WO2023210370A1 - 有機溶媒の精製方法及び精製装置 - Google Patents

有機溶媒の精製方法及び精製装置 Download PDF

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WO2023210370A1
WO2023210370A1 PCT/JP2023/014876 JP2023014876W WO2023210370A1 WO 2023210370 A1 WO2023210370 A1 WO 2023210370A1 JP 2023014876 W JP2023014876 W JP 2023014876W WO 2023210370 A1 WO2023210370 A1 WO 2023210370A1
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organic solvent
exchange resin
ion exchange
purification
purifying
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PCT/JP2023/014876
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English (en)
French (fr)
Japanese (ja)
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夕佳里 似内
智子 ▲高▼田
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オルガノ株式会社
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Priority to JP2024517979A priority Critical patent/JPWO2023210370A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • 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
    • B01J39/05—Processes using organic exchangers in the strongly acidic form
    • 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
    • B01J39/07—Processes using organic exchangers in the weakly acidic form
    • 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
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • 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
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • 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
    • B01J47/026—Column or bed processes using columns or beds of different ion exchange materials in series
    • B01J47/028—Column or bed processes using columns or beds of different ion exchange materials in series with alternately arranged cationic and anionic 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
    • B01J47/04—Mixed-bed processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to an organic solvent purification method and purification apparatus.
  • the line width of semiconductor devices is determined by the photoresist process.
  • the photoresist process includes a process of applying a resist to a silicon wafer, an exposure process of irradiating short wavelength light from a light source through a mask, and a process of developing the resist mask. Furthermore, the method includes a step of etching the exposed portion through the resist mask, and a step of peeling off the resist mask.
  • the resist applied to the wafer is a composition in which an acid generator, a resin solution, and additives are dissolved in an organic solvent. (monomethyl ether) etc. are used. In addition, various organic solvents are used in developing solutions, rinsing solutions, stripping solutions, chemical mechanical polishing (CMP) slurries, cleaning solutions after CMP, and the like.
  • Patent Document 1 discloses a purifier that removes Cr from an organic solvent.
  • the purifier includes an ion exchange resin and a porous membrane downstream of the ion exchange resin within a housing having a fluid inlet and a fluid outlet in fluid communication.
  • Patent Document 2 discloses a depth filter that includes a porous molded body that is a sintered product of a mixed powder containing a dry gel powder and a thermoplastic resin powder or a swollen body thereof, in order to efficiently remove metal ions in water to be treated. is disclosed.
  • Patent Document 3 discloses that the method includes, in random order, a filtration step of filtering the object to be purified, an ion removal step of subjecting the object to purification to ion exchange or ion adsorption using a chelate group, and a distillation step of distilling the object to be purified.
  • a method for producing a drug solution is disclosed. This is to provide a drug that has excellent defect suppression performance even after long-term storage when used in the manufacturing process of semiconductor devices.
  • the purification device is installed in the order of distillation step, ion removal step using ion exchange resin, distillation step, and filtration step using a filter.
  • an object of the present invention is to provide a purification method and a purification apparatus that reduce metal impurities in an organic solvent.
  • the present invention is a purification method for reducing metal impurities in an organic solvent, which includes a filtration step of filtering the organic solvent with a particle removal filter, and an ion exchanger in which the organic solvent obtained in the filtration step is passed through an ion exchanger.
  • a method for purifying an organic solvent characterized in that it includes an exchange step.
  • the present invention also provides a purification device for reducing metal impurities in an organic solvent, which includes a particle removal filter for filtering the organic solvent, and an ion exchanger for passing the organic solvent obtained after the filtration.
  • An apparatus for purifying an organic solvent characterized in that it includes an ion exchange means for purification.
  • FIG. 1 is a conceptual diagram showing an embodiment of a purification device according to the present invention.
  • FIG. 1 is a conceptual diagram showing an embodiment of the purification device according to the present invention as a circulation system.
  • FIG. 3 is a conceptual diagram showing another embodiment of the purification device according to the present invention.
  • the purification method for reducing metal impurities in an organic solvent according to the present invention includes a filtration step of filtering the organic solvent of the liquid to be treated using a particle removal filter, and passing the organic solvent obtained in the filtration step through an ion exchanger. and an ion exchange step.
  • the organic solvent to be purified is not particularly limited as long as it is an organic solvent used in the manufacturing process of electronic equipment such as semiconductor devices, but EL grade organic solvents are preferable. According to studies by the present inventors, even with EL grade organic solvents, metal impurities in IPA (isopropyl alcohol) and thinner (PGMEA/PGME) can be removed using an ion exchange resin. However, in the case of PGMEA alone and nBA (n-butyl acetate), it has been found that removal of metal impurities, particularly Cr, is insufficient with ion exchange resin alone. As disclosed in the background art, even if a particle removal filter is provided after the ion exchange step, Cr ions remain in the organic solvent.
  • the upper limit of the concentration of each metal element in the organic solvent is not particularly limited, but for example, EL grade PGMEA manufactured by Tokyo Ohka Kogyo Co., Ltd. contains Na, Ca, Cr, and Fe as metal impurities. were included, and the concentration of each was 100 ppt or less.
  • Kanto Kagaku Co., Ltd.'s deer special grade PGMEA contains Na, Ca, Cr, Fe, Ni, Cu, and Zn, and the respective concentrations are 10 ppb or less for Na, and 10 ppb or less for Ca, Cr, Fe, and Ni. , Cu, and Zn were 200 ppt or less.
  • the lower limit is above the purification target concentration, specifically above the detection limit for concentration measurement.
  • examples of metal impurities contained in the organic solvent include Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Ag, Cd, Examples include Ba, Pb, etc., but the purification method and production apparatus of the present invention can particularly reduce Cr.
  • the particle removal filter is not particularly limited as long as it can remove metal impurity particles, but the pore diameter on the surface is preferably 1000 nm or less, more preferably 100 nm or less. Further, the lower limit of the pore diameter is preferably at a level where pressure load on the device does not become a problem, preferably 2 nm or more, and more preferably 5 nm or more.
  • the pore diameter refers to the average value of the pore diameters of the porous membrane, and is measured by the bubble point method using IPA or HFE-7200 (manufactured by 3M).
  • the material of the particulate filter is not particularly limited as long as it is resistant to the organic solvent to be purified.
  • the particle removal filter should be washed with a solvent that does not contain metal elements before use, and then it should be confirmed by measurement that no metal elements are leached from the particle removal filter. It is preferable to use it after
  • the ion exchanger of the present invention is not particularly limited as long as it is a substance that exhibits an ion exchange phenomenon, but is preferably an ion exchange resin.
  • Ion exchange resins include chelate resins, cation exchange resins, and anion exchange resins, and any of these resins may be used in the present invention.
  • the ion exchanger of the present invention also includes a monolithic ion exchanger comprising a continuous skeleton and continuous pores.
  • chelate resins and cation exchange resins must be purified by contacting them with a mineral acid solution that contains 1 mg/L or less of metal impurities and has a concentration of 5% by mass or more to obtain purified ion exchange resins.
  • mineral acids include hydrochloric acid, sulfuric acid, nitric acid, and the like.
  • the amount of total metal impurities eluted when hydrochloric acid having a concentration of 3% by mass is passed through the purified ion exchange resin at a volume ratio of 25 times is 5 ⁇ g/mL-R or less.
  • “25 times the volume ratio” means that 25 times the volume of hydrochloric acid is passed through the volume of the ion exchange resin.
  • the unit "/mL-R” means "per 1 mL volume of ion exchange resin in a saturated equilibrium state". Note that the saturated equilibrium state refers to a state in which the ion exchange resin is brought into a saturated state by contacting it with the atmosphere at 25° C. and 100% relative humidity for 30 minutes or more.
  • Passing hydrochloric acid includes passing hydrochloric acid through the ion exchange resin, as well as immersing the ion exchange resin in hydrochloric acid.
  • the total amount of metal impurities per mL of ion exchange resin volume ( ⁇ g/mL-R) is determined by the amount of each metal impurity eluted ( ⁇ g/L), the volume of the eluent used for elution (L), and the volume of the chelate resin ( mL), it can be calculated by the following formula.
  • Total amount of metal impurities ( ⁇ g/mL-R) (Amount of each metal impurity ( ⁇ g/L) x Volume of eluent (L)) / Volume of ion exchange resin (mL)
  • the ion exchange resin according to the present invention can be a single bed of a chelate resin or a cation exchange resin, or a mixed bed or double bed of these two types.
  • the cation exchange resin is preferably weakly acidic.
  • a cation exchange resin and a chelate resin may be used in a mixed bed or in a double bed.
  • the amount of chelate resin used is preferably 50% or more and 99% or less of the total amount of chelate resin and cation exchange resin.
  • the chelate resin used in the present invention is a resin that has a functional group (chelate group) that can form a chelate (complex) with a metal ion. Since chelate resins do not have strong acidic or strong basic functional groups, it is possible to purify ester-based organic solvents that are prone to hydrolysis to a high degree of purity. Therefore, it is preferable to use a single bed of chelate resin.
  • the functional group of the chelate resin include an aminomethyl phosphate group, an iminodiacetic acid group, a thiol group, and a polyamine group having a weak anionic exchange group. From the viewpoint of selectivity to a plurality of metal species, the chelate resin preferably has an aminomethyl phosphate group or an iminodiacetic acid group as a functional group.
  • the chelate resin is preferably in H form as an initial ionic form.
  • Orlyte (registered trademark) DS-21 (trade name, manufactured by Organo Co., Ltd., chelate group: aminomethyl phosphate group)
  • Orlyte (registered trademark) DS-22 (trade name, manufactured by Organo Co., Ltd., chelate group) : iminodiacetic acid group)
  • Ambersep (registered trademark) IRC747UPS trade name, manufactured by DuPont, chelate group: aminomethyl phosphate group
  • Ambersep (registered trademark) IRC748 (trade name, manufactured by DuPont, chelate group: iminodiacetic acid group
  • Ambersep (registered trademark) IRC743 (trade name, manufactured by DuPont, chelate group: N-methylglucamine), Diaion (registered trademark) CR11 (trade name, manufactured by Mitsubishi Chemical Corporation, chelate) S930 (trade name, produced by Pur
  • the initial ionic form of the resin is a salt form other than the H form (for example, a sodium ion form)
  • it can be used after being converted to the H form by a known method.
  • the salt form can be converted to the H form by washing with the mineral acid described above.
  • cation exchange resins used in the present invention include strongly acidic cation exchange resins having a sulfonic acid group (-SO 3 H) and weakly acidic cation exchange resins having a carboxylic acid group (-COOH).
  • cation exchange resins are of a transparent gel type with small pore diameters and macroliterular (MR type) or macroporous types (porous type, high porous type) that have macropores with large pore diameters. It may be either of the following.
  • Examples of the cation exchange resin used in the present invention include Orlite (registered trademark) DS-1 (trade name, manufactured by Organo Co., Ltd.), Orlite (registered trademark) DS-4 (trade name, manufactured by Organo Co., Ltd.) , Amberlight (registered trademark) IRC76 (product name, manufactured by DuPont), Amberlight (registered trademark) HPR8400H (product name, manufactured by DuPont), Orlite (registered trademark) 15JS-HG ⁇ DRY (product name, Organo Co., Ltd.) ), Amberlite (registered trademark) IRN99H (trade name, manufactured by DuPont), Amberlite (registered trademark) CR99 K/350 (trade name, manufactured by DuPont), etc., but are not limited to these. isn't it.
  • an anion exchange resin can also be used as a single bed.
  • the anion exchange resin is preferably weakly basic.
  • an anion exchange resin can be used in combination with the chelate resin and the cation exchange resin.
  • the anion exchange resin may be a mixed bed or double bed of at least one of a chelate resin and a cation exchange resin.
  • a cation exchange resin, a chelate resin, and an anion exchange resin may be used in a mixed bed or in a double bed.
  • the amount of the anion exchange resin used is preferably 25% or more and 100% or less based on the total amount of the cation exchange resin and any chelate resin.
  • anion exchange resin examples include strongly basic anion exchange resins having a quaternary ammonium base and weakly basic anion exchange resins having primary to tertiary amino groups.
  • anion exchange resins include Orrite (registered trademark) DS-2, DS-6, Orrite (registered trademark) B20-HG/DRY (all trade names manufactured by Organo Co., Ltd.), etc. It is not limited to these.
  • Pre-treatment process Before using cation exchange resins, chelate resins, and anion exchange resins (hereinafter collectively referred to as "ion exchange resins") for purification of organic solvents, if necessary, remove the ion exchange resin from the ion exchange resin.
  • the ion exchange resin may be dried, or a dried or undried product may be pretreated. That is, the purification method according to the present invention may include, before the filtration step and the ion exchange step, a pretreatment step of performing a drying step or pretreatment to suppress water elution from the ion exchange resin. .
  • Common methods for drying include heating drying using hot air below the maximum operating temperature of the ion exchange resin, freeze drying, and vacuum drying that combines heating and reduced pressure.
  • vacuum drying does not require extremely high temperatures, so it has the advantage of being applicable to anion exchange resins with low heat resistance, and is the most common method. Further, vacuum drying may be performed in combination after replacing water contained in the resin with a non-aqueous solution or the like.
  • Examples of the pretreatment method include contacting an ion exchange resin with an organic solvent to be purified, or contacting an ion exchange resin with an organic solvent for pretreatment having a dielectric constant higher than that of the organic solvent to be purified. It will be done. Specifically, the organic solvent to be purified is passed through a column filled with ion exchange resin before being used for purification until the water concentration in the solvent at the inlet and outlet of the column becomes similar. One method is to continue adding liquid. In addition, a pretreatment organic solvent with a dielectric constant higher than that of the organic solvent to be purified is passed through a column filled with ion exchange resin before being used for purification, and water in the solvent at the inlet and outlet of the column is removed.
  • An example of this method is to continue passing the solution until the concentration is about the same.
  • the organic solvent to be purified may be further passed through the column until the water concentration in the solvent at the inlet and outlet of the column becomes approximately the same.
  • the organic solvent for pretreatment alcohols such as methanol and ethanol having a dielectric constant of 20 or more at 25° C. are preferably used.
  • the method of bringing the organic solvent into contact with the ion exchange resin after passing through the particle removal filter is not particularly limited, and includes a batch treatment method and a continuous solution treatment method using a column. From the viewpoint of operability and efficiency, a continuous liquid flow treatment method is preferred.
  • the organic solvent is filtered using a particle removal filter, and the filtered organic solvent is recovered.
  • the recovered organic solvent is filled into a reaction tank equipped with a stirrer and loaded with an ion exchange resin.
  • the volume ratio is not particularly limited, it is preferable that the volume ratio is 2 to 200 parts of the organic solvent to 1 part of the resin. Thereafter, it is left for about 0.5 to 24 hours, for example.
  • a stirrer is operated to uniformly mix the ion exchange resin and organic solvent.
  • the stirring speed and stirring time may be appropriately determined depending on the size of the reaction tank, the throughput, etc. After the stirring is completed, by performing filtration or the like to separate the ion exchange resin and the organic solvent, a purified organic solvent with reduced metal impurities can be obtained.
  • the ion exchange resin is packed into a purification tower such as a column.
  • the height of the resin packed bed in the purification tower is not particularly limited, and can be, for example, 100 to 1500 mm.
  • an organic solvent is passed through, for example, at an SV (space velocity, h ⁇ 1 ) of 2 to 20 and 2 to 100 BV.
  • BV Bed volume
  • the organic solvent is preferably passed at SV 2 to 20, more preferably SV 5 to 10.
  • the direction of liquid flow may be either downward flow or upward flow.
  • the purification member such as the column used for the pretreatment can be used as is. can be used to carry out an ion exchange step in which an ion exchange resin is brought into contact with an organic solvent.
  • FIG. 1 shows a schematic diagram of an organic solvent purification apparatus according to the present invention, which includes a storage tank 2 for storing an organic solvent 1 to be purified, and a particle removal filter 3 for filtering the organic solvent from the storage tank 2. It includes a liquid line and purification means for purifying the filtered organic solvent by passing it through a column 4 filled with an ion exchange resin. Furthermore, a cleaning line for cleaning the particle removal filter and a cleaning line for cleaning the ion exchange resin can be provided. The purified organic solvent is recovered by measuring whether the metal concentration has reached a reference value using a metal content measuring means (not shown).
  • the organic solvent purification device may perform processing using a circulation system as shown in FIG.
  • the organic solvent purified by passing through the particle removal filter 3 and the column 4 filled with ion exchange resin is returned to the storage tank 2 through the circulation line CL and repeatedly purified.
  • the metal content in the storage tank 2 is measured, and it is recovered after confirming that the metal concentration has reached the standard value.
  • back pressure can be applied from the slow particle filter to the outlet of the column packed with ion exchanger during liquid flow.
  • the back pressure is preferably 0.01 MPa to 1 MPa, more preferably 0.05 MPa to 0.1 MPa.
  • ion exchange resins which are particulate ion exchangers, have more functional groups inside the resin than on the surface, so they are susceptible to short paths caused by the generation of bubbles. Furthermore, in high-level purification at ppt level, such short paths are particularly undesirable because they destabilize performance.
  • a distillation column capable of distilling the organic solvent can be provided before the organic solvent purification device. Distillation can also remove inorganic particles. Thereby, after a certain amount of metal impurities are separated by distillation, trace metals can be further reduced and the organic solvent can be highly purified using the organic solvent purification device.
  • a particle removal filter and an ion exchanger may be provided in this order for rough purification before the organic solvent purification device.
  • a particle removal filter may be further combined with the ion exchanger in the organic solvent purification device.
  • FIG. 3 shows a configuration in which a second particle removal filter 5 is disposed downstream of the purification means.
  • the amount of metal impurities is measured after the organic solvent is purified for the purpose of reducing metal impurities.
  • the metal content is monitored online, and if the metal content is higher than the standard value, the organic solvent is automatically returned to the organic solvent purification device and the organic solvent is purified again.
  • organic solvent purification apparatus With the organic solvent purification apparatus according to the present invention, metal impurities in the organic solvent used immediately before the point of use in the semiconductor manufacturing process can be reduced and the organic solvent can be purified to a high degree of purity.
  • a filter using an ion exchange membrane may be combined at a subsequent stage of the purification means using an ionic resin in the organic solvent purification device.
  • resin purification reduces the load of metal impurities on the downstream stage, so it can be expected that the life of the ion exchange membrane at the downstream stage will be extended.
  • ion exchange resin ⁇ Chelate resin (product name: Allite (registered trademark) DS-21, manufactured by Organo Co., Ltd.) ⁇ Cation exchange resin (product name: Allite (registered trademark) DS-4, manufactured by Organo Co., Ltd.) ⁇ Anion exchange resin (product name: Allite (registered trademark) DS-6, manufactured by Organo Co., Ltd.) (organic solvent) ⁇ PGMEA (propylene glycol monomethyl ether acetate, manufactured by Kanto Kagaku Co., Ltd.) ⁇ nBA (Normal Butyl Acetate, manufactured by Taiwan Maxwave) (particle removal filter) Particle removal filter: UPE disposable filter (pore diameter: 5 nm, membrane area: 2300 cm 2 )
  • Example 1 A PFA column (inner diameter: 16 mm, height: 300 mm) was connected in series after the particle removal filter.
  • the PFA column was filled with a chelate resin, a cation exchange resin, and an anion exchange resin so that the total amount was 72 mL.
  • the volume ratio of the chelate resin, cation exchange resin, and anion exchange resin was 75:25:100.
  • hydrochloric acid having a concentration of 3% by mass is passed through the purified ion exchange resin at a volume ratio of 25 times, the amount of total metal impurities eluted is 5 ⁇ g/mL-R or less.
  • alcohol with a water concentration of 50 ppm or less was passed through the column until the water content at the column outlet became 200 ppm or less.
  • PGMEA having a water concentration of 50 ppm or less was passed through the column until the water concentrations in the PGMEA at the column inlet and the column outlet became equal, thereby removing the water in the ion exchange resin.
  • Filtration step and ion exchange step PGMEA was purified by passing it through a PFA column filled with a particle removal filter and a pretreated ion exchange resin. During liquid passage, purification was performed by adjusting a back pressure of 0.01 MPa or more to be applied from the particle filter to the outlet of the PFA column packed with ion exchange resin. The treated solution before and after purification was sampled and the Cr concentration was measured. The Cr concentration was measured using an inductively coupled plasma mass spectrometer (ICP-MS). The rate at which PGMEA was passed was set at a rate of five times the total volume of the chelate resin, cation exchange resin, and anion exchange resin per hour.
  • ICP-MS inductively coupled plasma mass spectrometer
  • Example 2 PGMEA was purified in the same manner as in Example 1, except that a chelate resin and a cation exchange resin were used as the ion exchange resins, and the treated liquids before and after purification were sampled to measure the Cr concentration.
  • PGMEA was purified in the same manner as in Example 1, except that only a particle filter was used without using an ion exchange resin, and the treated liquid before and after purification was sampled to measure the Cr concentration.
  • Example 3 PGMEA was purified in the same manner as in Example 1, except that only a chelate resin was used as the ion exchange resin, and the treated solution before and after purification was sampled to measure the Cr concentration.
  • Comparative example 4 PGMEA was purified in the same manner as in Comparative Example 3, except that a chelate resin and an anion exchange resin were used as the ion exchange resins, and the treated liquids before and after purification were sampled to measure the Cr concentration.
  • Example 4 PGMEA was purified in the same manner as in Example 1, except that a particle filter with a pore size of 100 nm was used, and the treated liquid before and after purification was sampled to measure the Cr concentration.
  • Comparative example 5 PGMEA was purified in the same manner as in Comparative Example 1, except that a particle filter with a pore size of 1000 nm was used, and the treated liquid before and after purification was sampled to measure the Cr concentration.
  • Comparative example 6 PGMEA was purified in the same manner as in Comparative Example 5, except that a particle filter with a pore size of 3000 nm was used, and the treated liquid before and after purification was sampled to measure the Cr concentration.
  • Example 5 PGMEA was purified in the same manner as in Example 4, except that a particle filter with a pore size of 1000 nm was used, and the treated liquid before and after purification was sampled to measure the Cr concentration.
  • Example 6 Purification was performed in the same manner as in Example 2, except that nBA was used as the organic solvent, and the Cr concentration was measured by sampling the treated liquid before and after purification. However, as the ion exchange resin, a chelate resin and an anion exchange resin were used.
  • Example 7 nBA was purified in the same manner as in Example 6, except that a particle filter with a pore size of 1000 nm was used, and the treated liquid before and after purification was sampled to measure the Cr concentration.
  • Example 8 Purification was performed in the same manner as in Example 3, except that the PFA column and storage tank were connected in series after the particle removal filter, and the treated liquid before and after purification was sampled to measure the Cr concentration.
  • the storage tank was made of PFA and had a capacity of 1 L.
  • the PGMEA in the tank was returned to the fine particle filter by pumping, and a continuous circulation process was performed.
  • the rate at which PGMEA was passed was set at a rate of 5 times the volume of the chelate resin per hour, and the solution was passed for 18 hours. After passing the solution for 18 hours, the treatment solution was collected.
  • Example 1 when a chelate resin, a cation exchange resin, and an anion exchange resin were used as the ion exchange resin, in Example 2, when a chelate resin and a cation exchange resin were used, and in Example 3, a chelate resin It has become clear that Cr in an organic solvent can be reduced when only Cr is used. Furthermore, in Examples 4 and 5, it was revealed that Cr in the organic solvent could be reduced when the particle removal filter had a pore diameter of 100 nm or 1000 nm. Furthermore, in Examples 6 and 7, it was revealed that Cr could be reduced even when nBA was used instead of PGMEA as the organic solvent. In Example 8, it was revealed that Cr could be reduced even if PGMEA was purified by continuous circulation treatment.
  • Comparative Example 1 Cr could not be reduced even if the organic solvent was purified using only a particle removal filter without using an ion exchange resin.
  • Comparative Example 2 Cr could not be reduced even if the organic solvent was purified using an ion exchange resin and a particle removal filter in that order.
  • Comparative Example 3 Cr could not be reduced even when only a chelate resin was used as the ion exchange resin without using a particle removal filter.
  • Comparative Example 4 as in Comparative Example 3, only an ion exchange resin was used without using a particle removal filter, and even though a chelate resin and an anion exchange resin were used as the ion exchange resins, Cr could not be reduced.
  • Comparative Example 5 it was revealed that when the pore diameter of the particle removal filter was 1000 nm, it was possible to partially reduce Cr in the organic solvent.
  • Comparative Example 6 when the particle removal filter had a pore diameter of 3000 nm, Cr in the organic solvent could not be reduced at all.
  • Reference Example A thinner containing 30% PGMEA and 70% (volume ratio) PGMEA and IPA were purified using only an ion exchange resin.
  • the resin used was a mixed bed of a chelate resin (DS-21), a cation exchange resin (DS-1), and an anion exchange resin (DS-3). The results are shown in Table 2 below.
  • Cr can be reduced to less than 2 ppt using only a chelate resin. Furthermore, in the case of IPA, Cr can be reduced to below the detection limit with a mixed bed of cation exchange resin and anion exchange resin.
  • the present invention includes the following method.
  • [Method 1] A purification method for reducing metal impurities in an organic solvent, which comprises a filtration step of filtering the organic solvent with a particle removal filter, and an ion exchange step of passing the organic solvent obtained in the filtration step through an ion exchanger.
  • a method for purifying an organic solvent comprising: [Method 2] The method for purifying an organic solvent according to [Method 1], wherein the solution passed through the ion exchanger is circulated and purified by passing the solution through the particle removal filter.
  • [Method 3] The method for purifying an organic solvent according to [Method 1] or [Method 2], which includes a post-filtration step of filtering the organic solvent obtained in the ion exchange step with a second particle removal filter.
  • [Method 4] The method for purifying an organic solvent according to any one of [Method 1] to [Method 3], wherein the particle removal filter has a pore diameter of 5 nm or more and 1000 nm or less.
  • [Method 5] The method for purifying an organic solvent according to any one of [Method 1] to [Method 4], wherein the metal impurity is Cr.
  • [Method 6] The method for purifying an organic solvent according to any one of [Method 1] to [Method 5], wherein the ion exchanger is an ion exchange resin.
  • [Method 7] The organic solvent according to [Method 6], wherein the ion exchange resin is used as a single bed of any one of a chelate resin, a cation exchange resin, and an anion exchange resin, or as a mixed bed or double bed of two or more types. Purification method.
  • the ion exchange resin is a purified ion exchange resin in which the amount of total metal impurities eluted is 5 ⁇ g/mL-R or less when passed through hydrochloric acid with a concentration of 3% by mass in an amount 25 times the volume ratio [Method 6], or The organic solvent purification method described in [Method 7].
  • a purification device for reducing metal impurities in an organic solvent comprising: a particle removal filter for filtering the organic solvent; and a purification means for purifying the organic solvent obtained after the filtration by passing it through an ion exchanger.
  • An organic solvent purification device comprising:

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Publication number Priority date Publication date Assignee Title
WO2018051716A1 (ja) * 2016-09-15 2018-03-22 富士フイルム株式会社 有機溶剤の精製方法および有機溶剤の精製装置
CN110204442A (zh) * 2019-05-23 2019-09-06 安徽京控环境技术服务有限公司 一种从废有机溶剂回收提纯丙二醇甲醚醋酸酯的方法
WO2020013218A1 (ja) * 2018-07-13 2020-01-16 富士フイルム株式会社 薬液、キット、パターン形成方法、薬液の製造方法及び薬液収容体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018051716A1 (ja) * 2016-09-15 2018-03-22 富士フイルム株式会社 有機溶剤の精製方法および有機溶剤の精製装置
WO2020013218A1 (ja) * 2018-07-13 2020-01-16 富士フイルム株式会社 薬液、キット、パターン形成方法、薬液の製造方法及び薬液収容体
CN110204442A (zh) * 2019-05-23 2019-09-06 安徽京控环境技术服务有限公司 一种从废有机溶剂回收提纯丙二醇甲醚醋酸酯的方法

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