200932947 九、發明說明 【發明所屬之技術領域】 本發明係關於一種能夠在以銅質地之所形成之微細配 線圖型上呈直接地進行鍍金的取代型無電解鍍金液、以及 使用前述鍍金液的鍍金方法。本鍍液係可以不透過無電解 鍍鎳皮膜而直接地電鍍於銅質地，並且，不含有氰化合物 【先前技術】 〔背景技術〕 在近年來，行動電話、筆記型個人電腦等之電子機器 係由於技術之進步而進行輕量化、小型化、高性能化。作 爲這些電子機器之電子材料係使用於印刷電路板。即使是 在印刷電路板中，可彎曲之可撓性基板係也需求變大。 在印刷電路板之表面，形成由銅質地所組成之微細配 Q 線圖型。作爲微細配線圖型之表面處理係向來有無電解鍍 鎳處理和鍍金處理。但是，藉由鍍鎳處理所形成之鎳皮膜 係硬度高，因此，預測今後會無法使用在要求更加高之彎 曲性之可撓性基板。於是，在最近，不設置無電解鎳皮膜 而直接在銅質地之配線圖型來施行取代型鍍金之規格（ DIG規格）之可撓性基板逐漸增加。 在前述規格之可撓性基板之鍍金處理，使用向來在鎳 表面進行鍍金時之所採用之以氰化金鉀作爲金源之氰系取 代型鍍金液之電鏟方法則成爲主流。該氰系取代型鍍金液 -4- 200932947 係變得便宜。此外，由透過習知之鎳被覆膜來進行取代型 鍍金之製程而轉用至在銅質地呈直接地進行取代型鍍金之 製程之轉用係變得容易。但是，氰系鍍金液係毒性強，因 此，環境負荷大。此外，由作業環境、廢液處理等之觀點 來看的話，則顯著地限制氰系鍍金液之使用。 因此，要求開發非氰系之取代型鍍金。 現在開發之非氰系之取代型鍍金係以對於無電解錬底 Φ 材之電鍍處理，作爲目的。銅係比起鎳還更加不容易離子 化（離子化傾向低）。由於該理由，因此，在銅底材直接 地施行非氰系之取代型鍍金之時，不容易進行金還原之所 需要之取代反應。結果，得到之電鍍皮膜係有外觀不良、 密合不良等之問題。 在非氰系之取代型無電解鍍金液，通常配合亞硫酸金 錯合物，來作爲金源，並且，還添加亞硫酸鹽，來作爲其 安定劑。 φ 亞硫酸鹽係在鍍液中，以亞硫酸離子存在，接觸到空 氣，藉由以加熱器等之熱源，來進行加熱，而進行氧化，BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substituted electroless gold plating solution capable of directly performing gold plating on a fine wiring pattern formed of a copper texture, and a gold plating solution using the same. Gold plating method. This plating solution can be directly plated on a copper ground without passing through an electroless nickel plating film, and does not contain a cyanide compound. [Prior Art] In recent years, electronic devices such as mobile phones and notebook personal computers have been used. Lightweight, miniaturized, and high-performance due to advances in technology. The electronic materials used as these electronic devices are used in printed circuit boards. Even in printed circuit boards, flexible flexible substrate systems are becoming more demanding. On the surface of the printed circuit board, a fine Q-ray pattern composed of copper is formed. The surface treatment of the fine wiring pattern has always been subjected to electroless nickel plating treatment and gold plating treatment. However, since the nickel film formed by the nickel plating treatment has a high hardness, it is predicted that a flexible substrate which requires higher bending property cannot be used in the future. As a result, recently, flexible substrates having been subjected to the substitution type gold plating specification (DIG standard) directly in the copper wiring pattern without providing an electroless nickel film have been increasing. In the gold plating treatment of the flexible substrate of the above specifications, a shovel method using a cyanide-based substitution type gold plating solution using gold potassium cyanide as a gold source for gold plating on the nickel surface has been mainstream. The cyanide-substituted gold plating solution -4-200932947 is inexpensive. In addition, it is easy to switch to a nickel-plated film by a conventional nickel-coated film and switch to a process of directly performing a gold plating process in the copper texture. However, the cyanide-based gold plating system is highly toxic and therefore has a large environmental load. Further, from the viewpoints of the working environment, waste liquid treatment, etc., the use of the cyanide gold plating solution is remarkably restricted. Therefore, it is required to develop a non-cyanide substitution type gold plating. The non-cyanide substitution type gold plating which has been developed now is intended to be electroplated for the electroless ruthenium Φ material. Copper is less susceptible to ionization than nickel (lower ionization tendency). For this reason, when the copper substrate is directly subjected to the non-cyanide substitution type gold plating, the substitution reaction required for the gold reduction is not easily performed. As a result, the obtained plating film has problems such as poor appearance and poor adhesion. The non-cyanide-substituted electroless gold plating solution is usually used as a gold source in combination with a gold sulfite complex, and a sulfite is added as a stabilizer. The φ sulfite is contained in the plating solution in the presence of sulfite ions, is in contact with air, and is heated by a heat source such as a heater to be oxidized.
I 成爲硫酸離子。 亞硫酸金錯合物之安定性係藉由包含於鍍液中之游離 亞硫酸離子而維持。因此，在亞硫酸離子氧化成爲硫酸離 子時，急劇地降低鍍液之安定性，最後分解亞硫酸金錯合 物而產生沉澱。 亞硫酸離子係作用成爲亞硫酸金錯合物之安定劑。在 對於其反面、銅底材表面來進行取代型鍍金處理時，妨礙 -5- 200932947 銅和金之取代反應，引起生成之金皮膜之外觀不良、和銅 底材之密合不良等之問題。 在專利文獻1、2，揭示：作爲非氰系之取代型無電 解鍍金液係包含水溶性亞硫酸金化合物、亞硫酸鹽、水溶 性聚胺基羧酸、水溶性胺和鉈化合物之鍍金液。該鍍液係 不含有氰化合物，因此，毒性變低，環境負荷變小。 專利文獻1、2所記載之鍍金液係以在鎳皮膜上進行 φ 鍍金，來作爲目的。在該鍍液，爲了達到亞硫酸金錯合物 之安定化，因此，使用亞硫酸鹽。在使用該鍍金液而在銅 質地表面來進行鍍金之狀態下，無法正常地進行銅質地和 金之取代反應。結果，在金皮膜之外觀、金皮膜和銅質地 之密合性，產生問題，無法得到均勻之金皮膜。 〔專利文獻1〕日本專利第3 030 1 1 3號公報（申請專 利範圍） 〔專利文獻2〕日本專利第3482402號公報（申請專 0 利範圍） 【發明內容】 〔發明之揭示〕 〔發明所欲解決之課題〕 本發明之目的係提供一種環境負荷小之非氰系之取代 型鍍金液而可以在銅質地之表面不透過鎳皮膜來直接地形 成均勻之金皮膜且具有良好之鍍液安定性和高度之電鍍速 度的取代型鍍金液以及鍍金方法。 -6 - 200932947 〔用以解決課題之手段〕 本發明人係全心地進行檢討。結果發現：在使用水溶 性胺基羧酸化合物來取代向來使用之亞硫酸鹽而作爲亞硫 酸金錯合物之安定劑時，能夠在銅質地之表面，直接地形 成均勻且密合性高之取代型鍍金皮膜，以致於完成本發明 〇 H 達成前述目的之本發明係記載於以下。 [1] : 一種銅質地用取代型無電解鍍金液，係含有作 爲金離子濃度之亞硫酸金鹽0.5〜10g/L和水溶性胺基羧 酸化合物1 0〜150g/ L的銅質地用取代型無電解鍍金液， 且不包含亞硫酸金鹽以外之亞硫酸鹽。 [2] : —種鏟金方法，係藉由將銅質地之被鑛物浸漬 於[1]所記載之銅質地用取代型無電解鍍金液，而直接地 取代鍍金於銅質地上。 G [3]: —種配線係由以銅來形成於基板或晶圓上之配 線圖型與直接地被覆前述配線圖型之鍍金皮膜所組成。 [4]: [3]所記載之配線之形成方法係在以銅來形成於 基板或晶圓上之配線圖型上，使用[1]所記載之銅質地用 取代型無電解鍍金液而進行鍍金。 〔發明之效果〕 本發明之取代型無電解鍍金液係不含有氰系化合物， 因此，毒性變低，對於環境之負荷小，廢液處理等變得容 200932947 易。 本發明之取代型無電解鍍金液係含有水溶性胺基羧酸 化合物，該化合物係發揮亞硫酸金錯合物之安定劑之功能 。結果，抑制鍍液中之水溶性亞硫酸金化合物之自行分解 0 前述之水溶性胺基羧酸化合物係藉由成爲質地金屬之 銅等和金進行取代反應，溶解於鍍液中，而也作用成爲隱 0 蔽增加之金屬不純物之錯合劑。水溶性胺基羧酸化合物係 有助於亞硫酸金錯合物之安定化，並且，作用成爲金屬不 純物之錯合劑，因此，本發明之取代型無電解鍍金液係具 有高度之液體安定性。可以藉由使用本發明之無電解鍍金 ，而不產生沉澱，將圖型性良好且外觀良好之金皮膜，析 出於銅質地之表面。此外，本發明之取代型無電解鍍金液 係不包含亞硫酸金鹽以外之亞硫酸鹽，含有胺基羧酸《胺 基羧酸係具有不容易由亞硫酸金化合物來脫離亞硫酸離子 ❹ 之作用，藉由該作用而抑制亞硫酸由金離子游離。因此， 即使是亞硫酸離子氧化成爲硫酸離子，也持續地保持某種 程度之液體安定性，可以長時間的使用。 【實施方式】 〔發明之最佳實施形態〕 本發明之鍍金液係以亞硫酸金鹽和水溶性胺基羧酸化 合物，作爲必要成分，這些溶解於水中。實質不含有亞硫 酸金鹽以外之亞硫酸鹽。包含於本發明之鍍金液之亞硫酸 200932947 離子係由來於亞硫酸金鹽。 作爲配合於本發明之無電解鍍金液之亞硫酸金鹽係可 以列舉例如亞硫酸金銨、亞硫酸金钾、亞硫酸金鈉等。亞 硫酸金鹽之添加量係作爲金離子濃度，成爲0.5〜10g/L ，但是，最好是1〜5g/ L。在金離子濃度未滿0.5g/ L 時，電鍍反應之進行速度係變得緩慢。另一方面，在金離 子濃度超過l〇g/L時，降低液體安定性，因此，認爲有 0 容易引起鍍液之自行分解之傾向發生，容易在鍍金液中及 電鍍槽之底部，生成金粒子。 在本發明之取代型無電解鍍金液，配合水溶性胺基羧 酸化合物。作爲水溶性胺基羧酸化合物係使用水溶性胺基 羧酸或其鹽。作爲水溶性胺基羧酸係可以列舉例如乙烯二 胺四乙酸、乙烯二胺四乙酸二鈉、乙烯二胺四乙酸二鉀、 乙烯二胺四乙酸二銨、硝基三乙酸、亞胺基二乙酸、甘胺 酸、麩胺酸、天冬胺酸等。 Q 在本發明之取代型無電解鍍金液，前述水溶性胺基羧 酸化合物之配合量係10〜150g/L。水溶性胺基羧酸化合 物之理想配合量係30〜100g/ L，更加理想之配合量係50 〜8 0g/ L。在水溶性胺基羧酸化合物之含有量未滿l〇g/ L之狀態下，亞硫酸金錯合物之安定性變差，並且，容易 受到因爲取代反應而由銅質地溶出之銅離子之影響，結果 ，降低鑛液之液體安定性。在超過15 0g/ L時，沒有相稱 於添加量之優點，因此，不具經濟效益。 本發明之無電解鍍金液係可以使用於pH値5.0〜10.0 -9- 200932947 ，但是’最好是使用於pH値6.0〜8.0。在pH値低於5.0 之狀態下’鍍液係容易自行分解。在pH値高於10.0之狀 態下’得到之金皮膜之外觀係紅色化，有無法得到正常之 金皮膜之傾向發生。作爲pH値調整劑係可以列舉氫氧化 鈉、氫氧化鉀、氫氧化銨及稀釋硫酸水等。 在使用本發明之取代型無電解鍍金液而進行電鏟時之 鍍液溫度係30〜90 °C，但是，最好是50〜80 °C。在鍍液 0 之液溫低於30°C時，幾乎不引起電鍍反應，在高於9(TC 時，分解亞硫酸金錯合物，鍍液容易自行分解。 在本發明之取代型無電解鍍金液，除了前述之必要成 分以外，還可以在不妨礙本發明效果之範圍內，包含檸檬 酸鹽、磷酸鹽、焦磷酸鹽、硫酸鹽等之傳導鹽、緩衝劑等 之任意成分。本發明之取代型無電解鍍金液係在配合鉈化 合物、鉛化合物、砷化合物等之結晶調整劑之時，無法得 到正常之金皮膜，有成爲不均勻之外觀之傾向發生。因此 Q ，這些化合物係最好是不配合。 圖1係顯示使用本發明之鍍金液而形成之印刷電路板 上之配線之某一例子之槪略剖面圖。 在圖1中，1係印刷電路板。在印刷電路板1之表面 ，形成由銅組成之配線圖型3。配線圖型3之厚度係通常 爲20〜50/zm。在配線圖型3上，形成取代型無電解鍍金 皮膜5。藉由以鍍金皮膜5，來被覆配線圖型3之表面， 而使得印刷電路板之配線7呈化學地安定，保護不受到腐 蝕等。在配線7，包含凸塊、電極、端子等。 -10- 200932947 取代型無電解鍍金皮膜5之厚度係最好是0.01〜〇·2 #m、更加理想是〇.01〜〇.1//„1。在鍍金皮膜之膜厚未滿 O.Ol^m之狀態下’以銅所形成之配線圖型3對於腐蝕等 之保護作用呈不足。在超過〇.2μηι時，析出之皮膜之形 狀容易變形，在配線間，容易產生交聯。 藉由以形成銅質地之配線圖型3之印刷電路板，作爲 被鍍物，在配線圖型3上，使用前述之取代型無電解鍍金 液，施行取代型無電解鍍金，而形成配線7。可以在鏟金 皮膜5上，由於需要而還進行還原型之無電解鍍金。還原 型之無電解鍍金係可以使用習知之鍍液。 此外，即使是就取代印刷電路板1而形成於1C導線 架、陶瓷基板或晶圓等之銅微細配線圖型而言，也可以藉 由相同之方法而進行鍍金。 〔實施例〕 ❹ 使用太陽油墨製造（股）公司製之銲錫阻劑PSR4000 ，在基板上，形成以線幅寬50〜1000/zm、尺寸5x5cm之 銅質地之所構成之微細電路。在該基板，施行酸性脫脂、 化學硏磨、酸洗淨而得到使用於實施例之試料。 實施例1 將含有作爲AU之亞硫酸金鈉3g/ L和乙烯二胺四乙 酸50g/L之pH値6.0之鍍金液，保持在液溫70°C。在 前述之鍍液，浸漬試料之基板30分鐘。在30分鐘後，取 -11 - 200932947 出試料，藉由 SII公司製之螢光X射線膜厚測定器 SFT3200而測定析出之膜厚。在30分鐘後之金膜厚係 0.0 5 ym。藉由目視及實體顯微鏡而觀察電鍍表面。阻劑 係並無變色。析出之金皮膜係色調均勻之檸檬黃。也就是 說，藉由目視之所造成之金皮膜之色調係在外觀無不均勻 而成爲良好之外觀。不認爲有鍍液之分解。 在此，電鍍表面之不均之判斷基準係正如以下。 有不均··指明是藉由目視來進行觀察而電鍍表面之色 調呈不均勻之狀態。例如顯示電鍍表面之色調爲黃金色狀 態、白很多之金色狀態、紅很多之金色狀態之狀態等。在 藉由電子顯微鏡所造成之觀察，正如圖3所示，成爲金粒 子呈不均勻地析出之狀態。 無不均：藉由目視來進行觀察而成爲均勻之檸檬黃之 狀態。 將在實施例1所得到之鍍金皮膜之電子顯微鏡相片， 顯示於圖2。由圖2而明確地得知：鍍金皮膜係無不均而 均句地附著金。 實施例2 除了將含有作爲Au之亞硫酸金鈉3 g/L和氰基三乙 酸50g/ L之pH値6.0之鍍金液，保持在液溫70°C以外 ，其餘係相同於實施例1而進行操作。在3 0分鐘後之金 膜厚係0.05；um。阻劑係並無變色。析出之金皮膜係色調 爲檸檬黃，外觀係無不均而成爲良好之外觀。不認爲有鍍 -12- 200932947 液之分解。 實施例3 除了將含有作爲Au之亞硫酸金鈉3 g/L和亞胺基二 乙酸50g/L之pH値6.0之鍍金液，保持在液溫70°C以 外，其餘係相同於實施例1而進行操作。在30分鐘後之 金膜厚係0.04/zm。阻劑係並無變色。析出之金皮膜係色 調爲檸檬黃，外觀係無不均而成爲良好之外觀。不認爲有 鍍液之分解。 實施例4 除了將含有作爲Au之亞硫酸金鈉3g/L和乙烯二胺 四乙酸15g/ L之pH値6.0之鍍金液，保持在液溫70°C 以外，其餘係相同於實施例1而進行操作。在3 0分鐘後 之金膜厚係〇.〇5 μ m。不認爲阻劑有變色，析出之金皮膜 Q 係色調爲檸檬黃，外觀係無不均而成爲良好之外觀。此外 ，不認爲有鍍液之分解》 比較例1 除了將含有作爲Au之亞硫酸金鈉3g/L、亞硫酸鈉 50g/L和乙烯二胺四乙酸l〇g/L之pH値7.0之鍍金液 ，保持在液溫7〇°C以外，其餘係相同於實施例1而進行 操作。在30分鐘後之金膜厚係〇.〇6 y m。不認爲阻劑有 變色。析出之金皮膜係色調變紅，在外観有不均。此外， -13- 200932947 不認爲有鍍液之分解。 將在比較例1所得到之鍍金皮膜之電子顯微鏡相片， 顯示於圖3。由圖3而明確地得知：金係附著成爲粒狀， 在金皮膜有不均。 比較例2 將含有作爲Au之亞硫酸金鈉lg/ L、亞硫酸鈉100g /L、檸檬酸50g/L和乙烯二胺四乙酸60g/L之pH値 6.0之鍍金液，保持在液溫70 °C »在該鍍液，浸漬試料之 基板10分鐘。在10分鐘後，取出試料，藉由螢光X射 線膜厚測定器而測定析出之膜厚。在10分鐘後之金膜厚 係0.05/zm。在藉由目視及實體顯微鏡而進行觀察時，並 無阻劑之變色。析出之金皮膜係色調變紅，在外觀有不均 。不認爲有鍍液之分解。 ❾ 比較例3 將含有作爲Au之亞硫酸金鈉3 g/ L和乙烯二胺四乙 酸5g/L之pH値6.0之鏟金液，保持在液溫70°C。在該 鍍液，浸漬試料之基板30分鐘。在30分鐘後，取出試料 ，藉由螢光X射線膜厚測定器而測定析出之膜厚。在3 〇 分鐘後之金膜厚係0.05/zm。藉由目視及實體顯微鏡而進 行觀察。並無阻劑之變色。析出之金皮膜係色調變紅，在 外觀有不均。不認爲在鍍液有分解。 -14- 200932947 【圖式簡單說明】 圖1係顯示使用本發明之取代型無電解鍍金液而形成 之配線之某一例子之槪略剖面圖。 圖2係在實施例1所得到之鍍金皮膜之圖式代用電子 顯微鏡相片。 圖3係在比較例1所得到之鍍金皮膜之圖式代用電子 顯微鏡相片。 〇 【主要元件符號說明】 1 :印刷電路板 3 :配線圖型 5 :鍍金皮膜 7 :配線I becomes a sulfate ion. The stability of the gold sulfite complex is maintained by the free sulfite ions contained in the bath. Therefore, when the sulfite ion is oxidized to a sulfuric acid ion, the stability of the plating solution is drastically lowered, and finally, the gold sulfite complex is decomposed to cause precipitation. The sulfite ion acts as a stabilizer for the gold sulfite complex. When the substitution type gold plating treatment is performed on the reverse side and the surface of the copper substrate, the substitution reaction of copper and gold of -5-200932947 is hindered, and the appearance of the formed gold film is poor, and the adhesion of the copper substrate is poor. Patent Documents 1 and 2 disclose that a non-cyanide substituted electroless gold plating solution contains a gold-plated solution of a water-soluble gold sulfite compound, a sulfite, a water-soluble polyaminocarboxylic acid, a water-soluble amine, and a ruthenium compound. . Since the plating solution does not contain a cyanide compound, the toxicity is lowered and the environmental load is reduced. The gold plating liquids described in Patent Documents 1 and 2 are intended to be φ plated on a nickel film. In the plating solution, in order to achieve stabilization of the gold sulfite complex, sulfite is used. In the state where gold plating is performed on the surface of the copper material using the gold plating solution, the substitution reaction of copper and gold cannot be performed normally. As a result, there was a problem in the appearance of the gold film, the adhesion between the gold film and the copper texture, and a uniform gold film could not be obtained. [Patent Document 1] Japanese Patent No. 3 030 1 1 3 (Application Patent Field) [Patent Document 2] Japanese Patent No. 3,482,402 (Application Patent No.) [Disclosure of Invention] [Disclosure of Invention] [Invention Office] SUMMARY OF THE INVENTION The object of the present invention is to provide a non-cyanide-substituted gold plating solution having a small environmental load, which can directly form a uniform gold film on the surface of a copper texture without a nickel film and has a good bath stability. Substituted gold plating solution and gold plating method for the plating speed of the character and the height. -6 - 200932947 [Means for Solving the Problem] The inventors conducted a thorough review. As a result, it has been found that when a water-soluble aminocarboxylic acid compound is used in place of the sulfite used in the past as a stabilizer for the gold sulfite complex, it is possible to form a uniform and high adhesion directly on the surface of the copper texture. The substituted gold-plated film is such that the present invention which achieves the above object is completed in the following. [1] : A copper-based substituted electroless gold plating solution containing a gold-based gold salt having a gold ion concentration of 0.5 to 10 g/L and a water-soluble aminocarboxylic acid compound of 10 to 150 g/L. Type electroless gold plating solution, and does not contain sulfite other than gold sulfite. [2]: A method of shovel gold is directly substituted for gold plating on a copper ground by immersing the mineral of the copper texture in the copper-based substituted electroless gold plating liquid described in [1]. G [3]: The wiring is composed of a wiring pattern formed of copper on a substrate or a wafer and a gold plating film directly covering the wiring pattern. [4] The method of forming the wiring described in [3] is performed on a wiring pattern formed of copper on a substrate or a wafer, and the copper-based substitution type electroless gold plating liquid described in [1] is used. Gold plated. [Effects of the Invention] The substituted electroless gold plating liquid of the present invention does not contain a cyanide compound, so that the toxicity is low, and the environmental load is small, and the waste liquid treatment and the like become easy to be used. The substituted electroless gold plating solution of the present invention contains a water-soluble aminocarboxylic acid compound which functions as a stabilizer for the gold sulfite complex. As a result, the self-decomposition of the water-soluble gold sulfite compound in the plating solution is suppressed. The water-soluble aminocarboxylic acid compound described above is substituted by gold and the like as a metallic metal, and is dissolved in the plating solution. It becomes a faulty mixture of metal impurities that are hidden. The water-soluble aminocarboxylic acid compound contributes to the stabilization of the gold sulfite complex and acts as a complexing agent for the metal impurities. Therefore, the substituted electroless gold plating liquid of the present invention has a high liquid stability. The gold film having good pattern properties and good appearance can be deposited on the surface of the copper texture by using the electroless gold plating of the present invention without causing precipitation. Further, the substituted electroless gold plating solution of the present invention does not contain a sulfite other than the gold sulfite salt, and contains an aminocarboxylic acid. The aminocarboxylic acid has a bismuth sulfite which is not easily removed by a gold sulfite compound. Acting, by this action, inhibits the sulfite from being freed by gold ions. Therefore, even if the sulfite ion is oxidized to a sulfate ion, the liquid stability is maintained to a certain extent, and it can be used for a long period of time. [Embodiment] [Best Embodiment of the Invention] The gold plating solution of the present invention contains a gold sulfite salt and a water-soluble aminocarboxylic acid compound as essential components, and these are dissolved in water. It does not substantially contain sulfite other than the gold salt of sulfite. Sulfite contained in the gold plating solution of the present invention 200932947 The ion system is derived from a gold salt of sulfurous acid. The gold sulfite salt to be incorporated in the electroless gold plating solution of the present invention may, for example, be gold ammonium sulfite, gold potassium sulfite or gold sodium sulfite. The amount of the gold sulfite added is 0.5 to 10 g/L as the gold ion concentration, but it is preferably 1 to 5 g/L. When the gold ion concentration is less than 0.5 g/L, the progress of the electroplating reaction becomes slow. On the other hand, when the concentration of gold ions exceeds l〇g/L, the liquid stability is lowered. Therefore, it is considered that there is a tendency that the plating solution is easily decomposed by itself, and it is easy to generate in the gold plating liquid and the bottom of the plating tank. Gold particles. In the substituted electroless gold plating solution of the present invention, a water-soluble aminocarboxylic acid compound is blended. As the water-soluble aminocarboxylic acid compound, a water-soluble aminocarboxylic acid or a salt thereof is used. Examples of the water-soluble aminocarboxylic acid system include ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, dipotassium ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate, nitrotriacetic acid, and iminodiamide. Acetic acid, glycine acid, glutamic acid, aspartic acid, and the like. Q In the substituted electroless gold plating solution of the present invention, the amount of the water-soluble aminocarboxylic acid compound is 10 to 150 g/L. The water-soluble aminocarboxylic acid compound is preferably compounded in an amount of from 30 to 100 g/L, more preferably in an amount of from 50 to 80 g/L. When the content of the water-soluble aminocarboxylic acid compound is less than 10 g/L, the stability of the gold sulfite complex is deteriorated, and copper ions which are eluted from the copper by the substitution reaction are easily exposed. The effect, as a result, reduces the liquid stability of the mineral fluid. At more than 150 g/L, there is no advantage in the amount of addition, and therefore, it is not economical. The electroless gold plating solution of the present invention can be used at a pH of 5.0 to 10.0 -9 to 200932947, but is preferably used at a pH of 6.0 to 8.0. The plating solution is easily decomposed by itself in a state where the pH 値 is less than 5.0. When the pH 値 is higher than 10.0, the appearance of the gold film obtained is red, and there is a tendency that a normal gold film cannot be obtained. Examples of the pH oxime adjusting agent include sodium hydroxide, potassium hydroxide, ammonium hydroxide, and diluted sulfuric acid water. The plating bath temperature at the time of using the substituted electroless gold plating solution of the present invention to carry out the shovel is 30 to 90 ° C, but preferably 50 to 80 ° C. When the liquid temperature of the plating solution 0 is lower than 30 ° C, the electroplating reaction is hardly caused, and when it is higher than 9 (TC, the gold sulfite complex is decomposed, the plating solution is easily decomposed by itself. In the substituted electroless type of the present invention The gold plating solution may contain any component such as a conductive salt such as citrate, phosphate, pyrophosphate or sulfate, or a buffering agent, in addition to the above-mentioned essential components, without departing from the effects of the present invention. When the substitution type electroless gold plating solution is blended with a crystal modifier such as a ruthenium compound, a lead compound or an arsenic compound, a normal gold film cannot be obtained, and a tendency to be uneven tends to occur. Therefore, these compounds are the most BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of wiring on a printed circuit board formed using the gold plating solution of the present invention. In Fig. 1, a printed wiring board of a type 1. On a printed circuit board 1 On the surface, a wiring pattern 3 composed of copper is formed. The thickness of the wiring pattern 3 is usually 20 to 50/zm. On the wiring pattern 3, a substitution type electroless gold plating film 5 is formed. , The surface of the wiring pattern 3 is covered, so that the wiring 7 of the printed circuit board is chemically stabilized, and the protection is not corroded, etc. The wiring 7 includes bumps, electrodes, terminals, etc. -10- 200932947 Substituted electroless gold plating film The thickness of 5 is preferably 0.01 to 〇·2 #m, more preferably 〇.01~〇.1//„1. In the state where the film thickness of the gold-plated film is less than O.Ol^m, the copper is used. The formed wiring pattern 3 is insufficient for the protection of corrosion, etc. When it exceeds 〇.2μηι, the shape of the deposited film is easily deformed, and cross-linking easily occurs between the wirings. In the printed circuit board, as the object to be plated, the substitution type electroless gold plating liquid is used on the wiring pattern 3, and the substitution type electroless gold plating is performed to form the wiring 7. The gold foil film 5 can be used as needed. A reduction-type electroless gold plating is also carried out. A conventional plating solution can be used for the reduction type electroless gold plating. Further, the copper fine wiring formed on the 1C lead frame, the ceramic substrate or the wafer, in place of the printed circuit board 1, is used. In terms of graphics, it can also Gold plating was performed by the same method. [Examples] 焊 A solder resist PSR4000 manufactured by Sun Ink Co., Ltd. was used to form a copper material having a line width of 50 to 1000/zm and a size of 5x5 cm on a substrate. A fine circuit composed of the substrate was subjected to acid degreasing, chemical honing, and acid washing to obtain a sample used in the example. Example 1 Containing gold sulphite 3 g/L and ethylene diamine as AU The gold plating solution of acetic acid 50 g/L pH 値 6.0 was kept at a liquid temperature of 70 ° C. The substrate was immersed in the above-mentioned plating solution for 30 minutes. After 30 minutes, the sample was taken from -11 - 200932947, by SII The film thickness of the precipitate was measured by a fluorescent X-ray film thickness measuring device SFT3200. The gold film thickness after 30 minutes is 0.0 5 ym. The plated surface was observed by visual and solid microscope. The resist is not discolored. The gold film deposited is a lemon yellow with a uniform color tone. That is to say, the hue of the gold film caused by the visual appearance is a non-uniform appearance and becomes a good appearance. It is not considered that there is decomposition of the plating solution. Here, the criterion for determining the unevenness of the plating surface is as follows. There is unevenness. · It is indicated by visual observation that the color of the plating surface is uneven. For example, the color of the plating surface is displayed in a gold color state, a white gold state, and a red gold state. As a result of observation by an electron microscope, as shown in Fig. 3, gold particles are unevenly precipitated. No unevenness: It is observed by visual observation and becomes a state of uniform lemon yellow. An electron micrograph of the gold-plated film obtained in Example 1 is shown in Fig. 2 . It is clear from Fig. 2 that the gold-plated film has no unevenness and is uniformly attached to gold. Example 2 except that a gold plating solution containing 3 g/L of gold sodium sulfite as Au and 50 g/L of cyanotriacetic acid was maintained at a liquid temperature of 70 ° C, the same was carried out in the same manner as in Example 1. Take action. The gold film thickness after 30 minutes is 0.05; um. The resist system has no discoloration. The gold film of the precipitated color is lemon yellow, and the appearance is uneven and becomes a good appearance. It is not considered to have the decomposition of plating -12- 200932947 liquid. Example 3 except that a gold plating solution containing 3 g/L of gold sulfite sulfite and 50 g/L of iminodiacetic acid at pH 値 6.0 was maintained at a liquid temperature of 70 ° C, the same procedure as in Example 1 was carried out. And operate. The gold film thickness after 30 minutes was 0.04/zm. The resist system has no discoloration. The gold film color of the precipitate is adjusted to lemon yellow, and the appearance is not uneven and becomes a good appearance. It is not considered that there is decomposition of the plating solution. Example 4 Except that a gold plating solution containing 3 g/L of gold sodium sulfite as Au and 15 g/L of ethylenediaminetetraacetic acid was maintained at a liquid temperature of 70 ° C, the same procedure as in Example 1 was carried out. Take action. The gold film thickness after 30 minutes is 〇.〇5 μm. It is not considered that the resist has discoloration, and the precipitated gold film Q is a khaki yellow color, and the appearance is uneven and becomes a good appearance. Further, it is not considered that there is decomposition of the plating solution. Comparative Example 1 In addition to a gold plating solution containing a gold sulfite of 3 g/L of sodium sulfite, 50 g/L of sodium sulfite, and a pH of 7.0 g/L of ethylenediaminetetraacetic acid. The operation was carried out in the same manner as in Example 1 except that the liquid temperature was 7 ° C. The gold film thickness after 30 minutes is 〇.〇6 y m. The resist is not considered to be discolored. The gold film of the precipitated color became red and uneven in the outer layer. In addition, -13- 200932947 does not consider the decomposition of the plating solution. An electron micrograph of the gold-plated film obtained in Comparative Example 1 is shown in Fig. 3 . As is clear from Fig. 3, the gold-based attachment is granular and uneven in the gold film. Comparative Example 2 A gold plating solution containing gold lg/L of sulfite sulfite lg/L, sodium sulfite 100 g/L, citric acid 50 g/L, and ethylenediaminetetraacetic acid 60 g/L at pH 値 6.0 was maintained at a liquid temperature of 70 ° C. »In the plating solution, the substrate of the sample was immersed for 10 minutes. After 10 minutes, the sample was taken out, and the film thickness of the precipitate was measured by a fluorescent X-ray film thickness measuring device. The gold film thickness after 10 minutes was 0.05/zm. When observed by visual observation and a stereoscopic microscope, there is no discoloration of the resist. The gold film of the precipitated color became red and uneven in appearance. It is not considered that there is decomposition of the plating solution. ❾ Comparative Example 3 A shovel solution containing 3 g/L of gold sulfite sulfite and 5 g/L of ethylenediaminetetraacetic acid at pH 値 6.0 was kept at a liquid temperature of 70 °C. In the plating solution, the substrate of the sample was immersed for 30 minutes. After 30 minutes, the sample was taken out, and the film thickness of the precipitate was measured by a fluorescent X-ray film thickness measuring device. The gold film thickness after 0.05 minutes was 0.05/zm. Observations were made by visual and solid microscopes. There is no discoloration of the resist. The gold film of the precipitated color became red and uneven in appearance. It is not considered to be decomposed in the plating solution. -14-200932947 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a wiring formed by using a substitution type electroless gold plating solution of the present invention. Fig. 2 is a schematic electron micrograph of the gold-plated film obtained in Example 1. Fig. 3 is a schematic electron micrograph of the gold-plated film obtained in Comparative Example 1. 〇 [Main component symbol description] 1 : Printed circuit board 3 : Wiring pattern 5 : Gold-plated film 7 : Wiring
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