1310792 (1) 玖、發明說明 【發明所屬之技術領域〕 本發明係關於一種蝕刻液之管理方法以及飽刻液之管 理置’特別是關於爲反覆使用的金屬類材料用触刻液 的成分濃度大略維持一定之蝕刻液之管理方法以及|虫刻 '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’利用於硏磨鋼鐡的洗鋼處 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 成分依據被蝕刻的金屬而不同。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2 0 0 ] - 7 7 0 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- 1310792 (2) 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2 74764 7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 的酸ί辰度。根據該測疋結果，藉由於触刻液中補充酸或 純水，保持蝕刻速率。但是，於日本專利第2 74764 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 1 - 3 0 9 4 〇 3號公報、 特開平1 ] - 3 094 04號公報、特開平2000- 1 ] 9 8 74號公報、 以及特開平2 000- 1 990 84號公報，利用旋轉機（Spinner ) 將蝕刻液附於基板上，鈾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f虫刻 液蒸發造成的濃度變化。 【發明內容】 -6- 1310792 (3) 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纟虫刻'液Φ 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 蝕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，計算蝕刻 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、硝酸铈鞍（cerium ammonium nitrate C e (Ν Η 4) 2 (Ν Ο 3) 6 )、過硫酸銨、氯化錢組成的群。 上述蝕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、氫氧化钟、氫氧化耗、氫氧化鞍、 重鉻酸鉀、鐵氰化鉀、氰化紳、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、碟酸、鹽酸、硫酸、氫 氟酸、草酸、過氯酸、氫氰酸、硝酸铈銨、過硫酸銨、氯 -7- 1310792 (4) 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、重鉻酸鉀、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（1 )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 = EdNn 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 用蝕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 算蝕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 1310792 (5) 【實施方式】 以下，參照所附圖示的同時，詳細說明本發 態樣。該實施態樣不超過本發明的一例，但本發 於該例示。而且，對圖面的說明同一要件賦予同 以省略重複說明。 圖1表示本實施態樣的裝置1 0 0的槪略示意 1 0 0係由蝕刻槽1 〇 1、回收管路1 0 3、蝕刻液用 收槽1 0 4、滴定·測量機構2 0 0、計算機構U 0 充液儲存槽]〇 5、以及連接各機器之配管類等所 刻槽101，係內藏淋浴噴嘴102 ( shower nozzle 蝕刻應被鈾刻之金屬類材料。回收管路1 〇3，係 刻槽1 〇 1使用過的蝕刻液。 於鈾刻槽1 〇 1，應被蝕刻之金屬類材料1 〇 浴噴嘴1 0 2噴射出之蝕刻液，進行蝕刻。而且， 雖以淋浴噴嘴式的蝕刻裝置說明，然而亦可使用 蝕刻裝置。 本說明書所謂「金屬類材料」，係包含鋰、 鐵、銅、鉬以及銀等金屬，以及其氧化物與氮化 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 於酸性溶液，例如包含至少一種選自硝酸、醋酸 鹽酸 '硫酸、氫氟酸、草酸、過氯酸、氫氰酸等 硝酸姉銨、過硫酸銨、氯化銨等酸性鹽組成的群 一方面，於鹼性溶液，例如包含至少一種選自氫 明的實施 明不限定 一符號， 圖。裝置 儲存·回 、原液/補 構成。貪虫 )，用以 回收從蝕 藉由從淋 本說明書 浸泡式的 銘、I太、 物、矽、 性溶液。 、磷酸、 酸、以及 較佳。另 氧化鈉、 1310792 (6) 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。 用於蝕刻槽1 01的蝕刻液，爲了重複使用，暫且回收 於儲存·回收槽1 04。重複使用之蝕刻液的成分濃度，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， 因蝕刻液噴霧的薄霧，因蝕刻槽1 0 1內的溫度上升的蒸發 ，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]0 0，具備如圖2所示般之滴定·測量機構2 0 0 。滴定·測量機構2 00，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201、爲定量導入蝕刻 液之計量注射器2 1 0、將純水導入反應容器2 (Π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2 0 4以及2 0 5、以及反應 容器20]內測量蝕刻液導電度的導電度計203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，在鈾刻 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，在鈾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- 1310792 (7) 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 —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、以及硝酸铈銨、過硫酸鞍、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鈾刻液之成分’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p AN (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2 0 9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 〇，計量約1 毫升的蝕刻液，將該蝕刻液導入反應容器2 0 1，以攪拌裝 置2〇2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2〇4預先儲存0.]n的NaOH溶 液’由該處將一定量（例如每次]毫升）或適當已知量導 入反應容器201內，攪拌後，測量其導電度。餓刻液中的 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2 0 5預先儲存]n的N a Ο Η溶液，與〇 . ] N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 - 1310792 (8) 軸爲導電度。圖3的實線，表示導電度計2 03實際的測 値的趨勢。滴定係由強酸性的酸進行。本實施例的情況 由蝕刻液中的硝酸進行。從圖3的圖的左端點至P 1爲 的線爲硝酸的滴定線，由P 1至P 2爲止的線爲醋酸的滴 線，然後由P2至P3爲止的線爲磷酸的滴定線。該滴定 的交叉點 P1、P2、以及P3爲各個酸成分的滴定點 NaOH溶液的導入量與該等滴定點的關係，表示每次變 蝕刻液的成分濃度 例如蝕刻液中的成分濃度爲微量，以N a Ο Η溶液等 一般鹼性溶液的滴定困難的情況，含有所欲計量的酸成 來源的鈉鹽之水溶液等的鹼性溶液，作爲逆性溶液（滴 溶液）使用時，滴定線上的轉折點（例如Ρ1、Ρ2、以 Ρ 3 )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] 排出，反應容器20]，以純水導入管]09所導入的純水 淨。 如上述方式，可簡單測量含於蝕刻液中複數成分的 度。 計算機構1 1 0，使用由上述滴定·測量機構所測得 儲存.回收槽]0 4中的蝕刻液的成分濃度，計算應補充 儲存·回收槽]04的補充成分量。作爲計算機構1 ] 〇， 例如個人電腦、工作站以及順序器等。該等可由業者適 選擇。依照該計算機構1〗〇的指示，由原液/補充槽] 將需要量的原液以及/或補充液補充予儲存.回收槽I 〇 4 里 > 止 定 線 〇 化 的 分 定 及 07 洗 濃 之 予 舉 當 05 1310792 (9) 於本實施態樣，儲存回收槽]〇4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 〇4的補充液的重量，可由下 式（I )導出。 d =^dNn1310792 (1) 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 〕 〕 〕 〕 〕 〕 〕 〕 〕 〕 〕 〕 〕 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻We will maintain a certain management method for etching liquid and the management device for insects. [Prior Art] Conventionally, the processing method of the etching liquid is, for example, a processing of a printed circuit board, an IT0 film, and a lead frame, and the like, and is used for a steel washing process of a honing steel shovel. Specifically, on the substrate of the array substrate of the flat display device constituting the liquid crystal display and the organic electroluminescence display, on the substrate of the germanium wafer constituting the semiconductor element, a metal thin film pattern 〇 general etching liquid is formed by using an etching liquid 'The system consists of water and several volatile components. These components vary 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, an etching solution in which nitric acid, acetic acid, phosphoric acid, and water are mixed in a predetermined ratio is used to form a metal thin film pattern (Japanese Laid-Open Patent Publication No. 2000-77-85). The etching liquid in the etching process is blown to the substrate in a shower shape, or the substrate is immersed in an etching solution. Moreover, the etching solution is generally recycled in order to process a plurality of substrates in such a step. However, the repeatedly used etching liquid, the substrate is taken out, the mist during blowing, evaporation, etc., causes the composition of -5-1310792 (2) to change over time. As a result, over time, there is a problem that a sufficient etching effect cannot be obtained. Further, such a change in the composition of the composition causes the etching liquid not only to be frequently exchanged, but also the etching liquid after use is discarded, which causes a problem such as an increase in cost. For example, Japanese Patent No. 2 74764 7 discloses an etching liquid management device including an etching liquid discharge mechanism that detects an dissolved indium concentration of an etching liquid for a transparent conductive film using an absorption photometer, and discharges an etching liquid; The liquid level of the etching liquid is detected by the liquid level level meter to supplement the etching stock solution and the pure water; and the second replenishing mechanism uses the conductivity meter to detect the acid concentration of the etching liquid 'replenishing the etching stock solution and the pure water. In the apparatus, the concentration of the dissolved metal in the etching solution is measured by an absorptiometer, and then the conductivity of the single sheet is measured by a conductivity meter. According to the test result, the etching rate is maintained by the addition of acid or pure water in the etchant. However, in the invention described in Japanese Patent No. 2 74764, it is difficult to manage the concentration of the etching liquid composed of a plurality of components. Further, for example, Japanese Laid-Open Patent Publication No. Hei 1 1 - 3 0 9 4 〇 3, Japanese Patent Laid-Open No. Hei 1 - 3 094 04, Japanese Patent Laid-Open No. 2000-1, No. 9 8 74, and Special Kaiping 2 000-1 In 990, the etchant is attached to the substrate by a spinner, and the uranium engraving liquid is taken out to the outside of the coating device, and the amount of mist reduction is prevented. However, it is still unable to cope with the concentration change caused by the evaporation of the insect fluid. [Explanation] -6- 1310792 (3) Problem to be Solved by the Invention The present invention is intended to maintain the concentration of a component which is easily changed over a long period of time by a sputum-like liquid Φ. Means for Solving the Problem In one aspect, the present invention relates to a management method for maintaining a constant concentration of a component of an etching liquid for a metal material to be used repeatedly. The method includes: titrating and measuring the step, titrating the etching liquid using a solution in which the etching liquid is opposite to the etching liquid, and simultaneously measuring the conductivity of the etching liquid: a calculation step, and a measurement obtained by the titration and measurement step Calculate the amount of the insufficient component in the etching solution; the replenishing step is supplemented to the etching liquid by using the component stock solution and/or the replenishing liquid according to the amount of the insufficient component calculated in the calculation step. The above etching solution may also contain an acidic solution. The acidic solution may comprise 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 (Ν Η 4) 2 ( Ν Ο 3) 6), a group consisting of ammonium persulfate and chlorinated money. The above etching solution may also contain an alkaline solution. The alkaline solution may comprise at least one group selected from the group consisting of sodium hydroxide, hydrazine hydroxide, hydrogen hydroxide consumption, saddle hydroxide, potassium dichromate, potassium ferricyanide, cesium cyanide, sodium carbonate, and potassium acetate. The above-mentioned reversed solution may also contain an acidic solution, the acidic solution, and may comprise at least one selected from the group consisting of nitric acid, acetic acid, dish acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, perchloric acid, hydrocyanic acid, and lanthanum nitrate. a group consisting of ammonium, ammonium persulfate, and chloro-7-1310792 (4) ammonium. The above-mentioned reversed solution may also contain an alkaline solution. The alkaline solution ' may comprise at least one group selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, potassium dichromate, potassium ferricyanide, potassium cyanide, sodium carbonate, and potassium acetate. In the titration and measurement step, the above-mentioned etching liquid can be titrated by a quantitative injection method using the above-mentioned reversed solution. In the replenishing step, the above-mentioned replenishing liquid determined by the following formula (1) may be used to supplement the above-mentioned etching liquid to the above etching liquid. d = EdNn Formula (I) In the formula, d is the weight of the replenishing liquid, N is the component contained in the etching solution, dN is the insufficient weight of the N component in the etching solution, and n is an integer of 1 or more. On the other hand, the present invention relates to a management apparatus for maintaining a constant concentration of a component of an etching solution for a metal material to be used repeatedly. The apparatus includes at least a titration/measurement mechanism that titrates the etching liquid using a solution in opposition to the etching liquid, and simultaneously measures the conductivity of the etching liquid; the calculation mechanism's measurement by the titration measuring mechanism値, the amount of the insufficient component in the etching solution is calculated; the replenishing means is supplemented to the upper 1310792 by using the component stock solution and/or the replenishing liquid calculated according to the calculation means. [Embodiment] Hereinafter, reference is made to the drawings. At the same time, the present aspect will be described in detail. This embodiment does not exceed an example of the present invention, but the present invention is exemplified. Further, the same reference numerals are given to the same elements to omit redundant description. Fig. 1 shows a schematic representation of the apparatus 100 of the present embodiment. The system is composed of an etching bath 1 〇1, a recovery line 1 0 3, an etchant receiving tank 1 0 4, a titration/measurement mechanism 2 0 0 The calculation mechanism U 0 liquid storage tank] 〇 5, and the groove 101 for connecting the piping of each machine, etc., is a built-in shower nozzle 102 (the shower nozzle is etched with a metal material such as uranium engraved. Recycling line 1 〇 3. The etchant used in the groove 1 〇1 is used. In the uranium groove 1 〇1, the etching solution which is to be etched by the metal material 1 〇 bath nozzle 1 0 2 is etched. The nozzle type etching apparatus is described, but an etching apparatus may be used. The "metal material" in the present specification includes metals such as lithium, iron, copper, molybdenum, and silver, and oxides thereof and boron nitride, arsenic, and selenium. An oxide and a nitride of an element such as ruthenium. For use in the present invention as an etchant, for example, an acidic solution and an alkali in an acidic solution, for example, comprising at least one selected from the group consisting of nitric acid, acetic acid hydrochloric acid, hydrofluoric acid, oxalic acid, perchloric acid, Ammonium cerium nitrate such as hydrocyanic acid, ammonium persulfate, ammonium chloride In the case of an alkaline solution, for example, an alkaline solution, for example, comprising at least one selected from the group consisting of hydrogen, is not limited to a symbol, and the device is stored, returned, and the liquid/complement is formed. The eclipse is immersed in the instructions, I, sputum, sputum, and sexual solution. , phosphoric acid, acid, and preferably. In addition, sodium oxide, 1310792 (6) potassium hydroxide, calcium hydroxide, ammonium hydroxide and other hydroxides, potassium dichromate, potassium ferricyanide, potassium cyanide, sodium carbonate, potassium acetate and other basic salts The group is better. The use of any of the etching liquids can be appropriately selected depending on the type of the metal material 10 to be etched. The etching solution for etching the groove 101 is temporarily recovered in the storage/recovery tank 104 for repeated use. The concentration of the component of the etching liquid to be repeatedly used is brought out of the apparatus due to the component adhering to the metal material 10 to be etched, and the mist which is sprayed by the etching liquid is evaporated due to the temperature rise in the etching bath 10 1 Due to the influence of the composition of the metal material 10 to be etched, it changes over time. If an etching solution having a changed composition concentration is used, it is difficult to maintain the etching rate. The device]0 0 has a titration/measurement mechanism 2 0 0 as shown in FIG. 2 . The titration/measurement mechanism 00 is a reaction container 201 that introduces an etching liquid from the storage/recovery tank 104 through the sample introduction pipe 109, a dosing syringe 2 1 0 for introducing an etching liquid quantitatively, and introduces pure water into the reaction container 2 (纯 pure water introduction pipe 2 0 9, storage and etching solution is reversed (hereinafter, referred to as "reverse solution" in this specification) reverse solution tank 2 0 4 and 2 0 5, and reaction vessel 20] The conductivity meter 203 or the like for measuring the conductivity of the etching liquid is used. The "solution (inverse solution) which is opposite to the etching liquid" in the present specification means an alkaline solution when the etching solution is an acidic solution. In the case where the uranium engraving solution is an alkaline solution, it means an acidic solution. The reverse solution used in the present invention, in the case where the uranium engraving solution is an acidic solution, for example, contains at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and hydroxide. A hydroxide group such as calcium or ammonium hydroxide or a basic salt composed of potassium dichromate, potassium ferricyanide, cyanogen-10-1310792 (7) potassium, sodium carbonate or potassium acetate is preferred. On the one hand, 'in the case where the etching solution is an alkaline solution', reverse dissolution For example, it comprises 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, hydrocyanic acid, and the like, and an ammonium salt such as ammonium cerium nitrate, sodium persulfate, ammonium chloride or the like. The group is preferably used. The use of any of the inverse solutions may be appropriately selected depending on the composition of the uranium engraving solution to be titrated. The so-called "titration" of the present invention means "neutralization titration". The etching solution p AN (a mixed solution of phosphoric acid, acetic acid and nitric acid) and the reverse solution NaOH (sodium hydroxide) solution generally used in aluminum etching illustrate the titration step of the etching solution. The reaction container washed with pure water 2 0 1. The sensing portion of the conductivity meter 2 0 3 is immersed in the liquid, and the pure water is introduced through the pure water introduction pipe 2 0 9 . After the residual liquid in the sample introduction pipe 109 is discharged, the measuring syringe 2 1 〇 is used, and the measurement is performed. About 1 ml of the etching solution, the etching solution was introduced into the reaction vessel 210, and the solution in the reaction vessel 201 was made uniform by stirring with the stirring device 2〇2. Then, the conductivity vessel was measured by the conductivity meter 2 0 3 by the reaction vessel 20 1 pure water thin The conductivity of the etching solution is pre-stored in the reverse solution tank 2〇4. The NaOH solution of 'n] is introduced into the reaction vessel 201 by a certain amount (for example, each time) or a suitable amount is introduced into the reaction vessel 201, and stirred. After that, the conductivity is measured. When the concentration difference of each component (phosphoric acid, acetic acid, and nitric acid) in the hungry solution is large, the n a Ο Η solution in the reverse solution tank 2 0 5 is pre-stored with 〇 The N NaOH solution was similarly introduced into the reaction vessel 201, and the conductivity of each was measured. As shown in Fig. 3, the introduction amount of the 1N NaOH solution on the horizontal axis and the vertical -11 - 1310792 (8) axis were electrically conductive. The solid line in Figure 3 shows the actual trend of the conductivity meter. The titration is carried out by a strongly acidic acid. The case of this embodiment is carried out by nitric acid in the etching solution. The line from the left end point of the graph of Fig. 3 to P 1 is a titration line of nitric acid, the line from P 1 to P 2 is a dropping line of acetic acid, and the line from P2 to P3 is a titration line of phosphoric acid. The intersections P1, P2, and P3 of the titration are the relationship between the introduction amount of the titration point NaOH solution of each acid component and the titration points, and indicate that the concentration of the component of the etching solution is, for example, a trace amount in the etching solution. When the titration of a general alkaline solution such as a Na Ο Η solution is difficult, an alkaline solution containing an aqueous solution of a sodium salt derived from an acid to be measured is used as a reverse solution (drop solution), on the titration line. Turning points (such as Ρ 1, Ρ 2, Ρ 3) will be more noticeable. After the measurement is completed, the liquid in the reaction vessel 20 1 is discharged through the discharge pipe, and the reaction vessel 20] is purified by the pure water introduced into the pure water introduction pipe]09. As described above, the degree of the plural components contained in the etching solution can be simply measured. The calculation means 1 10 determines the amount of the supplementary component to be replenished in the storage/recovery tank] 04 using the component concentration of the etching liquid in the storage/recovery tank]0 measured by the above-described titration/measurement means. As a computing mechanism 1 ], such as personal computers, workstations, and sequencers. These can be chosen by the industry. According to the instruction of the calculation mechanism 1 〇, the required amount of the stock solution and/or the replenishing liquid is replenished to the storage by the stock solution/supplement tank]. In the recovery tank I 〇 4 > 05 1310792 (9) In this embodiment, the storage recovery tank 〇4 is supplemented by using a component stock solution contained in the etching solution and/or a component contained in the etching solution to be mixed in a desired ratio. liquid. In the case where the stock solution and/or the replenishing solution need to be plural, a plurality of stock solutions/supplement tanks 1 〇 5 (not shown) may be provided. The weight of the replenishing liquid to be replenished to the storage/recovery tank 1 〇4 can be derived from the following formula (I). d =^dNn
此式中，d爲補充液重量，N爲蝕刻液中所含成分， d N爲對蝕刻液N成分的不足重量，n表示]以上的整數 應補充予儲存·回收槽1 〇 4的補充液的重量d (式（ I ))，係由如下述方式導出。 倉虫刻液’由於蝕刻時發生蝕刻液薄霧、0φ刻液蒸氣的 排氣、以及因金屬類材料〗〇將蝕刻液朝蝕刻槽1 〇 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 N 1 ' N 2 ' N 3 > . . .、Ν η。此外，金屬類材料1 〇於蝕刻 日寸所使用触Μ液的重量爲a公斤重，触刻液排氣重®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 0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 - 1310792 (10) a-b-c + d- a、匕叫 + ^、d==b + c、d = i + v + c。 由此’包含於蝕刻液的成分N的重量增減，則具有 下列關係： aN-bN-c.N + 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 0攜出之蝕刻液中所含 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In the formula, d is the weight of the replenishing liquid, N is the component contained in the etching solution, d N is the insufficient weight of the N component of the etching solution, and n is an integer equal to or larger than the amount of the replenishing solution of the storage/recovery tank 1 〇4 The weight d (formula (I)) is derived as follows. The worm-like engraving liquid is reduced by the etching liquid mist generated during etching, the venting of the 0 φ etched vapor, and the etchant liquid being carried out outside the etching bath 1 〇 1 by the metal material. In order to maintain the concentration of the component of the etching solution to a certain extent, it is preferable to supplement the amount of the reducing portion by the replenishing liquid. Here, the component contained in the etching liquid is N 1 ' N 2 ' N 3 > . . . , Ν η. In addition, the weight of the contact liquid used in the metal material 1 is etched to a kilogram, and the etched liquid exhaust weight is b kg (the etchant mist is i kilogram and the etching vapor is v kg). The sum of the 'etching liquid carried by the metal material 10 is c kg weight' and the weight of the replenishing liquid is d kg, the relationship is as follows: -13 - 1310792 (10) abc + d- a, Howling + ^, d==b + c, d = i + v + c. Thus, the weight increase or decrease of the component N contained in the etching liquid has the following relationship: aN-bN-c.N + dN = aN, bN = iN + bN, dN = bN + cN, dN = iN + vN + cN. The content ratio of the component N contained in the etching liquid mist to the etching liquid carried out by the metal material 10 is regarded as not changing the content ratio of the component N contained in the original etching liquid. 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 liquid which is carried out to the outside by evaporation is considered to be different from the content ratio of the component N contained in the original etching liquid. Depending on the composition, it has a different vapor pressure. The weight vN of the component N carried out by evaporation to the outside is in accordance with
v N = W N / Σ W = W m N X p N / Σ W = W m N X (m N / M ) X P N / Σ W 所表示。此處，ΡΝ表示蝕刻液常溫時的成分蒸氣壓 ，ρΝ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， WmN表示成分的分子量、以及 WN表示成分的可能蒸發 量。 因此，應補充予儲存.回收槽1 04的補充液重量d， -14 - 1310792 (11) 變成 d = dN 1 + dN2 + dN3 + ... . + dNn = IdNn .....式（I)。 將触刻液中所含的各成分的原液，補充予儲存.回收 槽1 〇4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1 04在空槽初始建浴時，打開開關閥1〇61)，運轉 鲁 幫浦（pump ) 1 06p ’經由管路丨〇6供給蝕刻液予儲存· 回收槽1 0 4 °儲存·回收槽1 〇 4儲滿蝕刻液時，關閉開關 閥1 0 6 b，停止幫浦1 0 6 p，停止供給蝕刻液。 金屬類材料1 0藉由搬送裝置運送至蝕刻槽1 〇丨。運 轉幫浦]0 4 p，將鈾刻液從儲存·回收槽〗〇 4經由管路 1 〇4 a供給予蝕刻槽1 〇 1。供給予蝕刻槽]〇 ]之蝕刻液，在 倉虫刻槽1 0 1內從淋浴噴嘴1 〇 2朝運送中的金屬類材料1 〇 淋浴噴霧。1¼霧至金屬類材料1 0之餓刻液，触刻金屬類 g 材料1 0的表面’ 一部分由金屬類材料1 0攜出蝕刻槽I 〇 ] ’男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 03回收於儲存.回收槽。 回收於儲存·回收槽1 04之蝕刻液，因上述—部分蒸 發’其成分濃度改變。金屬類材料1 〇的蝕刻作業繼續進 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I 09b，經 -15- 1310792 (12) 由管路1 0 9供給予滴定·測量機構2 0 0。供給滴定·測量 所需量的蝕刻液後，關閉開關閥I 〇9b。將滴定·測量機 構2 0 0的測量結果供給予計算機構π 0。計算機構]1 〇， 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〗丨0，依照計算結果，傳送電信號予流量調 節閥105b以及/或幫浦l〇5b，控制流量調節閥i〇5b以及/ 或幫浦1 0 5 b ’使其供給適量的原液以及/或補充液予儲存 •回收槽1 0 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2 03的感測部浸泡的程度，將純水經由純水 導入管209導入反應容器201內。滴定·測量所需量的蝕 对丨液’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 胃@量的蝕刻液。成分濃度改變之蝕刻液，以計量注射器 2 1 〇計量，供給予反應容器 2 0 1。此時，運轉攪拌裝置 2 Q 2 ’使反應容器2 0 ]內的溶液均勻。 ’ 預先決定重量的逆性溶液，從逆性溶液槽2 0 4或2 0 5 經管路2 0 4 a或2 0 5 a供給予反應容器2 0 1。所供給的逆性 € ί夜的重量，依照構成蝕刻液的成分種類決定。其間，藉 &導電度計2 0 3，測量蝕刻液滴定的進行狀態。該測量結 果’逐〜傳送至計算機構1 1 0。 滴定結束時，將反應容器201內的溶液，由管路107 排出。然後，將純水經由純水導入管209導入反應容器 -16 - 1310792 (13) 201內，洗淨反應容器201。 如此，可維持儲存·回收槽1 04內之蝕刻液成分濃度 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 00，使用如圖 4所示之滴定·測量機構22 0。滴定.測量機構220，與 滴定·測量機構200不同之處在於設置分光光度計222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2 22的上游。 分光光度計222，測量從儲存·回收槽1 04經管路 1 〇 9所傳送之蝕刻液的分光吸收強度。脫色處理裝置2 2 4 係對在分光測定前的鈾刻液進行脫色處理。鈾刻液的脫色 ’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2 2 2取得的測量値，傳送至計算機構 1 1 0。計算機構1 1 0使用該測量値，算出蝕刻液的成分濃 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- 1310792 (14) 發明的效果 依本發明，可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。而且依本發明，可 使含複數成分之蝕刻液的成分濃度大略維持一定。再者於 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。 元件符號說明： ]〇 :金屬類材料 〗0 0 :蝕刻液管理裝置 1 0 1 :蝕刻槽 102 :淋浴噴嘴 1 0 3 :回收管路 1 〇 4 :蝕刻液用儲存·回收槽 l〇4a :管路 -18- 1310792 (15) l〇4p :幫浦 105 :原液/補充液儲存槽 1 〇 5 a :管路 1 0 5 b :開關閥 1 〇 5 p :幫浦 ]〇 6 :管路 1 0 6 b :開關閥 l〇6p :幫浦 拳 1 0 7 :管路 1 〇 7 b :開關閥 1 〇 8 b :開關閥 I 0 9 :管路 1 〇 9 b :開關閥 1 1 0 :計算機構 2 0 0 :滴定·測量機構 2 0 ]:反應容器 _ 202 :攪拌裝置 2 0 3 :導電度計 2 0 4 :逆性溶液槽 2 0 4 a :管路 2 0 5 :逆性溶液槽 2 0 5 a :管路 209 :純水導入管 2 1 0 :計量注射器 -19 - 1310792 (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v N = W N / Σ W = W m N X p N / Σ W = W m N X (m N / M ) X P N / Σ W is expressed. Here, ΡΝ indicates the component vapor pressure at the normal temperature of the etching solution, ρ Ν indicates the component vapor pressure, mN/M indicates the component molar fraction of the etching solution, mN indicates the component molar concentration, Μ indicates the total component molar concentration, and WmN indicates The molecular weight of the component, and WN, indicate the amount of possible evaporation of the component. Therefore, it should be added to the storage tank. The weight of the replenishing liquid of the recovery tank 104 is -14 - 1310792 (11) becomes d = dN 1 + dN2 + dN3 + ... . + dNn = IdNn ..... ). The stock solution of each component contained in the etchant is replenished for storage. In the case of the recovery tank 1 〇 4, the replenishing amount of each component is introduced in accordance with the above dN. Then, the control function of the device 1 图 shown in Fig. 1 will be explained. Storage and recovery tank 1 04 Open the on-off valve 1〇61) during the initial construction of the empty tank, run the pump 1 06p ' supply the etchant via the line 丨〇6 to the storage · Recycling tank 1 0 4 ° Storage/Recycling Tank 1 When 蚀刻4 is filled with the etching solution, the on-off valve 1 0 6 b is closed, and the pump 1 0 6 p is stopped to stop the supply of the etching liquid. The metal material 10 is transported to the etching bath 1 by the transfer device. Run the pump]0 4 p, the uranium engraving from the storage and recovery tank 〇 4 through the pipeline 1 〇 4 a for the etching tank 1 〇 1. The etching solution for giving the etching bath] 淋浴 is sprayed from the shower nozzle 1 〇 2 toward the metal material 1 in the transport in the worm groove 101. 11⁄4 fog to metal material 10, the hungry engraving, the metallized material g, the surface of the material 10, part of the surface of the metal material 10, the etching channel I 〇] 'the part of the male became a mist by a catheter not shown Drain to the outside. A further portion of the evaporation is discharged through the conduit to the outside. Thus, most of the etching liquid is recovered in the storage and recovery tank via the recovery line 103. The etchant recovered in the storage/recovery tank 104 is changed in concentration due to the above-mentioned partial evaporation. At the same time as the etching operation of the metal material 1 继续 continues, the concentration of the etching liquid component in the storage/recovery tank 104 is changed. The etchant having a changed composition concentration is supplied to the titration/measurement mechanism 200 by the line 1 0 9 by opening the on-off valve I 09b via -15 - 1310792 (12). After the titration is measured and the required amount of etching liquid is measured, the on-off valve I 〇 9b is closed. The measurement result of the titration/measuring mechanism 200 is supplied to the calculation mechanism π 0 . The calculation means is 1 〇, and the concentration of the etching liquid component in the storage/recovery tank 104 is returned to the initial enthalpy, and the weight of the component stock solution and/or the replenishing liquid required to maintain a substantially constant concentration is calculated. The calculation mechanism 丨0, according to the calculation result, transmits an electric signal to the flow regulating valve 105b and/or the pump l〇5b, and controls the flow regulating valve i〇5b and/or the pump 1 0 5 b ' to supply an appropriate amount of the original liquid. And/or replenishing solution to the storage and recovery tank 1 0 4. In the following, the control function of the titration and measuring mechanism 200 shown in Fig. 2 will be described. The degree of immersion of the sensing unit of the conductivity meter 203 is introduced into the reaction container 201 via the pure water introduction pipe 209. Titration · Measurement of the required amount of eclipse The sputum ' is supplied to the metering injector 2 1 from the storage/recovery tank 1 0 4 via the line 1 0 9 . By using the metering syringe 2 10 , the titration and measurement of the stomach etchant can be measured. The etching solution having a changed composition concentration is measured by a metering syringe 2 1 , for administration to the reaction container 2 0 1 . At this time, the stirring device 2 Q 2 ' is operated to make the solution in the reaction vessel 2 0 ] uniform. The counter-determined weight of the reverse solution is supplied to the reaction vessel 2 0 1 from the reverse solution tank 2 0 4 or 2 0 5 via the line 2 0 4 a or 2 0 5 a. The weight of the reversed € ί night is determined by the type of component constituting the etching solution. In the meantime, the state of progress of the etching droplet was measured by the & conductivity meter 2 0 3 . The measurement result is transmitted to the computing unit 110. At the end of the titration, the solution in the reaction vessel 201 is discharged from the line 107. Then, pure water is introduced into the reaction vessel -16 - 1310792 (13) 201 via the pure water introduction pipe 209, and the reaction vessel 201 is washed. Thus, the concentration of the etching liquid component in the storage/recovery tank 104 can be kept substantially fixed. Hereinabove, the present invention will be described in detail based on the embodiments. However, the present invention is not limited to the above embodiment. Various changes may be made without departing from the scope of the invention. For example, instead of the above-described titration/measurement mechanism 200, a titration/measurement mechanism 22 0 as shown in Fig. 4 may be used. The measurement unit 220 differs from the titration/measurement mechanism 200 in that a spectrophotometer 222 and a decoloring treatment device 224 are provided in the line 109. The other configuration of the measurement unit 220 is the same as that of the titration/measurement unit 200. Further, the spectrophotometer 222 may also be disposed in the etching tank circulation line. Further, the decoloring treatment device 224 is disposed upstream of the spectrophotometer 2 22 . The spectrophotometer 222 measures the spectral absorption intensity of the etching liquid transferred from the storage/recovery tank 104 through the line 1 〇 9. The decoloring treatment device 2 2 4 performs decolorization treatment on the uranium engraving liquid before the spectrometry. The decolorization of the uranium engraving is carried out by at least one or more of increasing the temperature of the etching solution, deaeration under reduced pressure, bubbling, and pressurization. The measurement enthalpy obtained by the spectrophotometer 2 2 2 is transmitted to the calculation means 1 1 0. Using the measurement 値, the calculation means 1 10 calculates the component concentration of the etching solution, and calculates the amount of the insufficient component in the etching solution using the calculated component concentration. When the splitting ratio is more accurately measured by using a conductivity meter to accurately measure the concentration of the etching liquid, the calculating means 1 10 uses the measuring enthalpy of the spectrophotometer to calculate the amount of the insufficient component in the etching liquid, and the etching liquid may be replenished. -17- 1310792 (14) Effects of the Invention According to the present invention, the concentration of the component which can be changed over a long period of time in the etching solution can be maintained substantially constant. Further, according to the present invention, the concentration of the component of the etching liquid containing the plurality of components can be kept substantially constant. Further, in the present invention, the components which have been changed for a long time in the etching liquid are appropriately replenished, and the cost required for the exchange and disposal of the etching liquid can be greatly reduced. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an embodiment of an etching solution management device. Fig. 2 is a schematic view showing an example of a titration/measurement mechanism. Fig. 3 is a graph showing the titration line of the etching solution which appears depending on the amount of addition of the reverse solution and the conductivity. Fig. 4 is a schematic diagram showing another example of the titration and measuring mechanism. Description of the component symbols: ]〇: Metallic material 〗 0 0 : Etching liquid management device 1 0 1 : etching tank 102: shower nozzle 1 0 3 : recovery line 1 〇 4 : storage and recovery tank for etching liquid l〇4a: Piping -18- 1310792 (15) l〇4p : Pump 105 : stock solution / replenishing solution storage tank 1 〇 5 a : line 1 0 5 b : switching valve 1 〇 5 p : pump 〇 6 : piping 1 0 6 b : On-off valve l〇6p : Bangpu 1 0 7 : Line 1 〇 7 b : On-off valve 1 〇 8 b : On-off valve I 0 9 : Line 1 〇 9 b : On-off valve 1 1 0 : Calculation mechanism 2 0 0 : titration and measuring mechanism 2 0 ]: reaction vessel _ 202 : stirring device 2 0 3 : conductivity meter 2 0 4 : reverse solution tank 2 0 4 a : line 2 0 5 : reverse Solution tank 2 0 5 a : Line 209 : Pure water introduction tube 2 1 0 : Metering syringe -19 - 1310792 (16) P 1 : Intersection point of titration line P 2 : Intersection point of titration line P 3 : Titration line Intersection 2 2 0 : titration and measurement mechanism 222 : spectrophotometer 224 : decolorization processing device