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 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. ,

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.

The reaction mechanism of regeneration can be:

After 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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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

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 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 X. Patent application scope: A method for recovering tetramethylammonium hydroxide (tmah) from a developing waste liquid, comprising at least the following steps: Performing 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 For 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