200417627 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於一種触刻液之管理方法以及蝕刻液之管 理裝置’特別是關於爲了反覆使用的金屬類材料用鈾刻液 的成分濃度大略維持一定之蝕刻液之管理方法以及蝕刻液 之管理裝置。 【先前技術】 歷來所謂蝕刻液的加工方法，係例如印刷基板、IT0 膜以及引線架等的加工，再者，利用於硏磨鋼鐵的洗鋼處 理等。具體地’構成液晶顯示器以及有機電激發光顯示器 的平面顯示裝置的陣列基板的基板上，構成半導體元件的 矽晶圓片的基板上，藉由使用蝕刻液，形成金屬薄膜圖型 〇 一般蝕刻液，係由水以及幾個揮發性成分組成。該等 成分依據被飽刻的金屬而不同。例如在液晶顯示器的情況 ，基板上的金屬薄膜係由導電率高的鋁系金屬薄膜以及如 鉬般的高融點金屬膜所構成。於該情況，使用硝酸、醋酸 、磷酸以及水以既定比例混合成的蝕刻液，形成金屬薄膜 圖型（日本公開專利特開200 1 -770 8 5號公報）。 在該蝕刻加工步驟的蝕刻液，係以淋浴狀吹向基板， 或者將基板浸泡於蝕刻液中使用。而且，蝕刻液在如此的 步驟，爲了處理複數基板，一般循環重複使用。但是，重 複使用之蝕刻液，基板取出、吹時的薄霧、蒸發等造成其 -5- (2) (2)200417627 組成成分歷時改變。其結果，隨時間經過’產生無法得到 足夠的蝕刻效果的問題。 再者，如此成分組成的變化造成蝕刻液不僅必須頻繁 的交換，亦必須廢棄使用後的蝕刻液，產生費用增加等的 問題。 例如，日本專利第2747647號公報揭露一蝕刻液管理 裝置，具備：蝕刻液排出機構，使用吸光光度計檢測透明 導電膜用蝕刻液的溶解銦濃度，排出蝕刻液；第一補給機 構，藉由液面位準計檢測蝕刻液的液面，補充蝕刻原液以 及純水；第二補給機構，使用導電度計檢測蝕刻液的酸濃 度，補充蝕刻原液以及純水。該裝置，利用吸光光度計， 測量蝕刻液內溶解金屬的濃度，然後利用導電度計測量單 一的酸濃度。根據該測定結果，藉由於蝕刻液中補充酸或 純水，保持蝕刻速率。但是，於日本專利第2 7 4 7 6 4 7號公 報所記載的發明’難以對由複數成分所構成的蝕刻液的成 分濃度進行管理。 而且，例如日本公開專利特開平1丨_ 3 0 9 4 0 3號公報、 特開平1 1 -3 09404號公報、特開平200^^ 98 74號公報、 以及特開平2000- 1 99084號公報，利用旋轉機（Spinner) 將蝕刻液附於基板上，蝕刻液朝塗布裝置外部帶出，以及 防止由於薄霧（mist)的減量。但是依然無法應付因蝕刻 液蒸發造成的濃度變化。 【發明內容】 -6- (3) (3)200417627 發明所欲解決之課題 本發明’係爲了使反覆使用的金屬類材料用蝕刻液中 容易歷久變化的成分濃度大略維持一定的課題。 解決課題之手段 一方面，本發明係關於了使反覆使用的金屬類材料用 倉虫刻液的成分濃度大略維持一定的管理方法。該方法，具 備：滴定·測量步驟，使用與上述蝕刻液呈逆性的溶液， 滴定上述蝕刻液，與其同時進行量測上述蝕刻液的導電度 ;計算步驟，由滴定·測量步驟所得的測量値，計算0虫刻 液中的不足成分量；補給步驟，依計算步驟所算出之不足 成分量，使用成分原液以及/或補充液，補充予上述蝕刻 液。 上述蝕刻液亦可含酸性溶液。該酸性溶液，可包含至 少一種選自硝酸、醋酸、磷酸、鹽酸、硫酸、氫氟酸、草 酸、過氯酸、氫氰酸、硝酸鈽錢（cerium ammonium nitrate C e (Ν Η 4 ) 2 (Ν Ο 3) 6 )、過硫酸銨、氯化銨組成的群。 上述飩刻液亦可含鹼性溶液。該鹼性溶液，可包含至 少一種選自氫氧化鈉、氫氧化鉀、氫氧化銘、氫氧化錢' 重鉻酸鉀、鐵氰化鉀、氰化鉀、碳酸鈉、醋酸鉀組成的群 〇 上述呈逆性的溶液，亦可含酸性溶液。該酸性溶液’ 可包含至少一種選自硝酸、醋酸、磷酸、鹽酸、硫酸、氫 氟酸、草酸、過氯酸、氫氰酸、硝酸鈽銨、過硫酸銨 '氯 -7 - (4) (4)200417627 化銨組成的群。 上述呈逆性的溶液’亦可含鹼性溶液。該鹼性溶液， 可包含至少一種選自氫氧化鈉、氫氧化鉀、氫氧化鈣、氫 氧化銨 '重絡酸鉀、鐵氰化鉀、氰化鉀、碳酸鈉、醋酸鉀 組成的群。 滴定.測量步驟，可利用上述呈逆性的溶液，以定量 注入方式滴定上述蝕刻液。 補給步驟，亦可使用下式（I )所決定的上述補充液 ，補充上述不足成分量予上述蝕刻液。 d = [dNn 式（I ) 此式中，d爲補充液重量，N爲蝕刻液中所含成分， dN爲對蝕刻液中N成分的不足重量，n表示1以上的整 數。 另一方面，本發明係關於了使反覆使用的金屬類材料 用鈾刻液的成分濃度大略維持一定的管理裝置。該裝置， 至少具備：滴定·測量機構，使用與上述蝕刻液呈逆性的 溶液，滴定上述蝕刻液，與其同時進行量測上述蝕刻液的 導電度；計算機構，由滴定·測量機構所得的測量値，計 算鈾刻液中的不足成分量；補給機構，依計算機構所算出 之不足成分量’使用成分原液以及/或補充液，補充予上 述蝕刻液。 (5) (5)200417627 【實施方式】 以下，參照所附圖示的同時，詳細說明本發明的實施 態樣。該實施態樣不超過本發明的一例，但本發明不限定 於該例示。而且，對圖面的說明同一要件賦予同一符號， 以省略重複說明。 圖1表示本實施態樣的裝置丨〇 〇的槪略示意圖。裝置 1 0 0係由蝕刻槽1 0 1、回收管路1 〇 3、蝕刻液用儲存·回 收槽1 0 4、滴定·測量機構2 0 0、計算機構1 1 〇、原液/補 充液儲存槽1 〇 5、以及連接各機器之配管類等所構成。蝕 刻槽101’係內藏淋浴噴嘴102 (shower nozzle)，用以 蝕刻應被蝕刻之金屬類材料。回收管路1 0 3，係回收從蝕 刻槽1 〇 1使用過的蝕刻液。 於蝕刻槽1 01，應被蝕刻之金屬類材料1 0藉由從淋 浴噴嘴1 02噴射出之蝕刻液，進行蝕刻。而且，本說明書 雖以淋浴噴嘴式的蝕刻裝置說明，然而亦可使用浸泡式的 蝕刻裝置。 本說明書所謂「金屬類材料」，係包含鋰、鋁、鈦、 鐵、銅、鉬以及銀等金屬，以及其氧化物與氮化物、矽、 硼、砷、硒、碲等元素的氧化物與氮化物。 用於本發明作爲蝕刻液，例如酸性溶液與鹼性溶液。 於酸性溶液，例如包含至少一種選自硝酸、醋酸、磷酸、 鹽酸、硫酸、氫氟酸、草酸、過氯酸、氫氰酸等酸、以及 硝酸鈽銨、過硫酸銨、氯化銨等酸性鹽組成的群較佳。另 一方面，於鹼性溶液，例如包含至少一種選自氫氧化鈉、 -9- (6) (6)200417627 氫氧化鉀、氫氧化鈣、氫氧化銨等的氫氧化物、重鉻酸鉀 、鐵氰化鉀、氰化鉀、碳酸鈉、醋酸鉀等的鹼性鹽組成的 群較佳。使用該等任一的蝕刻液，可依蝕刻對象物的金屬 類材料1 0的種類，業者可作適當選擇。 用於鈾刻槽1 〇 1的鈾刻液，爲了重複使用，暫且回收 於儲存·回收槽1 0 4。重複使用之鈾刻液的成分濃度，因 附著於被蝕刻的金屬類材料1 0的成分被帶出裝置外部， 因鈾刻液噴霧的薄霧，因蝕刻槽1 0 1內的溫度上升的蒸發 φ ，以及因被蝕刻的金屬類材料1 0的成分的影響，而歷時 產生變化。若使用成分濃度變化後之蝕刻液，難以維持蝕 刻速率。 裝置100，具備如圖2所示般之滴定·測量機構200 。滴定·測量機構200，係由經樣品導入管1 09從儲存. 回收槽1 04導入蝕刻液之反應容器2 01、爲定量導入鈾刻 液之計量注射器2 1 0、將純水導入反應容器2 01之純水導 入管2 0 9、儲存與蝕刻液呈逆性的溶液（以下，本說明書 · 稱爲「逆性溶液」）逆性溶液槽204以及20 5、以及反應 容器2 0 1內測量蝕刻液導電度的導電度計2 〇 3等所構成。 於本說明書之「與蝕刻液呈逆性的溶液（逆性溶液） 」，在蝕刻液爲酸性溶液的情況，係指鹼性溶液，在蝕刻 液爲鹼性溶液的情況，係指酸性溶液。 用於本發明之逆性溶液，在蝕刻液爲酸性溶液的情況 ’例如包含至少一種選自氫氧化鈉、氫氧化鉀、氫氧化鈣 、氫氧化銨等的氫氧化物、以及重鉻酸鉀、鐵氰化鉀、氰 -10- (7) (7)200417627 化鉀、碳酸鈉、醋酸鉀等的鹼性鹽組成的群較佳。另一方 面，在蝕刻液爲鹼性溶液的情況，逆性溶液例如包含至少 一種選自硝酸、醋酸、磷酸、鹽酸、硫酸、氫氟酸、草酸 、過氯酸、氫氰酸等酸、以及硝酸姉銨、過硫酸銨 '氯化 銨等酸性鹽組成的群較佳。使用該等任一種逆性溶液，依 包含成爲滴定對象的蝕刻液之成分，業者可作適當選擇。 本發明所謂「滴定」，即所謂「中和滴定」。以下， 舉例以鋁蝕刻中一般所使用的蝕刻液PAN (磷酸、醋酸以 及硝酸的混合溶液）以及其逆性溶液NaOH (氫氧化鈉） 溶液，說明蝕刻液的滴定步驟。 在由純水洗淨之反應容器2 0 1，導電度計2 0 3的感測 部浸入液中。經由純水導入管209導入純水。樣品導入管 1 09內的殘留液排出後，使用計量注射器2 1 0，計量約1 毫升的蝕刻液，將該蝕刻液導入反應容器20 1，以攪拌裝 置202攪拌使反應容器201內的溶液均勻。然後，使用導 電度計2 0 3測量藉由反應容器2 0 1內的純水稀釋之蝕刻液 的導電度。於逆性溶液槽204預先儲存0.1N的NaOH溶 液’由該處將一定量（例如每次1毫升）或適當已知量導 入反應谷器2 0 1內，攪样後，測量其導電度。触刻液中的 每一成分（磷酸、醋酸以及硝酸）的濃度差大的情況，於 逆性溶液槽20 5預先儲存1N的NaOH溶液，與o.in的 NaOH溶液同樣的導入反應容器201內，測量其每次的導 電度。 如圖3所示，橫軸爲1N的NaOH溶液的導入量，縱 -11 - (8) (8)200417627 軸爲導電度。圖3的實線，表示導電度計2 0 3實際的測量 値的趨勢。滴定係由強酸性的酸進行。本實施例的情況’ 由鈾刻液中的硝酸進行。從圖3的圖的左端點至p 1爲止 的線爲硝酸的滴定線，由P 1至P 2爲止的線爲醋酸的滴定 線，然後由P2至P3爲止的線爲磷酸的滴定線。該滴定線 的交叉點 P1、P 2、以及P 3爲各個酸成分的滴定點。 N a Ο Η溶液的導入量與該等滴定點的關係，表示每次變化 蝕刻液的成分濃度。 例如蝕刻液中的成分濃度爲微量，以NaOH溶液等的 一般鹼性溶液的滴定困難的情況，含有所欲計量的酸成分 來源的鈉鹽之水溶液等的鹼性溶液，作爲逆性溶液（滴定 溶液）使用時，滴定線上的轉折點（例如P1、P2、以及 P3 )會更顯著。 測量結束後，反應容器2 0 1內的液體經由排出管1 〇 7 排出，反應容器2 0 1，以純水導入管1 0 9所導入的純水洗 淨。 如上述方式，可簡單測量含於蝕刻液中複數成分的濃 度。 計算機構1 1 0，使用由上述滴定·測量機構所測得之 儲存·回收槽1 04中的蝕刻液的成分濃度，計算應補充予 儲存·回收槽1 04的補充成分量。作爲計算機構1 1 〇，舉 例如個人電腦、工作站以及順序器等。該等可由業者適當 選擇。依照該計算機構1 1 0的指示，由原液/補充槽1 〇 5 將需要量的原液以及/或補充液補充予儲存·回收槽104。 -12- (9) (9)200417627 於本實施態樣，儲存·回收槽1 04的補充，係使用包 含於蝕刻液的成分原液以及/或包含於蝕刻液的成分以所 期望的比例混合的補充液。原液以及/或補充液需爲複數 的情況，可設置複數個原液/補充槽1 〇 5 (未圖示）° 應補充予儲存·回收槽1 04的補充液的重量’可由下 式（I )導出。 d = XdNn 式（I ) 此式中，d爲補充液重量，N爲蝕刻液中所含成分’ dN爲對蝕刻液N成分的不足重量，η表示1以上的整數 〇 應補充予儲存·回收槽1 04的補充液的重量d (式（ I))，係由如下述方式導出。 蝕刻液，由於蝕刻時發生蝕刻液薄霧、蝕刻液蒸氣的 排氣、以及因金屬類材料1 0將蝕刻液朝鈾刻槽1 0 1外部 攜出而減量。爲使蝕刻液的成分濃度維持大略一定，藉由 補充液補充該減量份較佳。此處，包含於蝕刻液的成分爲 N1、N 2、N 3.....Ν η。此外，金屬類材料1 0於餓刻 時所使用蝕刻液的重量爲a公斤重，蝕刻液排氣重量爲b 公斤重（蝕刻液薄霧爲i公斤重與蝕刻液蒸氣v公斤重的 總和），因金屬類材料1 〇攜出的蝕刻液的重量爲c公斤 重，以及補充液重量爲d公斤重，該等的關係如下： -13- (10) (10)200417627 a-b-c + d = a、b = i + b、 d = b + c、 cK + v + c。 由此，包含於鈾刻液的成分N的重量增減，則具有 下列關係： aN-bN-cN + dN = aN、bN = iN + bN、dN = bN + cN、dN = iN + vN + cN。 蝕刻液薄霧與被金屬類材料1 〇攜出之蝕刻液中所含 φ 的成分N的含有比例，係視爲不改變原來蝕刻液中所含 的成分N的含有比例。該等並不伴隨化學反應，僅是物 理上攜出至外部。但是，由蒸發而攜出至外部的蝕刻液中 所含的成分N的含有比例，則視爲與原來蝕刻液中所含 的成分N的含有比例不同。依照成分，具有不同的蒸氣 壓。 由蒸發而攜出至外部的成分N的重量vN，係依照200417627 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for managing an etching solution and an apparatus for managing an etching solution ', and particularly to a component concentration of a uranium etching solution for metal materials used repeatedly. The management method of the etching solution and the management device of the etching solution are substantially maintained. [Prior art] Conventionally, the processing method of the so-called etching solution is processing of printed substrates, IT0 films, lead frames, etc., and is also used for steel washing processing of honing steel. Specifically, a metal thin film pattern is formed by using an etchant on a substrate of an array substrate of a flat display device constituting a liquid crystal display and an organic electroluminescence display, and a substrate of a silicon wafer constituting a semiconductor element. An ordinary etchant It consists of water and several volatile components. These ingredients differ depending on the metal being etched. For example, in the case of a liquid crystal display, the metal thin film on the substrate is composed of an aluminum-based metal thin film having high conductivity and a high-melting point metal film such as molybdenum. In this case, a pattern of a metal thin film is formed using an etching solution in which nitric acid, acetic acid, phosphoric acid, and water are mixed in a predetermined ratio (Japanese Laid-Open Patent Publication No. 200 1-770 85). The etching solution in this etching processing step is blown onto the substrate in a shower shape, or the substrate is immersed in the etching solution and used. In addition, in order to process a plurality of substrates in such a step, the etchant is generally used repeatedly in cycles. However, the repeated use of the etching solution, the mist and evaporation during substrate removal, blowing, etc. caused its composition to change over time. As a result, there is a problem that a sufficient etching effect cannot be obtained over time. Furthermore, such a change in the composition of the composition causes not only frequent exchange of the etchant, but also the use of the etchant after disposal, which causes problems such as increased costs. For example, Japanese Patent No. 2747647 discloses an etching solution management device including: an etching solution discharge mechanism that detects the dissolved indium concentration of an etching solution for a transparent conductive film using an absorbance photometer and discharges the etching solution; The level gauge detects the liquid level of the etching solution and replenishes the etching solution and pure water. The second supply mechanism uses a conductivity meter to detect the acid concentration of the etching solution and replenish the etching solution and pure water. This device uses an absorbance photometer to measure the concentration of dissolved metals in the etching solution, and then uses a conductivity meter to measure a single acid concentration. Based on this measurement result, the etching rate is maintained by adding acid or pure water to the etching solution. However, in the invention described in Japanese Patent Publication No. 2 7 4 7 6 4 7 ', it is difficult to manage the component concentration of an etchant composed of a plurality of components. Further, for example, Japanese Laid-Open Patent Publication No. 1 丨 _ 3 0 9 4 0 3, Japanese Unexamined Patent Publication No. 1 1-3 09404, Japanese Unexamined Patent Publication No. 200 ^^ 98 74, and Japanese Unexamined Patent Publication No. 2000-1 99084, A spinner is used to attach the etchant to the substrate, the etchant is taken out of the coating device, and the reduction by mist is prevented. However, it still cannot cope with the concentration change caused by the evaporation of the etchant. [Summary of the Invention] -6- (3) (3) 200417627 Problems to be Solved by the Invention The present invention 'is a problem for maintaining a constant concentration of components in an etching solution for a metal-based material that is easily used over and over. Means for Solving the Problem On the one hand, the present invention relates to a management method for maintaining a constant concentration of a component of a silage engraving solution for metal materials used repeatedly. This method includes a titration and measurement step, titrating the etching solution with a solution that is inverse to the etching solution, and measuring the conductivity of the etching solution simultaneously; a calculation step, and a measurement obtained by the titration and measurement step. ， Calculate the amount of insufficient components in the 0 insect engraving solution; in the replenishing step, use the component stock solution and / or replenishment liquid to replenish the etching solution according to the amount of insufficient components calculated in the calculation step. The etching solution may contain an acidic solution. The acidic solution may include at least one selected from the group consisting of nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid, hydrocyanic acid, and cerium ammonium nitrate C e (N Η 4) 2 ( ΝΟ 3) 6), a group consisting of ammonium persulfate and ammonium chloride. The etching solution may also contain an alkaline solution. The alkaline solution may include at least one group selected from the group consisting of sodium hydroxide, potassium hydroxide, hydroxide hydroxide, sodium hydroxide, potassium dichromate, potassium ferricyanide, potassium cyanide, sodium carbonate, and potassium acetate. The above-mentioned inverse solution may also contain an acidic solution. The acidic solution 'may include at least one selected from the group consisting of nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid, hydrocyanic acid, ammonium nitrate, and ammonium persulfate' chloride-7-(4) ( 4) A group consisting of 200417627 ammonium chloride. The above-mentioned inverse solution 'may contain an alkaline solution. The alkaline solution may include at least one group selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, potassium double barium acid, potassium ferricyanide, potassium cyanide, sodium carbonate, and potassium acetate. Titration. In the measurement step, the above-mentioned inverse solution can be used to titrate the etching solution by quantitative injection. In the replenishing step, the above-mentioned replenishing solution determined by the following formula (I) may be used to replenish the above-mentioned insufficient component amount to the etching solution. d = [dNn Formula (I) In this formula, d is the weight of the replenishing solution, N is the component contained in the etching solution, dN is the insufficient weight of the N component in the etching solution, and n represents an integer of 1 or more. On the other hand, the present invention relates to a management device that maintains a constant concentration of a component of a uranium etching solution for metal materials used repeatedly. This device includes at least: a titration and measurement mechanism that titrates the etching solution using a solution that is inverse to the etching solution, and simultaneously measures the conductivity of the etching solution; a calculation mechanism that measures the measurement obtained by the titration and measurement mechanism Plutonium, calculate the amount of insufficient components in the uranium etch solution; the supply mechanism, based on the amount of insufficient components calculated by the calculation mechanism, uses the component stock solution and / or replenishment solution to replenish the etching solution. (5) (5) 200417627 [Embodiment] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This embodiment does not exceed one example of the present invention, but the present invention is not limited to this example. In addition, the same reference numerals are given to the same elements in the description of the drawings, and redundant descriptions are omitted. FIG. 1 shows a schematic diagram of a device according to this embodiment. The device 1 0 0 is composed of an etching tank 1 0, a recovery pipeline 1 0 3, an etching solution storage and recovery tank 1 0 4, a titration and measurement mechanism 2 0 0, a calculation mechanism 1 1 0, and a stock solution / replenisher storage tank. 105, and piping connected to each device. The etching groove 101 'is a shower nozzle 102, which is used to etch a metal material to be etched. The recovery pipe 103 recovers the etching solution used from the etching groove 101. In the etching bath 101, the metal material 10 to be etched is etched by the etchant sprayed from the shower nozzle 102. In addition, although the present specification is described using a shower nozzle type etching device, an immersion type etching device may be used. The "metal materials" in this specification include metals such as lithium, aluminum, titanium, iron, copper, molybdenum, and silver, as well as oxides and nitrides, silicon, boron, arsenic, selenium, tellurium, and other elements. nitride. As the etching solution used in the present invention, for example, acidic solution and alkaline solution. In an acidic solution, for example, at least one acid selected from the group consisting of nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid, and hydrocyanic acid; Groups composed of salt are preferred. On the other hand, the alkaline solution contains, for example, at least one hydroxide selected from sodium hydroxide, -9- (6) (6) 200417627 potassium hydroxide, calcium hydroxide, ammonium hydroxide, and potassium dichromate. A group consisting of alkaline salts such as potassium ferricyanide, potassium cyanide, sodium carbonate, potassium acetate and the like is preferred. The use of any of these etching solutions can be appropriately selected by the operator depending on the type of the metal material 10 to be etched. The uranium engraving solution used in the uranium etch tank 101 is temporarily recovered in the storage and recovery tank 104 for reuse. The component concentration of the uranium etching solution used repeatedly is taken out of the device due to the components attached to the etched metal material 10, the mist of the uranium etching solution spray, and the evaporation due to the temperature rise in the etching tank 101 φ and the influence of the composition of the etched metal-based material 10 change over time. It is difficult to maintain the etching rate if an etching solution having a changed component concentration is used. The device 100 includes a titration and measurement mechanism 200 as shown in FIG. 2. The titration and measurement mechanism 200 is stored from the sample introduction tube 1 09. The recovery tank 1 04 is the reaction container 2 for introducing the etching solution. 01, the metering syringe 2 is used for quantitatively introducing the uranium etching solution 2 1 0, and the pure water is introduced into the reaction container 2. Pure water introduction tube 01 of 01 9. Store a solution that is inverse to the etching solution (hereinafter, this specification will be referred to as "inverse solution") in the inverse solution tanks 204 and 20 5 and in the reaction container 2 01 It is constituted by a conductivity meter such as conductivity of the etching solution. In the present specification, "a solution inverse to an etching solution (reversing solution)" means an alkaline solution when the etching solution is an acidic solution, and an acidic solution when the etching solution is an alkaline solution. When the etching solution is an acidic solution, the inverse solution used in the present invention includes, for example, at least one hydroxide selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, and the like, and potassium dichromate , Potassium ferricyanide, cyano-10- (7) (7) 200417627 potassium salt, sodium carbonate, potassium acetate and the like are preferred. On the other hand, when the etching solution is an alkaline solution, the inverse solution contains, for example, at least one acid selected from the group consisting of nitric acid, acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid, and hydrocyanic acid, and A group consisting of acid salts such as ammonium nitrate, ammonium persulfate and ammonium chloride is preferred. The use of any of these inverse solutions may be appropriately selected by the supplier depending on the composition of the etching solution to be titrated. The so-called "titration" in the present invention is the so-called "neutralization titration". In the following, the etching solution PAN (a mixed solution of phosphoric acid, acetic acid, and nitric acid) and its inverse solution NaOH (sodium hydroxide) solution, which are commonly used in aluminum etching, are used to describe the titration step of the etching solution. The reaction vessel 201, which was washed with pure water, and the sensing part of the conductivity meter 203 were immersed in the liquid. Pure water is introduced through a pure water introduction pipe 209. After the residual liquid in the sample introduction tube 1 09 is discharged, use a measuring syringe 2 10 to measure about 1 ml of the etching solution, introduce the etching solution into the reaction container 201, and stir with the stirring device 202 to make the solution in the reaction container 201 uniform. . Then, the conductivity of the etching solution diluted with pure water in the reaction vessel 201 was measured using a conductivity meter 203. A 0.1N NaOH solution is stored in the reverse solution tank 204 in advance, and a certain amount (for example, 1 ml each time) or an appropriate known amount is introduced into the reaction valleyr 211 from the place, and the conductivity is measured after stirring the sample. If the concentration difference of each component (phosphoric acid, acetic acid, and nitric acid) in the etching solution is large, a 1N NaOH solution is stored in the reverse solution tank 20 5 in advance, and the same is introduced into the reaction container 201 as the o.in NaOH solution. , And measure its conductivity each time. As shown in Fig. 3, the horizontal axis is the amount of NaOH solution introduced, and the vertical axis is -11-(8) (8) 200417627. The solid line in Fig. 3 shows the actual measurement of radon by the conductivity meter 203. Titration is performed with a strongly acidic acid. The case of this embodiment is performed by nitric acid in the uranium etching solution. The line from the left end of the graph in FIG. 3 to p 1 is a titration line for nitric acid, the line from P 1 to P 2 is a titration line for acetic acid, and the line from P2 to P3 is a titration line for phosphoric acid. The intersection points P1, P2, and P3 of the titration line are the titration points of the respective acid components. The relationship between the amount of N a Η Η solution introduced and these titration points indicates the component concentration of the etching solution each time it changes. For example, if the concentration of the component in the etching solution is in a trace amount, and the titration with a general alkaline solution such as a NaOH solution is difficult, an alkaline solution such as an aqueous solution containing a sodium salt derived from a desired acid component is used as a reverse solution (titration Solution), the turning points on the titration line (such as P1, P2, and P3) will be more significant. After the measurement is completed, the liquid in the reaction container 201 is discharged through the discharge pipe 107, and the reaction container 201 is washed with pure water introduced by the pure water introduction pipe 1009. As described above, the concentration of a plurality of components contained in the etching solution can be simply measured. The calculation mechanism 110 calculates the amount of the additional component to be stored in the storage and recovery tank 104 using the component concentration of the etching solution in the storage and recovery tank 104 measured by the titration and measurement mechanism. Examples of the computing mechanism 1 10 include a personal computer, a workstation, and a sequencer. These can be appropriately selected by the operator. According to the instruction of the computing unit 110, the required amount of the stock solution and / or the replenishment solution is replenished from the stock solution / replenishment tank 105 to the storage / recovery tank 104. -12- (9) (9) 200417627 In this embodiment, the storage and recovery tank 104 is replenished by using the component stock solution contained in the etching solution and / or the components contained in the etching solution in a desired ratio. Replenishment fluid. If the original solution and / or replenishment solution need to be plural, a plurality of original solutions / replenishment tanks 1 05 (not shown) can be provided. The weight of the replenishment solution that should be replenished to the storage and recovery tank 104 can be expressed by the following formula (I) Export. d = XdNn Formula (I) In this formula, d is the weight of the replenishment liquid, N is the component contained in the etchant 'dN is the insufficient weight of the N component of the etchant, and η is an integer of 1 or more. The weight d (formula (I)) of the make-up liquid in the recovery tank 104 is derived as follows. The etchant is reduced due to the mist of the etchant, the exhaust of the etchant vapor, and the metal material 10 carrying the etchant out of the uranium groove 101. In order to maintain the component concentration of the etching solution approximately constant, it is preferable to supplement the reduced portion with a replenishing solution. Here, the components included in the etching solution are N1, N2, N3,... Nη. In addition, the weight of the etchant used when the metal material 10 is engraved is 10 kg, and the weight of the etchant exhaust gas is 2 kg (the sum of the etchant mist is 1 kg and the etchant vapor v kg) Since the weight of the etching solution carried by the metallic material 10 is c kg and the weight of the replenishment liquid is d kg, the relationship is as follows: -13- (10) (10) 200417627 abc + d = a, b = i + b, d = b + c, cK + v + c. Therefore, the weight of the component N contained in the uranium etching solution has the following relationship: aN-bN-cN + dN = aN, bN = iN + bN, dN = bN + cN, dN = iN + vN + cN . The content ratio of the component N contained in the etching solution mist and the φ component N contained in the etching solution carried by the metal material 10 is considered not to change the content ratio of the component N contained in the original etching solution. These are not accompanied by chemical reactions, but are physically carried out to the outside. However, the content ratio of the component N contained in the etching solution carried to the outside by evaporation is considered to be different from the content ratio of the component N contained in the original etching solution. Depending on the composition, it has different vapor pressures. The weight vN of the component N carried to the outside by evaporation is in accordance with
vN = WN/ZW = WmNxpN/IW-WmNx(mN/M)xPN/IW 所表示。此處，PN表示蝕刻液常溫時的成分蒸氣壓 ，pN表示成分蒸氣壓，mN/M表示蝕刻液的成分莫耳分率 ，mN表示成分莫耳濃度，Μ表示全部成分莫耳濃度，vN = WN / ZW = WmNxpN / IW-WmNx (mN / M) xPN / IW. Here, PN represents the component vapor pressure of the etching solution at normal temperature, pN represents the component vapor pressure, mN / M represents the composition molar fraction of the etching solution, mN represents the component molar concentration, and M represents the molar concentration of all components.
WmN表不成分的分子量、以及 WN表不成分的可能蒸發 量。 因此，應補充予儲存·回收槽1 〇4的補充液重量d， -14- (11) (11)200417627 變成 d = dN1+dN2 + dN3 + ….+ dNη = ΣdNη .....式（I) 〇 將蝕刻液中所含的各成分的原液，補充予儲存.回收 槽1 04的情況，依上述dN導入各成分的補充量。 然後，說明圖1所示的裝置1 〇 〇的控制功能。儲存· 回收槽104在空槽初始建浴時，打開開關閥10 6b，運轉 幫浦（p ump ) 1 0 6 p，經由管路1 0 6供給蝕刻液予儲存. 回收槽1 0 4。儲存·回收槽1 0 4儲滿蝕刻液時，關閉開關 閥106b，停止幫浦106p，停止供給蝕刻液。 金屬類材料1 〇藉由搬送裝置運送至蝕刻槽1 0 1。運 轉幫浦1 04p，將蝕刻液從儲存·回收槽1 〇4經由管路 1 〇4a供給予蝕刻槽1 0 1。供給予蝕刻槽1 〇1之蝕刻液，在 蝕刻槽101內從淋浴噴嘴102朝運送中的金屬類材料10 淋浴噴霧。噴霧至金屬類材料1 0之蝕刻液，鈾刻金屬類 材料1 0的表面，一部分由金屬類材料1 0攜出鈾刻槽1 0 1 ，另一部分變成薄霧由未圖示的導管排出至外部。再另外 一部分蒸發，經導管排出至外部。於是，大部分的蝕刻液 經由回收管路1 0 3回收於儲存·回收槽1 〇 4。 回收於儲存·回收槽1 04之蝕刻液，因上述一部分蒸 發，其成分濃度改變。金屬類材料1 0的蝕刻作業繼續進 行的同時，儲存·回收槽1 04內之蝕刻液成分濃度改變。 成分濃度改變之蝕刻液，藉由打開開關閥1 〇9b ’經 (12) (12)200417627 由管路1 09供給予滴定·測量機構200。供給滴定·測量 所需量的蝕刻液後，關閉開關閥1 〇9b。將滴定·測量機 構2 0 0的測量結果供給予計算機構1 1 〇。計算機構π 0， 使儲存·回收槽1 04內之蝕刻液成分濃度回復爲初始値， 計算維持大略一定濃度所需成分原液以及/或補充液的重 量。計算機構1 1 0，依照計算結果，傳送電信號予流量調 節閥1 0 5 b以及/或幫浦1 0 5 b，控制流量調節閥1 〇 5 b以及/ 或幫浦105b，使其供給適量的原液以及/或補充液予儲存 •回收槽1 〇 4。 以下說明圖2所示的滴定·測量機構2 0 0的控制功能 。使導電度計203的感測部浸泡的程度，將純水經由純水 導入管2 0 9導入反應容器2 0 1內。滴定·測量所需量的蝕 刻液，從儲存·回收槽1 0 4經由管路1 0 9供給予計量注射 器2 1 〇。藉由使用計量注射器2 1 0，可計量滴定.測量所 需適量的蝕刻液。成分濃度改變之鈾刻液，以計量注射器 2 1 〇計量，供給予反應容器20 1。此時，運轉攪拌裝置 202，使反應容器201內的溶液均勻。 預先決定重量的逆性溶液，從逆性溶液槽204或205 經管路204a或20 5 a供給予反應容器201。所供給的逆性 溶液的重量，依照構成蝕刻液的成分種類決定。其間，藉 由導電度計203，測量蝕刻液滴定的進行狀態。該測量結 果’逐一傳送至計算機構丨丨〇。 滴定結束時，將反應容器2 0 1內的溶液，由管路1 0 7 排出。然後，將純水經由純水導入管2 0 9導入反應容器 (13) (13)200417627 201內，洗淨反應容器201。 如此，可維持儲存·回收槽1 04內之鈾刻液成分濃度 大略固定。 以上，依該實施態樣詳細說明本發明。但是，本發明 並不限於上述實施態樣。在不超出本發明要旨的範圍，可 有各種改變。 例如，亦可取代上述滴定·測量機構2 0 0，使用如圖 4所示之滴定·測量機構2 2 0。滴定.測量機構2 2 0，與 馨 滴定·測量機構2 0 0不同之處在於設置分光光度計2 2 2以 及脫色處理裝置224於管路109中。滴定·測量機構220 的其他構成，與滴定·測量機構200相同。此外，分光光 度計222亦可配置於蝕刻槽循環管路中。而且，脫色處理 裝置224配置於分光光度計222的上游。 分光光度計222，測量從儲存·回收槽104經管路 109所傳送之蝕刻液的分光吸收強度。脫色處理裝置224 係對在分光測定前的蝕刻液進行脫色處理。蝕刻液的脫色 φ ，係對蝕刻液進行增溫、減壓脫氣、冒泡以及加壓之中至 少一種以上的處理。 由分光光度計222取得的測量値，傳送至計算機構 1 1 0。計算機構1 1 〇使用該測量値，算出触刻液的成分濃 度，再使用算出之成分濃度，算出蝕刻液中的不足成分量 。當分光比使用導電度計滴定可較精確測量蝕刻液的成分 濃度時，計算機構1 1 0使用分光光度計的測量値，算出蝕 刻液中的不足成分量，進行蝕刻液的補充亦可。 -17- (14) (14)200417627 發明的效果 依本發明’可使反覆使用的金屬類材料用触刻液中容 易歷久變化的成分濃度大略，維持一定。而且依本發明，可 使含複數成分之鈾刻液的成分濃度大略維丨寺。胃#方A 本發明’因蝕刻液中歷久變化的成分適當補充，可大幅減 少蝕刻液交換與廢棄所需的費用。 【圖式簡單說明】 圖1表示蝕刻液管理裝置的一實施態樣的槪略示意圖 〇 圖2表示滴定·測量機構的一例的槪略示意圖。 圖3表示依據逆性溶液的添加量與導電度所顯現之蝕 刻液的滴定線圖。 圖4表示滴定·測量機構的另一例的槪略示意圖。 ❿ 元件符號說明： 1 〇 :金屬類材料 100 :蝕刻液管理裝置 1 0 1 :蝕刻槽 102 :淋浴噴嘴 103 :回收管路 104 :蝕刻液用儲存·回收槽 1 0 4 a :管路 -18- (15) (15)200417627 l〇4p :幫浦 105 :原液/補充液儲存槽 1 0 5 a :管路 1 0 5 b :開關閥 1 〇 5 p :幫浦 1 〇 6 :管路 l〇6b :開關閥 1 0 6 p :幫浦 1 〇 7 :管路 l〇7b :開關閥 1 〇 8 b :開關閥 1 0 9 :管路 1 〇 9 b :開關閥 1 1 0 :計算機構 200 :滴定·測量機構 201 :反應容器 202 :攪拌裝置 2 03 :導電度計 204 :逆性溶液槽 2 0 4 a :管路 20 5 :逆性溶液槽 2 0 5 a :管路 2 0 9 :純水導入管 2 1 0 :計量注射器 -19- 200417627 (16) p 1 :滴定線的交叉點 P 2 :滴定線的交叉點 P 3 :滴定線的交叉點 2 2 0 :滴定.測量機構 222 :分光光度計 224 :脫色處理裝置WmN indicates the molecular weight of the constituents, and WN indicates the possible evaporation of the constituents. Therefore, the weight d of the replenishment liquid to be stored in the storage and recovery tank 1 〇4, -14- (11) (11) 200417627 becomes d = dN1 + dN2 + dN3 +…. + DNη = ΣdNη ..... ( I) 〇 In the case where the stock solution of each component contained in the etching solution is replenished to the storage tank 104, a supplemental amount of each component is introduced in accordance with the above-mentioned dN. Next, the control function of the device 100 shown in FIG. 1 will be described. In the storage and recovery tank 104, when the bath is initially set up in the empty tank, the on-off valve 10 6b is opened, and the pump (pump) 1 0 6 p is operated, and the etching solution is supplied to the storage via the pipeline 106. The recovery tank 1 104. When the storage / recovery tank 104 is filled with the etching solution, the on-off valve 106b is closed, the pump 106p is stopped, and the supply of the etching solution is stopped. The metal-based material 10 is transported to the etching tank 101 by a transfer device. The pump 104 was operated, and the etching solution was supplied from the storage / recovery tank 104 to the etching tank 101 through the pipeline 104a. An etching solution to be applied to the etching bath 101 is sprayed from the shower nozzle 102 toward the metal material 10 being transported in the etching bath 101. The etching solution sprayed on the metallic material 10, the surface of the metallic material 10 is etched by the uranium, a part of the uranium engraving groove 1 0 1 is carried by the metallic material 10, and the other part becomes a mist and discharged from a duct (not shown) to external. Another part evaporates and is discharged to the outside through the duct. Then, most of the etching solution is recovered in the storage / recovery tank 104 through the recovery line 103. The etching solution recovered in the storage / recovery tank 104 was partially evaporated due to the above-mentioned evaporation, and its component concentration changed. As the etching operation of the metallic material 10 continues, the concentration of the etchant composition in the storage / recovery tank 104 changes. The etching solution having a changed composition concentration is supplied to the titration and measurement mechanism 200 through the pipeline 1 09 by opening the on-off valve 1 09b ′ through (12) (12) 200417627. After the required amount of etching solution for titration and measurement is supplied, the on-off valve 10b is closed. The measurement result of the titration and measurement mechanism 2000 is given to the calculation mechanism 110. The calculation mechanism π 0 restores the concentration of the etching solution component in the storage and recovery tank 104 to the initial value, and calculates the weight of the component original solution and / or replenishment liquid required to maintain a substantially constant concentration. The calculation mechanism 1 10 transmits an electric signal to the flow regulating valve 10 5 b and / or the pump 105 b according to the calculation result, and controls the flow regulating valve 1 0 5 b and / or the pump 105 b to supply an appropriate amount. The stock solution and / or replenishment solution are stored in the recovery tank 104. The control function of the titration and measurement mechanism 2000 shown in FIG. 2 will be described below. To the extent that the sensing part of the conductivity meter 203 is immersed, pure water is introduced into the reaction container 201 through the pure water introduction tube 209. The required amount of etching solution is titrated and measured, and is supplied to the metering injector 2 1 0 from the storage and recovery tank 104 through the pipe 10 9. By using a measuring syringe 2 10, titration can be metered. The required amount of etching solution is measured. The uranium engraved solution having a changed component concentration is measured by a measuring syringe 2 10 for administration to the reaction container 201. At this time, the stirring device 202 is operated to make the solution in the reaction container 201 uniform. The inverse solution having a predetermined weight is supplied to the reaction container 201 from the inverse solution tank 204 or 205 through the line 204a or 20 5 a. The weight of the supplied reverse solution is determined according to the type of the components constituting the etchant. In the meantime, the state of progress of the titration of the etching liquid was measured by the conductivity meter 203. The measurement results are transmitted to the calculation mechanism one by one. At the end of the titration, the solution in the reaction container 201 is discharged through the pipeline 107. Then, pure water was introduced into the reaction container (13) (13) 200417627 201 through the pure water introduction pipe 209, and the reaction container 201 was washed. In this way, the concentration of the uranium etching solution in the storage and recovery tank 104 can be maintained substantially constant. The present invention has been described in detail according to this embodiment. However, the present invention is not limited to the above embodiments. Various changes may be made without departing from the gist of the present invention. For example, instead of the titration and measurement mechanism 200 described above, a titration and measurement mechanism 220 as shown in FIG. 4 may be used. The titration. Measuring mechanism 2 2 0 differs from the Xin titration and measuring mechanism 2 0 0 in that a spectrophotometer 2 2 and a decoloring treatment device 224 are provided in the pipeline 109. The other structures of the titration and measurement mechanism 220 are the same as those of the titration and measurement mechanism 200. In addition, the spectrophotometer 222 can also be arranged in the circulation channel of the etching tank. The decoloring processing device 224 is disposed upstream of the spectrophotometer 222. The spectrophotometer 222 measures the spectroscopic absorption intensity of the etching solution transferred from the storage / recovery tank 104 through the pipeline 109. The decoloring treatment device 224 performs a decoloring treatment on the etching solution before the spectroscopic measurement. The decoloring φ of the etching solution is at least one process of increasing the temperature of the etching solution, degassing under reduced pressure, bubbling, and pressurizing. The measurement chirp obtained by the spectrophotometer 222 is transmitted to the calculation mechanism 1 1 0. The calculation mechanism 110 calculates the component concentration of the etching solution using the measurement 値, and calculates the amount of the insufficient component in the etching solution using the calculated component concentration. When the spectrophotometric titration with a conductivity meter can accurately measure the component concentration of the etching solution, the calculation mechanism 110 uses a spectrophotometer's measurement 値 to calculate the amount of insufficient components in the etching solution, and can also supplement the etching solution. -17- (14) (14) 200417627 Effect of the Invention According to the present invention, the concentration of a component that can be easily changed over time in a metal-based material for a metal material used repeatedly can be kept substantially constant. Moreover, according to the present invention, the component concentration of the uranium etching solution containing a plurality of components can be made substantially larger. Stomach # 方 A The present invention 'is appropriately supplemented with the components that have changed over time in the etching solution, which can significantly reduce the cost of exchange and disposal of the etching solution. [Brief description of the drawings] FIG. 1 shows a schematic diagram of an embodiment of an etching solution management device. FIG. 2 shows a schematic diagram of an example of a titration and measurement mechanism. Fig. 3 shows a titration diagram of an etching solution which appears based on the addition amount and conductivity of a reverse solution. FIG. 4 is a schematic diagram showing another example of a titration and measurement mechanism.符号 Symbol description: 1 〇: Metal material 100: Etching liquid management device 1 0: Etching tank 102: Shower nozzle 103: Recovery line 104: Storage and recovery tank for etching liquid 1 0 4a: Line-18 -(15) (15) 200417627 l04p: pump 105: stock solution / replenishment liquid storage tank 1 0 5 a: pipeline 1 0 5 b: on-off valve 1 〇5 p: pump 1 〇6: pipeline 1 〇6b: On-off valve 1 0 6 p: Pump 1 〇7: Pipe 107b: On-off valve 1 〇8 b: On-off valve 1 0 9: Pipe 1 〇9 b: On-off valve 1 1 0: Calculation mechanism 200: Titration and measurement mechanism 201: Reaction container 202: Stirring device 2 03: Conductivity meter 204: Reverse solution tank 2 0 4 a: Pipe 20 5: Reverse solution tank 2 0 5 a: Pipe 2 0 9 : Pure water introduction tube 2 1 0: Measuring syringe-19- 200417627 (16) p 1: Cross point of the titration line P 2: Cross point of the titration line P 3: Cross point of the titration line 2 2 0: Titration. Measuring mechanism 222: Spectrophotometer 224: Decolorization processing device