5 cm. -14- 201002870 After electrolysis, the cathode plate 3 was taken out, 20 mm from the upper side of the lower end 3b of the cathode plate, from the end of the cathode plate 3a toward the other end of the cathode plate 3 c from the position P of 1 mm toward the end The portion 3c measures the thickness of the plating film at intervals of 5 mm. The film thickness of the film thickness to 0.01 μ*η or less was measured. The distance (q) between the position where the film thickness was 〇·〇 km and the position p was determined. For the measurement of the film thickness, a fluorescent X-ray film thickness meter (SFT-3200 manufactured by SII) was used. The film thickness Ο.ΟΙιη is the adjacent 値 which can be measured by the above film thickness meter. When the thickness of the plating film to be set is 0.2 μm, and the film thickness at the position 设为 is (Ρ), the plating plating property defined by the following formula (1) is obtained. Uniform plating (mm) = [〇.2(pm)/p(pm)]xq(mm). ♦ '(1) The uniformity of the electrical conductivity of the plating solution is shown in Figure 2, for plating The uniformity of the electrolytic voltage at the time of application is shown in Fig. 3. Regarding the relationship between the electrical conductivity of each plating solution and the plating plating property, it is understood from Fig. 2 that the plating plating property of the comparative examples 1 and 2 is improved, and the plating plating property is improved, and the range is wide. Being plated. On the other hand, the low-conductivity plating tanks of Examples 1 and 2 using glycine and alanine as additives were plated and the plating plating properties were 1/4 to 1/5 of Comparative Examples 1 and 2. The relationship between the electrolysis voltage and the plating efficiency of plating is shown in Fig. 3. In Comparative Examples 1 and 2, electrolysis was carried out at a low electrolysis voltage of 3.7 V or so. In this case, the uniform plating property was good. In Examples 1 and 2, the electroplating voltage was about 5 · 5 v, and the uniform plating property was as small as described above. -15-201002870 From the above results, it was found that the plating solutions of Examples 1 and 2 using glycine and alanine have a low electrical conductivity and a small plating plating property. The plating solutions of Examples 1 and 2 were partially plated with good uniform plating properties. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a schematic perspective view showing the constitution of a plating plating evaluation device. Fig. 2 is a graph showing the relationship between the plating plating property and the electrical conductivity of the plating solution. Fig. 3 is a graph showing the relationship between plating plating property and electrolytic voltage (battery voltage). [Description of main components] 1 : Electrolyzer 2 : Anode plate 3 : Cathode plate 3 a : End 3 b : Lower end of cathode plate 3 c : End of the other side 4 : Masking plate (full resin coating) 5 : Plating solution -16-