TW200921298A - Method for recycling tetramethylammonium hydroxide (TMAH) from waste developer - Google Patents

Abstract

Disclosed is a method for recycling tetramethylammonium hydroxide (TMAH) from waste developer, primarily comprising the steps of PR (photoresist)-removal, ion-removal, regeneration, electrodialysis, and adjustment of concentration. According to the method, PR inside waste developer is removed, and then extract tetramethylammonium ions inside waste developer by solid absorption. Next, the tetramethylammonium ions are separated from the solid absorber. During electrodialysis, tetramethylammonium ions are separated from acid ions and transformed into TMAH.

Description

200921298 九、發明說明： 【發明所屬之技術領域】 ’特別係有關於一種顯影廢 本發明係有關於顯影廢液之回收技術 液中回收氫氧化四甲基銨(TMAH)之方法 【先前技術】 顯影劑能將曝光顯影之光阻作成所預定之圖案，廣泛運用在積體 電路與液晶面板之製造產業。以目前技術而言，—種正姐係包含 25〜55%酚醛樹脂（novolak resin)、5〜20%感光劑（如重氮萘醌 (diazonaphthoquinone，DNQ))、以及 60〜8〇〇/。溶劑（如 Pr〇pylene glyc〇1 mcmomethyl ether acetate，PGMEA)，在顯影後可溶解於驗性水溶 液。因此，目前是採用氫氧化四曱基銨(TMAH)溶液作為顯影劑。 使用過的顯影劑除了原本的顯影劑成份之外，還會有被溶光阻、 金屬離子（例如，鈉、鐵及鋁離子等等）、無機陰離子、有機陰離子、 表面活性物質以及懸浮顆粒等等。然目前的回收方法，是採用生物 分解法或是簡單的過濾再回流以低比例混入新鮮的顯影劑，並無法 高比例地有效回收氫氧化四曱基銨。 我國專利公告575796號「氫氧化四曱基銨顯影液的回收系統及 其方法」’其利用量測顯影回收液的波長吸收度，直到與所添加的新 鮮氫氧化四甲基銨能符合標準值。因此，回收比例與所添加的新顯 影液有關連’無法完全回收。並且，無法除去顯影回收液内的金屬 離子與陰離子。 我國專利公開編號200615238號「顯影廢液的處理方法」，利用 在顯影廢液中添加過氧化氫，並施予一紫外光照射而產生了氫氧自 由基’與顯影廢液中的光阻等有機物質進行反應，並使其分解成水 200921298 以及一乳化碳後予以去除 值後回收再使用^ ‘顯㈣液中的顯影劑也能經由調整ΡΗ 嶋蝴咖晴財光阻等有機 =的除=方法，尚未建立可除去㈣廢液巾金屬離子、錢陰離= 專的完整回收機制。 十 【發明内容】 树明之主要目的係在於提供一種顯影廢液中回收氫氧化四甲 基銨(ΤΜΑΗ)之方法’能建立完整的回收卿，具有高时率與易於 線上監控之功效。 、200921298 IX. Description of the invention: [Technical field to which the invention pertains] 'Specially related to a development waste The present invention relates to a method for recovering tetramethylammonium hydroxide (TMAH) from a recovery technology liquid for developing waste liquid [Prior Art] The developer can form a predetermined pattern by exposure to light, and is widely used in the manufacturing industry of integrated circuits and liquid crystal panels. In the current technology, a positive sister system contains 25 to 55% of novolak resin, 5 to 20% of a sensitizer (such as diazonaphthoquinone (DNQ)), and 60 to 8 Å. A solvent such as Pr〇pylene glyc〇1 mcmomethyl ether acetate, PGMEA can be dissolved in an aqueous solution after development. Therefore, a tetramethylammonium hydroxide (TMAH) solution is currently used as a developer. In addition to the original developer component, the used developer may have dissolved photoresist, metal ions (for example, sodium, iron, aluminum ions, etc.), inorganic anions, organic anions, surface active substances, suspended particles, and the like. Wait. However, the current recovery method uses a biodegradation method or a simple filtration and reflow to mix a fresh developer in a low ratio, and it is not possible to efficiently recover tetradecylammonium hydroxide in a high proportion. China Patent Publication No. 575796 "Recovery System and Method for Reducing Tetraammonium Hydroxide Development Solution", which utilizes the measurement of the wavelength absorbance of the development recovery liquid until it meets the standard value of the added fresh tetramethylammonium hydroxide . Therefore, the recovery ratio is related to the new developer added and cannot be completely recovered. Further, metal ions and anions in the development recovery liquid cannot be removed. Chinese Patent Publication No. 200615238, "Processing Method for Developing Waste Liquid", by adding hydrogen peroxide to a developing waste liquid, and applying an ultraviolet light to generate a hydroxyl radical 'and a photoresist in the developing waste liquid, etc. The organic matter is reacted and decomposed into water 200921298 and an emulsified carbon, and then the value is removed and then recovered. The developer in the liquid (4) can also be adjusted by adjusting the organic light such as ΡΗ 嶋 晴 晴 晴 晴= method, has not been established to remove (four) waste metal ions, money and yin = dedicated complete recycling mechanism. [Explanation] The main purpose of Shuming is to provide a method for recovering tetramethylammonium hydroxide (ΤΜΑΗ) in developing waste liquid, which can establish a complete recovery, which has high time rate and easy on-line monitoring. ,

本發明的目的及解決其技術問題是採用以下技術方案來實現 的。本發明揭示一種顯影廢液中回收氫氧化四甲基錢(ΤΜΑΗ)之方 法:至少包含以下步驟：進行—去光阻步驟，以去除—顯影廢液内 之光阻’其中賴影廢液内含四甲基絲子(ΤΜΑ+);進行一去離子 ^驟其係利用固態吸附方式抽取該顯影廢㈣之四甲基按離子， 而與内含金屬離子之顯影廢液分離；進行_再生步驟，以使四甲基 錄離子與固態吸附劑分離；進行—電解透析步驟，以使四甲基敍離 子Ά根離子分離而轉化成氫氧化四甲基敍；以及，進行一濃度調 配步驟’以使氫氧化四甲基錄之漢度調配在2^至25加％之間。 本發明的目的及解決其技術問題還可採用以下技術措施進一步 實現。 在别述的回收方法中’上述去離子步驟係可包含離子交換。 在m述的回收方法中，上述去離子步驟係可採用流體化床方式。 在前述的回收方法中’該固態吸附劑係可為陽離子交換樹脂或有 機碳。 在削述的回收方法中，上述去光阻步驟係可包含酸鹼中和。 200921298 在前述的回收方法中，該酸根離子係包含氣離子。 在前述的回收方法中，上述去光阻步驟係包含奈米膜過淚。 在前述的回收方法中，在上述再生步驟中係添加鹽酸(HC1)，而 使固態吸附劑再生。 【實施方式】 在本發明之一具體實施例中’第1圖係為一種顯影廢液中回收氫 氧化四甲基銨(TMAH)之方法之流程圖。第2圖係為該顯影廢液之回 收設備示意圖。 如第1圖所示，本發明之顯影廢液中回收氫氧化四甲基敍（TMAH) 之方法主要包含有「去光阻」之步驟1、「去離子」之步驟2、「再生」 步驟3、「電解透析」步驟4及「濃度調配」之步驟5。第2圖為對 應於上述方法之回收設備示意圖，該回收設備1〇〇主要包含有 TMAH吸附床、奈米過遽系統、TMAH電解系統、濃度調配系統。 首先’進行「去光阻」之步驟1。如第2圖所示，去除一顯影廢 液内之殘留光阻（R-COOH)，其中該顯影廢液内含四曱基銨離子 (TMA+)。上述去光阻步驟係可包含酸驗中和與一般過濾，例如添加 鹽酸(HC1)或疏酸。以鹽酸為例，「去光阻」之反應機構可為·· TMAH + HC1 — [TMA]+[C1]· + H20 TMAH :即為氫氧化四曱基錢，tetramethylammonium hydroxide 之簡稱，化學式為（CH3)4NOH，分子量為91，一種強鹼毒性物質， 可溶於水。 藉此，顯影廢液之酸鹼值（pH value)將由強驗性被調整到中性或 酸性，TMAH被轉換成四甲基銨離子（TMA+)而失去溶解光阻的能 力。故光阻等有機物質將會自動沉澱，藉由一般濾紙或簡單過遽器 200921298 便可過遽除去光阻或其它有機物質。較佳地，上述去光阻步驟可更 包含奈米膜過濾，用以除去微小顆粒。因此，可利用即時的pH量 測進行「去光阻」之步驟1的線上監控。 進打「去離子」之步驟2,其係利用固態吸附方式抽取該顯影廢 液内之四甲基銨離子，而與内含金屬離子之顯影廢液分離。該固態 吸附劑係可為1¼離子交換樹脂或有機碳。上述去離子步驟係可包含 離子交換。「去離子」之反應機構可為： [Resin] [H]+ + [TMA]+[〇H]' [Resin]'[TMA]+ + H20 較佳地，更重要的方法是用流體化床方式與去離子步驟中同時將 溶解或不溶解的光阻一起去除，本設計方式能將含有175%之光阻 去除降至〇·〇〇以下（實驗室實際測量之數據為〇 〇〇53%)，本實驗 。又》十使用之陽離子交換樹脂為Rc)hm & Haas AMBERIET 150犯與 Mitsubishi SKT 20L。上述去離子步驟設計採用流體化床方式，同時 在去離子化的過程中也同則巴TMAH從廢液中分離，以達到連續式 操作並易於更換離子交換樹脂管。因此，在「去離子」之步驟2中， (J流出㈣酸驗錢為酸性，若逐漸Μ巾性或驗性 ，表示樹脂管失The object of the present invention and solving the technical problems thereof are achieved by the following technical solutions. The invention discloses a method for recovering tetramethyl hydrazine hydroxide in a developing waste liquid: at least comprising the steps of: performing a photoresist removal step to remove the photoresist in the developing waste liquid. Containing tetramethyl ray (ΤΜΑ+); performing a deionization process by using a solid-state adsorption method to extract the tetramethyl cation of the developing waste (4), and separating it from the developing waste liquid containing the metal ion; a step of separating the tetramethylated ions from the solid adsorbent; performing an electrolysis dialysis step to separate the tetramethylsulfonium ions into a tetramethylammonium hydroxide; and performing a concentration blending step In order to make the tetramethyl oxyhydroxide recorded in the range of 2 ^ to 25 plus %. The object of the present invention and solving the technical problems thereof can be further realized by the following technical measures. In the recovery method described separately, the above deionization step may comprise ion exchange. In the recovery method described in m, the above deionization step may be carried out by a fluidized bed method. In the foregoing recovery method, the solid adsorbent may be a cation exchange resin or an organic carbon. In the illustrated recovery method, the above-described photoresist removal step may comprise acid-base neutralization. 200921298 In the aforementioned recovery method, the acid ion system contains gas ions. In the foregoing recovery method, the above-mentioned photoresist removal step comprises a tear film of a nano film. In the above recovery method, hydrochloric acid (HC1) is added in the above regeneration step to regenerate the solid adsorbent. [Embodiment] In a specific embodiment of the present invention, the first drawing is a flow chart of a method for recovering tetramethylammonium hydroxide (TMAH) in a developing waste liquid. Fig. 2 is a schematic view of the recycling apparatus of the developing waste liquid. As shown in Fig. 1, the method for recovering tetramethyl sulfonate (TMAH) in the developing waste liquid of the present invention mainly comprises the steps of "removing the photoresist", step 2 of "deionization", and "regeneration". 3. Step 5 of “Electrolysis Dialysis” and Step 5 of “Density Preparation”. Fig. 2 is a schematic view of a recovery apparatus corresponding to the above method, which mainly comprises a TMAH adsorption bed, a nano-pass system, a TMAH electrolysis system, and a concentration preparation system. First, proceed to step 1 of "going to the photoresist." As shown in Fig. 2, the residual photoresist (R-COOH) in a developing waste liquid containing tetramethylammonium ion (TMA+) is removed. The above-described photoresist removal step may comprise acid neutralization and general filtration, such as the addition of hydrochloric acid (HC1) or acid. Taking hydrochloric acid as an example, the reaction mechanism of "de-blocking" can be TMH + HC1 - [TMA] + [C1] · + H20 TMAH: it is tetramethylammonium hydroxide, the chemical formula is ( CH3) 4NOH, molecular weight 91, a strong base toxic substance, soluble in water. Thereby, the pH value of the developing waste liquid is adjusted to be neutral or acidic by the potency, and TMAH is converted into tetramethylammonium ion (TMA+) to lose the ability to dissolve the photoresist. Therefore, organic substances such as photoresist will be precipitated automatically, and photoresist or other organic substances can be removed by general filter paper or simple filter 200921298. Preferably, the above-mentioned photoresist removal step may further comprise nano membrane filtration for removing minute particles. Therefore, on-line monitoring of step 1 of "de-blocking" can be performed using an instant pH measurement. In step 2 of "deionization", the tetramethylammonium ion in the developing waste liquid is extracted by solid-state adsorption, and separated from the developing waste liquid containing metal ions. The solid adsorbent can be 11⁄4 ion exchange resin or organic carbon. The above deionization step can comprise ion exchange. The reaction mechanism for "deionization" can be: [Resin] [H]+ + [TMA]+[〇H]' [Resin]'[TMA]+ + H20 Preferably, the more important method is to use a fluidized bed. The method and the deionization step simultaneously remove the dissolved or insoluble photoresist. This design can reduce the photoresist with 175% to below 〇·〇〇 (the actual measured data in the laboratory is 〇〇〇53%). ),this experiment. Also, the cation exchange resin used in the tenth was Rc)hm & Haas AMBERIET 150 and Mitsubishi SKT 20L. The above deionization step is designed in a fluidized bed mode, and is also separated from the waste liquid during the deionization process to achieve continuous operation and easy replacement of the ion exchange resin tube. Therefore, in step 2 of "deionization", (J) (4) acid test is acidic, if it is gradually smeared or inspective, it means that the resin tube is lost.

再生」之反應機構可為：The reaction mechanism of regeneration can be:

200921298 之後，進行一「電解透析」之步驟4 ’以使四曱基銨離子與酸根 離子分離而轉化成氫氧化四甲基銨。在本步驟實驗裡，我們使用單 位電流量為10〜30Amp/dm2 ’反應溫度控制於20〜6(TC中，電解槽 電壓為5〜20V，電解透析膜可選使用DupontNafion 424的透析膜， 在本實施例中’該酸根離子係包含氣離子。「電解透析」之反應機構 可為： 2[TMA] + [C1]· + 2H20 2[TMAH] + CI2 + H2 个 故可得到高純度的氫氧化四曱基銨(Tmah)，詳細的操作說明可 參考第3圖，酸根四曱基銨溶液置於—電解槽1〇，一側為陽極π， 另一側為陰極12，在陽極11與陰極12之間設置一透析膜2〇。在陽 極11處之半反應式為，氣根(cr)能與四甲基銨離子（ΤΜΑ+)分離而 成為氣氣或是鹽酸。四甲基銨離子(TMA+)帶正電，通過該透析膜2〇 往該陰極12移動。在陰極12處之半反應式為，四曱基銨離子(TMA+) 結合氫氧根（〇H_)而反應成氫氧化四甲基敍（TMAH)。因此 ，在此步 驟中，能高純度高百分比回收氫氧化四甲基銨。 最後’進行一濃度調配步驟，以使氫氧化四甲基銨之濃度調配在 2 wt%至 25 vn%之間。 因此本發明提供了一種由顯影廢液中完整回收氫氧化四曱基銨 的機制’具有高回收率與易於線上監控之功效。 下列附表為具體實施之結果 200921298 ΙΙΒέΛΟ /% ^ooz/SI/SJ-'SBPSXgAJaAS^J-'SBAVKVSHJO tessns +^^110-----0-3-3 svslAfter 200921298, an "electrolytic dialysis" step 4' is performed to separate the tetramethylammonium ion from the acid ion and convert it to tetramethylammonium hydroxide. In this experiment, we use a unit current of 10~30Amp/dm2. The reaction temperature is controlled at 20~6 (TC, the cell voltage is 5~20V, and the electrodialysis membrane can be selected with DupontNafion 424 dialysis membrane. In the present embodiment, the acid ion contains gas ions. The reaction mechanism of "electrolytic dialysis" can be: 2[TMA] + [C1]· + 2H20 2 [TMAH] + CI2 + H2, so that high-purity hydrogen can be obtained. Tetramethylammonium oxide (Tmah), detailed operation instructions can refer to Figure 3, the acid tetradecyl ammonium solution is placed in the electrolytic cell 1〇, one side is the anode π, the other side is the cathode 12, the anode 11 and A dialysis membrane 2 is disposed between the cathodes 12. The semi-reaction mode at the anode 11 is that the gas radicals (cr) can be separated from the tetramethylammonium ions (ΤΜΑ+) to become gas or hydrochloric acid. The ion (TMA+) is positively charged and moves through the dialysis membrane 2 to the cathode 12. The semi-reaction at the cathode 12 is that tetrakisyl ammonium ion (TMA+) is combined with hydroxide (〇H_) to form hydrogen. Tetramethyl sulphide (TMAH) is oxidized. Therefore, in this step, tetramethylammonium hydroxide can be recovered in high purity and high percentage. Thereafter, a concentration preparation step is carried out to adjust the concentration of tetramethylammonium hydroxide between 2 wt% and 25 vn%. Therefore, the present invention provides a complete recovery of tetradecylammonium hydroxide from the developing waste liquid. The mechanism 'has high recovery and easy on-line monitoring. The following schedule is the result of the implementation 200921298 ΙΙΒέΛΟ /% ^ooz/SI/SJ-'SBPSXgAJaAS^J-'SBAVKVSHJO tessns +^^110-----0 -3-3 svsl

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TMAH Waste TMAC1 After Desorption TMAH After Electrolysis ΤΜΑΗ (%) 0.29 TMACl 4.92 Ar (ppm) <0.30 <0.30 <0.30 A1 (ppm) <0.30 <0.30 <0.30 B (ppm) <0.30 <0.30 <0.30 Ba (ppm) <0.30 <0.30 <0.30 Bi (pnm) <0.30 <0.30 <0.30 Cd (ppm) <0.30 <0.30 <0.30 Co (ppm) <0.30 <0.30 <0 30 Cr (ppm) <0.30 <0.30 <〇 3〇 Cu (ppm) <0.30 <0.30 <〇 3〇 Fe (ppm) 1.16 <0.30 <〇^〇 Ga (ppm) <0.3 0 _ . <0.30 < 〇 Ί π In (ppm) <0.30 <0.30 ^ U . j U <〇 0 Λ Li (ppm) <0.3 0 <0.30 ^ u . j U Mg (ppm) <0.30 <0.30 ^U. J u Mn (ppm) <0.30 <0.3 0 — . 3 U Ni (ppm) <0.30 7.82 <U.30 Pb _ (PPm) __<0.30 <0.30 Sr T 1 (ppm) _ <0.30 —~--------- <0.30 -_ <0.30 <0.30 1 1 Zn (ppm) (ppm) <0.3 0 <0.30 __<0.3 0 ---- 0 S3 -_50.30 Ca (ppm) <0.30 ---<0.30 K 766.490 …<〇.3〇 -- ---<0.30 Na (ppm) <0.30 ----ί 兮· i 7 ---20.47 —_ —__ TMAH回收中樹脂吸附與AH % % % % 9 9 9 9 9 9 0.30 < 0.30 Ba (ppm) < 0.30 < 0.30 < 0.30 Bi (pnm) < 0.30 < 0.30 < 0.30 Cd (ppm) < 0.30 < 0.30 < 0.30 Co (ppm) < 0.30 <0.30 <0 30 Cr (ppm) <0.30 <0.30 <〇3〇Cu (ppm) <0.30 <0.30 <〇3〇Fe (ppm) 1.16 <0.30 <〇^〇 Ga (ppm) <0.3 0 _ . <0.30 < 〇Ί π In (ppm) <0.30 <0.30 ^ U . j U <〇0 Λ Li (ppm) <0.3 0 <0.30 ^ u . j U Mg (ppm) <0.30 <0.30 ^U. J u Mn (ppm) <0.30 <0.3 0 — . 3 U Ni (ppm) <0.30 7.82 <U.30 Pb _ ( PPm) __<0.30 <0.30 Sr T 1 (ppm) _ <0.30 —~--------- <0.30 -_ <0.30 <0.30 1 1 Zn (ppm) (ppm) <;0.3 0 <0.30 __<0.3 0 ---- 0 S3 -_50.30 Ca (ppm) <0.30 ---<0.30 K 766.490 ...<〇.3〇-- ---<0.30 Na (ppm) <0.30 ----ί 兮· i 7 ---20.47 —_ —__ Resin adsorption and recovery in TMAH recovery

電解後金屬離子含量 200921298 以上所述，僅是本發明的較佳實施例而已，並非對 本發明作任何形式上的限制，雖然本發明已以較佳實 施例揭露如上，然而並非用以限定本發明。任何熟悉 本項技術者，在不脫離本發明之技術範圍内，所作的 任何簡單修改、等效性變化與修飾，均仍屬於本發明 的技術範圍内。 【圖式簡單說明】 第1圖：依據本發明之一具體實施例，一種顯影廢液 ( ' 中回收氫氧化四曱基銨（TMAH)之方法之流 程圖。 第2圖：依據本發明之一具體實施例，一種TMAH廢 液之回收設備示意圖。 第3圖：依據本發明之一具體實施例，TMAH廢液之 回收過程中電解透析之示意圖。 【主要元件符號說明】The metal ion content after electrolysis 200921298 is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Although the present invention has been disclosed above in the preferred embodiments, it is not intended to limit the present invention. . Any simple modifications, equivalent changes, and modifications made by those skilled in the art without departing from the scope of the present invention are still within the technical scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a method for recovering waste tetrahydrocarbylammonium hydroxide (TMAH) in a developing waste liquid according to an embodiment of the present invention. FIG. 2: According to the present invention A specific embodiment, a schematic diagram of a recycling apparatus for TMAH waste liquid. Fig. 3 is a schematic diagram of electrolytic dialysis in the recovery process of TMAH waste liquid according to an embodiment of the present invention.

2 3 4 5 10 20 去光阻步驟 去離子步驟 再生步驟 電解透析步驟 濃度調配步驟 電解槽 1 1 陽極 12 陰極 透析膜 122 3 4 5 10 20 De-resistance step Deionization step Regeneration step Electrolysis dialysis step Concentration preparation step Electrolyzer 1 1 Anode 12 Cathode Dialysis membrane 12

Claims (1)

200921298 十、申請專利範圍： 一種顯影廢液中回收氫氧化四甲基銨（tmah)之方法， 至少包含以下步驟：200921298 X. Patent application scope: A method for recovering tetramethylammonium hydroxide (tmah) from a developing waste liquid, comprising at least the following steps: 進行一去光阻步驟， 其中該顯影廢液内含 進行一去離子步驟， 廢液内之四甲基銨離 分離； 以去除一顯影廢液内之殘留光阻， 四甲基銨離子（Τμα+；); 其係利用固態吸附方式抽取該顯影 子’而與内含金屬離子之顯影廢液 、仃再生步驟’以使四甲基銨離子與固態吸附劑分離; t行一電解透析步驟，以使四甲基錄離子與酸根離子分 離而轉化成氫氧化四甲基銨；以及 進行一〉展度調配步驟，以伟S 使虱虱化四曱基銨之濃度調配 在2 wt%至25 wt%之間。 2Performing a photoresist removal step, wherein the developing waste liquid contains a deionization step, and the tetramethylammonium in the waste liquid is separated; to remove residual photoresist in the developing waste liquid, tetramethylammonium ion (Τμα) +;); it uses the solid state adsorption method to extract the developer 'and the development waste liquid containing metal ions, the regeneration step 'to separate the tetramethylammonium ion from the solid adsorbent; t to an electrolytic dialysis step, In order to separate the tetramethylated ion from the acid ion and convert it into tetramethylammonium hydroxide; and perform a dispersion preparation step, the concentration of the tetradecyl ammonium is adjusted to 2 wt% to 25 Between wt%. 2 如申請專利範圍第 甲基銨之方法，其 如申請專利範圍第 甲基銨之方法，其 式。 1項所述之顯影廢液中回收氫氧化四 中上述去離子步驟係包含離子交換。 1項所述之顯影廢液中回收氫氧化四 中上述去離子步騍係採用流體化床方 4、如申請專利範圍帛1項所述之顯影廢: 甲基銨之方法，其t該固態吸附劑係Z 或有機碳。 中回收氫氧化四 陽離子交換樹脂 5、 如申請專利範圍第 甲基銨之方法，其 6、 如申請專利範圍第 液中回收氫氧化 係包含酸鹼中和 1項所述之顯影廢 中上述去光阻步驟 1或5項所述之顯 四 影廢液中回收氫氧 13 200921298 : = 其中該酸根離子係包含氯離子。 甲基銨之方法，盖1項所述之顯影廢液中回收氫氧化四 ,φ ^ '、 述去光阻步驟係包含奈米臈過濾。 如申印專利範圍第1項所述 < 員景y廢液中回收氫氧化四 甲基錢之方法，装Φ方μ、+，$ f 具中在上4再生步驟中係添加鹽酸 (HC1)，而使固態吸附劑再生。 9、如申請專利議Μ所述之顯影廢液中回收氫氧化四 甲基錢之方法’其巾上述電解透析步驟巾係使用隔膜式 電解槽’工作單位電流量為10〜30Amp/dm2，電解 反應溫度控制於20〜60。C中，電解槽電壓為5〜2〇v。 1 0、如申請專利範圍第9項所述之顯影廢液中回收氫氧化 四曱基銨之方法，其中該電解透析膜係使用Dup〇nt NaHon 424的透析膜。 14For example, the method of applying the patent range of methylammonium, such as the method of applying for the patent range of methylammonium, is as follows. The above-mentioned deionization step in the development waste liquid described in the above item 1 contains ion exchange. The above-mentioned deionized step of recovering the above-mentioned deionized step in the developing waste liquid of the above-mentioned one is a fluidized bed 4, and the method of developing waste as described in the scope of claim 1 of the invention: methylammonium, which is the solid state The adsorbent is Z or organic carbon. Recovering the tetracationic exchange resin of the hydrogen peroxide 5, as in the method of applying the methyl ammonium salt of the patent range, 6. The recovery of the hydrogen hydroxide system in the first liquid of the patent application range includes the above-mentioned development waste of the acid base and the neutralization Recovery of hydrogen and oxygen in the four-shadow waste liquid described in the resisting step 1 or 5 200921298 : = wherein the acid ion system contains chloride ions. In the method of methylammonium, the hydrogen hydride is recovered from the developing waste liquid described in the above item 1, φ^', and the step of removing the photoresist comprises nanofiltration. For example, in the method of claim 1, the method for recovering tetramethylammonium hydroxide from the waste liquid of the member, the Φ square μ, +, $ f is added to the upper 4 regeneration step to add hydrochloric acid (HC1). ), while the solid adsorbent is regenerated. 9. A method for recovering tetramethylammonium hydroxide from a developing waste liquid as described in the patent application. The above-mentioned electrolytic dialysis step towel uses a diaphragm type electrolytic cell to have a working current of 10 to 30 Amp/dm2, and electrolysis. The reaction temperature is controlled at 20 to 60. In C, the cell voltage is 5 to 2 〇v. A method for recovering tetramethylammonium hydroxide in a developing waste liquid according to claim 9, wherein the electrolytic dialysis membrane is a dialysis membrane of Dup〇nt NaHon 424. 14