WO2023166999A1 - Procédé de fabrication d'une solution aqueuse de composé d'ammonium quaternaire purifié - Google Patents

Procédé de fabrication d'une solution aqueuse de composé d'ammonium quaternaire purifié Download PDF

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WO2023166999A1
WO2023166999A1 PCT/JP2023/005436 JP2023005436W WO2023166999A1 WO 2023166999 A1 WO2023166999 A1 WO 2023166999A1 JP 2023005436 W JP2023005436 W JP 2023005436W WO 2023166999 A1 WO2023166999 A1 WO 2023166999A1
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quaternary ammonium
aqueous solution
ammonium compound
cation exchange
exchange resin
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English (en)
Japanese (ja)
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幸太朗 水田
龍之助 小西
裕史 井上
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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
    • 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
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms

Definitions

  • the present invention relates to a method for producing a purified aqueous quaternary ammonium compound solution, and more particularly, to the production method for reducing the content of metal impurities from a crude aqueous quaternary ammonium compound solution containing metal impurities as impurities.
  • Quaternary ammonium compounds are used as phase transfer catalysts, surfactants, disinfectants, etc.
  • quaternary ammonium hydroxide compounds represented by tetramethylammonium hydroxide are organic alkali It is used as a pH adjuster, and in the form of an aqueous solution for cleaning, etching, and developing solutions during the manufacture of semiconductors.
  • metal impurities such as Na, K, Li, Ca, Mg, and Sr to 100 ppt or less.
  • aqueous solutions of quaternary ammonium compounds are produced by a synthesis method using a tertiary amine and an alkyl salt, or an electrolytic decomposition method using an electrolytic cell using an ion-exchange membrane.
  • an aqueous quaternary ammonium hydroxide solution is synthesized by subjecting an aqueous quaternary ammonium salt solution to electrolysis or the like.
  • the above metal impurities are in an unsatisfactory number from the viewpoint of the effect of preventing defects in the semiconductor application. It has a high content level of 100 ppt or more.
  • Filter treatment is commonly used as a method for purifying such a crude quaternary ammonium compound aqueous solution.
  • the filter treatment has an excellent effect of reducing particulate matter even in the above-mentioned metal impurities, but on the other hand, it has no effect of removing dissociated ions due to the limit of the pore size. I had a problem that was barely addressed.
  • the adsorption treatment with the cation exchange resin is applied for the purpose of recovering the quaternary ammonium hydroxide compound from the waste liquid when the aqueous solution of the quaternary ammonium hydroxide compound is used in the photoresist developer for semiconductor manufacturing.
  • Patent Document 2 the strongly acidic cation exchange resin product used in Example 1 as a representative example of the cation exchange resin is described in Patent Document 3 as having a degree of cross-linking of 2 to 10%. ing.
  • JP-A-06-025880 Japanese Patent Application Laid-Open No. 2003-190949 JP-A-1-98617
  • the present invention provides a technique for removing metal ions from an aqueous solution of a quaternary ammonium compound with a low content of organic impurities, such as that obtained by synthesis, even if the amount of treatment continues to be large.
  • the purpose is to develop a method that can maintain a high degree of effectiveness.
  • the inventors of the present invention have conducted intensive research in order to achieve this object, and found that the above problems can be solved by bringing the liquid to be treated into contact with a cation exchange resin having a specific degree of cross-linking.
  • the present invention has been completed.
  • the present invention provides a purified quaternary ammonium compound aqueous solution using a crude quaternary ammonium compound aqueous solution containing metal impurities and containing 1000 ppm or less of organic impurities having a 1 mol molecular weight of 1000 or more. wherein the purified quaternary ammonium compound is brought into contact with an aqueous solution of the crude quaternary ammonium compound with a cation exchange resin having a degree of cross-linking of 8 or more and a counter ion of the non-metal ion type.
  • a method for producing an aqueous compound solution is provided.
  • the degree of cross-linking of the cation exchange resin is preferably 11-30.
  • the cation exchange resin is preferably a strongly acidic cation exchange resin.
  • the contact between the cation exchange resin and the crude quaternary ammonium compound aqueous solution is carried out in a liquid flow system, and the cation exchange resin is subjected to It is preferable that the crude quaternary ammonium compound aqueous solution is processed at a throughput of 2000 (L/L-resin) or more.
  • At least 1 mol % of counter ions in the cation exchange resin are in the hydrogen ion type.
  • the cation exchange resin is of the metal ion type, it is preferable to use one that has been brought into contact with an acid aqueous solution as a pretreatment.
  • the cation exchange resin is of the hydrogen ion type
  • using an aqueous solution of a quaternary ammonium compound having the same quaternary ammonium ion as the crude quaternary ammonium compound aqueous solution as a pretreatment. is preferred.
  • the crude quaternary ammonium compound aqueous solution is preferably a crude quaternary ammonium hydroxide aqueous solution, a crude halogenated quaternary ammonium compound aqueous solution, or a crude quaternary ammonium carbonate compound aqueous solution.
  • the present invention provides an aqueous solution of a crude quaternary ammonium compound containing metal impurities and having a content of organic impurities having a molecular weight of 1000 or more per mol of 1000 ppm or less, which has a degree of cross-linking of 8 or more, and A quaternary ammonium compound aqueous solution contacted with a cation exchange resin in which is a non-metal ion type, wherein the total content of metal impurities consisting of Na, K, Li, Ca, Mg, and Sr is 100 ppt or less
  • an aqueous quaternary ammonium compound solution characterized by:
  • the quaternary ammonium compound is preferably a quaternary ammonium hydroxide compound, a quaternary ammonium halide compound, or a quaternary ammonium carbonate compound.
  • the quaternary ammonium compound is a quaternary ammonium halide compound or a quaternary ammonium carbonate compound, and the total content of metal impurities composed of Fe, Ni, Cu, and Pb is 100 ppt or less. preferable.
  • metal ions contained in a crude quaternary ammonium compound aqueous solution with a low content of organic impurities, such as obtained by synthesis can be adsorbed and removed with an excellent reduction effect.
  • This excellent reduction effect can be maintained at a high level even when a large amount of the crude quaternary ammonium compound aqueous solution is treated. Therefore, the present invention is extremely useful as an industrial method for producing a purified quaternary ammonium compound aqueous solution.
  • the crude quaternary ammonium compound aqueous solution which is the liquid to be treated that is brought into contact with the cation exchange resin, has a cleanliness of 1000 ppm or less of organic impurities having a molecular weight of 1000 or more per mol. Since high-purity raw materials are used in the synthesis of the quaternary ammonium compound, the resulting aqueous quaternary ammonium compound solution usually satisfies the requirements for cleanliness of organic impurities.
  • the crude quaternary ammonium compound aqueous solution may contain such organic impurities having a small molecular weight, but the content thereof is preferably 3% by mass or less.
  • Such low-molecular-weight organic impurities are considered to be mixed from unreacted components and impurities of raw materials used in the process of synthesizing the quaternary ammonium compound aqueous solution, and organic solvents such as methanol and ethanol, surfactants, etc. is mentioned.
  • the content of organic impurities having a 1 mol molecular weight of 1000 or more is more preferably 500 ppm or less, particularly preferably 100 ppm or less.
  • the organic impurities in the crude quaternary ammonium compound aqueous solution are measured according to the following procedure. First, a sample of a crude quaternary ammonium compound aqueous solution is injected into a gel permeation chromatography (GPC) column, and a liquid containing 1000 g/mol or more of organic impurities is separated and recovered. After that, the TOC concentration of the collected liquid and the eluent used for separation was measured with a total organic carbon (TOC) meter, and the TOC concentration contained in the eluent was subtracted from the TOC concentration of the collected liquid.
  • GPC gel permeation chromatography
  • quaternary ammonium compound hydroxides and salts of quaternary ammonium can be applied without limitation.
  • quaternary ammonium salts include chloride salts, halide salts of bromide salts, and carbonates (including bicarbonates, carbonates, and mixtures thereof).
  • a quaternary ammonium ion has, for example, the following general formula: [ R4N + ] (Wherein, R represents an alkyl group, a hydroxyalkyl group or an aryl group, and the four R may be the same group or different groups) Those represented by are preferable.
  • the alkyl group preferably has 4 or less carbon atoms such as methyl group, ethyl group, propyl group and butyl group.
  • the hydroxyalkyl group is preferably a substituted product of the above alkyl group with a hydroxyl group.
  • the aryl group preferably has 6 to 7 carbon atoms such as phenyl group, benzyl group and tolyl group.
  • quaternary ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, hydroxyethyltrimethylammonium hydroxide, Hydroxides such as benzyltrimethylammonium; chloride salts such as tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, ethyltrimethylammonium chloride, hydroxyethyltrimethylammonium chloride, benzyltrimethylammonium chloride; Bromide salts such as tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide,
  • the concentration of the quaternary ammonium compound is not particularly limited. % by mass or more is preferable, and 20% by mass or more is more preferable. On the other hand, if the concentration of the quaternary ammonium compound becomes too high, it crystallizes or the viscosity increases. In addition, in the case where crystallization occurs at a high concentration, it may be carried out within a range that does not reach that concentration. In the present invention, the concentration of the quaternary ammonium compound in the aqueous solution can be measured by ion chromatography or potentiometric titration.
  • the water component constituting the crude quaternary ammonium compound aqueous solution is preferably as clean as possible, more preferably ultrapure water.
  • These crude quaternary ammonium compound aqueous solutions usually contain metal impurities of 1000 ppt or more, or more than 100 ppt even if the amount is small. And even this level of content is not satisfactory from the viewpoint of defect suppression when these are used for the above-mentioned semiconductor applications, and it is necessary to perform the refining treatment according to the present invention.
  • metal impurities are specifically elements consisting of Na, K, Li, Ca, Mg, and Sr, and their content is evaluated by their total content.
  • the content of the metal impurities in the quaternary ammonium compound aqueous solution refers to the value analyzed by a high frequency inductively coupled plasma mass spectrometer (ICP-MS).
  • the crude quaternary ammonium compound aqueous solution can be of any origin as long as it satisfies the respective content requirements for organic impurities and metal impurities. Generally, it is preferable to use an aqueous quaternary ammonium hydroxide solution synthesized by electrolysis or the like, or an aqueous quaternary ammonium salt solution which is a raw material for carrying out this.
  • At least one cation exchange membrane is placed between an anode and a cathode, and a raw material chamber for supplying an aqueous quaternary ammonium salt solution as a raw material and water
  • An electrolytic cell provided with a base compartment (cathode compartment) in which an aqueous quaternary ammonium oxide solution is produced is generally used.
  • quaternary ammonium ions pass through a cation exchange membrane placed on the cathode side, and an aqueous quaternary ammonium hydroxide solution is produced in the base chamber.
  • an electrolytic cell with multiple sheets of cation exchange membranes, anion exchange membranes, and bipolar membranes membrane laminated with cation exchange membrane and anion exchange membrane
  • bipolar membranes membrane laminated with cation exchange membrane and anion exchange membrane
  • the crude quaternary ammonium compound aqueous solution is brought into contact with a cation exchange resin to adsorb and remove impurity metal ions to the cation exchange resin to reduce the content of metal impurities. Since the crude quaternary ammonium compound aqueous solution exhibits neutral to basic properties, the above cation exchange resin, even if the cation exchange group is a strongly acidic cation exchange resin in which the cation exchange group is a sulfonic acid group, does not contain carboxyl groups or phenolic groups. Any of weakly acidic cation exchange resins having organic hydroxyl groups and the like can be used satisfactorily.
  • the crude quaternary ammonium compound aqueous solution may be mixed with a trace amount of acid during the production process and exhibit acidity, it is preferable to use a strongly acidic cation exchange resin that can be exchanged even in a strong acid range.
  • the acid may be neutralized with a hydroxide having the same quaternary ammonium ion as the crude quaternary ammonium compound aqueous solution and then contacted with the weakly acidic cation exchange resin.
  • the above strongly acidic cation exchange resin generally has a structure in which a sulfonic acid group is introduced into a crosslinkable resin matrix composed of a copolymer of a cation exchange group-introduced precursor monovinyl monomer and a crosslinkable monomer.
  • cation-exchange group-introduced precursor monovinyl monomers include styrene, alkyl-substituted styrenes such as methylstyrene and ethylstyrene, and halogen-substituted styrenes such as bromostyrene, and these may be used alone. , may be used in combination of two or more.
  • the monovinyl monomer styrene or a monomer mainly composed of styrene is particularly preferable.
  • crosslinkable monomers examples include divinylbenzene, trivinylbenzene, divinyltoluene, divinylnaphthalene, divinylxylene, divinylbiphenyl, bis(vinylphenyl)methane, bis(vinylphenyl)ethane, bis(vinylphenyl)propane, bis( Examples thereof include crosslinkable monomers having a plurality of vinyl groups such as vinylphenyl)butane, and these may be used singly or in combination of two or more. Divinylbenzene is particularly preferred as the crosslinkable monomer.
  • weakly acidic cation exchange resins include copolymers of monovinyl monomers and crosslinkable monomers having weakly acidic cation exchange groups such as acrylic acid and methacrylic acid. Particularly preferred are acrylic acid-divinylbenzene copolymer and methacrylic acid-divinylbenzene copolymer.
  • the cation exchange resin with which the aqueous solution of the crude quaternary ammonium compound is brought into contact has a degree of cross-linking of 8 or more and a non-metal ion type counter ion.
  • the degree of cross-linking of the cation exchange resin is determined as [(weight of cross-linking monomer/weight of all charged monomers) ⁇ 100] at the time of producing the resin.
  • the cation exchange resin is a strongly acidic cation exchange resin
  • the crosslinkable resin matrix is first synthesized, and the cation exchange groups are introduced in a post-treatment, as described above.
  • the degree of cross-linking is calculated without considering the weight of the cation exchange groups, which are often introduced in the post-treatment, and without including them in the above formula.
  • the degree of crosslinking of the cation exchange resin to be used is unknown, the cation exchange resin is subjected to pyrolysis gas chromatography/mass spectrometry (GC/MS) to determine the crosslinkable monomer and other monomers. can be calculated by obtaining the ratio of
  • the effect of maintaining a high level of the effect of removing the metal ions is as follows. This is an effect that is peculiarly manifested when a product with a low impurity content is used. In other words, in the treatment with a photoresist developer waste liquid as in Patent Document 2, this effect is scarcely exhibited because a large amount of organic impurities having a large molecular weight are contained.
  • this selective and excellent removal action is due to the fact that the crude quaternary ammonium compound aqueous solution contains a large amount of organic impurities having a molecular weight of 1,000 or more per mol exceeding 1,000 ppm. It is significantly exerted only at the beginning of the refining process. This is because in the crude quaternary ammonium compound aqueous solution, the long molecular chains of the organic impurities are homogeneously dispersed in the liquid until the beginning of the purification process, and they hardly affect the adsorption properties of the cation exchange resin. However, as the purification is continued, this is thought to be due to the fact that the particles gradually become entangled on the surface of the resin particles, eventually covering most of the surface. That is, when most of the particle surface of the cation exchange resin is covered with organic impurities, even metal ions are strongly inhibited from diffusing into the interior. It is presumed that the effective removal action will not be exhibited smoothly.
  • the degree of cross-linking of the cation exchange resin is preferably 11 or more, particularly preferably 16 or more. If the degree of cross-linking of the cation exchange resin is too high, the diffusion speed of even metal ions will be slow, and the capture speed of the metal will be slow. , particularly preferably 22 or less.
  • the shape of the cation exchange resin may be any shape such as gel type or macroporous type.
  • the macroporous type is more preferably used in the present invention.
  • the cation exchange resin used in the present invention preferably has a cation exchange capacity of 1.0 to 5.0 equivalents/L, more preferably 1.5 to 3.0 equivalents/L. be done.
  • the shape of the cation exchange resin is not particularly limited, and may be in the form of a film or the like, but is usually preferably in the form of particles.
  • the counter ion of the cation exchange resin is usually in the hydrogen ion type or the metal ion type. It cannot be used in the present invention because it prevents reduction of the metal ion concentration of the purified quaternary ammonium compound aqueous solution. Therefore, the counter ions of the cation exchange resin include cations other than metal ions, specifically hydrogen ions, ammonium ions (NH 4 + ), primary to quaternary ammonium ions, and the like. things are used.
  • the counter ion of the cation exchange resin is preferably of the hydrogen ion type.
  • the counter ion is an ammonium ion (NH 4 + ) or a primary to quaternary ammonium ion type, except for the case where the cation is the same quaternary ammonium ion as the crude quaternary ammonium compound aqueous solution.
  • the elution of the different cations may cause contamination of the resulting purified quaternary ammonium compound aqueous solution with the different ammonium compound, and if this occurs, separation becomes difficult.
  • the hydrogen ion type hydrogen ions are released by exchanging with metal ions. Even if the quaternary ammonium compound is other than a hydroxide, neutralizing the released hydrogen ion-derived acid by adding a hydroxide having the same quaternary ammonium ion as the crude quaternary ammonium compound , the acid becomes the crude quaternary ammonium compound and water and the contamination is easily removed.
  • the proton form is also preferred as part of the counterions, where better at least 1 mol % is in the proton form, better at least 3 mol %, at least 10 mol %, most preferably at least 20 mol %.
  • the cation exchange resin having a degree of cross-linking of 8 or more and having a counter ion of a non-metal ion type can only be prepared when the counter ion is a metal ion type, or when a certain amount of metal ions is included and the metal ion is When it is desired to reduce the ion concentration, metal ions can be removed by contacting with an aqueous solution containing cations other than metal ions as a pretreatment, and a non-metal ion type can be obtained.
  • aqueous solution containing rapidly exchangeable small-sized cations is an aqueous solution in which the cations are hydrogen ions, ie, contact with an acid aqueous solution is preferred.
  • the cation exchange resin having a degree of cross-linking of 8 or more and having a hydrogen ion type counter ion is used as the cation exchange resin having the same quaternary ammonium ions as the crude quaternary ammonium compound aqueous solution. It is a particularly preferred embodiment to use it in contact with an aqueous quaternary ammonium compound solution. That is, according to this treatment, some of the counter ions of the cation exchange resin remain hydrogen ions due to the diffusivity inhibition of the quaternary ammonium ions, but a considerable amount of the hydrogen ions are converted into the crude quaternary ammonium ions.
  • the resulting cation exchange resin has a substantial proportion of the counterions exchanged with the same quaternary ammonium ions as the crude quaternary ammonium compound aqueous solution, and the cation exchange resin in such a state If it is a resin, the quaternary ammonium ion of the liquid to be treated is adsorbed on the cation exchange resin at the start of purification of the crude quaternary ammonium compound aqueous solution according to the present invention, so the purified quaternary ammonium compound aqueous solution is temporarily This is preferable because it can prevent a phenomenon in which the concentration is lowered to a certain degree during production.
  • one of the hydrogen ions is used as the counter ion of the highly crosslinked cation exchange resin. part remains.
  • the preferred residual amount of the hydrogen ion is in the range described for at least the amount of the hydrogen ion form of the counter ion.
  • the counter ions of the cation exchange resin are non-metallic ions, but this does not mean that all the counter ions are completely other than metal ions, as long as they do not greatly affect the effect. If so, it is permissible to contain to the extent that metal ions are unavoidably mixed. Specifically, metal ions contained in the counter ion in an amount of 3 mol% or less, preferably 0.1 mol% or less, and particularly preferably 0.001 mol% or less are acceptable within the scope of the present invention. be.
  • the counter ion of the cation exchange resin is brought into contact with an acid to elute non-metal ions other than metal ions and hydrogen ions, and each component can be quantified by ion chromatography.
  • Hydrogen ions can be quantified by contacting with a salt to elute the hydrogen ions and performing neutralization titration.
  • an inorganic acid aqueous solution such as sulfuric acid, hydrochloric acid, or nitric acid is used.
  • An aqueous solution or an aqueous sulfuric acid solution is preferably used.
  • the acid concentration can be used without limitation, if it is contacted with a high-concentration acid, the counter ion will be replaced in a short time, and there is a possibility that cracks and breakage will occur due to a sudden volume change, so 1 mol / L
  • the following is preferable, more preferably 0.5 mol/L or less, and still more preferably 0.3 mol/L or less. It is preferable to treat with an acid equivalent to 1.2 to 5 times the total amount of exchange groups of the cation exchange resin used, more preferably 1.5 to 3 times equivalent.
  • the contact treatment there are no particular restrictions on the contact treatment, whether it is a batch type or liquid flow type.
  • a flow-through type in which a resin tower is formed either an upward flow or a downward flow may be used, and an acid containing an amount equivalent to three times or more the amount of exchange groups of the ion exchange resin to be treated is passed through.
  • SV is preferably in the range of 1 to 20 (1/hr).
  • the total content of metal impurities composed of Na, K, Li, Ca, Mg, and Sr contained in the acid aqueous solution is preferably 100 ppt or less, more preferably 10 ppt or less, and still more preferably 1 ppt or less.
  • the acid aqueous solution preferably has a total content of metal impurities consisting of Fe, Ni, Cu, and Pb of 100 ppt or less, more preferably 10 ppt or less, and even more preferably 1 ppt or less.
  • the cation exchange resin is preferably washed with ultrapure water after being brought into contact with the acid aqueous solution.
  • ultrapure water excess acid that has not entered as a counterion due to adhesion to the surface of the resin is removed, and contamination of the acid in subsequent steps can be prevented.
  • the quaternary ammonium compound contained in the crude quaternary ammonium compound aqueous solution is quaternary ammonium hydroxide, if the acid remains in the cation exchange resin, a rapid heat generation occurs due to the neutralization reaction. Washing with ultrapure water is preferred because there is a risk of resin destruction due to rapid swelling of the resin.
  • the quaternary ammonium compound used when the counter ion is a hydrogen ion type and the cation exchange resin is brought into contact with an aqueous quaternary ammonium compound solution having the same quaternary ammonium ion as the crude quaternary ammonium compound aqueous solution.
  • concentration, contact method, and metal ion content of the aqueous ammonium compound solution are preferably the same as those described for the acid aqueous solution.
  • the method of contacting the cation exchange resin with the crude quaternary ammonium compound aqueous solution may be a batch method or a flow-through method. It is preferable to have In the liquid flow type, purification is performed by providing a resin tower and passing liquid through it. The direction of liquid flow may be either upward flow or downward flow, and downward flow is preferable from the viewpoint of enhancing purification efficiency.
  • the excellent effect of removing metal ions in the method of the present invention is remarkably exhibited when the treatment amount of the crude quaternary ammonium compound aqueous solution is large. It is more effective to set the cation exchange resin to 2000 (L/L-resin) or more, more preferably 10000 (L/L-resin) or more to the quaternary ammonium compound aqueous solution. However, if the treatment amount is still too large, the effect of removing metal ions is reduced. resin) or less.
  • the batch-type purification it is preferable to immerse the crude quaternary ammonium compound aqueous solution in an amount of 200 L/L-resin or more from the viewpoint of significantly exhibiting the excellent effect of removing the metal ions. Moreover, it is preferable because the amount of metal ions can be further reduced by repeating the batch treatment. A good number of repetitions is 2 to 5 times.
  • the crude quaternary ammonium compound aqueous solution contains particulate metal impurities
  • it is subjected to a filter treatment as a pre- or post-process of bringing it into contact with the cation exchange resin. is preferably removed.
  • the metal ion removal by the cation exchange resin in the present invention may be hindered or may be impeded. In some cases, clogging may occur, so it is preferable to perform filter treatment as a pretreatment.
  • the filter treatment is preferably performed as a post-treatment.
  • the average pore size of the filter used is preferably 1 ⁇ m or less, more preferably 0.02 to 1 ⁇ m.
  • the average pore size of the filter is unknown, the value measured by the bubble point method is used as the average pore size.
  • the inner walls of equipment such as containers, tanks, resin towers, and pipes used to carry out the production method of the present invention have chemical resistance and are made of materials that minimize metal contamination. Therefore, it is preferable to use a material such as polyethylene, polypropylene, or fluororesin, or to use a lining.
  • fluorine-based resins are most suitable from the viewpoint of preventing metal contamination.
  • the surfaces of these members are preferably washed in advance before use. For example, they are preferably cleaned by washing with an aqueous quaternary ammonium hydroxide solution or acid.
  • the total content of metal impurities consisting of Na, K, Li, Ca, Mg, and Sr is 100 ppt or less, more preferably 50 ppt or less, and still more preferably 20 ppt or less. It is also possible to obtain The content of each of these metal elements in the quaternary ammonium compound aqueous solution can also be 30 ppt or less, more preferably 10 ppt or less, and even more preferably 5 ppt or less.
  • the quaternary ammonium compound when the quaternary ammonium compound is a hydroxide salt, the quaternary ammonium compound aqueous solution is strongly alkaline. Alternatively, it may take a non-ionic form, and its removal effect may not be sufficient. However, when the quaternary ammonium compound is a quaternary ammonium halide compound or a quaternary ammonium carbonate compound other than a hydroxide, the effect of reducing each metal element other than the above is also highly exhibited.
  • the total content of metal impurities composed of Fe, Ni, Cu, and Pb is 100 ppt or less, more preferably 50 ppt or less, and still more preferably 20 ppt or less. It is also possible to obtain an aqueous quaternary ammonium compound solution.
  • Example 1 Powder of synthetic tetramethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd., general grade) was dissolved in water and adjusted to 60% by mass to prepare a crude tetramethylammonium chloride aqueous solution.
  • the content of metal impurities in this crude tetramethylammonium chloride aqueous solution was measured, and the total content of metal impurities Na, K, Li, Ca, Mg, and Sr is shown in Table 1, Fe, Ni, Cu, and Pb.
  • Table 2 shows the total content of metal impurities consisting of Further, the content of organic impurities having a molecular weight of 1000 or more per mol (large molecular weight organic impurities) was also measured and found to be 372 ppm.
  • the total content of metal impurities composed of Na, K, Li, Ca, Mg, and Sr is 100 ppt or less, and The total content of metal impurities consisting of Fe, Ni, Cu, and Pb was also 100 ppt or less.
  • the ultrapure water used was a liquid containing 1 ppt or less of total metallic impurities composed of Na, K, Li, Ca, Mg, Sr, Fe, Ni, Cu, and Pb.
  • the percentage of hydrogen ions contained in the counter ions of the strongly acidic ion exchange resin after the pretreatment was measured and found to be 20 mol %.
  • Example 2 In Example 1, the strongly acidic ion exchange resin used was the same as in Example 1 except that it was changed to Diaion (registered trademark) UBK16 (crosslinking degree 16, cation exchange capacity 2.3 equivalents / L, Mitsubishi Chemical Corporation). A similar operation was performed. At this time, the ratio of hydrogen ions contained in counter ions of the strongly acidic ion exchange resin after pretreatment was measured and found to be 11 mol %. The measurement results of the metal impurity content are shown in Tables 1 and 2, respectively.
  • Diaion registered trademark
  • UBK16 crosslinking degree 16, cation exchange capacity 2.3 equivalents / L, Mitsubishi Chemical Corporation
  • Example 3 Example 1 except that the strongly acidic ion exchange resin used in Example 1 was changed to Diaion (registered trademark) SK112 (degree of crosslinking: 12, cation exchange capacity: 2.1 equivalents/L, manufactured by Mitsubishi Chemical Corporation). performed the same operation. At this time, the ratio of hydrogen ions contained in counter ions of the strongly acidic ion exchange resin after pretreatment was measured and found to be 3 mol %. The measurement results of the metal impurity content are shown in Tables 1 and 2, respectively.
  • Example 4 Example 1 except that the strongly acidic ion exchange resin used in Example 1 was changed to Diaion (registered trademark) SK1B (crosslinking degree 8, cation exchange capacity 2.0 equivalent/L, manufactured by Mitsubishi Chemical Corporation). performed the same operation. At this time, the ratio of hydrogen ions contained in counter ions of the strongly acidic ion exchange resin after pretreatment was measured and found to be 1 mol %. The measurement results of the metal impurity content are shown in Tables 1 and 2, respectively.
  • Diaion registered trademark
  • SK1B crosslinking degree 8, cation exchange capacity 2.0 equivalent/L, manufactured by Mitsubishi Chemical Corporation
  • Example 1 except that the strongly acidic ion exchange resin used in Example 1 was changed to Diaion (registered trademark) PK212 (crosslinking degree 6, cation exchange capacity 1.5 equivalents/L, manufactured by Mitsubishi Chemical Corporation). performed the same operation.
  • PK212 crosslinking degree 6, cation exchange capacity 1.5 equivalents/L, manufactured by Mitsubishi Chemical Corporation.
  • the ratio of hydrogen ions contained in the counter ions of the strongly acidic ion exchange resin after pretreatment was measured, it was 0.1 mol % or less.
  • the measurement results of the metal impurity content are shown in Tables 1 and 2, respectively.
  • Comparative example 2 A tetramethylammonium hydroxide aqueous solution waste liquid discharged from a liquid crystal display factory was neutralized with hydrochloric acid, the insolubilized resist was filtered, and further concentrated by an evaporation method. By this neutralization step, tetramethylammonium hydroxide was converted to tetramethylammonium chloride, and concentration by evaporation was adjusted so that tetramethylammonium chloride was 60% by mass, and used as a crude tetramethylammonium chloride aqueous solution. The metal impurity content of this liquid was measured, and the results are shown in Tables 3 and 4, respectively. The content of organic impurities having a molecular weight of 1000 or more per mol was also measured and found to be 1267 ppm.
  • the metal impurity content was measured by the same operation as in Example 1.
  • 10 L (200 L/L-resin) and 100 L (2000 L/L-resin) were sampled for measuring the content of metal impurities.
  • the measurement results of the metal impurity content are shown in Tables 3 and 4, respectively.
  • Examples 5-8 and Comparative Example 3 A synthetic tetramethylammonium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Ltd., high purity grade) adjusted to 25% by mass was used as a crude tetramethylammonium hydroxide aqueous solution. The metal impurity content of this liquid was measured, and the results are shown in Tables 5 and 6, respectively. The content of organic impurities having a molecular weight of 1000 or more per mol was also measured and found to be 43 ppm.
  • the excellent effect of reducing the metal impurity concentration in each of the above examples is that the crude quaternary ammonium compound aqueous solution to be treated contains organic impurities having a molecular weight of 1000 or more per mol, and the amount of organic impurities exceeds 1000 ppm.
  • Comparative Example 2 in which the amount of liquid passing is 10 L (200 L/L of resin), the effect is relatively high at the beginning of the treatment. ), the result was a rapid decline.

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Abstract

La présente invention concerne le développement d'un procédé grâce auquel il est possible de maintenir un effet d'élimination élevé d'ions métalliques à partir d'un composé d'ammonium quaternaire brut (par exemple, un composé d'hydroxyde d'ammonium quaternaire ou une solution aqueuse de composé d'ammonium quaternaire halogéné) ayant une faible quantité contenue d'impuretés organiques, même si l'élimination est poursuivie pour une grande quantité de traitement de celui-ci. Ce procédé de fabrication d'une solution aqueuse de composé d'ammonium quaternaire purifié utilise une solution aqueuse de composé d'ammonium quaternaire brut qui contient des impuretés métalliques et dans laquelle la quantité contenue d'impuretés organiques ayant un poids moléculaire par mole d'au moins 1000 est de 1000 ppm ou moins, le procédé étant caractérisé par la mise en contact de la solution aqueuse de composé d'ammonium quaternaire brut avec une résine échangeuse de cations ayant un degré de réticulation d'au moins 8 et ayant des contre-ions qui sont des ions non métalliques.
PCT/JP2023/005436 2022-03-03 2023-02-16 Procédé de fabrication d'une solution aqueuse de composé d'ammonium quaternaire purifié WO2023166999A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03167160A (ja) * 1989-11-22 1991-07-19 Sumitomo Chem Co Ltd 水酸化第四級アンモニウム水溶液の精製方法
JPH06173054A (ja) * 1992-10-08 1994-06-21 Sumitomo Chem Co Ltd 炭酸（水素）テトラアルキルアンモニウム水溶液の精製方法及び水酸化テトラアルキルアンモニウム水溶液の製造方法
JPH11190907A (ja) * 1996-11-21 1999-07-13 Japan Organo Co Ltd フォトレジスト現像廃液の再生処理方法
JP2000319233A (ja) * 1999-05-10 2000-11-21 Lion Akzo Kk ハロゲン化第四級アンモニウム塩溶液の精製方法
JP2004512315A (ja) * 2000-10-20 2004-04-22 サッチェム，インコーポレイテッド オニウム化合物を含む溶液からオニウム水酸化物を除去するためのプロセス
JP2007181833A (ja) * 2007-04-05 2007-07-19 Japan Organo Co Ltd テトラアルキルアンモニウムイオン含有液の処理方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03167160A (ja) * 1989-11-22 1991-07-19 Sumitomo Chem Co Ltd 水酸化第四級アンモニウム水溶液の精製方法
JPH06173054A (ja) * 1992-10-08 1994-06-21 Sumitomo Chem Co Ltd 炭酸（水素）テトラアルキルアンモニウム水溶液の精製方法及び水酸化テトラアルキルアンモニウム水溶液の製造方法
JPH11190907A (ja) * 1996-11-21 1999-07-13 Japan Organo Co Ltd フォトレジスト現像廃液の再生処理方法
JP2000319233A (ja) * 1999-05-10 2000-11-21 Lion Akzo Kk ハロゲン化第四級アンモニウム塩溶液の精製方法
JP2004512315A (ja) * 2000-10-20 2004-04-22 サッチェム，インコーポレイテッド オニウム化合物を含む溶液からオニウム水酸化物を除去するためのプロセス
JP2007181833A (ja) * 2007-04-05 2007-07-19 Japan Organo Co Ltd テトラアルキルアンモニウムイオン含有液の処理方法

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