539773 五、 發明說明 ( 1 ) [ 技 術 領 域 ] 本 發 明 係 相 關 鈀 去 除 液 ， 及 使 用 該 去 除 液 的 鈀 去 除 方 法 0 更 詳 言 之 係 指 關 於 將 存在 於 被 處 理 基 板 表 面 上 的 鈀 j 爲 在 基 板 上 未 賦 予 金 屬 鑲 嵌 而 予 以 去 除 的 去 除 液 及 去 除 方 法 〇 [ 背 景 技 術 ] 電 路 圖 案 形 成 法 之 一 的 加 層 法 〇 在 此 加 層 法 中 於 絕 緣 性 基 板 整 體 表 面 上 賦 予 鈀 之 後 再 於 鈀 層 上 利 用 化 學 鍍 銅 法 形 成 電 鑛 〇 僅 將 形 成 此 鍍 銅 層 電 路 圖 案 的 部 分 覆 蓋 蝕 刻 光 阻 接 著 在 將 未 被 覆 光 阻 部 分 的 銅 > 經 由 蝕 刻 而去 除 〇 然 後 去 除 蝕 刻 光 阻 而形成 電 路 圖 案 0 依 照 此 習 知 方 法 雖 在 形 成 電 路 圖 案 後 出 現 絕 緣 性 基 板 表 面 但在 此 絕 緣 性 基 板 表 面 上 卻 殘 存 上 述 鈀 〇 鈀 在 化 學 鍍 銅 時 當 作 觸 媒 使 用 9 雖 有助 於 容 易 形 成 導 體 層 y 但 因 爲 較 不 易 溶 解 於 普 通 的 蝕 刻 液 中 因 此 在 上 述 銅 飩 刻 後 亦 會 殘 餘 而 降 低 電 路 圖 案 的 絕 緣 性 〇 另 在 電 路 圖 案 整 體 表 面 或 元 間 接 合 用 墊 部分 雖 可 施 行 表 面 處 理 的 化 學 鍍 鎳 、 化 學 鍍 金 等 5 但若在 絕 緣 性 基 板 上 殘 存 鈀 的 話 即 便 不 需 要 此 爲 觸 媒 之 鈀 的 部 分 處 理 亦 將 附 著 上 鎳 或 金 ， 而 造 成 電 路 圖 案 絕 緣 性 的: 惡‘ 化 〇 所 以 1 將 此 殘 餘 鈀 去 除 對 獲 得 局 品 質 的 電 路 基 板 而 言 屬 極 其 重 要 〇 因 此 在 習 知加 層 法 中 便 於 剝 離 蝕 刻光 阻 之 後 將 基 板 上 不 需 要 的 鈀 1 -3 依 如 下 的 方法予, 以: 去1 徐 〇 539773 五、發明說明（2) (1 )將基板浸漬於碘/碘化鉸溶液中，而溶解銷的方、法。 (2 )將基板浸漬於過鍤酸鉀溶液中，而溶解銷的方法。 (3 )採用R I E (反應離子蝕刻）等真空排氣裝置，將_由基 板表面脫離的方法。 惟，上述習知鈀的去除方法，存在有以下所示問題。 (1 )在浸漬於碘/碘化銨溶液中的方法，因爲隨鈀溶解， 同時銅亦將溶解，而容易造成產生配線變細或斷線。 (2 )在浸漬於過錳酸鉀溶液中的方法，樹脂基板表面將 被氧化，而使表面上形成細微凹凸狀。因爲此樹脂氧化隨 鈀的溶解而快速進行，所以存在於樹脂氧化層凹部中的鈀 ’將較不易接觸到處理液，造成部分殘餘鈀的情形發生。 (3 )在採用真空排氣裝置的方法，相較於上述濕式處理 之下’不僅裝置屬高價格，且可處理基板的片數亦將容易 受到限制，而造成配線板製造成本的增加。 再者，在特開平3- 25 4 1 79號公報及特開平4-179191號 公報等中，則開示有將基板浸漬於過錳酸鉀溶液後，配合 需要進行超音波水洗，在浸漬於含芳香族硝化物、胺化物 、胺基羧酸、羧酸、氫氧化鈉、及硫酸羥基銨的溶液中， 而去除銷的方法。惟，在該等去除液中’因爲基板表面的 樹脂氧化層會與鈀一倂被去除，而產生不僅隨過錳酸鉀溶 液造成基板表面粗造化，同時銅電路圖案與基板之界面亦 將被侵蝕等多種缺點。 【發明開示】 539773 五、 發明說明 ( 3 ) 本 發 明 之 巨 的 在 於提供解決上述問題，即爲將 存 在 於 被 處 理 基 板 表 面 中 的 鈀去除被處理基板上未賦予金 屬 鑲 嵌 的 去 除 液 及 去 除 方 法 。更詳言之，本發明之目的在於 提 供 在 電 路 基 板 製 造 程 序 中，於電路圖案形成後，可輕 易 去 除 殘 餘 絕 緣 性 基 板 表 面 上的鈀，且不侵蝕配線材料或 絕 緣 性 基 板 等 鈀 去 除 液 5 以 及使用該去除液的去除方法。 本 發 明 者 爲 達 上 述目的，經深入鑽硏結果，終 於 發 現 由 (a )硝酸鹽 、（b) 將 鈀氧化物水溶化的水溶化劑、 ( c )水 、 及 配 合 需 要 (d )濕潤劑及/或螯合劑所組成的溶液 利 用 加 層 法 便 可在 短 時 間 內輕易的去除殘餘在形成電路 圖 案 後 之 絕 緣 性 基 板 表 面 上 的鈀，而可提升電路圖案的絕 緣 性 5 並 製 造 局 信 賴 性 的 印 刷電路配線基板，遂根據此發 現 而 兀 成 本 發 明 〇 即 1 本 發 明 之 第 一態樣係一種钯去除液，其特徵在於： 包含有 (a )硝酸鹽、 (b )將鈀氧化物水溶化的水溶/ it ) 割 、( ：c) 水 、 及 配 合 需 要 (d )濕潤劑及/或（e )螯合劑的溶液， 本 發 明 之 第 二 態 樣係一種鈀之去除方法，乃在 絕 緣 性 基 板 表 面 上 附 著 鈀 而 形成鈀層，再於鈀層上形成鍍 銅 層 ， 於 該 鍍 層 上 施 行 光 阻 後，經蝕刻而形成電路圖案， 再 將 光 阻 剝 離 後 將 殘 存 於 基板表面上的鈀，採用上述鈀 去 除 液 予 以 去 除 0 [ 圖 式 簡 單 說 明 ] 第 1 a〜 Id 圖 1係在 印刷電路基板的製造中，經本 -5- 發 明 之 鈀 539773 五、發明說明（4 ) 去除液處理，直到電路圖案形成於基板爲止的製造程序示 意圖。 【發明較佳實施態樣】 上述（a )硝酸鹽係可舉例如硝酸銨、硝酸鋰、硝酸鋅、 硝酸錳、硝酸鎳、硝酸鈷、硝酸鈉、及硝酸鉀。其中尤以 硝酸銨爲佳。硝酸鹽具有氧化鈀的作用。硝酸鹽在鈀去除 液中的濃度爲0.001〜40重量％，最好爲0.005〜30重量％。 上述（b )將鈀氧化物水溶化的物質（水溶化劑），譬如無 機酸及其鹽類。最好爲如鹽酸、硝酸、硫酸、氯化銨、氯 化銘等氯酸鹽；硫酸銨、硫酸銘等硫酸鹽等等。水溶化劑 在鈀去除液中的濃度爲0.01〜50重量％，最好爲0.05〜30 重量％ 〇 在不損及本發明效果的範圍下，亦可混合爲提高氧化例 之其他的鈀氧化性物質、或爲提昇鈀氧化物水溶化能力之 其他的鈀氧化物水溶化的物質。 本發明之鈀去除液，除上述成分（a )〜（c )之外，亦可再 添加濕潤劑（d )。濕潤劑（d )可舉例如界面活性劑、醇類、 醚類。界面活性劑有如陰離子系、非離子系、陽離子系等 。醇類有如乙醇、異丙醇、丁醇、乙二醇、二乙二醇、丙 二醇、二丙二醇。醚類有如乙二醇單乙醚、乙二醇單丁醚 、二乙二醇單甲醚、二乙二醇單乙醚、乙二醇單丁醚、丙 二醇單甲醚、丙二醇單乙醚、丙二醇單丁醚、二丙二醇單 甲醚、二丙二醇單乙醚、二丙二醇單丁醚、二乙二醇二甲 539773 五、發明說明（5) 醚、二丙二醇二甲醚、聚氧乙烯甲基苯醚、聚氧乙烯辛基 苯醚、聚氧乙烯壬基苯醚等。 上述濕潤劑可單獨使用，亦可組合二種以上使用。上述 濕潤劑在鈀去除液中的濃度爲0 . 001〜1 0重量％，最好爲 〇.05〜5重量％。尤以0.0 05〜1重量％爲佳。 本發明之鈀去除液，除上述成分（a )〜（c )、或成分 (a )〜（d )之外，尙可再含螯合劑（e )。所謂螯合劑係指將鈀 形成錯體的化合物，譬如二甲基二乙肟、硫脲、硫代草酸 基（8 -锍基喹啉）、雙硫腙、2 -亞硝基-1 -萘醇、對亞硝基 二甲苯胺等。其中尤以二甲基二乙肟及硫脲爲佳。 螯合劑（e )不僅作爲金鈀氧化物之水溶化劑用，同時亦 與絕緣性基板表面粗糙化凹部中少量殘餘的鈀形成錯體， 而使鈀對電路形成後的化學鍍鎳、化學鍍金等形成非活性 ’俾防止在不必要部分上附著鎳、金等而造成電路圖案絕 緣性的惡化。 螯合劑在鈀去除液中的濃度爲〇 . 〇 1〜5重量％，最好爲 〇.〇1〜2重量％。尤以〇.〇 5〜2重量％爲佳。 本發明之鈀去除液係由上述硝酸鹽、水溶化劑、任意成 分的濕潤劑及/或螯合劑、以及殘餘部分爲水所組成的水 性液。其狀態可爲分散液或懸浮液，通常爲水溶液。 本發明之鈀去除液係利用將成分（a )〜（b )、及任意成分 U )及/或（e )，溶解、分散、或懸浮於水中而製得。各成 分的添加順序並無特別的限制。 539773 五、 發明說明 ( 6 ) 本 發 明的 鈀 去 除 方法，通常在常溫〜80°C下， 將被 處 理 基 板 在 鈀去 除 液 中 浸漬1〜1 0分鐘。鈀去除液的 pH， 通 常 使 用 0 〜5範圍。 pH的調整係利用改變成分（b )所 使用 的 4ixc 機 酸 添 加量 而 進 行 調整。鈀去除液使用量係將鈀 由被 處 理 基 板 去 除的 有 效 量 ，僅要屬此技術之業者均可輕 易的 決 定 〇 藉 由 本發 明 之 鈀 去除方法，便可將電路圖案形 成後 所 殘 餘 的 鈀 ，實 質 上 完 全（相對電路基板的殘餘鈀濃度在 5 ppm 以 下 )去除。 其 次 ，利 用 實 施 例與比較例，對本發明進行更 具體 的 說 明 〇 惟 ，本 發 明 並 不僅限於該等實施例。 第 1 圖戶ϋ i電 :路基板製造中，截至電路圖案 形成 爲 止 的 程 序 〇 第 1 a圖J 听示係絕緣性基板1上形成鈀觸媒層 2的狀 態 示 意 圖 。此 鈀 通 常 以吸附在絕緣性基板上之狀態 ，形 成 極 薄 層 並在化 學 鑛 時具有觸媒的功能。 在 絕 緣性 基 板 表 面的鈀觸媒層2上，如第1 b 圖所 示 5 利 用 化 學鍍 形 成 由 鍍銅層所構成的導體層3。此 導體 層 在 化 學 鍍 面上 1 配 合 需要，亦可施行電鑛而形成導體層 〇 其 次 ，如 第 1 C 圖所示，將應形成導體層3電 路之 部 分 5 被 覆 上光 阻 層 4 ，然後將導體層3未被覆部分 ，利 用 鈾 刻 液 予 以溶 解 去 除 。此情況的光阻，可採用如乾 光阻 膜 光 阻油 rrpt 墨、 網 板 印 刷光阻等。鈾刻液可採用硫酸 與過 氧 化 氫 混 合 液、 含 氯 化 亞銅溶液、含氯化亞鐵溶液等 1 〇 539773 五、發明說明（7) 蝕刻後，經去除光阻後，便可如第1 d圖所示，在絕緣 性基板1表面上形成導體電路3 a。將鍍銅層經蝕刻後，附 著於絕緣性基板1表面上的鈀2 a，未去除而吸附於絕緣性 樹脂上的狀態，直接殘餘著。 實施例1〜7 將上述殘餘鈀的電路基板，採用表1所示鈀去除液，依 特定條件浸漬後，以純水潤濕並乾燥。然後，針對電路間 隔20微米的電路部分，測量絕緣阻抗値，針對絕緣性基 板表面，利用螢光X線分析法及X線微分析器，測量鈀殘 餘量，針對電路圖案部分，觀察施行化學鍍鎳時，在絕緣 基板表面有無鎳析出，並針對電路圖案部分觀察有無銅的 腐蝕性。其測量結果與觀察結果，分別依照下示判斷基準 進行評估。結果如表1中所示。 1絕緣性 A :處理前絕緣阻抗値數μ Q 4處理後絕緣阻抗値〇〇 C :處理前絕緣阻抗値數μ Q 處理後絕緣阻抗値數μ Ω 2鈀去除性 A :完全被去除 B :部分殘餘 C :大邰分殘餘 3鎳析出 A+:完全未發現析出 A :幾乎未發現析出 539773 五、發明說明（8) B :發現部分析出 C :出現析出 4銅腐蝕性 A :未出現腐倉虫 B :出現部分腐蝕 C :出現整面腐飩 表1 鈀去除液組成 硝酸鹽 水溶化劑 濕潤劑 2K 種類 濃度 種類 濃度 種類 濃度 濃度 (重量％) (重量％) (重量％)(重量％) 實施例 1 硝酸銨 2 _ 5 一 — 部分殘餘 2 硝酸銨 5 鹽酸 5 — —· 部分殘餘 3 硝酸銨 0.5 鹽酸 5 一 一 部分殘餘 4 硝酸銨 2 鹽酸 1 a氺 3 部分殘餘 5 硝酸銨 2 鹽酸 1 b氺 0.1 部分殘餘 6 硝酸銨 2 硫酸 3 — — 部分殘餘 7 硝酸銨 2 硝酸 5 — 一 部分殘餘 b* =聚氧乙烯壬基苯醚 -10- 539773 五、發明說明（9) 表1 (續） 去除條件 評估結果 温度 (0〇 時間 ⑼ 絕緣性 P d除去 Ni去除 C u腐触 實施例 1 60 5 A A .A A 2 60 5 A A A A 3 70 5 A A A A 4 50 3 A A A A 5 50 3 A A A A 6 60 5 A A A A 7 60 5 A A A A 比較例1〜8 除採用表3 中所示組成的鈀去除液之外 ，其餘均如同實 施例 1〜7。結果如表2所示 o 表2 鈀去除液組成 硝酸鹽 種類 濃度 (重量％) 水溶化劑 種類 濃度 (重量％) ll 種類 i潤劑 濃度 (重量％) tK 濃度 (重量％) 比較例 1 硝酸銨 5 — — — — 部分殘餘 2 — — 鹽酸 5 — — 部分殘餘 3 — — 硫酸 3 — 一 部分殘餘 4 — — 氯化銨 5 — — 部分殘餘 5 硝酸銨 5 — — a伞 3 部分殘餘 6 硝酸銨 5 — — b氺 0.1 部分殘餘 7 — — 鹽酸 5 a氺 3 部分殘餘 8 — — 氯化銨 5 a氺 3 部分殘餘 -11- 539773 五、發明說明（1〇) a * =異丙二醇 b * =.聚氧乙丨希壬基苯醚 表2 (續） 去除條件 _評估結果 温度 (°C) 時間 ⑼ 絕緣性 P d去除 N i析出 C U腐蝕 比較例 1 60 5 C C C A 2 60 5 B B C A 3 60 5 C C C A 4 60 5 C C C A 5 60 5 C C C A 6 60 5 C C C A 7 60 5 B B C A 8 60 5 C C C A 實施例8〜9 除採用含螯合劑的鈀去除液之外 其餘均如同實施例 1〜7 ° 結果如表 3所示 〇 表3 鈀去除液組成 硝酸鹽 種類 濃度 (重量％) 水溶化劑 種類 濃度 (重量％) 螯合劑 種類 濃度 (重量％) zK 濃度 (重量％) 實施例 8 硝酸銨 2 鹽酸 1 c氺 0.1 .部份殘餘 9 硝酸銨 2 鹽酸 1 d氺 0.1 部份殘餘 -12- 539773 五、發明說明（11) c*二二甲基二乙月亏 d * =硫脲539773 V. Description of the Invention (1) [Technical Field] The present invention relates to a palladium removal solution and a palladium removal method using the same. More specifically, it means that the palladium j existing on the surface of the substrate to be processed is Removal liquid and method for removing metal inlay on a substrate and removing method. [Background Art] A layering method, which is one of circuit pattern forming methods. In this layering method, palladium is applied to the entire surface of an insulating substrate, and then palladium is added. Electroless copper is formed on the layer by electroless copper plating. Only the portion forming the circuit pattern of the copper plating layer is covered with the etching photoresist, and then the copper that is not covered with the photoresist is removed by etching. Then the etching photoresist is removed and formed. Circuit pattern 0 Although insulation is formed after the circuit pattern is formed according to this conventional method The surface of the insulating substrate, but the above-mentioned palladium is left on the surface of the insulating substrate. Palladium is used as a catalyst in electroless copper plating. 9 Although it is easy to form a conductive layer, it is not easily dissolved in ordinary etching solutions. After the copper engraving described above, the insulation of the circuit pattern will remain and the insulation of the circuit pattern will be reduced. In addition, although electroless nickel plating and electroless gold plating can be applied to the entire surface of the circuit pattern or the pads for bonding between elements, 5 it will remain on the insulating substrate. In the case of palladium, even if this part of the catalyst is not required for palladium treatment, nickel or gold will be adhered to it, which will cause the circuit pattern to be insulative: so it is removed. Therefore, removing this residual palladium is important for obtaining a circuit board of local quality. It is extremely important. Therefore, in the conventional layering method, it is convenient to peel off the photoresist after etching, and the unnecessary palladium 1-3 on the substrate is as follows Method I, in order: 1 to 539,773 square Xu V. invention is described in (2) (1) The substrate is immersed in an iodine / iodide solution hinges, pin dissolved square, France. (2) A method of dissolving a substrate by immersing a substrate in a potassium perrhenate solution. (3) A method of using a vacuum exhaust device such as R I E (Reactive Ion Etching) to detach the substrate from the surface of the substrate. However, the conventional method for removing palladium has the following problems. (1) In the method of immersion in an iodine / ammonium iodide solution, as the palladium dissolves, the copper will also dissolve at the same time, and it is easy to cause thinning or disconnection of the wiring. (2) In the method of immersing in a potassium permanganate solution, the surface of the resin substrate is oxidized, and a fine unevenness is formed on the surface. Since this resin oxidation progresses rapidly with the dissolution of palladium, the palladium 'existing in the recessed portion of the resin oxide layer will be less likely to contact the treatment liquid, resulting in the occurrence of some residual palladium. (3) Compared with the above-mentioned wet processing method using a vacuum exhaust device, not only the device is expensive, but also the number of substrates that can be processed will be easily limited, resulting in an increase in the manufacturing cost of the wiring board. Furthermore, in Japanese Unexamined Patent Publication No. 3-25 4 1 79 and Japanese Unexamined Patent Publication No. 4-179191, it is disclosed that the substrate is immersed in a potassium permanganate solution, and then ultrasonically washed as necessary. A method of removing pins from a solution of an aromatic nitrate, an amine compound, an amino carboxylic acid, a carboxylic acid, sodium hydroxide, and a hydroxyl ammonium sulfate. However, in these removal solutions, 'because the resin oxide layer on the surface of the substrate will be removed with palladium, not only will the substrate surface be roughened with the potassium permanganate solution, but the interface between the copper circuit pattern and the substrate will also be Erosion and other disadvantages. [Invention] 539773 V. Description of the invention (3) The great thing of the present invention is to provide a solution and a method for removing the palladium existing on the surface of the substrate to be treated without removing the metal inlay on the substrate to be treated. . More specifically, the object of the present invention is to provide a palladium removal solution 5 that can easily remove residual palladium on the surface of the insulating substrate after the circuit pattern is formed in the manufacturing process of the circuit substrate without eroding the wiring material or the palladium removing solution such as the insulating substrate. And a removal method using the removal liquid. In order to achieve the above-mentioned object, the inventor finally found through drilling drill collars that (a) nitrate, (b) a water-solubilizing agent that dissolves palladium oxide in water, (c) water, and (d) a wetting agent. The solution composed of the chelating agent and / or the chelating agent can easily remove the palladium remaining on the surface of the insulating substrate after the circuit pattern is formed in a short time by using the layer-adding method, and can improve the insulation of the circuit pattern. 5 Based on this discovery, a flexible printed circuit wiring substrate was developed according to the present invention. That is, the first aspect of the present invention is a palladium removal solution, which is characterized by: (a) nitrate, (b) palladium oxide Water-soluble water-soluble / it) cutting, (: c) water, and a solution that requires (d) a wetting agent and / or (e) a chelating agent. The second aspect of the present invention is a method for removing palladium, which is in On the surface of the insulating substrate, palladium is adhered to form a palladium layer, a copper plating layer is formed on the palladium layer, and a photoresist is applied to the plating layer. The circuit pattern is formed by etching, and the palladium remaining on the surface of the substrate is removed after the photoresist is peeled off. The above palladium removing solution is used to remove 0. [Schematic description] The first a to Id Figure 1 is in the manufacture of printed circuit boards After the palladium 5397973 of this -5- invention 5. The description of the invention (4) Schematic diagram of the manufacturing process until the circuit pattern is formed on the substrate. [A preferred embodiment of the invention] The above (a) nitrate may be ammonium nitrate, lithium nitrate, zinc nitrate, manganese nitrate, nickel nitrate, cobalt nitrate, sodium nitrate, and potassium nitrate. Among them, ammonium nitrate is preferred. Nitrate has the effect of palladium oxide. The concentration of nitrate in the palladium removing solution is 0.001 to 40% by weight, and preferably 0.005 to 30% by weight. (B) The substance (water-solubilizing agent) that dissolves palladium oxide in water, such as inorganic acids and their salts. Preferred are chlorate salts such as hydrochloric acid, nitric acid, sulfuric acid, ammonium chloride, and chlorinated salts; sulfates such as ammonium sulfate and sulfated salts, and the like. The concentration of the water-solubilizing agent in the palladium removal solution is 0.01 to 50% by weight, preferably 0.05 to 30% by weight. 〇In the range that does not impair the effect of the present invention, it can also be mixed to improve other oxidation properties of the palladium in the oxidation example. Substance, or other palladium oxide water-soluble substance which enhances the water-solubility of palladium oxide. In the palladium removing solution of the present invention, in addition to the above components (a) to (c), a wetting agent (d) may be further added. Examples of the wetting agent (d) include surfactants, alcohols, and ethers. Surfactants include anionic, nonionic, and cationic. Examples of the alcohols include ethanol, isopropanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. The ethers are such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether. Ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol dimethyl 539773 5. Description of the invention (5) ether, dipropylene glycol dimethyl ether, polyoxyethylene methyl phenyl ether, poly Oxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and the like. These humectants may be used alone or in combination of two or more. The concentration of the humectant in the palladium removing solution is from 0.001 to 10% by weight, preferably from 0.05 to 5% by weight. Especially preferred is 0.005 to 1% by weight. The palladium removing solution of the present invention may further contain a chelating agent (e) in addition to the above components (a) to (c), or components (a) to (d). The so-called chelating agent refers to a compound that forms palladium, such as dimethyldiacetoxime, thiourea, thiooxalate (8-fluorenylquinoline), dithizone, 2-nitroso-1-naphthalene Alcohol, p-nitrosoxylamine, etc. Among them, dimethyldiacetoxime and thiourea are preferred. The chelating agent (e) is not only used as a water-solubilizing agent for gold-palladium oxide, but also forms a wrong body with a small amount of residual palladium in the roughened recess on the surface of the insulating substrate, so that the electroless nickel plating and electroless gold plating after circuit formation are performed by palladium. The formation of inactive materials prevents the adhesion of circuit patterns to nickel, gold, and the like, thereby deteriorating the insulation of circuit patterns. The concentration of the chelating agent in the palladium removal solution is from 0.01 to 5 wt%, preferably from 0.01 to 2 wt%. Especially preferably, it is 0.05 to 2% by weight. The palladium removing solution of the present invention is an aqueous liquid composed of the above-mentioned nitrate, a water-solubilizing agent, an optional component of a wetting agent and / or a chelating agent, and a remainder of water. The state can be a dispersion or a suspension, usually an aqueous solution. The palladium removal solution of the present invention is prepared by dissolving, dispersing, or suspending components (a) to (b), and optional components U) and / or (e) in water. There is no particular restriction on the order in which the components are added. 539773 V. Description of the invention (6) The palladium removal method of the present invention is usually immersed in a palladium removal solution for 1 to 10 minutes at a temperature of normal temperature to 80 ° C. The pH of the palladium removal solution usually ranges from 0 to 5. The pH was adjusted by changing the amount of 4ixc organic acid used for the component (b). The amount of palladium removal solution is an effective amount for removing palladium from the substrate to be processed, and only those skilled in the art can easily determine it. With the palladium removal method of the present invention, the palladium remaining after the circuit pattern is formed, Substantially completely (residual palladium concentration to the circuit board is 5 ppm or less). Secondly, the present invention will be described more specifically using examples and comparative examples. However, the present invention is not limited to these examples. Fig. 1 Electricity: The process up to the formation of a circuit pattern in the manufacture of circuit substrates. Fig. 1a Fig. J shows the state of the palladium catalyst layer 2 formed on the insulating substrate 1 of the auditory system. This palladium is usually adsorbed on an insulating substrate, forms an extremely thin layer, and has a catalyst function in chemical ore. On the surface of the insulating palladium catalyst layer 2 on the surface of the insulating substrate, as shown in Fig. 1b, 5 a conductive layer 3 composed of a copper plating layer is formed by chemical plating. This conductor layer on the electroless plating surface 1 can be used to meet the needs, and it can also be used to form a conductor layer. Secondly, as shown in Figure 1C, the part 5 of the circuit that should form the conductor layer 3 is covered with a photoresist layer 4, and then The uncoated portion of the conductor layer 3 is dissolved and removed by using a uranium etching solution. In this case, the photoresist can be used, for example, dry photoresist film, photoresist oil, rrpt ink, and screen printing photoresist. The uranium engraving solution can be a mixed solution of sulfuric acid and hydrogen peroxide, a solution containing cuprous chloride, and a solution containing ferrous chloride, etc. 10539773 V. Description of the invention (7) After etching, the photoresist can be removed as described in Section 1. As shown in FIG. 1D, a conductor circuit 3 a is formed on the surface of the insulating substrate 1. After the copper plating layer was etched, the palladium 2 a attached to the surface of the insulating substrate 1 remained in a state of being adsorbed on the insulating resin without being removed. Examples 1 to 7 The above-mentioned residual palladium circuit boards were impregnated with the palladium removal liquid shown in Table 1 under specific conditions, and then wetted with pure water and dried. Then, measure the insulation resistance 値 for circuit parts with a 20-micron circuit interval. Use fluorescent X-ray analysis and an X-ray microanalyzer to measure the residual amount of palladium on the surface of the insulating substrate. Observe the electroless plating for the circuit pattern part. In the case of nickel, the presence or absence of nickel precipitation on the surface of the insulating substrate, and the presence or absence of the corrosiveness of copper in the circuit pattern portion were observed. The measurement results and observation results are evaluated according to the judgment criteria shown below. The results are shown in Table 1. 1 Insulation A: Insulation resistance before treatment μ Q 4 Insulation resistance after treatment: μC: Insulation resistance before treatment μ Q Insulation resistance after treatment μ Ω 2 Palladium removal A: Completely removed B: Partial Residual C: Residual Nitrogen 3 Nickel Precipitation A +: No Precipitation Found at All A: Precipitate Hardly Found 5397973 V. Description of the Invention (8) B: Precipitated C Found: Precipitation 4 Copper Corrosion A: No Corrosion Swarmworm B: Partial corrosion appears. C: Whole rot appears. Table 1 Composition of palladium removal solution, nitrate salt solubilizer, humectant, 2K species concentration species concentration species concentration concentration (wt%) (wt%) (wt%) (wt%) Example 1 Ammonium nitrate 2 _ 5 One—partial residue 2 ammonium nitrate 5 hydrochloric acid 5 — ·· part residual 3 ammonium nitrate 0.5 hydrochloric acid 5 one part residual 4 ammonium nitrate 2 hydrochloric acid 1 a 氺 3 part residual 5 ammonium nitrate 2 hydrochloric acid 1 b氺 0.1 part of the residual 6 ammonium nitrate 2 sulfuric acid 3 — — part of the residual 7 ammonium nitrate 2 nitric acid 5 — part of the residual b * = polyoxyethylene nonylphenyl ether -10- 539773 5. Description of the invention (9) Table 1 (continued) Removal condition Estimated result temperature (0 〇 time 绝缘 insulation P d removal Ni removal Cu corrosion contact Example 1 60 5 AA .AA 2 60 5 AAAA 3 70 5 AAAA 4 50 3 AAAA 5 50 3 AAAA 6 60 5 AAAA 7 60 5 AAAA Comparative Examples 1 to 8 are the same as in Examples 1 to 7, except that the palladium removal solution with the composition shown in Table 3 was used. The results are shown in Table 2. Table 2 Nitrate concentration (wt%) ) Type concentration of water-solubilizing agent (% by weight) ll Type concentration of wetting agent (% by weight) tK concentration (% by weight) Comparative Example 1 Ammonium nitrate 5 — — — — Partial residual 2 — — Hydrochloric acid 5 — — Partial residual 3 — — Sulfuric acid 3 — part of residual 4 — — ammonium chloride 5 — — part of residual 5 ammonium nitrate 5 — — a umbrella 3 part of residual 6 ammonium nitrate 5 — — b 氺 0.1 part of residual 7 — — hydrochloric acid 5 a 氺 3 part of residual 8 — — Ammonium chloride 5 a 氺 3 Partial residue-11- 539773 V. Description of the invention (1〇) a * = isopropyl glycol b * =. Polyoxyethylene 丨 hexylphenyl ether Table 2 (continued) Removal conditions _ evaluation resultsTemperature (° C) Time 绝缘 Insulation P d Removal Ni Precipitation CU Corrosion Comparative Example 1 60 5 CCCA 2 60 5 BBCA 3 60 5 CCCA 4 60 5 CCCA 5 60 5 CCCA 6 60 5 CCCA 7 60 5 BBCA 8 60 5 CCCA Examples 8 to 9 are the same as in Examples 1 to 7 except that a chelating agent-containing palladium removal solution is used. The results are shown in Table 3. Table 3 Palladium removal solution composition Nitrate species concentration (wt%) Water solubilizer Species concentration (wt%) Chelating agent species concentration (wt%) zK concentration (wt%) Example 8 Ammonium nitrate 2 Hydrochloric acid 1 c 氺 0.1. Partial residue 9 Ammonium nitrate 2 Hydrochloric acid 1 d 氺 0.1 Partial residue -12- 539773 V. Description of the invention (11) c * dimethyl diethyl ether loss d * = thiourea
表3 (續） 去除條件 評估結果 温度 時間 (°C) ⑼ 絕緣性 P d去除 N i析出 C u腐触 實施例 8 50 3 A A A + A 9 50 3 A A A + A 【產業上可利用性】 藉由浸漬於本發明之鈀去除液，便可將存在於被處理基 板表面上的鈀予以去除。本發明之鈀去除液，特別適用於 去除殘餘在絕緣性基板表面上的鈀，因爲不致侵蝕銅配線 ，且絕緣性基板表面亦不致粗糙，所以可提升電路圖案的 絕緣性。 此外，即便在電路圖案上施行化學鑛鎳或化學鍍金等化 學鍍處理時，因爲表面的鈀已被去除，所以便可防範鑛層 附著於絕緣性基板表面所導致絕緣性的降低於未然。 【圖示符號說明】 1 絕緣性基板 2 鈀觸媒層 2a 鈀 3 導體層 3a 導體電路 4 光阻層 -13-Table 3 (continued) Evaluation results of removal conditions Temperature time (° C) ⑼ Insulation P d Removal Ni Precipitation C u Corrosion Example 8 50 3 AAA + A 9 50 3 AAA + A [Industrial availability] Borrow The palladium present on the surface of the substrate to be treated can be removed by immersing in the palladium removing solution of the present invention. The palladium removing solution of the present invention is particularly suitable for removing palladium remaining on the surface of an insulating substrate, because the copper wiring is not eroded, and the surface of the insulating substrate is not rough, so the insulation of the circuit pattern can be improved. In addition, even when chemical plating treatments such as chemical ore nickel or chemical gold plating are performed on the circuit pattern, the surface palladium has been removed, so it is possible to prevent deterioration of the insulation caused by the mineral layer adhering to the surface of the insulating substrate. [Illustration of symbols] 1 Insulating substrate 2 Palladium catalyst layer 2a Palladium 3 Conductor layer 3a Conductor circuit 4 Photoresistive layer -13-