TW200827944A - Method of neutralizing developer waste liquid containing tetraalkylammonium hydroxide - Google Patents

Abstract

A method of neutralizing a developer waste liquid containing a tetraalkylammonium hydroxide wherein an organic matter derived from photoresist is dissolved through reaction with carbon dioxide gas, in which clogging by intra-column resist precipitation at neutralization can be effectively prevented and in which resist precipitated at neutralization ensures a high filterability and can be effectively removed. The method of neutralizing a developer waste liquid containing a tetraalkylammonium hydroxide comprises adding carbon dioxide gas to a developer waste liquid containing tetraalkylammonium hydroxide of 13 or higher pH value in which an organic matter derived from photoresist is dissolved to thereby carry out neutralization to a pH value of 11.5 or below, wherein the rate of carbon dioxide gas added from the time at which the pH of the developer waste liquid is 13 to the time at which the pH reaches 12 is 0.15 L/hr or less per mol of tetraalkylammonium hydroxide contained in the developer waste liquid at the time of pH 13.

Description

200827944 IX. Description of the Invention: [Technical Field] The present invention relates to a solution containing a tetraalkylammonium hydroxide (hereinafter abbreviated as TAAH) as a photoresist, which is dissolved from a photoresist. A biological waste (hereinafter referred to as an organic substance derived from a resist), a development waste liquid containing TAAH, a neutralization method neutralized by carbonic acid gas, and a deuterium, which is a development waste liquid containing TAAH. During neutralization, it prevents the precipitation of the residual agent in the end of the column, and the anti-catalytic agent precipitated during neutralization has high filterability, so that the resist contained in the developing waste liquid can be effectively removed. And method. [Prior Art] (4) Conductor. The liquid crystal manufacturing step is formed on a substrate such as a wafer or a glass, and a negative film or a positive film is applied to a metal layer formed on the surface of the substrate, and the photomask for forming the pattern is exposed. After the unhardened and hardened portion is developed (four), the material is processed to form a pattern on the layer. With the semiconductor rhyme in the process of 卞 阿 阿 阿 阿 阿 阿 阿 阿 阿 阿 阿 阿 阿 阿 阿 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于 用于Therefore, in the lithography step, the TAAH of the lye of the genus of the genus is the main component, especially in recent years, with the discharge amount of the liquid of the semiconductor. Η之纟, 衫衫废 Until now, the above-mentioned TAAH-containing developing waste liquid is by conventional row

2030-9240-PF 5 200827944 The water treatment is harmless and discarded. For the purpose of efficient use of resources, it is possible to recover TAAH from the above-mentioned waste liquid and purify the regeneration method using ταμ. For example, the proposal includes: a concentrated aqueous solution of cerium that is concentrated at a concentration of TAAH and used in an amount of 1% by mass or more, and is neutralized by a hydrazine of a carbonic acid gas or the like until the pH of the aqueous solution becomes 10 or less, so that it is derived from the resist "" a step of separating and extracting the material; a separation step of separating the organic substances of the anti-caries agent from the neutralization step; and a method of electrolyzing the A TAAH by the liquid in the separation step ( Referring to the patent literature, in the development waste liquid containing TAAH in carbonic acid gas, the reaction of 7, the formation of ΤΑΑίί carbonate, and the heavy carbon brewing salt 'reducing the ratio of τααη dissolved from the organic substance of the anti-surname agent Then, since the solubility of the organic substance derived from the anti-money agent in the developing waste liquid is low, and the organic substance derived from the anti-money agent is precipitated, it can be removed by filtration or the like.

_ 2TAAH + C〇2 (TAA)2C〇3 (Formula D (taa)2c〇3 + H2〇+ c〇2 Today 2 (TAA) HC〇3 (Formula 2) The above-mentioned regeneration method can be used for the main impurity Mussels are organic substances from the resist, which are removed by simple operation such as filtration. Especially when the carbonic acid gas is used as the acid for neutralization, the metal ion towers in the temple is a problem in the + conductor manufacturing step. Since the mixing of the impurities is small, it is necessary to carry out a regeneration method of the development waste liquid containing ΊΑΑ] which is industrially advantageous. Patent Document: Patent No. 3110513 No. 2030-9240-PF 6 200827944 [Summary of the Invention] The problem], acid gas == 吏 impurities come from the organic matter, the carbon body is blown into the developing waste liquid of the second and second steps, the adhesion of the carbonic acid organic substance is ancient, #from the resist It will be attached to the inner wall of the reaction tank or the official line connected to it, and the organic matter of the agent will be smashed: sub:: Because the above precipitation comes from the resistance difference, there is a drop::: The ":" is based on the fact that the removal step is very toxic, so the problem is. TAAH is a strong and fat question: dangerous, plugged in the pipeline of the coffee ^ [means to solve the problem] 0 ^ ^ Ming, in order to achieve the above objectives, repeatedly researched "scientific, found by dissolution From the "developing waste liquid" of the developing waste liquid containing the tetra-(di)ammonium of the organic matter of the above-mentioned "preparation of the organic matter of the ut", ", and the fruit material (4), the addition of the organic matter of the carbonic acid gas After two m, neutralize to. When h reaches near u·5, most of it is finished. H is the precipitation of the organic matter of the song. The area at the point of the above-mentioned development waste % point to the time of reaching 12 is particularly remarkable. The carbonic acid gas in the region is added to the above-mentioned developing waste liquid, and is added to the η]3 tetraalkylammonium per lm, which is a pinched floc in the Q liquid, which is available. From 丄 =:, the organic matter that can form granules is extremely highly filterable. Further, in this operation, since the organic substance derived from the anti-money agent is precipitated in the state of near recrystallization of 2030-9240-PF 7 200827944, it is confirmed that the removal efficiency of the organic substance is high. And the stunned is that the above analysis is found to have a low viscosity, which can prevent the piping from being plugged up to the completion of the date. There is a method for neutralization of a developing waste liquid containing tetraammonium hydride (4), which is prepared by adding a carbonic acid to a substance containing a substance derived from a photoresist. The neutralization of the gas to the pH is as follows: the amount of the carbonic acid gas at the point where the pH of the developing waste liquid reaches the time point from i 3 to 12, in the developing waste liquid at the time point of 13 It is carried out with a molar ratio of 〇.15L/hr per gram of the base of the chemical vaporization. Further, a neutralization method of H kinds of developing waste liquid containing deuterated tetraalkylammonium is carried out by developing waste containing tetraalkylammonium having a pH of more than 13.7 in which the organic substance derived from the photoresist is dissolved. The liquid is added to the neutralization of the carbonation gas to a temperature of 9.5 or less, and the enthalpy of the development waste liquid is 13 or more, and the first of any pH in the range of 13.7 or less is 1/, The second neutralization after reaching the pH of 4 Rensi is carried out in another reaction tank, and the amount of carbonic acid gas added to the pH of the developing waste liquid from the time point of 13 to the point of reaching 12 is In the developing waste liquid at the time point of the pH of 13, the 3rd searched tetraalkylammonium is carried out every 1 molar equivalent, 〇·15 L/hr or less. [Effect of the Invention] According to the present invention, φ and the method can be precipitated by the organic flocculating agent from the anti-money agent, so that a highly filterable precipitate can be obtained.

Therefore, it is effective to carry out the electrolysis step after the neutralization reaction to 2030-9240-PF 8 200827944 to ask for the removal of the organic matter from the anti-Ember. In addition, since the above-mentioned analytic smuggling is low, and the shovel is not attached to the shovel, the S10 S line is adhered, so that the pipeline is not plugged, and it is safe and effective. In addition, the pH of the above-mentioned developing waste liquid is 13 or more, 13 7 is the first of any Ρίί, ϋ·7 or less, /, the first + and after reaching the arbitrary ρ ίί, Reaction _ push / ^ owe to the heart of a younger ~ trough into the 仃, because each can be shortened in the neutralization of the Ding also into the 仃, your time, industrial efficiency. [Embodiment] (Dissolving the right-hand side of the anti-reagent from the detailed description of the use of the developing waste liquid),,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The organic waste material 5 has a developing waste liquid (^ X ^ ^ is widely used as a developing waste liquid containing ΤΑΑίί.). In the present invention, A A Η 曰 / 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Among the above, 'the use of hydroxylated tetramethyl ketone can be used more widely in the point of use of the developing solution of the semi-conducting ^ ^ / ± 千V system. The TAAH irradiance in the developing waste liquid containing THH and arbitrage AAH used in the method and method of the present invention is not particularly limited, and various developing waste liquids of TAAH concentration are used. In the semiconductor manufacturing process, the concentration of ΤΑΑ ί ί ί ί ί ί ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ^ 砚^, Furthermore, from the viewpoint of reducing the transportation cost of the developing waste liquid, it is preferable to carry out the development waste liquid containing TAAH in order to increase the TAAH content. ΤΛΑΙί ^ ^ 茨3 has a smashing development waste liquid, as described above, the processing cost becomes lower than the cost of the package.

2030-9240-PF 200827944 High, too high, the processing cost required for the shrinking is changed, so the concentration of the sputum containing #τΑΜ is preferably 10~30% by mass. The range of the pH of the developing waste liquid containing the enthalpy of the enthalpy of the present invention is from 13 to 15 and is generally in the range of from 14 to 14.7. Further, in the above-mentioned developing waste liquid containing ruthenium, an organic substance derived from a resist is dissolved. The concentration of the organic substance derived from the anti-(4) is different depending on the solubility of the organic substance derived from the anti-(tetra) antimony after development, and the solubility of the organic substance derived from the anti-stripping agent in the concentration of the deuterium after the concentration, but the present invention In the neutralization method, since the concentration of the organic substance derived from the anti-depletion dissolved in the developing waste liquid containing hydrazine in the neutralization reaction is high, the removal efficiency of the organic substance is high, which is effective. The concentration of the organic substance derived from the anti-# agent dissolved in the above-mentioned developing waste liquid containing ruthenium is, for example, tens to hundreds of _ of the developing waste liquid containing UAH discharged in the semiconductor manufacturing step in terms of (10). Further, near: 'Proposal has a development waste liquid containing # Τααη for the development step: after adding the developing waste liquid containing hydrazine to adjust the hydrazine concentration, the solution is directly reused in the development step" In the effective use method of the developing waste liquid, the trace of the organic substance derived from the anti-(4) in the simple developing waste liquid tends to be higher than the above concentration. As described above, the slag of the sputum is increased by the concentration, etc., and the organic matter from the anti-(4) is concentrated. Therefore, the concentration of the organic substance derived from the anti-surname agent in the developing waste liquid having a side concentration of ～3°% by mass is usually in the range of (10) to several thousands. (Carbonate gas) 10 2030-9240-pf 200827944 In the present invention, a method is used to neutralize a developing waste liquid having a pH of 13 or more by adding carbonic acid gas. The use of the carbon dioxide gas which is industrially usable can be used without any limitation. X, a carbonic acid gas diluted with an inert gas may also be used. After the development waste liquid containing TAAH is neutralized by carbonic acid gas, the produced carbonate and heavy money salt are electrolyzed, and a by-product electrolytic gas is mainly produced, and the electrolytic emulsion mainly contains carbonic acid gas or carbonic acid gas. The reuse gas is used as the carbonic acid gas for the neutralization reaction. (Addition amount of carbonic acid gas) Maoyue is added to carbon dioxide gas neutralization by developing waste liquid containing TAAH having a pH of 13 or more

The neutralization method of the shackle Shichi, Liu Y, and the TAAH-containing sap waste liquid, which is below the pH of U·5, i, is characterized by: the pH of the developing waste liquid is 13 a# $ η , soil 4 ^ , , ", the addition of carbonic acid gas at the time of reaching 12" is adjusted to 〇. 15L/h, r (below, 蛟, in the amount of leakage per ear in the developing waste liquid at the time of ΡΗ13) The volume of the acid gas is indicated by the volume of the acid gas. The chaotic/hr or less is better. As described above, the precipitation of the organic matter from the anti-caries agent ', visit Η Η ^ 』 is based on the above-mentioned developing waste liquid The pH is from the vicinity of 13 to ^ γ ^, ",, 'to reach the 10 o'clock of the pH of the region is significant. Therefore, by adjusting the Bu, Shi, factory mussels% 敫 10 A, the above areas of carbonic acid The amount of gas added is positively derived from the organic precipitate of the resist. The precipitation of the precipitate is ', and the addition amount of the above-mentioned carbonic acid having high filterability is obtained, Wei Xiao ^ ΛΑ ^ The final precipitation of the organic substance from the resist The higher the speed adjustment effect, the 3 Λ田, 竹出,,, 疋, if too little, because of the neutralization process, so the test Industrial efficiency is double-beneficial, preferably 0.05L/hr or more, preferably 2030-924 0~pp 200827944 〇· 01L/hr or more. λ, and 'organic matter from anti-silver agent, at PH When the time reaches 11.5, the large knife exits the outlet. The pH of the liquid waste liquid is adjusted from the time point of 13 to the point of reaching 1. 5 to the above-mentioned addition amount, and the point of the precipitate of the filterability is obtained. Preferably, the addition amount of the carbonic acid gas in the above region is less than the TAAH# i molar equivalent in the developing waste liquid at the time point of pH 13, and the adjustment effect of the precipitation rate from the organic substance resistant to (d) is low, The organic substance derived from the anti-agent is precipitated in a state of high adhesion or fine particles. On the other hand, if the amount of the carbonic acid gas added is too low, the time due to the reaction of the medium # is longer, so industrial consideration is considered. Efficiency, etc., from P Η from 1 3 to 5! 丨; check 1 9 1 1 r , , , the time to reach I2 or 11.5 is appropriate to determine the amount of carbon dioxide added. Usually, by ρ Η by 13 The time required from the time point to the time of material 12 is U~10 hours. It is preferable that the time of 2. 〇 10 hours is good or the time of the above-mentioned developing waste liquid is from the time point of 13 to the point k of reaching u. 5 is 3 to 3 hours, and it is preferable to appropriately determine the carbon dioxide gas at the time. (1) When the carbon dioxide gas is added at the above-mentioned addition amount (hereinafter, it is referred to as a stone acid reflux gas addition adjustment point, a key start point), as long as the pH of the above-mentioned TAAH-containing development waste liquid reaches 13 Yes, consider the process of neutralizing the equipment, and handle this force. The appropriate decision can be made. For example, considering the safety, the starting point of the addition of the carbonated milk can be set to be higher than PH13. &, the addition amount of all the μ P ^ , , and 7 hundred ΡΗ & carbonic acid gases from the start to the end of the neutralization may be the above-mentioned addition amount, but the neutralization and the rattan The reaction time becomes longer, and it is hard to say that there is work.

2030-9240-PF 12 200827944 Efficiency in the industry. Therefore, it is particularly suitable for the tarax-containing photographic waste liquid of 7.3, which is particularly suitable for setting the carbonic acid gas addition adjustment starting point to an arbitrary ρ 范围 in the range of ρΗ]3 or more and 3.7 or less. (Method of Adding Carbonic Acid Gas) ^ A method of adding a carbonic acid gas in the above-described addition amount, as long as the carbonic acid gas is supplied in a range of the above-mentioned amount of the carbonic acid gas, a known method can be used, for example, a method of intermittently supplying carbonic acid gas A method in which carbonic acid gas is continuously supplied in a certain amount. Among the above methods for adding carbonic acid gas, the method of continuously and quantitatively supplying carbonic acid gas is preferable because industrial management is easy and the reaction apparatus is simple. (to the middle of the adjustment of the addition of carbonic acid gas); ^ to the above-mentioned stone anaerobic fluorine addition adjustment starting point and (under the nickname referred to as the first neutralization), regarding the reaction conditions and other considerations in progress It is sufficient to determine the processing ability of the reaction equipment. As described above, it is possible to add the amount of the neutralization & acid gas addition amount to the neutralization after the start of the addition of the carbonic acid gas (hereinafter, -% is the neutralization), but the neutralization reaction The reaction time required will become longer, and it is difficult to say that the efficiency of the health industry is higher than the addition amount of the second neutralized acid gas. However, depending on the conditions, due to the channel flow or backmixing caused by the bias of the supplied carbonic acid gas, the post-acid gas emulsion does not uniformly diffuse in the reaction tank, resulting in a high concentration of carbonic acid gas. P knife. The high concentration of the above carbonic acid gas is due to the preparation of the waste liquid, and the low amount of the developing waste liquid.

2030-9240-PF 13 200827944 There is a branch, which is deposited in a state of high adhesion before the above-mentioned carbonic acid gas addition adjustment starting point, adheres to the pipeline, etc., and is likely to be plugged. Therefore, the amount of the carbonic acid gas to be added in the first neutralization is such that the amount of the hydroxylated tetraalkylammonium in the developing waste liquid of the neutralized uranium is 1 or less, and is less than or equal to 0.7 L/hr. More suitable. Further, the smaller the amount of the carbonic acid gas added, the higher the precipitation prevention effect of the organic substance derived from the anti-drug neutralized by the second, but the neutralization process takes too much if it is too small, so industrial efficiency is considered. More than 1 L/hr is preferred. (End point of neutralization) In the present invention and method, the developing waste liquid containing TAAH is neutralized with carbonic acid gas, and the scent of the developing waste liquid can be ιΐ5 or less, and after the neutralization step, use The durability of the filtration membrane at the separation step of the organic substance from the resist or the influence of the pH of the development waste liquid in the electrolysis step is specifically set. The above neutralization end point is usually set as long as the range of PH8 to 11·5 is appropriately set. In addition, it is sufficient that the pH of the developing waste liquid is lower than the time of 11.5, and the processing ability such as the reaction condition for the neutralization reaction, etc., may be appropriately determined. In particular, in the method and method of the present invention, since the organic substance derived from the resist precipitates most of the pH of the developing waste liquid when it reaches 12 to η·5, the neutralization end point is suitably set to ρΗη~η. · The range of 5 is particularly suitable. The end point of the neutralization is set within the above range, and in addition to the above reasons, since the time required for the neutralization can be shortened, the reaction of the carbon dioxide gas neutralized by TAAH carbonate is not satisfied. The efficiency will be reduced, so the point of neutralization requires an excess of carbonic acid gas. In the electrolysis step, 2 mol of TAAH is generated by electrolysis of 20 mol of 2030-9240-PF 14 200827944 carbonate, and 1 f of bicarbonate is used. The generated TAAH is 1 mol, so the more the proportion of the stone acid salt in the developing waste liquid for electrolysis is, the higher the electric power efficiency is, and the like is also preferable (the method of the neutralization method). The above is the present invention. In the method of the neutralization method, a method of neutralizing one reaction tank and a method of neutralizing a complex reaction tank of two or more may be used. Wherein, the sum of the squares of the i-reaction tanks is used, and the Taah per mole equivalent in the developing waste liquid at the time when the pH of the king's body is neutralized is set to be less than or equal to 15 L/hr. The method of adding the amount of carbonic acid gas to the neutralization reaction; in the above first neutralization and the second neutralization, changing the carbonation amount: the method. Further, a method of using the above two or more complex reactions, and a method of performing the first neutralization and the grooves can be mentioned. In the above method, the first neutralization and the second neutralization are neutralized by individual reaction tanks using a complex reaction tank of 2 or more, and the fulcrum can be independently managed in each reaction tank. 'It is better to perform the operation in parallel and to shorten the working time. Further, (4)-neutralization is carried out with the number of reaction tanks. The bet is that the anti-return 2 will be complicated by the step management or reaction operations of the various neutralizations, and the problems accompanying the cost, etc., will be placed in the middle of the four (4) and the other The reaction tank is pumped in. (The method of neutralizing the two reaction tanks) 2 = The neutralization method of the present invention in which the first neutralization and the second neutralization are respectively reversed. Fig. 1 shows In the present invention,

2030-9240-PF 15 200827944 Schematic diagram of the best neutralization of the first neutralization and the second neutralization with individual reaction tanks. (First Neutralization) • In the reaction tank 1, the first neutralization was performed. The developing waste liquid containing TAAH is supplied in a developing waste liquid supply pipe 3 containing TAAH. In the reaction tank, carbonic acid gas is supplied to the reaction tank 1 for neutralization by the carbon dioxide gas supply pipe 4, and the reaction liquid is discharged from the reaction tank 1 by the pump 5 to process the fertilization limb supply line 6, so as to appeal the supply line 6, and supply the reaction. Slot 2. Unreacted carbonic acid gas or the like is discharged outside the system by the unreacted gas discharge line 7. As described above, the amount of the carbonic acid gas to be neutralized in the first neutralization may be appropriately determined in consideration of the equipment for the reaction, the processing ability, and the like, but the viewpoint of industrial efficiency is to use the second neutral carbon dioxide gas. The amount of addition is preferably a large amount. Further, considering the influence of the flow or the back-mixing of the carbon dioxide gas in the reaction tank 1, the hydrogenated tetraalkylammonium in the developing waste liquid before the neutralization is made per 1 molar equivalent, 1. Ο It is better to do it below /hr. φ Further, by providing the pump 8 and the circulation line 9 in the reaction tank 1, the reaction measuring device 1 is provided in the above-mentioned circulation line, and the reaction in the reaction tank i can be managed. In the reaction measuring apparatus, as long as the concentration of the developing waste liquid containing taah for the reaction is known, the TAA Η and the carbonate of the reaction tank 1 and the end point can be easily calculated. In addition, a conventional measuring device for measuring the concentration of solute in an easy manner can also be used by using an ultrasonic concentration agent or the like. In the above neutralization, when the foaming of the reaction liquid is a problem, a carbonic acid gas supply line may be disposed in the circulation line, and the carbonic acid gas may be mixed by the line 2030-9240-PF 16 200827944 through the circulation line. The circulation line is supplied to the reaction tank. Regarding the reaction temperature in the reaction tank 1 and the reaction, the development waste liquid containing ruthenium is used as an aqueous solution, and when the temperature is too high, the anti-surname agent in the development waste liquid containing _ is precipitated or solidified and lowered. With carbonic acid gas: the point of reaction efficiency 'in °. ". . . In particular, it is better to neutralize between 2 sales. Specifically, the type of the reaction tank is exemplified by a reaction tank having a stirring blade, and the filling of the (4) money gas is filled (4) to enhance the filling tower, and the developing waste liquid having the enthalpy is distributed from the top of the tower to the bottom of the tower. The gas is supplied to the bottom of the column to make the reaction between the ruthenium and the carbonic acid gas and the tower. Among the above reaction tanks, by neutralizing the column to the flow operation, it is possible to continuously perform neutralization and is more suitable. In the above-mentioned "first neutralization", the above-mentioned neutralization tower is neutralized by a multi-stage tower having a plurality of trays, and the above-mentioned developing waste liquid can be easily disposed in each section of the tray u partition. The PH remains constant, by the above development X night. The top side flows to the bottom side of the column through the respective stages, and the pH of the developing waste liquid can be lowered stepwise, which is particularly preferable. Used for the tray of the above multi-stage tower! j is formed by a porous plate bovine plate 12 which penetrates a plurality of holes. The TAAH developing waste liquid flows through the bottom of the downcomer plate to the bottom of the column, and the carbonic acid gas flows through the pores of the perforated plate from the bottom of the column to the top of the column to flow through the β TAAH developing waste liquid and in the column. It can be controlled by the inner diameter of the downcomer 12. If the inner diameter of the downcomer 12 is too low, the reaction required for the neutralization reaction becomes long and uneconomical. If the temperature is too high, the adjustment effect of the flow rate of the developing waste liquid of the above 2030-9240-PF 17 200827944 is low, so In the middle of the tower, it is better to use 5%·〇〇.5%, especially 〇·2~1.0%, and the flow rate of carbonic acid gas can be controlled by the numerical aperture of the perforated plate. When the reaction is low, the reaction required for the neutralization reaction becomes long and uneconomical. If the reaction speed is too high, the effect of adjusting the flow rate of the development waste liquid is low. Therefore, it is preferable that the inner diameter of the neutralization column is 3 to 1%. 'With regard to the number of trays 1 1 of the above-mentioned multi-stage tower, the greater the number, the higher the number of sections, the higher the adjustment effect of pH, and the excessive partitioning cost the manufacturing cost of the multi-stage tower, so the tray U The number is 2 to 4, that is, the number of stages in which the developing waste liquid is circulated is preferably 3 to 5 stages. Further, in order to promote the uniform diffusion of the carbonic acid gas, it is particularly preferable to fill the filler in each section of the tray 11 partition. The filler can be used without any limitation as a conventional filler for gas-liquid reaction. (second neutral)

with. In the reaction tank! The treatment liquid supply line 6 is supplied to the reaction tank 2 by the development waste liquid (hereinafter referred to as reaction tank treatment waste liquid) neutralized in the reaction tank i. The reaction tank is supplied to the reaction tank 2! After the waste liquid is treated, carbonic acid gas is supplied to the carbonic acid gas supply line 13' for neutralization. After the end of the neutralization, the reaction liquid is supplied to the treatment liquid supply line 15 by the pump 14 and sent to the separation step for performing the separation of the resist. The unreacted carbonic acid gas or the like is discharged outside the system by the unreacted gas discharge line 16. Starting from the second neutralization, the pH of the developing waste liquid is increased from the carbon point to 12 or 11. 5, and the carbonic acid gas is added to adjust the addition amount to be at 2030-9240-PF 18 200827944 at a pH of 13. TAAH in the developing waste liquid is carried out at a molar ratio of 0·15 L/hr per 1 molar amount for the purpose of stirring the efficiency of the Tylenan reaction solution, and is set in the reaction tank 2 to follow the jade clothes line 1 8 'can be pumped 17 The solution in the reaction tank 2 is circulated and reacted. In the case where the bubble of the night becomes a problem, a f-carbonation gas supply line may be provided in the above-mentioned circulation line, and the carbonic acid gas is supplied to the circulation line by the on-line agitator and the injector in the "', the mouth hand # The circulation line is introduced into the reaction - the reaction can be carried out by the reaction measuring device 1 9 in the above-mentioned circulation line. The reaction measuring device is supplied to the reaction tank of the reaction tank 2! The concentration of carbonate in the waste liquid is treated, and the concentration is continued. Because of: easy to calculate the pH, carbonate, and heavy carbon bite at the middle, end, and end points, it is outside the pH meter. A conventional measuring device for measuring the concentration of solute in a solution such as a supersonic meter can also be used. (Removal of the deposited resist)

In the present invention, the method and the method are characterized in that the floc is greatly degraded, and the (four) anti-consumption organic matter: the removal step of the organic substance of the organic substance of the surname is used for the removal of the organic matter, and the plate and frame dehydrator The method of super-ruthenium film and the like is derived from anti-(4)/:=Γ" The present invention is used for the solid-liquid consumption and consumption. With the above characteristics, it can be directly added with additives and mixed: after the second is better "filter effect For the purpose, it can be added to Wang (4):: Separation operation. For the solid-liquid separation/consultation aid, it can be activated carbon, Shixiazao, cellulose, etc. Among them, 2030-9240-pf 19 200827944 It is preferable to use a filter aid such as activated carbon or diatomaceous earth. The embodiment is a more specific description of the method of the present invention, and the following examples are described, but the present invention is not limited to the implementation. Example 1 The composition shown in Fig. 1 made of transparent vinyl chloride was used for the middle and the mounting of the Φ. The size of the reaction tank 1 was 100 mm in diameter and 1 000 in height, and it was lowered at 3 places in the inner Denghan. The tray of the liquid plate. The size of the reaction tank 2 is 250mm in diameter and 8 in height. In addition, the development waste liquid containing TAAH uses a development waste liquid containing hydroxylated tetramethylammonium (hereinafter referred to as ruthenium) of ρΗ14·7. Further, the development waste liquid has a ruthenium concentration of 20 The mass %, the content of the organic material from the resist, and the COD exchange rate is 5000 ριη. First, 6 L of the developing waste liquid containing ruthenium is placed in the reaction tank 1, and carbonic acid gas is supplied from the carbon dioxide gas supply pipe 4 at the lower portion of the reaction tank 1. 17. 3L/hr 'neutralization to a pH of 13. After that, carbonic acid gas is supplied at 17·3 L/hr, and the developing waste liquid supply line 3 containing the TAAH in the upper portion of the reaction tank 1 is supplied to the developing waste liquid 4·6 L/ Hr, continuous neutralization in the flow operation. The reaction tank 2 is sampled and discharged from the supply line 6 for treating the waste liquid. The waste liquid is treated to confirm the pH, and the pH is 13. At this time, the addition of the carbonic acid gas in the reaction tank! The amount of TMAH1 in the developing waste liquid before and after the neutralization is 0.39 L/hr (hereinafter, the supply amount of the carbon dioxide gas is expressed by the volume of the standard state.) In the above neutralization operation, the reaction tank Not confirmed from 2030-9240-PF 20 200827944 The organic matter of the etchant is precipitated. Then, after the treatment liquid in the reaction tank 1 is stored in the reaction tank 2 for 20 L, the carbonic acid gas is supplied from the lower portion of the reaction tank 2 to the carbon dioxide gas, so that the pH is 13 at the time of tmah. The amount of addition of 1 mol of carbonic acid gas is neutralized by 〇·01 L/hr to obtain a treatment liquid of ρΗ11·5. The time required for the pH of the development waste liquid from the time point of 13 to the point of reaching 12 is 9, 7 hours. The time required for pH from 13 o'clock to 11 o'clock is 2 8 · 5 hours. Adding an egret to the treatment solution at a ratio of 1 · 〇wt% as a filter aid (live stone, product name, manufactured by Envir〇chemi cai s, Japan), stirring

After the transition, the pressure filter KST-142-UH (trade name: manufactured by ADVANTECH Toyo Co., Ltd., diameter 142_), and membrane filter membrane H100A142C (trade name, ADVANTECH Toyo Co., Ltd., aperture, 〇.15MPa plus The mixture was filtered under pressure to obtain a clear filtrate. The COD of the filtrate was 6 〇ppm. Further, the filtration rate of the treatment liquid was calculated from the filtration rate to be 500 L/m 3 · Hr. Examples 2 to 6 The supply speed of the developing waste liquid shown in Table 1, the supply rate of the carbonic acid gas, and the amount of the TMAH1 molar carbonic acid gas added to the developing waste liquid before the neutralization are carried out in the reaction tank i, and then shown in Table! When the pH of the developing waste liquid was 13, the amount of the TMAH1 molar carbonic acid gas added was carried out in the reaction tank 2, and the neutralization reaction was carried out in the same manner as in the example j. The developing waste liquid in the reaction tank 2 was used. The time from the time of 13 to the arrival and the time required for ιΐ 5 and the filtration results after neutralization are shown in the table. 2030-9240-PF 21 200827944 [Table 1]

Ο 8 α V a § S g § S_y QQ LO g LO oo LO <3>〇> LO CD CZ5 LO οα CO 2*上m LO 〇6 CN! CO — r—1 cnJ CO inch·τ—H卜·r—< CO οα ^ r—1 卜 05 05 or—H 1 CO CD —_.上 V雠1 t <3) CD s CD CO T—to CO <3><3> Csl C3> 〇· τ—^ —_上上,2 οα CD ο CO CD σ^ CO CD CD CD CD CD CD CD CD τ··Η CO 卜·r—1 od CO r—H Zhao Office A Si上Si^^o 蘧寒 U Cvl CD CO CO CO oi CO 呀·Cvl CO 寸 LO CO SE*wtt^LO.u^CN3IfH-fslwcol-ffiHaw^竣磙蘧:^:.※ ¥浚筚| |¥拳^》骏^斋鲽vrrH·衅i HVW1銮+蟛礆蘧蟛礆蘧wfe^-s-^: One ※ Example 7 Using the same neutralization device as in Example 1, first, in the reaction tank 1 8L/hr, 中中22 The carbon dioxide gas supply gas is supplied to the lower part of the reaction tank 1

5。 The pH is 13. 5. Thereafter, the carbon dioxide gas is supplied in a 24/team, and the developing waste liquid supply pipe and the line 3 are supplied to the developing waste liquid 7·5 L/hr from the upper port of the reaction tank 1 and the line 3 to perform the flow operation. Continuous neutralization. The reaction tank 1 was treated by the reaction tank, and the reaction tank 1 sampled and discharged from the night supply line 6 was treated to have a pH of pH of 1.25. At this time, in the addition of the carbonic acid gas in the reaction tank 1, the tmahi molar in the developing waste liquid which is neutralized is in the state of the above-mentioned neutralization operation, and the reaction tank is in the above-mentioned neutralization operation! The precipitation of organic substances from anti-corrosion agents was not confirmed. Then, after the treatment liquid in the reaction tank 1 is stored in the reaction tank 2 for 2 GL, the carbonic acid gas is supplied from the lower portion of the reaction tank 2 to the carbon dioxide gas, and the carbonic acid gas is at a pH of 13% per point of TMAH per 1 mol of carbonic acid. The addition of gas was neutralized with 〇·07 L/hr to obtain a treatment liquid of ρΗη·5. The time required for the pH of the developing waste liquid from the time point of 13 to the time point of reaching 〖2 is 2 · 8 J. The pH is from the date of the day of the 13th to the time when the point of reaching 11 · 5 is 6 · 3 hours. The λ and λ treatment liquids were filtered in the same manner as in Example 1, and were well filtered to obtain a clear filtrate. The (3)D of the filtrate is 6〇ρ_. Further, the filtration treatment rate of the treatment liquid calculated from the filtration rate was 400 L/in3 · Hr. (Example 8) Neutralization was carried out in the same manner as in Example 7 except that the content of the organic substance derived from the antisynthesis agent was 8 〇〇〇ppm in terms of C0D and the TMAHi developing waste liquid of pH 14.7 was used. Further, the developing waste liquid had a TMAH concentration of 20% by mass.

2030-9240-PF 23 200827944 This treatment liquid was subjected to filtration in the same manner as in Example 7 to obtain a clear filtrate. The filtrate had a COD of 9 〇 ppm. Further, the filtration treatment speed of the treatment liquid calculated from the filtration rate was 400 L/m3 · Hr. Further, the development waste liquid containing TAAH similar to that of Example 1 was used in the same manner as in Example 6 in the reaction tank 1.

Next, after the treatment liquid in the reaction tank 1 is stored in the reaction tank 2 for 2 〇L, the carbonic acid gas is supplied from the lower portion of the reaction tank 2 to the carbon dioxide gas at the time point of PHI U. The amount of the carbonic acid gas added was neutralized to pH 12 with a supply of L2 L/hr, and then the addition rate of the carbonic acid gas was increased to G.5 GL/hr to obtain a treatment liquid which was neutralized to pH 115. The time required for the pH of the developing waste liquid from the time point of 13 to the point of reaching 12 is 6.0 hours, and the time required from the time point of pH* 13 to the point of reaching 115 is 6.5 hours. The operation is filtered, and the COD of the solution is 70 ppm. The filtration rate and the treatment rate of the liquid were the same as those of Example 1 to obtain a clear filtrate. Further, the above-described processing calculated from the filtration speed is 350 L/m3 · Hr. Comparative Examples 1 to 2 In the reaction tank 1', the supply speed of the developing waste liquid, the carbonation gas supply rate, and the amount of the tmahi molar carbonic acid gas added to the developing waste liquid before the neutralization were carried out in the reaction tank. Neutralization, as shown in Table 2, the amount of carbonic acid gas added to the developing waste liquid is 13

2030-9240-PF 200827944 Neutralization reaction was carried out in the same manner as in Example 1 except that it was carried out in the reaction tank 2. The filtration time of the developing waste liquid in the reaction tank 2 from the time point of 13 to the time of reaching 1 2 and 11.5, and the filtration result after the neutralization are shown in Table 2. Further, in Comparative Example 2, since the pressure filter was plugged during the filtration, the filtration could not be completed. Therefore, the filtration speed cannot be calculated. [Table 2] COD of filtration filtrate (ppm) § Filtration capacity (L/m3 · Hr) CD CD r-< i Reaction tank 2 pHll.5 Arrival time % (hr) oo 1—< r-H pH12 Arrival Time % (hr) CO CD LTD <3> Acid-breaking gas»jv , Tian*2 Add 篁(L/hr) tH CN1 ◦· CN1 ◦· Reaction tank 1 Addition amount of carbonation gas ~ (L/hr) 0.20 0. 39 Carbon dioxide gas supply rate (L/hr) Bu oo CO rH Development waste liquid supply speed (L/hr) CO oi CO a r—ί (N1 s£#BW^^LO.H^zi?^fsiBWcoI- ffiHdw^^^ii:i^ ¥浚婆 ll^f^瞀w馊^跻鲽衾i: pants ίHVMW3⁄4'BWcol_3⁄4w pain _ff蘧3⁄4:¢Nl※ 雄窜鲚鲽3⁄4^裨svlus+赵础磙蘧^靛恭斗葙:一※ 2030-9240-PF 25 200827944 [Simplified description of the drawings] Fig. 1 shows a preferred aspect of the present invention in which the first neutralization reaction and the second neutralization reaction are carried out in individual reaction tanks. Schematic diagram of the main components: 1~reaction tank; 2~reaction tank; 3~developing waste supply line; • 4~carbonate supply line; 5~help; 6~ supply line; 7~unreacted gas Discharge line; 8~ pump; 9~ Pipeline; 10~ reaction measuring device; 0 11~ tray; 12~ downflow plate; 13~ carbonic acid gas supply line; 14~ pump; 15~ neutralizing treatment liquid supply line; 16~ unreacted gas discharge line; ~ pump; 18 ~ circulation line; 19 ~ reaction measuring device. 2030-9240-PF 26

Claims (1)

200827944 X. Patent application scope: h A method for neutralizing a developing waste liquid containing hydroxylated tetraalkylammonium by: developing a light-weight tetraterpene group containing 13 or more organic substances dissolved from a photoresist The waste liquid is neutralized to a pH of 115 or less by adding carbonic acid gas, and is characterized in that: / 吏 of the developing waste liquid from the time point of 13 to the point of reaching 12:::: the amount of the body added, in the Qiu At the time of 13th, the development waste liquid is interesting. The four-burning base wire 1 molar equivalent m is less than the 仃0 sendan/= the neutralization method of the chemical-containing four-burning base recorded in the first item of the patent scope' The time required to make the point (10) of the developing waste liquid "at 12" is 0.8 to 1 hour. The method for neutralizing the liquid containing the chemistry of the sulphuric acid according to the first aspect of the patent application, wherein the amount of the carbonic acid gas at the time of the development of the waste liquid 13 is at the time of the It is carried out for each of the molar equivalents of U.sub.15 L/hr, which is contained in the developing waste liquid of 13 =. "=! The range of the PH containing the tetrabasic ammonium amide according to the third paragraph of the patent range from the point of time of 13 to the point of reaching the point of 丄5 is 3 to 30 hours. 5_# The developing waste liquid containing the hydroxylated tetraalkylammonium is dissolved by the carbonic acid gas to the pH of n. 5 by dissolving the right (four) ^ from the photoresist #丨2030-9240-PF 27 200827944 The following is characterized in that the pJJ of the developing waste liquid is made up of 叩 田 风 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 The second neutralization after the pH of the "" 任思, is carried out in another reaction tank, and neutralized in the first _ η η - 士 -, to make the pH of the developing waste liquid 3% to At the time of reaching 12, the amount of citric acid gas added is as a point at which the pH is 13 at the time of development, and the nano-u night contains the hydroxylated tetraalkylammonium every 1 旲 fighting field, 0· Performed below 15L/hr. 6 · A method for neutralizing a hair styling liquid containing a hydroxylated tetraalkylammonium as described in the scope of the patent application, wherein the amount of carbon dioxide gas in the middle of the brother is neutralized. The amount of carbon dioxide added by the younger brother and the middle is more than 7. The neutralization method of the waste liquid containing the chemistry of the four-burning base according to the sixth paragraph of the patent application, the basin _ Θ /, the middle is in the first The addition of a neutralized carbonic acid gas is carried out to neutralize the hydroxylated tetraalkylammonium in the waste liquid of the a θ 29 shirt every 1 mole, and is carried out at a temperature of 1 〇 L/hr or less. 8 · If applying for a patent, the method of neutralization of the 35-shirt waste liquid containing the hydroxylated four-burning base described in the 5th edition of the brother-in-law, with Zhongdi Yizhong and the multi-stage neutralization tower. A method for neutralizing a developing waste liquid having a hydroxylated tetraalkylammonium, which is a developing waste liquid containing deuterated:: ammonium chloride having a pH of more than 13.7 from the organic substance of the photoresist, and neutralized by adding carbonic acid gas to The pH is 11.5 or less, and the pH of the developing waste liquid > ^ 1 ^ is 13 or more, and the range of 13.7 or less is 2030-9240-PF 28 200827944. And the second neutralization after reaching the arbitrary pH changes the rate of addition of the carbonic acid gas and in the second "" the development waste pH is increased from 13 o'clock to the point of arrival of j2 at the point of the addition of the disc acid gas 'With the pH of 13 neck wb 夕 bow sdan / ten defensive, *, accounted for 33 of the sap waste liquid containing hydroxylated tetraalkylammonium per 1 mole of 詈, D 1ςτ / κ, Sheng Tianli 〇. It is carried out below 15L/hr, and the amount of added gas per unit time of the first neutralized carbonic acid gas is large. It is more in the middle-and-neutralized carbonic acid 10. As claimed in the patent range 5~1 ^ ^ ^ The neutralized 5 of the developing waste liquid containing deuterated tetraalkylammonium contains _tetraoxane A # The basic chemical ammonium of the chemical system in the development waste liquid of the basic knowledge: agricultural production is 10~30% by mass. 2030-9240-PF 29