WO2015016230A1 - Procédé de préparation de solution aqueuse de sel d'ammonium tétra-alkyle - Google Patents

Procédé de préparation de solution aqueuse de sel d'ammonium tétra-alkyle Download PDF

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WO2015016230A1
WO2015016230A1 PCT/JP2014/069973 JP2014069973W WO2015016230A1 WO 2015016230 A1 WO2015016230 A1 WO 2015016230A1 JP 2014069973 W JP2014069973 W JP 2014069973W WO 2015016230 A1 WO2015016230 A1 WO 2015016230A1
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exchange resin
cation exchange
photoresist
packed tower
waste liquid
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PCT/JP2014/069973
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English (en)
Japanese (ja)
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渡邉　淳
直幸 梅津
喜文 山下
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株式会社トクヤマ
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/02—Column or bed processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
    • B01J49/06—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing cationic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/60—Cleaning or rinsing ion-exchange beds

Definitions

  • the present invention relates to a novel method for producing a tetraalkylammonium salt aqueous solution (hereinafter, tetraalkylammonium may be abbreviated as “TAA”) using a cation exchange resin.
  • TAA tetraalkylammonium salt aqueous solution
  • a negative or positive resist such as a novolac resin or polystyrene resin is applied to the metal layer formed on the substrate surface. Then, the metal layer is exposed to light through a photomask for pattern formation and developed on a non-cured portion or a cured portion using a developer mainly composed of TAA hydroxide, followed by etching.
  • a developing process for forming a pattern is performed, and in this developing process, a developing process waste liquid containing TAA hydroxide is discharged.
  • TAA hydroxide-containing development waste liquid After developing with the developer, cleaning with ultrapure water is performed to remove the developer remaining on the substrate, and the cleaning process waste liquid containing TAA hydroxide is discharged from the cleaning process. Is done. These development waste liquid and washing process waste liquid are usually mixed and then discharged as TAA hydroxide-containing development waste liquid. In recent years, as the production amount of semiconductors and liquid crystals increases, the consumption of the developer increases, and the discharge amount of the TAA hydroxide-containing developer waste also increases. Recently, a method for recovering TAA hydroxide has been proposed in which TAA hydroxide is recovered from the TAA hydroxide-containing developer waste, purified, and reused.
  • TAA hydroxide-containing developer waste liquid (hereinafter referred to as photoresist and TAA hydroxide) that is discharged after mixing the development process waste liquid and the cleaning process waste liquid may be referred to as “photoresist development waste liquid”.
  • concentration of TAA hydroxide is usually as low as about 100 to 10,000 ppm, and the pH is about 10 to 14.
  • a concentration means for increasing the concentration of TAA ions in the waste liquid is indispensable.
  • a concentration means for increasing the concentration of TAA ions for example, a photoresist developing waste solution containing TAA hydroxide is brought into contact with a cation exchange resin, TAA ions are adsorbed on the cation exchange resin, and then an aqueous acid solution is subjected to cation exchange.
  • a method for obtaining a TAA salt aqueous solution by contacting a resin and eluting TAA ions from the resin see Patent Document 1.
  • the photoresist developing waste solution containing TAA hydroxide is an alkaline aqueous solution
  • the photoresist contained in the photoresist developing waste solution is generally easily dissolved in an alkaline aqueous solution.
  • the photoresist development waste liquid in the liquid flow is acidic or neutral (pH 3 to 3) in the packed tower. 7), so that the solubility of the photoresist in the photoresist developing waste liquid is lowered.
  • a photoresist deposits as suspended impurities in the cation exchange resin packed tower. Therefore, when the photoresist developing waste liquid is passed through the cation exchange resin packed tower, photoresist deposits may accumulate in the cation exchange resin packed tower.
  • the TAA ion adsorption rate of the cation exchange resin is lowered.
  • the adsorption rate of TAA ions liquid flow rate
  • the ratio of the amount of TAA ions adsorbed to the cation exchange resin with respect to the total amount of TAA ions in the photoresist developing waste liquid is greatly reduced.
  • the cation exchange resin swells.
  • the deposited photoresist is physically adsorbed on the cation exchange resin and acts like an adhesive, so that the cation exchange resins are bonded together and the flow path in the packed tower is remarkably closed.
  • the pressure loss in the packed tower is greatly increased, and it becomes difficult to pass the photoresist developing waste liquid through the cation exchange resin.
  • Patent Document 2 discloses a technique related to purification of condensate returned to a boiler from a turbine condenser of a steam power generation facility.
  • Patent Document 2 discloses that condensate containing an ionic component that is an impurity in condensate and a suspended solid component mainly composed of metal oxide fine particles is subjected to ion exchange and adsorption in a mixed bed type condensate demineralizer.
  • the condensate demineralizer is back-washed when suspended impurities accumulated in the packed tower packed with ion exchange resin reach a certain range of the water flow differential pressure increase value. It is described to be removed.
  • the condensate passed through the condensate demineralizer contains a suspended solid component regardless of the change in pH. This is because the main component of the suspended solid component in the condensate is metal oxide fine particles. Therefore, the water flow differential pressure of the condensate demineralizer gradually increases. Moreover, the removal by backwashing is also easy. In contrast, when the photoresist development waste liquid is passed through the cation exchange resin packed tower, the dissolved photoresist is deposited all at once as the pH of the solution changes. As a result, the pressure loss in the packed tower rises rapidly.
  • the photoresist deposit has adhesiveness and is physically adsorbed on the ion exchange resin, even if the packed tower is backwashed after the pressure loss is increased, the removal is not easy. Further, when the photoresist precipitate is adsorbed on the ion exchange resin particles, the photoresist precipitate becomes an adhesive and binds the ion exchange resin particles to form a lump. Once such a lump is formed, it is difficult to unravel the ion-exchange resin particles and to regenerate them by ordinary backwashing treatment.
  • the present invention effectively increases the pressure loss in the packed tower packed with the cation exchange resin when the photoresist developing waste liquid is passed through the cation exchange resin to adsorb the TAA ions to the resin.
  • An object of the present invention is to provide a method for producing a high-concentration TAA salt aqueous solution efficiently.
  • the inventor measured the physical property value of the discharged liquid discharged from the packed tower when passing the photoresist development waste liquid through the packed tower filled with the cation exchange resin, and the physical property value was When the value changes to a predetermined threshold value or more, the flow of the photoresist developing waste liquid is temporarily interrupted, and a back washing process is performed to back wash the cation exchange resin in the packed tower. By resuming the liquid, it was found that the problem of pressure loss in the packed tower was remarkably improved, and the present invention was completed.
  • the present invention is a method for producing an aqueous tetraalkylammonium salt solution from a photoresist developing waste solution, Adsorption process for adsorbing tetraalkylammonium ions on cation exchange resin by passing photoresist development waste solution containing tetraalkylammonium hydroxide through packed tower filled with hydrogen ion type cation exchange resin
  • Elution step of eluting the tetraalkylammonium ions adsorbed in the adsorption step as an aqueous solution of a tetraalkylammonium salt In the adsorption step, the physical property value of the effluent discharged from the packed tower is measured, and when the physical property value changes to a threshold value or more, the flow of the photoresist developing waste liquid is temporarily interrupted, and the cation in the packed tower
  • a method for producing an aqueous tetraalkylammonium salt solution comprising performing a backwashing
  • the physical property value of the effluent is at least one selected from the group consisting of conductivity, pH and / or tetraalkylammonium ion concentration.
  • air scrubbing is preferably performed in the backwashing step.
  • the photoresist developing waste liquid is treated while effectively suppressing an increase in pressure loss in the cation exchange resin packed tower and a decrease in the adsorption rate of TAA ions on the cation exchange resin.
  • TAA salt aqueous solution can be produced efficiently.
  • the photoresist developing waste liquid is not particularly limited, but is preferably a photoresist developing waste liquid generated in a semiconductor manufacturing process, a liquid crystal display manufacturing process, or the like. These waste liquids are waste liquids discharged when developing the exposed photoresist with an alkaline developer.
  • Photoresist, tetraalkylammonium hydroxide hereinafter, tetraalkylammonium hydroxide is abbreviated as “TAAH”).
  • TAAH tetraalkylammonium hydroxide
  • the photoresist developing waste liquid is usually an aqueous solution.
  • Photoresist developing waste liquid usually exhibits an alkalinity with a pH of 10 to 14.
  • acid groups such as carboxyl groups and phenolic hydroxyl groups are dissolved by acid dissociation. . Further, under acidic or neutral conditions, the solubility of the photoresist in the aqueous solution decreases and precipitates.
  • Specific examples of the photoresist include indene carboxylic acid produced by photolysis of the photosensitizing agent o-diazonaphthoquinone, and phenols derived from novolak resin.
  • a typical photoresist waste liquid discharged from the development process in semiconductor manufacturing and liquid crystal display manufacturing will be described in detail.
  • a sheet-fed automatic developing device is usually used frequently.
  • the step of using a developer containing TAAH and the subsequent rinsing (substrate cleaning) with pure water are performed in the same tank.
  • the rinsing step 5 to 10 times the amount of pure water is used. used.
  • the developer used in the development step is usually a waste solution diluted 5 to 10 times.
  • the composition of the photoresist waste liquid discharged in the development process is such that the TAAH concentration is about 100 to 10,000 ppm, the photoresist concentration is about 1 to 300 ppm, and the surfactant concentration is about 0 to 30 ppm. It becomes.
  • the waste liquid of another process may mix, and a TAAH density
  • concentration may become still lower. Specifically, it may be 100 ppm or less (about 10 to 100 ppm).
  • the photoresist developing waste liquid discharged from the liquid crystal display manufacturing process often has a TAAH concentration of 10 to 5000 ppm, and the method of the present invention is particularly useful for producing a TAA salt from such a photoresist developing waste liquid. It can be suitably employed.
  • TAAH in the photoresist development waste liquid is an alkali used in a photoresist developer used in the production of various electronic components.
  • Specific examples of TAAH include tetramethylammonium hydroxide (hereinafter sometimes abbreviated as “TMAH”), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, water Trimethylethylammonium oxide, dimethyldiethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydroxide, dimethyldi (2-hydroxyethyl) ammonium hydroxide, diethyldi (2- Hydroxyethyl) ammonium, methyltri (2-hydroxyethyl) ammonium hydroxide, ethyltri (2-hydroxy
  • the cation exchange resin for adsorbing TAA ions is not particularly limited, and known ones can be used. Specifically, either a strongly acidic cation exchange resin whose ion exchange group is a sulfonic acid group or a weakly acidic cation exchange resin whose ion exchange group is a carboxyl group can be used. Among them, it is preferable to use a weakly acidic cation exchange resin because many of them have a large ion exchange capacity and can reduce the amount of resin used. Further, when a weakly acidic cation exchange resin is used, elution of TAA ions described later is easy.
  • the structure of the cation exchange resin may be a gel type or an MR type (macroporous type).
  • the shape of the resin may be any of powder, granule, film, fiber and the like. From the viewpoints of processing efficiency, operability, economy, etc., it is preferable to use granular styrene-based or acrylic-based cation exchange resins.
  • the cation exchange resin is usually marketed in a state where the counter ion is hydrogen ion (H type) or sodium ion (Na type).
  • H type hydrogen ion
  • Na type sodium ion
  • an H-type cation exchange resin whose counter ions are hydrogen ions is used.
  • an acid such as hydrochloric acid or sulfuric acid is passed through a packed column pre-filled with a cation exchange resin and thoroughly washed with ultrapure water. Ions are used as hydrogen ions.
  • strongly acidic cation exchange resins include Amberlite IR120B and Amberlite IR124 manufactured by Rohm and Haas, Diaion SK112, Diaion PK228 manufactured by Mitsubishi Chemical, Duolite C255LFH manufactured by Sumika Chemtex, and LANXESS Examples include Lebatit Monoplus S100, Purolite Purolite C160, and the like.
  • Specific examples of the weakly acidic cation exchange resin include Amberlite IRC76 manufactured by Rohm and Haas, Diaion WK40L manufactured by Mitsubishi Chemical, Duolite C433LF and Duolite C476 manufactured by Sumika Chemtex, and Lexit CNP80WS manufactured by LANXESS. And Purolite Purolite C104.
  • the photoresist developing waste liquid is brought into contact with a cation exchange resin of a hydrogen ion type (hereinafter sometimes referred to as “H type”) packed in a packed tower, thereby the cation exchange resin.
  • H type hydrogen ion type
  • TAA ions are cations, they are adsorbed on the resin by causing ion exchange with hydrogen ions of the cation exchange resin by contacting with the H-type cation exchange resin. Therefore, TAA ions can be efficiently recovered from the waste liquid. In particular, even when a waste liquid having a low TAAH concentration is used, TAA ions can be recovered at a low cost.
  • the contact between the photoresist developing waste liquid and the H-type cation exchange resin is carried out by passing the photoresist developing waste liquid through a packed tower filled with the H-type cation exchange resin.
  • the adsorption step in the present invention is a step of adsorbing TAA ions to the cation exchange resin by passing a photoresist waste liquid through the packed tower.
  • a packed tower is a container that can be filled with a cation exchange resin and that can be circulated.
  • the tower body of the packed tower is not particularly limited, and known ones can be used. Specifically, for example, it is preferable that the tower body has a cylindrical structure made of SUS and has an internal structure having liquid inflow and outflow portions at the upper and lower portions.
  • the specific mode of passing the photoresist developing waste liquid through the packed tower can be appropriately determined according to the performance of the cation exchange resin.
  • the height (L) of the H-type cation exchange resin packed in the packed tower It is preferable that the ratio (L / D) to the packed tower diameter (D) is 0.5 or more and the space velocity (SV) of the photoresist developing waste liquid is 1 (h ⁇ 1 ) or more and 200 (h ⁇ 1 ) or less.
  • the amount of the photoresist developing waste solution to be passed is such that the adsorption amount of TAA ions is 70 to 90% with respect to the ion exchange capacity of the cation exchange resin.
  • TAA ion adsorption rate the amount of TAA ion adsorption relative to the ion exchange capacity of the cation exchange resin.
  • TAA ion adsorption rate When passing a photoresist waste liquid containing TAA ions through a packed column packed with an H-type cation exchange resin, for example, when a weakly acidic cation exchange resin is used, the TAA ion adsorption rate is about 40 to 60%. Until the TAA ions are adsorbed on the resin without flowing out of the packed tower, if the TAA ion adsorption rate exceeds about 40 to 60%, the TAA ion adsorption rate increases while the TAA ions gradually increase. Will flow out of the packed tower (hereinafter, TAA ions start to flow out of the packed tower may be referred to as “breakthrough”).
  • TAA ions In order to recover the TAA ions without loss, it is preferable to connect a plurality of packed towers in series and perform liquid flow. By passing through a plurality of packed towers connected in series, TAA ions that break through the preceding packed tower and flow out of the preceding packed tower can be adsorbed by the packed tower in the subsequent stage.
  • the photoresist development waste liquid contains a photoresist.
  • the pH of the photoresist developing waste liquid passing through the packed tower changes from acidic to neutral (pH 3 to 7).
  • the photoresist dissolves in an alkaline aqueous solution, and the solubility decreases in an acidic to neutral (pH 3 to 7) aqueous solution. Therefore, the solubility of the photoresist decreases with such a change in pH. Then, it is deposited and physically adsorbed on the cation exchange resin.
  • the photoresist precipitate physically adsorbed on the cation exchange resin prevents contact between the photoresist developing waste liquid and the cation exchange resin, and thus reduces the TAA ion adsorption rate of the cation exchange resin.
  • the pressure loss in the packed tower gradually increases until the TAA ions in the photoresist development waste liquid flow out (breakthrough) without being adsorbed by the cation exchange resin, and increase rapidly at the breakthrough timing. To do. After the breakthrough timing, the pH in the packed tower changes to alkaline, so that part of the deposited photoresist is redissolved and discharged out of the packed tower, and the pressure loss gradually decreases. That is, at the breakthrough timing, the amount of photoresist deposited in the packed tower is the largest, and the pressure loss is the largest due to the swelling of the resin.
  • the physical property value of the effluent from the packed tower before breakthrough occurs (hereinafter sometimes referred to as “pre-breakthrough effluent”) varies greatly depending on the content of the photoresist.
  • the conductivity is 0.005 to 0.1 mS / cm
  • the pH is about 3 to 7
  • the photoresist concentration is about 5 to 150 ppm.
  • the physical property value of the effluent from the packed tower after the start of TAA ion efflux from the packed tower (breakthrough) (hereinafter sometimes referred to as “discharge liquid after breakthrough”) is the pre-breakthrough discharge. From the range of the solution, the conductivity gradually increases to 0.05 to 25 mS / cm, pH to about 14, and photoresist concentration to about 10 to 200 ppm.
  • the TAAH concentration in the liquid discharged from the packed column packed with cation exchange resin is below the lower limit of quantification (5 ppm or lower) in the pre-breakthrough effluent, and from the lower limit of quantification in the pre-breakthrough effluent, Gradually increase to TAAH concentration in developer waste.
  • a solution having a high TAA ion concentration has high conductivity and pH.
  • the flow of the photoresist developing waste liquid is temporarily interrupted, and the cation exchange resin in the packed tower is washed.
  • the timing of the cleaning is the time when the physical property value of the effluent from the packed tower changes to a predetermined threshold value or more. Washing is performed by back washing.
  • Examples of the physical property value of the effluent from the packed tower include the conductivity and / or pH of the effluent. In the present invention, these physical property values are measured, and the monitored physical property value is a predetermined threshold value.
  • the flow of the photoresist developing waste liquid through the packed tower filled with the cation exchange resin is temporarily interrupted, and the cation exchange resin is back-washed.
  • the physical property value of the discharged liquid to be monitored can be appropriately selected and set by comparing various physical properties of the discharged liquid before breakthrough and the discharged liquid after breakthrough.
  • conductivity and / or pH are preferred.
  • the conductivity threshold is preferably selected from the range of 0.02 mS / cm to 0.1 mS / cm, and the pH threshold is 5 It is preferable to select from the range of 10 or less.
  • the TAAH concentration may be measured and used as a physical property value for monitoring.
  • the TAAH concentration threshold value it is preferable to select the TAAH concentration threshold value as the timing of interruption of liquid flow from the range of 5 ppm to 50 ppm.
  • a known method can be appropriately employed as a method for measuring the conductivity of the effluent from the packed tower. Specifically, a certain amount of the effluent discharged from the cation exchange resin packed tower is sampled, and the conductivity is measured using a conductivity meter, etc., or the in-line type conductivity is in the middle of the pipe through which the effluent passes. A method of measuring by installing a meter can be exemplified. According to the aspect using the in-line type conductivity meter, it is preferable because the liquid flow can be temporarily interrupted at the moment when the conductivity reaches a predetermined threshold without drawing the liquid halfway.
  • a threshold value based on a value obtained by statistically processing a plurality of measured values.
  • a known processing method can be appropriately employed. For example, a mode in which a value every predetermined time (for example, 0.1 second) is obtained and an arithmetic average or a geometric average value for a predetermined time (for example, 2 seconds) is employed can be cited.
  • Some commercially available conductivity meters are equipped with such statistical processing means and have a function of outputting the conductivity after statistical processing. In the present invention, such a conductivity meter is used as it is. It is also possible.
  • the time interval for measuring the conductivity needs to be changed mainly by the flow rate (flow velocity) of the effluent.
  • the flow rate flow velocity
  • pH When pH is adopted as the physical property value to be monitored, a known method can be appropriately employed as a method for measuring the pH of the effluent from the packed tower.
  • the pH of the fluid when the pH of the fluid is measured in-line using a general glass electrode type pH meter, it is about ⁇ 0.2 due to its characteristics and non-uniformity in the packing state of the resin in the adsorption tower. Often causes fluctuations. Therefore, in such a case, it is preferable to determine whether or not the pH value is equal to or greater than a threshold value based on a value obtained by statistically processing the pH value indicated by the pH meter. For example, when the statistical value reaches the predetermined threshold, the flow of the photoresist waste liquid to the packed tower can be interrupted.
  • Statistic processing methods can be appropriately adopted known processing methods. For example, a mode in which a value is obtained every predetermined time (for example, 0.1 seconds) and an arithmetic average or a geometric average value for a predetermined time (for example, 2 seconds) is employed can be exemplified.
  • Some commercially available pH meters are equipped with such statistical processing means and have a function of displaying the pH after statistical processing. In the present invention, such a pH meter can be used as it is. It is.
  • the backwashing step in the present invention is a step of washing the cation exchange resin during the adsorption step. Measure the physical property value of the effluent discharged from the packed tower as described above, and when the physical property value changes to a predetermined threshold value or higher, temporarily stop the flow of the photoresist developing waste liquid, and exchange the cation of the packed column. The resin is washed by backwashing.
  • Backwashing is an operation in which the photoresist deposited and physically adsorbed on the cation exchange resin is discharged from the packed tower by passing a cleaning solution in a direction opposite to the passing direction in the adsorption step.
  • the conditions for the backwashing are not particularly limited as long as the above-mentioned purpose is achieved, but the resin after backwashing with respect to the resin height at the time when the adsorption process (flow of the photoresist developing waste liquid to the packed tower) is temporarily interrupted. It is preferable to pass the liquid so that the height is 1.3 times or more and 2.0 times or less.
  • the washing liquid is preferably passed through until the discharged liquid discharged from the packed tower becomes transparent.
  • air scrubbing may be performed before backwashing or during backwashing to release the cation exchange resin. By performing air scrubbing, the cation exchange resin can be released, so that the amount of cleaning liquid used can be suppressed.
  • the gas used for air scrubbing is not particularly limited as long as the solubility in water is low, and various inert gases such as nitrogen, air, and the like can be used.
  • the air scrubbing method is not particularly limited as long as it can blow and blow the air in the direction opposite to the liquid flow in the adsorption process to develop and solve the cation exchange resin.
  • the liquid passing space velocity (SV) in the backwashing step is preferably 1 (h ⁇ 1 ) to 100 (h ⁇ 1 ), and preferably 3 (h ⁇ 1 ) to 50 (h ⁇ 1 ). More preferred.
  • the space velocity is higher, the cation exchange resin in the packed tower is sufficiently developed, and the photoresist is less likely to remain in the packed tower.
  • the space velocity is smaller, resin crushing due to physical collision between the resins due to the development of the cation exchange resin is less likely to occur, and the TAA ion adsorption rate is less likely to decrease.
  • the amount of the cleaning solution used in the backwashing step can be appropriately set according to the size of the adsorption tower, the type and amount of cation exchange resin used.
  • the liquid flow rate (BV) is 1 (L / L-resin) or more and 15 (L / L-resin) or less, more preferably 2 (L / L-resin) or more and 7 (L / L-). Resin)
  • the flow rate (BV) can be 2 (L / L-resin) or more and 4 (L / L-resin) or less.
  • the photoresist may not be sufficiently discharged from the packed tower. If it is greater than 4 (L / L-resin), the backwash process The amount of discharged liquid becomes large.
  • the cleaning liquid used in the reverse purification step is not particularly limited as long as it is a liquid that can discharge the photoresist from the packed tower without eluting TAA ions.
  • photoresist developing waste liquid TAAH aqueous solution, ultrapure water, pure water, and ion-exchanged water can be exemplified, and among them, the photoresist developing waste liquid is most preferable.
  • the determination as to whether or not the backwashing has been sufficiently performed is performed by, for example, UV / visible light of the effluent from the packed tower in the backwashing process. It can also be done by monitoring absorption and / or turbidity. UV / visible light absorption corresponds to the content of the photoresist component in the effluent, and turbidity corresponds to the content of the suspended component in the effluent. If the photoresist precipitate is not dissolved in the cleaning solution, the precipitate is suspended in the solution, thus increasing the turbidity of the effluent.
  • the backwashing process should be performed only for the time required for the required time without monitoring the effluent of the backwashing process. Is also possible.
  • the photoresist developing waste solution When the photoresist developing waste solution is used as a cleaning solution in the backwashing process, the photoresist developing waste solution contains TAAH, and the photoresist deposited and physically adsorbed on the cation exchange resin in the packed tower may be redissolved. Therefore, the photoresist deposit can be efficiently discharged out of the packed tower. Further, since the waste liquid is reused, the cost can be suppressed.
  • the cleaning liquid discharged from the packed tower in the backwashing step may be discarded, but since it contains a small amount of TAA ions, it can be returned to the photoresist developing waste liquid.
  • the discharged cleaning liquid is filtered by microfiltration, NF (nanofiltration), RO (reverse osmosis membrane filtration), crossflow filtration, etc. After removing the photoresist, it may be returned to the photoresist developing waste liquid.
  • the photoresist deposited and physically adsorbed on the cation exchange resin is discharged out of the packed tower, and further, the cation exchange resin particles adhered by the photoresist deposit are dispersed.
  • the pressure loss in the packed tower can be maintained at a low level even when the photoresist development waste liquid (adsorption process) is restarted.
  • the cation exchange resin particles in the packed tower are dissolved by passing through a backwashing process, and the photoresist that has precipitated and physically adsorbed on the cation exchange resin in the packed tower is dispersed or washed in the cleaning liquid. It is redissolved and discharged outside the packed tower.
  • the increase in pressure loss caused by the photoresist deposit is canceled, so that the adsorption process can be performed again efficiently.
  • TAA ions remain adsorbed on the cation exchange resin, so the concentration of the TAA salt recovered in the elution step described later is not affected.
  • the flow rate of the photoresist developing waste liquid in the resumed adsorption process may be set so that the TAA ion adsorption rate is 70 to 90%. As described above, when the adsorption rate of TAA ions is lower than this, the concentration of the recovered TAA salt is lowered in the elution step described later.
  • the photoresist deposits are discharged out of the packed tower by performing the backwashing earlier. Further, when a photoresist developing waste solution or a TAAH aqueous solution is used as a cleaning solution for backwashing, the pH in the packed tower becomes alkaline when the adsorption process is restarted. Therefore, an increase in pressure loss and a decrease in TAA ion adsorption rate are suppressed.
  • the elution step of recovering TAA ions adsorbed on the cation exchange resin as a TAA salt is not particularly limited, and a known method can be used.
  • a known method can be used.
  • TAA ions adsorbed on the cation exchange resin can be eluted, and the TAA salt can be recovered.
  • Specific examples of acids and salts that can be used in the elution step include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, carbonate, bicarbonate, and the like.
  • the concentration of the TAA salt obtained in the elution step is comparable to that in the case of not performing the backwashing step. Is.
  • the TAA salt obtained by the production method of the present invention can be converted to TAAH by electrolysis or electrodialysis. Further, prior to electrolysis and dialysis, metal ions can be removed with an ion exchange resin, a chelate resin, or the like, if necessary.
  • the conductivity was measured with a conductivity meter (measuring device: SC72-21JAA (manufactured by Yokogawa Electric Corporation)).
  • the pH was measured by the pH electrode method (measuring device: HM-30R (manufactured by Toa DKK Corporation)).
  • the TMAH concentration was measured by an ion chromatographic method (measuring device: DX320 (Dionex)). COD was analyzed by oxygen consumption by potassium permanganate at 100 ° C. (JIS K 0101).
  • TMAH-containing waste liquid discharged from a semiconductor factory was used.
  • the TMAH concentration was 6500 ppm
  • the conductivity was 15.92 mS / cm
  • the pH was 13.2
  • the COD was 121 ppm.
  • the water quality of the effluent discharged from the packed tower first after the start of liquid flow was TMAH concentration of 5 ppm or less, conductivity of 0.02 mS / cm, pH of 4.5, and COD of 82 ppm.
  • the pressure loss of the packed tower was 0.01 MPa.
  • the water quality of the discharged liquid from the packed tower was 50 ppm TMAH, conductivity 0.10 mS / cm, pH 6.1, and COD 102 ppm. Interrupted. At this time, the pressure loss of the packed tower was 0.02 MPa.
  • the water quality of the effluent discharged from the packed tower first after the start of liquid flow was TMAH concentration of 5 ppm or less, conductivity of 0.02 mS / cm, pH of 3.9, and COD of 77 ppm.
  • the pressure loss of the packed tower was 0.01 MPa.
  • the water quality of the discharged liquid was temporarily interrupted because the TMAH concentration was 40 ppm, the conductivity was 0.08 mS / cm, pH 5.8, and the COD was 95 ppm. At this time, the pressure loss of the packed tower was 0.02 MPa.
  • the water quality of the discharged liquid first discharged from the packed tower after the start of liquid flow was TMAH concentration of 5 ppm or less, conductivity of 0.02 mS / cm, pH of 4.2, and COD of 89 ppm.
  • the pressure loss of the packed tower was 0.01 MPa.
  • the water quality of the discharged liquid from the packed tower was 35 ppm for TMAH, 0.07 mS / cm for conductivity, pH 5.8, and 100 ppm for COD. Interrupted. At this time, the pressure loss of the packed tower was 0.02 MPa.
  • the water quality of the discharged liquid first discharged from the packed tower after the start of liquid flow was TMAH concentration of 5 ppm or less, conductivity of 0.03 mS / cm, pH 3.8, and COD of 92 ppm.
  • the pressure loss of the packed tower was 0.01 MPa.
  • the water quality of the discharged liquid was temporarily interrupted because TMAH was 50 ppm, conductivity was 0.10 mS / cm, pH 6.2, and COD was 118 ppm. At this time, the pressure loss of the packed tower was 0.03 MPa.
  • the water quality of the discharged liquid first discharged from the packed tower after the start of liquid flow was TMAH concentration of 5 ppm or less, conductivity of 0.02 mS / cm, pH 4.4, and COD of 79 ppm.
  • the pressure loss of the packed tower was 0.01 MPa.
  • the water quality of the discharged liquid was temporarily suspended because TMAH was 40 ppm, conductivity was 0.08 mS / cm, pH 5.9, and COD was 107 ppm. At this time, the pressure loss of the packed tower was 0.02 MPa.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

Cette invention concerne un procédé de préparation d'une solution aqueuse de sel d'ammonium tétra-alkyle à partir d'une solution résiduaire de développement de photoréserve, lequel procédé comprend une étape d'adsorption destinée à adsorber des ions d'ammonium tétra-alkyle dans une résine échangeuse de cations en faisant passer un liquide résiduaire de développement de photoréserve contenant un hydroxyde d'ammonium tétra-alkyle dans une colonne garnie remplie d'une résine échangeuse de cations de type ions d'hydrogène, et une étape d'élution pour éluer, en tant que solution aqueuse du sel d'ammonium tétra-alkyle, les ions d'ammonium tétra-alkyle adsorbés à l'étape d'adsorption. Dans l'étape d'adsorption, une valeur des propriétés physiques de l'effluent évacué de la colonne garnie est mesurée, et lorsque ladite valeur des propriétés physiques passe au seuil prédéfini ou au seuil supérieur, l'écoulement de la solution résiduaire de photoréserve est provisoirement interrompu et une étape de lavage à contre-courant est effectuée au cours de laquelle la résine échangeuse de cations de la colonne garnie est lavée à contre-courant, et ensuite, on fait passer à nouveau la solution résiduaire de développement de photoréserve dans la colonne garnie.
PCT/JP2014/069973 2013-07-30 2014-07-29 Procédé de préparation de solution aqueuse de sel d'ammonium tétra-alkyle WO2015016230A1 (fr)

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JP2013158229A JP2016174979A (ja) 2013-07-30 2013-07-30 テトラアルキルアンモニウム塩水溶液の製造方法
JP2013-158229 2013-07-30

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113200869A (zh) * 2021-04-28 2021-08-03 南京长江江宇环保科技有限公司 一种从半导体显影废水中回收四甲基氯化铵的方法

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JP7456027B1 (ja) 2023-01-18 2024-03-26 三福化工股▲分▼有限公司 現像廃液中の水酸化テトラメチルアンモニウムを回収して含窒素化合物を除去する方法及びその装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0515875A (ja) * 1990-11-09 1993-01-26 Ebara Corp イオン交換樹脂による混床式ろ過脱塩方法
JP2003340449A (ja) * 2002-05-27 2003-12-02 Babcock Hitachi Kk テトラアルキルアンモニウムヒドロキシド含有廃水の処理方法
WO2012090699A1 (fr) * 2010-12-28 2012-07-05 株式会社トクヤマ Procédé de production d'un sel de tétraalkylammonium, et procédé de production d'un hydroxyde de tétraalkylammonium utilisant celui-ci comme matière première
WO2012157448A1 (fr) * 2011-05-17 2012-11-22 オルガノ株式会社 Équipement échangeur d'ions
JP2012236939A (ja) * 2011-05-13 2012-12-06 Kotobuki Kakoki Kk 不凍液の再生処理方法、及び不凍液の再生処理システム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0515875A (ja) * 1990-11-09 1993-01-26 Ebara Corp イオン交換樹脂による混床式ろ過脱塩方法
JP2003340449A (ja) * 2002-05-27 2003-12-02 Babcock Hitachi Kk テトラアルキルアンモニウムヒドロキシド含有廃水の処理方法
WO2012090699A1 (fr) * 2010-12-28 2012-07-05 株式会社トクヤマ Procédé de production d'un sel de tétraalkylammonium, et procédé de production d'un hydroxyde de tétraalkylammonium utilisant celui-ci comme matière première
JP2012236939A (ja) * 2011-05-13 2012-12-06 Kotobuki Kakoki Kk 不凍液の再生処理方法、及び不凍液の再生処理システム
WO2012157448A1 (fr) * 2011-05-17 2012-11-22 オルガノ株式会社 Équipement échangeur d'ions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113200869A (zh) * 2021-04-28 2021-08-03 南京长江江宇环保科技有限公司 一种从半导体显影废水中回收四甲基氯化铵的方法
CN113200869B (zh) * 2021-04-28 2023-06-23 南京长江江宇环保科技股份有限公司 一种从半导体显影废水中回收四甲基氯化铵的方法

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