TWI607987B - Method for recycling tetramethylammonium hydroxide (tmah) from the secondary waste developer - Google Patents
Method for recycling tetramethylammonium hydroxide (tmah) from the secondary waste developer Download PDFInfo
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本發明是有關於一種顯影廢液的回收技術，特別是指一種顯影廢液之二次廢液中氫氧化四甲基銨的回收方法。 The invention relates to a recycling technology for developing waste liquid, in particular to a method for recovering tetramethylammonium hydroxide in a secondary waste liquid for developing waste liquid.
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。以目前而，以氫氧化四甲基銨(TMAH)溶液為主要之顯影劑來源。 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. At present, tetramethylammonium hydroxide (TMAH) solution is the main source of developer.
使用過的顯影劑除了原本的顯影劑成分之外，還會有被溶解的光阻、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。 Used developers in addition to the original developer component, there are dissolved photoresist, metal ions (such as sodium, iron and aluminum ions, etc.), inorganic anions, organic anions, surface active substances, and suspension. Particles and so on.
在台灣公告第575796號「氫氧化四甲基銨顯影液的回收系統及其方法」、第I366076「顯影廢液中回收氫氧化四甲基銨之方法」，以及公開第200615238號「顯影廢液的處理方法」等案件內，皆已揭露顯影廢液的回收處理方式。以第I366076「顯影廢液中回收氫氧化四甲基銨之方法」為例，其去光阻的方式是以奈米膜進行過濾，然而，當顯影廢液以該奈米膜進行過濾之後所產生之二次廢液，除了含有較高濃度的廢光阻之外，同時也含有氫氧化四甲基銨，其含量與原顯影廢液中的氫氧化四甲基銨相比，將近有5-20%。若將該二次廢液排入廢水處理系統中，除了造成回收率的降低之外，也衍生出廢水處理系統仍須 具有處理少量氫氧化四甲基銨之能力的問題。 In Taiwan, No. 575796 "Recovery system and method for developing tetramethylammonium hydroxide solution", No. I366076 "Method for recovering tetramethylammonium hydroxide from developing waste liquid", and Publication No. 200615238 "Developing waste liquid In the cases such as the "treatment method", the recycling treatment method of the development waste liquid has been disclosed. For example, in the case of the method of recovering tetramethylammonium hydroxide in the developing waste liquid, the method of removing the photoresist is filtered by a nano film, however, after the developing waste liquid is filtered by the nano film. The secondary waste liquid produced, in addition to containing a relatively high concentration of waste photoresist, also contains tetramethylammonium hydroxide, the content of which is close to that of tetramethylammonium hydroxide in the original developing waste liquid. -20%. If the secondary waste liquid is discharged into the wastewater treatment system, in addition to causing a decrease in recovery rate, the wastewater treatment system is still required to be derived. It has the problem of the ability to handle a small amount of tetramethylammonium hydroxide.
一般而言，因奈米膜過濾顯影廢液時所排出的顯影廢液，也就是二次廢液，該二次廢液中仍含有氫氧化四甲基銨，但是廢光阻的濃度會是原顯影廢液的5-20倍，因此不易將氫氧化四甲基銨回收。 In general, the developing waste liquid discharged by the nano membrane is used to filter the developing waste liquid, that is, the secondary waste liquid, and the secondary waste liquid still contains tetramethylammonium hydroxide, but the concentration of the waste photoresist is The original developing waste liquid is 5-20 times, so it is difficult to recover tetramethylammonium hydroxide.
因此，本發明之一目的，即在提供一種可以克服前述問題的顯影廢液之二次廢液中氫氧化四甲基銨的回收方法。 Accordingly, it is an object of the present invention to provide a method for recovering tetramethylammonium hydroxide in a secondary waste liquid of a developing waste liquid which can overcome the aforementioned problems.
該回收方法至少包含以下步驟：一收集步驟、一第一調整步驟、一過濾步驟、一純化步驟，及一電解透析步驟。該收集步驟是收集一顯影廢液進行氫氧化四甲基銨回收後所產生的二次廢液。該第一調整步驟是以酸液調整該二次廢液的酸鹼值，使其pH值≦7，而使該二次廢液中的氫氧化四甲基銨離子與酸液形成四甲基銨鹽水溶液，並使得廢光阻不溶於該二次廢液中。該過濾步驟是將調整過酸鹼值的該二次廢液進行過濾，以過濾出不溶於該二次廢液之廢光阻，而得到一不含有廢光阻的四甲基銨鹽水溶液。該純化步驟是以一樹脂塔純化該四甲基銨鹽水溶液中所含有的金屬離子，而得到一不含有金屬離子的四甲基銨鹽水溶液。該電解透析步驟是使不含有金屬離子的該四甲基銨鹽水溶液中的四甲基銨離子與相對離子分離而轉化成氫氧化四甲基銨，而得到一氫氧化四甲基銨水溶液。該濃度調配步驟是使該氫氧化四甲基銨水溶液之濃度在2wt%至25wt%之間。 The recovery method comprises at least the following steps: a collecting step, a first adjusting step, a filtering step, a purifying step, and an electrolytic dialysis step. The collecting step is to collect a secondary waste liquid generated after the development waste liquid is recovered by tetramethylammonium hydroxide. The first adjusting step is to adjust the pH value of the secondary waste liquid to a pH value of ≦7, so that the tetramethylammonium hydroxide ion in the secondary waste liquid forms a tetramethyl group with the acid liquid. An aqueous ammonium salt solution, and the waste photoresist is insoluble in the secondary waste liquid. The filtering step is to filter the secondary waste liquid adjusted for pH value to filter out the waste photoresist which is insoluble in the secondary waste liquid, thereby obtaining an aqueous solution of tetramethylammonium salt which does not contain waste photoresist. In the purification step, the metal ions contained in the aqueous solution of the tetramethylammonium salt are purified by a resin column to obtain a tetramethylammonium salt aqueous solution containing no metal ions. In the electrolytic dialysis step, tetramethylammonium ions in the aqueous solution of the tetramethylammonium salt containing no metal ions are separated from the relative ions to be converted into tetramethylammonium hydroxide to obtain a tetramethylammonium hydroxide aqueous solution. The concentration blending step is such that the concentration of the aqueous solution of tetramethylammonium hydroxide is between 2% and 25% by weight.
本發明的另一技術手段，是在於上述之回收方法還包含一接續該過濾步驟之後的第二調整步驟，是以鹼液調整該四甲基銨鹽水溶液的酸鹼值，使其pH值≧6。 Another technical means of the present invention is that the recovery method further comprises a second adjusting step after the filtering step, wherein the pH value of the tetramethylammonium salt aqueous solution is adjusted by an alkali solution to have a pH value of ≧ 6.
本發明的又一技術手段，是在於上述之回收方法還包含一在該純化步驟之前或之後的蒸餾步驟，是以減壓蒸餾的方式將四甲基銨鹽水溶液之水分去除，得到濃度較高的四甲基銨鹽水溶液。 Another technical means of the present invention is that the recovery method further comprises a distillation step before or after the purification step, and the water of the tetramethylammonium salt aqueous solution is removed by distillation under reduced pressure to obtain a higher concentration. An aqueous solution of tetramethylammonium salt.
本發明的再一技術手段，是在於該酸液是鹽酸、硫酸、硝酸、甲酸、醋酸、磷酸、碳酸之一或其組合。 A further technical means of the present invention is that the acid solution is one of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, phosphoric acid, carbonic acid or a combination thereof.
本發明的另一技術手段，是在於該過濾步驟是以一過濾器進行過濾，該過濾器是由傳統濾心式過濾器、燭台式過濾器、離心式過濾器，或具有括勺功能的薄膜式過濾器中擇一。 Another technical means of the present invention is that the filtering step is to filter by a filter which is a conventional filter filter, a candle filter, a centrifugal filter, or a film having a scoop function. Choose one of the filters.
本發明的又一技術手段，是在於該純化步驟的樹脂塔是由磺酸型的強陽性樹脂、羧酸型的弱陽性樹脂，或是硝酸型樹脂中擇一或其組合。 According to still another aspect of the present invention, the resin column of the purification step is a strong positive resin of a sulfonic acid type, a weakly positive resin of a carboxylic acid type, or a combination of a nitrate type resin or a combination thereof.
本發明的再一技術手段，是在於該鹼液是無機鹼，並選自於氫氧化鈉、氫氧化鉀、氫氧化鋰等，或氫氧化銨及氫氧化四級銨溶液之一或其組合。 A further technical means of the present invention is that the alkali liquid is an inorganic base and is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide or the like, or one of ammonium hydroxide and a quaternary ammonium hydroxide solution or a combination thereof. .
本發明的另一技術手段，是在於該第一調整步驟是以酸液調整該二次廢液的酸鹼值，使其pH值<6。 Another technical means of the present invention is that the first adjusting step adjusts the pH value of the secondary waste liquid with an acid solution to have a pH value of <6.
本發明的又一技術手段，是在於上述之該電解透析步驟中是使用隔膜式電解槽，工作單位電流量為10~30Amp/dm2，電解反應溫度控制於20~60℃中，電解槽電壓為5~20V。 Another technical means of the present invention is that in the electrolytic dialysis step, a diaphragm type electrolytic cell is used, and the working unit current amount is 10 to 30 Amp/dm 2 , and the electrolytic reaction temperature is controlled at 20 to 60 ° C, and the electrolytic cell voltage is It is 5~20V.
本發明的再一技術手段，是在於該隔膜式電解槽之電解透析膜是使用陽離子交換膜。 Still another technical means of the present invention is that the electrolytic dialysis membrane of the diaphragm type electrolytic cell uses a cation exchange membrane.
本發明之有益功效在於，藉由前述步驟降低該二次廢液中的廢光阻，而能提高該二次廢液中氫氧化四甲基銨的回收率。 The beneficial effect of the present invention is that the waste light resistance in the secondary waste liquid can be reduced by the foregoing steps, and the recovery rate of tetramethylammonium hydroxide in the secondary waste liquid can be improved.
21‧‧‧收集步驟 21‧‧‧Collection steps
22‧‧‧第一調整步驟 22‧‧‧First adjustment steps
23‧‧‧過濾步驟 23‧‧‧Filter step
24‧‧‧第二調整步驟 24‧‧‧Second adjustment steps
25‧‧‧純化步驟 25‧‧‧Purification step
26‧‧‧蒸餾步驟 26‧‧‧Distillation step
27‧‧‧電解透析步驟 27‧‧‧Electrolysis step
28‧‧‧濃度調配步驟 28‧‧‧Concentration deployment steps
31‧‧‧容器 31‧‧‧ Container
32‧‧‧奈米膜 32‧‧‧Nano film
33‧‧‧過濾器 33‧‧‧Filter
34‧‧‧樹脂塔 34‧‧‧ resin tower
35‧‧‧減壓蒸餾器 35‧‧‧Reduced distillation distiller
4‧‧‧隔膜式電解槽 4‧‧‧Separate electrolytic cell
41‧‧‧電解透析膜 41‧‧‧ electrolytic dialysis membrane
42‧‧‧陽極 42‧‧‧Anode
43‧‧‧陰極 43‧‧‧ cathode
A‧‧‧酸液 A‧‧‧Acid
B‧‧‧廢光阻 B‧‧‧Waste light resistance
C‧‧‧鹼液 C‧‧‧ lye
D‧‧‧水蒸氣 D‧‧‧Water Vapor
E‧‧‧四甲基銨鹽水溶液 E‧‧‧Tetramethylammonium salt aqueous solution
圖1是一流程圖，說明本發明顯影廢液之二次廢液中氫氧化四甲基銨的回收方法的一實施例；圖2是一示意圖，輔助說明圖1；圖3是一示意圖，說明一純化步驟與一蒸餾步驟之順序可以互換；及圖4是一示意圖，輔助說明電解透析之反應。 1 is a flow chart showing an embodiment of a method for recovering tetramethylammonium hydroxide in a secondary waste liquid of the developing waste liquid of the present invention; FIG. 2 is a schematic view, and FIG. It is indicated that the order of a purification step and a distillation step are interchangeable; and FIG. 4 is a schematic diagram illustrating the reaction of electrolytic dialysis.
有關本發明之相關申請專利特色與技術內容，在以下配合參考圖式之一個較佳實施例的詳細說明中，將可清楚的呈現。在進行詳細說明前應注意的是，類似的元件是以相同的編號來作表示。 The details of the related patents and the technical contents of the present invention will be apparent from the following detailed description of a preferred embodiment of the drawings. It should be noted that, before the detailed description, similar elements are denoted by the same reference numerals.
參閱圖1及圖2，為本發明顯影廢液之二次廢液中氫氧化四甲基銨的回收方法的實施例，其包含一收集步驟21、一第一調整步驟22、一過濾步驟23、一第二調整步驟24、一純化步驟25、一蒸餾步驟26、一電解透析步驟27，及一濃度調配步驟28。 Referring to FIG. 1 and FIG. 2, an embodiment of a method for recovering tetramethylammonium hydroxide in a secondary waste liquid of a developing waste liquid of the present invention comprises a collecting step 21, a first adjusting step 22, and a filtering step 23. A second adjustment step 24, a purification step 25, a distillation step 26, an electrolytic dialysis step 27, and a concentration preparation step 28.
要特別說明的是，本發明主要是要針對二次廢液進行氫氧化四甲基銨的回收，因此，該收集步驟21是以一容器31收集一顯影廢液進行氫氧化四甲基銨回收後所產生的二次廢液。於本實施例中，該二次廢液是以一奈米膜32過濾顯影廢液所排出的含有較高濃度廢光阻的顯影廢液。 It should be particularly noted that the present invention mainly relates to the recovery of tetramethylammonium hydroxide from the secondary waste liquid. Therefore, the collecting step 21 collects a developing waste liquid in a container 31 for tetramethylammonium hydroxide recovery. The secondary waste liquid produced afterwards. In the embodiment, the secondary waste liquid is a development waste liquid containing a higher concentration of waste photoresist discharged by filtering the development waste liquid by the one-tone film 32.
該第一調整步驟22是將酸液A加入該容器31中調整該二次廢液的酸鹼值，使其pH值≦7。於本實施例中，該酸液A是選自於鹽酸、硫酸、硝酸、甲酸、醋酸、磷酸、醋酸、碳酸之一或其組合。經由該第一調整步驟22之後，可以使得該二次廢液中的氫氧化四甲基銨離子與酸液A形成四甲基銨鹽水溶液，並使得廢 光阻B不溶於該二次廢液中。 The first adjusting step 22 is to add the acid solution A to the container 31 to adjust the pH value of the secondary waste liquid to have a pH of ≦7. In the present embodiment, the acid solution A is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, phosphoric acid, acetic acid, carbonic acid, or a combination thereof. After the first adjusting step 22, the tetramethylammonium hydroxide ion in the secondary waste liquid and the acid liquid A can be formed into an aqueous solution of tetramethylammonium salt, and waste Photoresist B is insoluble in the secondary waste liquid.
該過濾步驟23是將調整過酸鹼值的該二次廢液進行過濾，以過濾出不溶於該二次廢液之廢光阻，而得到一不含有廢光阻B的四甲基銨鹽水溶液。於本實施例中，該過濾步驟是以一過濾器33進行過濾，該過濾器33是由傳統濾心式過濾器(Cartridge Filter)、具有自動或手動逆洗與逆吹功能的燭台式過濾器(Candle Filter)、離心式過濾器，或具有括勺功能的薄膜式過濾器中擇一。 The filtering step 23 is to filter the secondary waste liquid adjusted to have a pH value to filter out the waste photoresist which is insoluble in the secondary waste liquid, thereby obtaining a tetramethylammonium salt not containing the waste photoresist B. Aqueous solution. In the present embodiment, the filtering step is filtered by a filter 33 which is a candle-top filter with a manual or manual backwashing and backflushing function by a conventional Cartridge Filter. (Candle Filter), centrifugal filter, or membrane filter with scoop function.
第二調整步驟24是以鹼液C調整該四甲基銨鹽水溶液的酸鹼值，使其pH值≧6。於本實施例中，該鹼液C是選自無機鹼，並選自於於氫氧化鈉、氫氧化鉀、氫氧化鋰等，或氫氧化銨及氫氧化四級銨溶液之一或其組合。其中，氫氧化四級銨溶液可以是例如：氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨。 In the second adjusting step 24, the pH value of the aqueous solution of the tetramethylammonium salt is adjusted by the alkali liquid C to have a pH of ≧6. In the present embodiment, the lye C is selected from the group consisting of inorganic bases, and is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, or the like, or one of ammonium hydroxide and quaternary ammonium hydroxide solution or a combination thereof. . The quaternary ammonium hydroxide solution may be, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide.
該純化步驟25是以一樹脂塔34純化該四甲基銨鹽水溶液中所含有的金屬離子，而得到一不含有金屬離子的四甲基銨鹽水溶液。於本實施例中，該樹脂塔34是由磺酸型的強陽性樹脂、羧酸型的弱陽性樹脂，或是硝酸型樹脂中擇一或其組合。透過該第二調整步驟來調整該四甲基銨鹽水溶液的酸鹼值，可以讓樹脂塔34有較佳的去除金屬離子的效果，進而提高該純化步驟25之效率。 In the purification step 25, the metal ions contained in the aqueous solution of the tetramethylammonium salt are purified by a resin column 34 to obtain a tetramethylammonium salt aqueous solution containing no metal ions. In the present embodiment, the resin column 34 is selected from a strong positive resin of a sulfonic acid type, a weakly positive resin of a carboxylic acid type, or a combination of a nitric acid type resin. By adjusting the pH value of the tetramethylammonium salt aqueous solution through the second adjustment step, the resin column 34 can have a better effect of removing metal ions, thereby improving the efficiency of the purification step 25.
該蒸餾步驟26是以一減壓蒸餾器35透過減壓蒸餾的方式將四甲基銨鹽水溶液之水分去除(形成水蒸氣D)，得到濃度較高的四甲基銨鹽水溶液E。 This distillation step 26 removes the water of the tetramethylammonium salt aqueous solution (forming water vapor D) by a vacuum distillation apparatus 35 by vacuum distillation to obtain a tetramethylammonium salt aqueous solution E having a relatively high concentration.
要特別說明的是，於圖2中，是先進行該純化步驟25，再進行該蒸餾步驟26。於實際實施時，也可以是如圖3所示，先進行該蒸餾步驟26，再進行該純化步驟25。 It is to be noted that, in Fig. 2, the purification step 25 is carried out first, and the distillation step 26 is carried out. In actual implementation, as shown in FIG. 3, the distillation step 26 may be performed first, and then the purification step 25 may be performed.
參閱圖4並配合圖1，該電解透析步驟27是使不含有金屬離子的該四甲基銨鹽水溶液中的四甲基銨離子與相對離子分離而轉化成氫氧化四甲基銨，而得到一氫氧化四甲基銨水溶液。於本實施例中，該電解透析步驟27中是使用隔膜式電解槽4，且該隔膜式電解槽4之電解透析膜41是使用陽離子交換膜。在以下之實驗例中，該隔膜式電解槽4之工作單位電流量為10~30Amp/dm2，電解反應溫度控制於20~60℃中，電解槽電壓為5~20V。其中，電解透析之反應機構可為：2[TMA]+[Cl]-+2H2O → 2[TMAH]+Cl2↑+H2↑ Referring to FIG. 4 and FIG. 1 , the electrolytic dialysis step 27 is carried out by separating tetramethylammonium ions in the tetramethylammonium salt aqueous solution containing no metal ions from relative ions and converting them into tetramethylammonium hydroxide. An aqueous solution of tetramethylammonium hydroxide. In the present embodiment, the electrolytic cell 4 is used in the electrolytic dialysis step 27, and the electrolytic dialysis membrane 41 of the diaphragm type electrolytic cell 4 is a cation exchange membrane. In the following experimental examples, the working current of the diaphragm type electrolytic cell 4 is 10 to 30 Amp/dm 2 , the electrolytic reaction temperature is controlled at 20 to 60 ° C, and the electrolytic cell voltage is 5 to 20 V. The reaction mechanism of electrolytic dialysis may be: 2[TMA] + [Cl] - +2H 2 O → 2[TMAH]+Cl 2 ↑+H 2 ↑
因此可得到高純度的氫氧化四甲基銨(TMAH)，詳細的操作說明可參考圖4，四甲基銨鹽溶液置於該隔膜式電解槽4內，該電解透析膜41的兩側設置有一陽極42及一陰極43。在陽極42處之半反應式為：氯根(Cl-)能與四甲基銨離子分離而成為氯氣或是鹽酸。四甲基銨離子(TMA+)帶正電，通過該電解透析膜41往該陰極43移動。在陰極43處之半反應式為：四甲基銨離子(TMA+)結合氫氧根(OH-)成氫氧化四甲基銨(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。 Therefore, high-purity tetramethylammonium hydroxide (TMAH) can be obtained. For detailed operation, refer to FIG. 4. A tetramethylammonium salt solution is placed in the diaphragm type electrolytic cell 4, and both sides of the electrolytic dialysis membrane 41 are disposed. There is an anode 42 and a cathode 43. The semi-reaction formula at the anode 42 is that chloride (Cl - ) can be separated from tetramethylammonium ions to become chlorine or hydrochloric acid. Tetramethylammonium ion (TMA + ) is positively charged, and moves through the electrolytic dialysis membrane 41 to the cathode 43. The half reaction formula at the cathode 43 is: tetramethylammonium ion (TMA + ) combined with hydroxide (OH - ) to tetramethylammonium hydroxide (TMAH). Therefore, in this step, tetramethylammonium hydroxide can be recovered in a high purity and a high percentage.
該濃度調配步驟28是使該氫氧化四甲基銨水溶液之濃度在2wt%至25wt%之間。前述濃度的調整可使該氫氧化四甲基銨水溶液直接作為顯影劑使用。 The concentration blending step 28 is such that the concentration of the aqueous solution of tetramethylammonium hydroxide is between 2% and 25% by weight. The above concentration adjustment allows the aqueous tetramethylammonium hydroxide solution to be used directly as a developer.
以下敘述為各實驗例及其具體實施結果： The following is a description of each experimental example and its specific implementation results:
實驗例一： Experimental example 1:
取二次廢液4L，其內TMAH 0.515%，廢光阻為0.415%，以2N硫酸中和至pH=3，再以20μm濾膜過濾，得到一澄清之四甲基銨鹽水溶液4.12L，其內四甲基銨離子(TMA+)濃度為0.402%，廢光阻檢測為<100ppm，換算成TMAH回收率為98.83%。 Take 4L of secondary waste liquid, which has TMAH 0.515%, waste photoresist is 0.415%, neutralize with 2N sulfuric acid to pH=3, and then filter with 20μm filter to obtain 4.21L of clear tetramethylammonium salt solution. The concentration of tetramethylammonium ion (TMA + ) was 0.402%, the waste photoresist was <100 ppm, and the recovery rate of TMAH was 98.83%.
實驗例二： Experimental example 2:
取二次廢液2.5L，其內TMAH 1.578%，廢光阻為1.236%，以2N硫酸中和至pH=5，再以5μm濾膜過濾，得到一澄清之四甲基銨鹽水溶液2.71L，其內四甲基銨離子(TMA+)濃度為1.168%，廢光阻檢測為<100ppm，換算成TMAH回收率為98.73%。 Take 2.5L of secondary waste liquid, which has TMAH 1.578%, waste photoresist is 1.236%, neutralize with 2N sulfuric acid to pH=5, and then filter with 5μm filter to obtain 2.71L of clear tetramethylammonium salt solution. The concentration of tetramethylammonium ion (TMA + ) was 1.168%, the detection of waste photoresist was <100ppm, and the recovery rate of TMAH was 98.73%.
實驗例三： Experimental example three:
取二次廢液8L，其內TMAH 2.148%，廢光阻為2.456%，以4N鹽酸中和至pH=1，再以10μm濾膜過濾，得到一澄清之四甲基銨鹽水溶液9.38L，其內四甲基銨離子(TMA+)濃度為1.482%，廢光阻檢測為<100ppm，換算成TMAH回收率為99.49%。 Take 8L of secondary waste liquid, which has TMAH 2.148%, waste photoresist is 2.456%, neutralize with 4N hydrochloric acid to pH=1, and then filter with 10μm filter to obtain 9.38L of clear tetramethylammonium salt solution. The concentration of tetramethylammonium ion (TMA + ) was 1.482%, the waste photoresist was <100 ppm, and the recovery rate of TMAH was 99.49%.
綜上所述，本發明顯影廢液之二次廢液中氫氧化四甲基銨的回收方法，先將二次廢液中的廢光阻去除，並以蒸餾的方式提高四甲基銨鹽水溶液的濃度，以提高二次廢液中氫氧化四甲基銨的回收率，故確實可以達成本發明之目的。 In summary, the method for recovering tetramethylammonium hydroxide in the secondary waste liquid of the developing waste liquid of the present invention first removes the waste photoresist in the secondary waste liquid, and increases the tetramethylammonium salt by distillation. The concentration of the aqueous solution is such as to increase the recovery rate of tetramethylammonium hydroxide in the secondary waste liquid, so that the object of the present invention can be achieved.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。 The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.
21‧‧‧收集步驟 21‧‧‧Collection steps
22‧‧‧第一調整步驟 22‧‧‧First adjustment steps
23‧‧‧過濾步驟 23‧‧‧Filter step
24‧‧‧第二調整步驟 24‧‧‧Second adjustment steps
25‧‧‧純化步驟 25‧‧‧Purification step
26‧‧‧蒸餾步驟 26‧‧‧Distillation step
27‧‧‧電解透析步驟 27‧‧‧Electrolysis step
28‧‧‧濃度調配步驟 28‧‧‧Concentration deployment steps
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Citations (3)
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|---|---|---|---|---|
| TW374868B (en) * | 1996-11-21 | 1999-11-21 | Organo Corp | Process for rejuvenation treatment of photoresist development waste |
| TWI366076B (en) * | 2007-11-09 | 2012-06-11 | San Fu Chemical Co Ltd | Method for recycling tetramethylammonium hydroxide (tmah) from waste developer |
| TW201247293A (en) * | 2011-05-27 | 2012-12-01 | Chang Chun Petrochemical Co Ltd | Process for recovering and purifying tetraalkyl ammonium hydroxide from waste solution containing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW374868B (en) * | 1996-11-21 | 1999-11-21 | Organo Corp | Process for rejuvenation treatment of photoresist development waste |
| TWI366076B (en) * | 2007-11-09 | 2012-06-11 | San Fu Chemical Co Ltd | Method for recycling tetramethylammonium hydroxide (tmah) from waste developer |
| TW201247293A (en) * | 2011-05-27 | 2012-12-01 | Chang Chun Petrochemical Co Ltd | Process for recovering and purifying tetraalkyl ammonium hydroxide from waste solution containing the same |
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