TW202302499A - Method for refining hydrolyzable organic solvent, and method for producing resin for refining hydrolyzable organic solvent - Google Patents
Method for refining hydrolyzable organic solvent, and method for producing resin for refining hydrolyzable organic solvent Download PDFInfo
- Publication number
- TW202302499A TW202302499A TW111111264A TW111111264A TW202302499A TW 202302499 A TW202302499 A TW 202302499A TW 111111264 A TW111111264 A TW 111111264A TW 111111264 A TW111111264 A TW 111111264A TW 202302499 A TW202302499 A TW 202302499A
- Authority
- TW
- Taiwan
- Prior art keywords
- organic solvent
- exchange resin
- resin
- cation exchange
- refining
- Prior art date
Links
Classifications
-
- 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
- B01J39/19—Macromolecular compounds obtained otherwise than 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
- 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
- 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
- B01J47/04—Mixed-bed processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本發明係關於水解性有機溶劑之精製方法及水解性有機溶劑精製用之樹脂之製造方法。The present invention relates to a method for refining a hydrolyzable organic solvent and a method for producing a resin for refining a hydrolyzable organic solvent.
半導體係經由多達數百個複雜的步驟製造而成。半導體的線寬係由光阻步驟決定。光阻步驟包含:將光阻塗布於矽晶圓的步驟、從光源透過光罩照射短波長之光線的曝光步驟、將光罩顯影的步驟、蝕刻無光阻部分的步驟以及剝離光阻的步驟。塗布於晶圓上的光阻,係使酸產生劑、樹脂溶液、添加劑溶解於有機溶劑而成的溶液,該有機溶劑係使用包含PGMEA(丙二醇單甲醚乙酸酯)、乳酸乙酯等酯系有機溶劑、PGME(丙二醇單甲醚)、環己酮等作為主成分者。Semiconductors are manufactured through hundreds of complex steps. The line width of the semiconductor is determined by the photoresist step. The photoresist step includes: the step of coating the photoresist on the silicon wafer, the exposure step of irradiating short-wavelength light from the light source through the photomask, the step of developing the photomask, the step of etching the part without photoresist, and the step of stripping the photoresist . The photoresist coated on the wafer is a solution obtained by dissolving an acid generator, resin solution, and additives in an organic solvent. The organic solvent uses esters such as PGMEA (propylene glycol monomethyl ether acetate) and ethyl lactate. It is mainly composed of organic solvents, PGME (propylene glycol monomethyl ether), cyclohexanone, etc.
近年來半導體之線寬的加工尺寸要求逐年變細。半導體之線寬的細微化促進IT設備的小型化、高機能化技術。隨著半導體之線寬的細微化,曝光步驟中使用的光源開始從g射線、i射線等級增加短波長的ArF、EUV、X射線之使用,用於光阻塗布周圍的有機溶劑中的雜質量亦設定為較低。有機溶劑所包含的雜質之中,尤其是大量殘留金屬元素的情況,該金屬元素會附著於晶圓而導致半導體的性能降低。因此必須將金屬元素列為減少項目。In recent years, the processing dimension of the line width of semiconductors has become smaller and smaller year by year. The miniaturization of the semiconductor line width promotes the miniaturization and high-performance technology of IT equipment. With the miniaturization of the line width of semiconductors, the light source used in the exposure step has begun to increase the use of short-wavelength ArF, EUV, and X-rays from g-rays and i-rays to reduce the amount of impurities in organic solvents around photoresist coating. Also set lower. Among the impurities contained in the organic solvent, especially in the case of a large amount of residual metal elements, the metal elements may adhere to the wafer and degrade the performance of the semiconductor. Therefore, metal elements must be listed as reduction items.
另一方面,已知用於半導體製造的PGMEA等酯系有機溶劑會因為與水分、酸、鹼接觸而發生水解,進而生成酸。因此有人提出了在酯系有機溶劑的精製中使用蒸餾法、螯合樹脂的方法以作為在不產生酸的情況下去除金屬雜質的方法。On the other hand, ester-based organic solvents such as PGMEA used in semiconductor manufacturing are known to be hydrolyzed by contact with moisture, acids, and alkalis to generate acids. Therefore, someone has proposed the method of using distillation and chelating resin in the refining of ester-based organic solvents as a method for removing metal impurities without generating acid.
專利文獻1中記載了下述方法:使用去離子水、無機酸溶液、並任意地使用氫氧化銨溶液清洗螯合樹脂,再以有機溶劑對其進行清洗之後,混合光阻組成物,並且進行加熱、過濾器過濾,藉此減少光阻組成物中的金屬離子。然而,根據此方法,尤其無法充分地去除Fe。The following method is described in patent document 1: use deionized water, inorganic acid solution, and use ammonium hydroxide solution to clean chelate resin arbitrarily, after it is cleaned with organic solvent again, mix photoresist composition, and carry out Heat and filter to reduce metal ions in the photoresist composition. However, according to this method, especially Fe cannot be sufficiently removed.
專利文獻2中記載了下述方法:將通液流量(SV值)降低至10h -1以下,使光阻膜形成用樹脂溶液通過已將離子交換基及/或螯合基固定於聚烯烴系不織布而成的過濾基材。然而,專利文獻2中僅記載Na濃度作為雜質濃度,根據本案發明人的研究明白,相較於使用螯合樹脂的情況,Fe、Cr等重金屬的去除性不佳。 Patent Document 2 describes a method in which the flow rate (SV value) of the passing liquid is reduced to 10 h -1 or less, and the resin solution for forming a photoresist film is passed through the resin solution in which ion exchange groups and/or chelating groups have been fixed to the polyolefin system. Filter substrate made of non-woven fabric. However, in Patent Document 2, only the Na concentration is described as the impurity concentration. According to the research of the present inventors, it is clear that compared with the case of using a chelating resin, the removal properties of heavy metals such as Fe and Cr are not good.
專利文獻3中記載了使用已利用無機酸溶液減少金屬雜質含量的螯合樹脂來去除PGMEA等被處理液中之金屬雜質的方法。然而,本案發明人進一步研究,結果明白取決於精製對象的被處理液,有時可能無法充分去除Fe、Cr等重金屬。 [先前技術文獻] [專利文獻] The method of using the chelating resin that has utilized the mineral acid solution to reduce the metal impurity content to remove the metal impurities in the treated liquids such as PGMEA is described in the patent document 3. However, as a result of further studies by the inventors of the present invention, it has been found that heavy metals such as Fe and Cr may not be sufficiently removed depending on the liquid to be treated which is the object of purification. [Prior Art Literature] [Patent Document]
專利文獻1:日本特表2000-501201號公報 專利文獻2:日本特開2013-061426號公報 專利文獻3:日本特開2019-141800號公報 Patent Document 1: Japanese PCT Publication No. 2000-501201 Patent Document 2: Japanese Patent Laid-Open No. 2013-061426 Patent Document 3: Japanese Patent Laid-Open No. 2019-141800
[發明所欲解決之課題][Problem to be Solved by the Invention]
因此,本發明之目的在於提供一種水解性有機溶劑精製用之樹脂之製造方法,其可抑制酸的生成並且減少水解性有機溶劑中的金屬雜質濃度;並提供使用該樹脂的水解性有機溶劑之精製方法。 [解決課題之手段] Therefore, the object of the present invention is to provide a method for producing a resin for refining a hydrolyzable organic solvent, which can suppress the generation of acid and reduce the concentration of metal impurities in the hydrolyzable organic solvent; Refining method. [Means to solve the problem]
鑒於上述問題,本案發明人詳細研究的結果,發現藉由使用任意混合了螯合樹脂的陽離子交換樹脂,可抑制水解性有機溶劑產生酸,並且減少僅以螯合樹脂無法充分去除的金屬,進而完成本發明。In view of the problems referred to above, the result of the inventor's detailed study of the present case found that by using the cation-exchange resin mixed with the chelating resin arbitrarily, the hydrolyzable organic solvent can be suppressed to produce acid, and the metal that cannot be fully removed only with the chelating resin can be reduced, and then Complete the present invention.
亦即,本發明之水解性有機溶劑之精製方法,其特徵為具有:精製步驟,使任意混合了螯合樹脂的陽離子交換樹脂與水解性有機溶劑接觸以進行精製;相對於該陽離子交換樹脂及任意的該螯合樹脂之總量,該陽離子交換樹脂的體積比例為10~100%。That is, the method for refining a hydrolyzable organic solvent of the present invention is characterized in that it has: a refining step in which a cation exchange resin mixed with a chelating resin is contacted with a hydrolyzable organic solvent for refining; with respect to the cation exchange resin and For any total amount of the chelating resin, the volume ratio of the cation exchange resin is 10-100%.
又,本發明之水解性有機溶劑精製用之樹脂之製造方法,其特徵為具有:在陽離子交換樹脂中任意混合螯合樹脂的步驟;相對於該陽離子交換樹脂及任意的該螯合樹脂之總量,該陽離子交換樹脂的體積比例為10~100%。 [發明之效果] Also, the method for producing the resin used for refining the hydrolyzable organic solvent of the present invention is characterized in that it has the step of arbitrarily mixing the chelating resin in the cation exchange resin; The volume ratio of the cation exchange resin is 10-100%. [Effect of Invention]
根據本發明,提供一種水解性有機溶劑精製用之樹脂之製造方法,其可抑制酸的生成,並且減少水解性有機溶劑中的金屬雜質濃度;以及提供使用該樹脂的水解性有機溶劑之精製方法。According to the present invention, there is provided a method for producing a resin for refining a hydrolyzable organic solvent, which can suppress the generation of acid and reduce the concentration of metal impurities in a hydrolyzable organic solvent; and a method for refining a hydrolyzable organic solvent using the resin .
本發明之水解性有機溶劑精製用之樹脂之製造方法,具有在陽離子交換樹脂中任意混合螯合樹脂的步驟。另外,在不使用螯合樹脂僅使用陽離子交換樹脂的情況中,該步驟亦可說是準備陽離子交換樹脂的步驟。又,本發明之水解性有機溶劑之精製方法具有精製步驟,該精製步驟係使任意混合了螯合樹脂的陽離子交換樹脂接觸水解性有機溶劑以進行精製。相對於該陽離子交換樹脂及任意的該螯合樹脂之總量,該陽離子交換樹脂的體積比例為10~100%。The manufacturing method of the resin used for refining hydrolyzable organic solvent of the present invention has the step of arbitrarily mixing chelating resin in cation exchange resin. In addition, in the case of using only a cation exchange resin without using a chelate resin, this step can also be said to be a step of preparing a cation exchange resin. Also, the purification method of the hydrolyzable organic solvent of the present invention has a purification step in which the cation exchange resin optionally mixed with the chelate resin is brought into contact with the hydrolyzable organic solvent for purification. Relative to the total amount of the cation exchange resin and any chelating resin, the volume ratio of the cation exchange resin is 10-100%.
(水解性有機溶劑) 本發明中作為精製對象液的水解性有機溶劑,係因水解而產生酸的酯系有機溶劑。另外,本發明中的精製對象液,亦可為將至少包含酯系有機溶劑之2種以上的有機溶劑混合而成的混合溶劑。精製對象液並未特別限定,可列舉:PGMEA(丙二醇單甲醚乙酸酯)、乙二醇單乙醚乙酸酯、乙基-3-乙氧基丙基乙酸酯、乳酸乙酯、乳酸丁酯、乙酸丁酯、乙酸異戊酯等酯系有機溶劑、此等酯系有機溶劑與PGME(丙二醇單甲醚)、環己酮等的混合溶劑。此等之中,宜為PGMEA或PGMEA/PGME的混合溶劑。PGMEA/PGME的混合溶劑中的PGMEA的比例並未特別限定,可因應目的適當調整。 (hydrolyzable organic solvent) The hydrolyzable organic solvent used as the liquid to be purified in the present invention is an ester-based organic solvent that generates acid by hydrolysis. In addition, the liquid to be purified in the present invention may be a mixed solvent obtained by mixing at least two or more organic solvents including an ester-based organic solvent. The liquid to be purified is not particularly limited, and examples thereof include: PGMEA (propylene glycol monomethyl ether acetate), ethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropyl acetate, ethyl lactate, lactic acid Organic ester solvents such as butyl ester, butyl acetate, and isoamyl acetate, and mixed solvents of these organic ester solvents with PGME (propylene glycol monomethyl ether), cyclohexanone, and the like. Among them, PGMEA or a mixed solvent of PGMEA/PGME is preferable. The ratio of PGMEA in the mixed solvent of PGMEA/PGME is not particularly limited, and can be appropriately adjusted according to the purpose.
本發明中所使用之水解性有機溶劑(精製前)的水分濃度,從抑制水解及金屬精製性能之穩定性的觀點來看,宜為20~10000mg/L。該水分濃度的上限值宜低,更佳為5000mg/L,再佳為1000mg/L。另外,水分濃度例如可使用卡爾費雪容量法水分計(商品名稱:Aquacounter AQ-2200,平沼產業股份有限公司製)以卡爾費雪法進行測量。The water concentration of the hydrolyzable organic solvent (before refining) used in the present invention is preferably 20 to 10000 mg/L from the viewpoint of hydrolysis inhibition and stability of metal refining performance. The upper limit of the water concentration should be low, more preferably 5000 mg/L, and even more preferably 1000 mg/L. In addition, the water concentration can be measured by the Karl Fisher method using, for example, a Karl Fisher volumetric moisture meter (trade name: Aquacounter AQ-2200, manufactured by Hiranuma Sangyo Co., Ltd.).
(陽離子交換樹脂) 離子交換樹脂,例如係將官能基導入於在觸媒與分散劑的共存下使苯乙烯與二乙烯苯(DVB)共聚合得到的具有三維網狀結構之共聚物而獲得。本發明中所使用的陽離子交換樹脂可列舉:具有磺酸基(-SO 3H)的強酸性陽離子交換樹脂及具有羧酸基(-COOH)的弱酸性陽離子交換樹脂。又,陽離子交換樹脂可為樹脂具有之細孔直徑小且透明的凝膠型以及細孔直徑大而具有大孔隙的大網格(macroreticular)型(MR型)或大孔(macroporous)型(亦稱為多孔(porous)型、高孔(high porous)型)。本發明中,從去除金屬的觀點來看,宜使用強酸性陽離子交換樹脂。其中,從酸生成的抑制與金屬去除性能之平衡的觀點來看,宜為MR型強酸性陽離子交換樹脂。又,從更有效抑制酸之生成的觀點來看,宜為高交聯的凝膠型強酸性陽離子交換樹脂。另外,所謂的高交聯的凝膠型強酸性陽離子交換樹脂,具體係指交聯度為16%~24%的凝膠型強酸性陽離子交換樹脂。 (Cation Exchange Resin) The ion exchange resin is obtained, for example, by introducing a functional group into a copolymer having a three-dimensional network structure obtained by copolymerizing styrene and divinylbenzene (DVB) in the presence of a catalyst and a dispersant. Examples of the cation exchange resin used in the present invention include strongly acidic cation exchange resins having sulfonic acid groups (—SO 3 H) and weakly acidic cation exchange resins having carboxylic acid groups (—COOH). Also, the cation exchange resin may be of a gel type in which the resin has a small pore diameter and is transparent, and a macroreticular type (MR type) or a macroporous type (also a macroporous type) in which the pore diameter is large and has large pores. Called porous (porous) type, high porous (high porous) type). In the present invention, it is preferable to use a strongly acidic cation exchange resin from the viewpoint of metal removal. Among them, an MR type strongly acidic cation exchange resin is preferable from the standpoint of the balance between acid generation suppression and metal removal performance. Also, from the viewpoint of more effectively suppressing acid generation, a highly cross-linked gel-type strongly acidic cation exchange resin is preferable. In addition, the so-called highly cross-linked gel-type strongly acidic cation exchange resin specifically refers to a gel-type strongly acidic cation-exchange resin with a cross-linking degree of 16% to 24%.
相對於陽離子交換樹脂及後述任意的螯合樹脂之總量,陽離子交換樹脂的體積比例為10~100%,宜為20~100%。此處,該比例為100%係指僅使用陽離子交換樹脂。根據本發明之精製方法,即使在僅使用陽離子交換樹脂的情況中,亦可抑制酸的生成,並減少精製對象液中的金屬雜質。從更有效抑制酸之生成的觀點來看,宜以混合床或複床使用陽離子交換樹脂與螯合樹脂。此情況中,相對於陽離子交換樹脂及螯合樹脂的總量,陽離子交換樹脂的體積比例宜為10%~50%,更佳為10%~33%。The volume ratio of the cation exchange resin is 10-100%, preferably 20-100%, relative to the total amount of the cation exchange resin and any chelating resin described below. Here, the ratio of 100% means that only the cation exchange resin is used. According to the purification method of the present invention, even when only a cation exchange resin is used, acid generation can be suppressed, and metal impurities in the liquid to be purified can be reduced. From the viewpoint of more effectively suppressing the generation of acid, it is preferable to use the cation exchange resin and the chelating resin in a mixed bed or double bed. In this case, relative to the total amount of the cation exchange resin and the chelating resin, the volume ratio of the cation exchange resin is preferably 10%-50%, more preferably 10%-33%.
本發明中使用的陽離子交換樹脂,可列舉例如:AMBERLITE(註冊商標) IRN99H(凝膠型的強酸性陽離子交換樹脂,商品名稱,杜邦公司製)、AMBERLITE(註冊商標) CR99 K/350、TAPTEC(註冊商標) HCRS Na(皆為凝膠型的強酸性陽離子交換樹脂,商品名稱,杜邦公司製)、AMBERJET(註冊商標)1060H(凝膠型的強酸性陽離子交換樹脂,商品名稱,奧璐佳瑙股份有限公司製)、ORLITE(註冊商標) DS-1(凝膠型的強酸性陽離子交換樹脂,商品名稱,奧璐佳瑙股份有限公司製)、ORLITE(註冊商標) DS-4(MR型的強酸性陽離子交換樹脂,商品名稱,奧璐佳瑙股份有限公司製)等,但不限於此等。陽離子交換樹脂的離子形,從去除金屬的觀點來看,宜為氫離子形(H形)。另外,使用其他離子形(例如,鈉離子形、鉀離子形等)之樹脂的情況,宜預先以習知方法轉換成H形後再使用。The cation exchange resins used in the present invention include, for example: AMBERLITE (registered trademark) IRN99H (gel-type strongly acidic cation exchange resin, trade name, manufactured by DuPont), AMBERLITE (registered trademark) CR99 K/350, TAPTEC ( Registered trademark) HCRS Na (both are gel-type strongly acidic cation exchange resins, trade name, manufactured by DuPont), AMBERJET (registered trademark) 1060H (gel-type strongly acidic cation exchange resin, trade name, Olucanau Co., Ltd.), ORLITE (registered trademark) DS-1 (gel-type strongly acidic cation exchange resin, trade name, Olucano Co., Ltd.), ORLITE (registered trademark) DS-4 (MR type Strongly acidic cation exchange resin, trade name, manufactured by Olucano Co., Ltd.), etc., but not limited thereto. The ionic form of the cation exchange resin is preferably a hydrogen ion form (H form) from the viewpoint of metal removal. In addition, when using resins in other ion forms (for example, sodium ion form, potassium ion form, etc.), it is advisable to convert the resin into H form by conventional methods before use.
(螯合樹脂) 本發明中,可在該陽離子交換樹脂中任意地混合螯合樹脂。混合螯合樹脂的情況,陽離子交換樹脂及螯合樹脂可為混合床,亦可為複床。任一情況皆可得到本發明的效果。螯合樹脂,係具有可與金屬離子形成螯合物(錯合物)之官能基(螯合基)的樹脂。該官能基只要是可與金屬離子形成螯合物(錯合物)的官能基即可,並未特別限定。該官能基可列舉例如:胺基甲基磷酸基、亞胺基二乙酸基、硫醇基及多胺基。從對於多種金屬物種之選擇性等的觀點來看,螯合樹脂宜具有胺基甲基磷酸基或亞胺基二乙酸基作為官能基。 (chelating resin) In the present invention, a chelate resin can be arbitrarily mixed with the cation exchange resin. In the case of mixing the chelating resin, the cation exchange resin and the chelating resin may be a mixed bed or a multiple bed. In either case, the effects of the present invention can be obtained. Chelating resins are resins with functional groups (chelating groups) that can form chelates (complexes) with metal ions. The functional group is not particularly limited as long as it can form a chelate (complex) with a metal ion. The functional group includes, for example, an aminomethyl phosphoric acid group, an iminodiacetoxy group, a thiol group, and a polyamine group. From the viewpoint of selectivity to various metal species, etc., the chelate resin preferably has an aminomethylphosphonic acid group or an iminodiacetoxy group as a functional group.
螯合樹脂的離子形宜為H形。螯合樹脂可列舉例如:AMBERSEP(註冊商標) IRC747UPS(商品名稱,杜邦公司製,螯合基:胺基甲基磷酸基)、AMBERSEP(註冊商標) IRC748(商品名稱,杜邦公司製,螯合基:亞胺基二乙酸基)、ORLITE(註冊商標) DS-21(商品名稱,奧璐佳瑙股份有限公司製,螯合基:胺基甲基磷酸基)、ORLITE(註冊商標) DS-22(商品名稱,奧璐佳瑙股份有限公司製,螯合基:亞胺基二乙酸基)、DIAION(註冊商標) CR11(商品名稱,三菱化學股份有限公司製,螯合基:亞胺基二乙酸基)、S930(商品名稱,Purolite股份有限公司製,螯合基:亞胺基二乙酸基)、S950(商品名稱,Purolite股份有限公司製,螯合基:胺基磷酸基)等,但不限於此等。另外,上述樹脂的離子形為鈉離子形(Na形)的情況,可以習知方法將離子形從Na形轉換成H形後再使用。The ionic form of chelating resin is preferably H form. Chelating resins include, for example: AMBERSEP (registered trademark) IRC747UPS (trade name, manufactured by DuPont, chelating group: aminomethylphosphoryl group), AMBERSEP (registered trademark) IRC748 (trade name, manufactured by DuPont, chelating group : iminodiacetoxy group), ORLITE (registered trademark) DS-21 (trade name, manufactured by Olucano Co., Ltd., chelating group: aminomethylphosphoryl group), ORLITE (registered trademark) DS-22 (trade name, manufactured by Olucano Co., Ltd., chelating group: iminodiacetoxy), DIAION (registered trademark) CR11 (trade name, manufactured by Mitsubishi Chemical Co., Ltd., chelating group: iminodiacetate) Acetate group), S930 (trade name, manufactured by Purolite Co., Ltd., chelating group: iminodiacetoxy group), S950 (trade name, manufactured by Purolite Co., Ltd., chelating group: aminophosphoryl group), etc., but Not limited to these. In addition, when the ionic form of the above-mentioned resin is sodium ion form (Na form), it can be used after converting the ionic form from Na form to H form by a known method.
本發明中所使用之螯合樹脂為氫離子形,且在以體積比25倍量使濃度3質量%的鹽酸通過該螯合樹脂時溶出的總金屬雜質量宜為5μg/mL-R以下。亦可使用這種市售產品作為螯合樹脂。此處,「體積比25倍量」,係指使相對於螯合樹脂的體積為25倍之體積的鹽酸通過。單位「/mL-R」,係指「飽和平衡狀態下的螯合樹脂之體積每1mL」。另外,所謂的飽和平衡狀態,係指使螯合樹脂接觸25℃相對濕度100%的大氣30分鐘以上而藉此成為飽和狀態的狀態。所謂的「使鹽酸通過」,除了使鹽酸通過螯合樹脂以外,亦包含將螯合樹脂浸漬於鹽酸等。螯合樹脂的體積每1mL之中的總金屬雜質量(μg/mL-R),可從已溶出的總金屬雜質量(μg/L)、用於溶出的溶離液之體積(L)及螯合樹脂的體積(mL)以下式算出。 總金屬雜質量(μg/mL-R)=(各金屬雜質量(μg/L)×溶離液的體積(L))/螯合樹脂的體積(mL) The chelating resin used among the present invention is a hydrogen ion form, and the total metal impurity amount dissolved when making the hydrochloric acid of concentration 3 mass % pass through this chelating resin with volume ratio 25 times amount should be below 5 μ g/mL-R. This commercially available product can also be used as a chelating resin. Here, "the volume ratio of 25 times" means passing hydrochloric acid having a volume 25 times the volume of the chelating resin. The unit "/mL-R" refers to "volume of chelating resin in saturated equilibrium per 1 mL". In addition, the so-called saturated equilibrium state refers to the state in which the chelate resin is brought into a saturated state by contacting the atmosphere at 25° C. with a relative humidity of 100% for more than 30 minutes. The so-called "passing hydrochloric acid" includes not only passing hydrochloric acid through the chelate resin, but also immersing the chelate resin in hydrochloric acid and the like. The total amount of metal impurities per 1 mL of the volume of the chelating resin (μg/mL-R), can be obtained from the amount of dissolved total metal impurities (μg/L), the volume of eluent used for dissolution (L) and the chelating The volume (mL) of the synthetic resin was calculated by the following formula. The total amount of metal impurities (μg/mL-R) = (the amount of each metal impurity (μg/L) × the volume of the eluent (L)) / the volume of the chelating resin (mL)
另外,上述總金屬雜質量為5μg/mL-R以下的螯合樹脂,例如可以專利文獻3記載的方法獲得。亦即,使螯合樹脂接觸金屬雜質含量1mg/L以下且濃度為5質量%以上的無機酸溶液而藉此進行精製的方法。藉此,可將以體積比25倍量使濃度3質量%之鹽酸通過螯合樹脂時溶出的總金屬雜質量(尤其是Na、Ca、Mg、Fe等溶出金屬量)降低至5μg/mL-R以下。藉由使用這樣已減少金屬雜質含量的螯合樹脂進行水解性有機溶劑的精製,可得到含有金屬雜質更少的高純度水解性有機溶劑。該無機酸溶液可使用鹽酸、硫酸、硝酸等。另外,使用Na形的螯合樹脂進行上述精製的情況,藉由實施上述精製,離子形轉換成H形。In addition, the above-mentioned total metal impurity amount is the chelate resin of 5 μ g/mL-R or less, for example, can obtain the method described in patent document 3. That is, it is a method of purifying by contacting the chelate resin with a mineral acid solution with a metal impurity content of 1 mg/L or less and a concentration of 5% by mass or more. Thereby, the total amount of metal impurities (especially the amount of dissolved metals such as Na, Ca, Mg, Fe, etc.) dissolved when the hydrochloric acid with a concentration of 3% by mass is passed through the chelating resin in an amount 25 times the volume ratio can be reduced to 5 μg/mL- R below. By using the chelating resin with reduced metal impurity content to carry out the refining of the hydrolyzable organic solvent, a high-purity hydrolyzable organic solvent containing less metal impurity can be obtained. As the inorganic acid solution, hydrochloric acid, sulfuric acid, nitric acid, etc. can be used. In addition, when the above-mentioned purification is performed using a Na-form chelate resin, the ionic form is converted to the H-form by performing the above-mentioned purification.
(陰離子交換樹脂) 如上所述,本發明中可將陽離子交換樹脂與螯合樹脂任意混合以使用,但亦可進一步組合陰離子交換樹脂。藉由使用陰離子交換樹脂,可確實地抑制酸的生成。因此,例如即使是僅使用陽離子交換樹脂的情況、有生成其他酸之疑慮的情況等,亦能藉由組合使用陰離子交換樹脂,進一步抑制酸的生成。使用陰離子交換樹脂的情況,該陰離子交換樹脂的使用量,相對於陽離子交換樹脂及任意的螯合樹脂之總量,例如可為0.1~100體積%。 (anion exchange resin) As above-mentioned, in this invention, a cation exchange resin and a chelate resin can be mixed arbitrarily and used, but an anion exchange resin can also be combined further. By using anion exchange resin, acid generation can be reliably suppressed. Therefore, for example, even when only a cation exchange resin is used, or when there is a possibility of generating other acids, the generation of an acid can be further suppressed by using an anion exchange resin in combination. When using an anion exchange resin, the usage-amount of this anion exchange resin can be 0.1-100 volume% with respect to the total amount of a cation exchange resin and arbitrary chelate resin, for example.
陰離子交換樹脂可列舉:具有4級銨鹽基的強鹼性陰離子交換樹脂及具有1級~3級胺基的弱鹼性陰離子交換樹脂。陰離子交換樹脂可列舉例如:ORLITE(註冊商標) DS-2(凝膠型的強鹼性陰離子交換樹脂,商品名稱,奧璐佳瑙股份有限公司製)、DS-5(MR型的強鹼性陰離子交換樹脂,商品名稱,奧璐佳瑙股份有限公司製)、DS-6(MR型的弱鹼性陰離子交換樹脂,商品名稱,奧璐佳瑙股份有限公司製)等,但不限於此等。此等之中,較佳為MR型的陰離子交換樹脂。Examples of anion exchange resins include strongly basic anion exchange resins having quaternary ammonium groups and weakly basic anion exchange resins having 1st to 3rd amine groups. Anion exchange resins include, for example: ORLITE (registered trademark) DS-2 (gel-type strongly basic anion-exchange resin, trade name, manufactured by Olucano Co., Ltd.), DS-5 (MR-type strongly basic Anion exchange resin, trade name, manufactured by Olucano Co., Ltd.), DS-6 (MR type weakly basic anion exchange resin, trade name, manufactured by Olucano Co., Ltd.), etc., but not limited to these . Among these, MR type anion exchange resins are preferable.
在用於精製水解性有機溶劑之前,亦可因應需求對於陽離子交換樹脂、任意的螯合樹脂及任意的陰離子交換樹脂(以下將此等統稱「離子交換樹脂」)進行抑制從樹脂溶出水分的前處理。亦即,本發明之精製方法中,在該精製步驟之前,亦可具有前處理步驟,該前處理步驟係對於陽離子交換樹脂、任意的螯合樹脂及任意的陰離子交換樹脂進行用以抑制從該樹脂溶出水分的前處理。Before being used to purify hydrolyzable organic solvents, cation exchange resins, arbitrary chelating resins, and arbitrary anion exchange resins (hereinafter collectively referred to as "ion exchange resins") can also be subjected to pre-suppression of water elution from the resins. deal with. That is to say, in the refining method of the present invention, before the refining step, there may also be a pretreatment step, and the pretreatment step is carried out for cation exchange resin, any chelating resin and any anion exchange resin in order to inhibit the Pre-treatment for the resin to dissolve water.
前處理的方法可列舉例如:使精製對象的水解性有機溶劑接觸離子交換樹脂,或使離子交換樹脂接觸在25℃中的相對介電常數大於精製對象之水解性有機溶劑的前處理用有機溶劑的方法。具體可列舉下述方法:在填充了用於精製之前的離子交換樹脂的管柱之中,通入精製對象的水解性有機溶劑,並持續通液直到該溶劑中的水分濃度在管柱的入口與出口成為相同程度為止。又可列舉下述方法:在填充了用於精製之前的離子交換樹脂的管柱中通入在25℃中的相對介電常數大於精製對象之水解性有機溶劑的前處理用有機溶劑,並持續通液直到溶劑中的水分濃度在管柱的入口與出口成為相同程度為止。此情況下,亦可在通入前處理用有機溶劑之後,再通入精製對象的水解性有機溶劑直到溶劑中的水分濃度在管柱的入口與出口成為相同程度為止。前處理用有機溶劑宜使用在25℃中的相對介電常數為20以上的甲醇、乙醇等醇。The pretreatment method includes, for example, contacting a hydrolyzable organic solvent to be purified with an ion exchange resin, or contacting an ion exchange resin with an organic solvent for pretreatment that has a higher relative dielectric constant at 25°C than the hydrolyzable organic solvent to be purified. Methods. Specifically, the following method can be enumerated: In the column filled with the ion exchange resin before purification, the hydrolyzable organic solvent to be purified is passed through, and the liquid is continuously passed until the water concentration in the solvent is below the inlet of the column. Until it becomes the same level as export. The following method can also be enumerated: in the column filled with the ion exchange resin before the purification, the pretreatment organic solvent whose relative dielectric constant is greater than the hydrolyzable organic solvent of the purification object at 25 ° C is passed, and continuously Pass the liquid until the water concentration in the solvent becomes the same level at the inlet and outlet of the column. In this case, after passing the pretreatment organic solvent, the hydrolyzable organic solvent to be purified may be passed until the water concentration in the solvent becomes the same level at the inlet and outlet of the column. As the organic solvent for pretreatment, it is preferable to use alcohols such as methanol and ethanol with a relative dielectric constant of 20 or more at 25°C.
又,用以抑制從樹脂溶出水分的其他前處理的方法可列舉:將填充了離子交換樹脂的耐熱容器設置於乾燥機內部並進行加熱(乾燥)處理數小時的方法。乾燥條件可因應離子交換樹脂的種類,在50℃~120℃、1小時~24小時之中設定適當的溫度及時間。藉由進行此處理,可將離子交換樹脂中的含水率降低至10質量%以下。乾燥方法可為常壓、減壓及真空乾燥的任一種,從乾燥時間短而效率良好的觀點來看,較佳為減壓或真空乾燥。另外,離子交換樹脂的含水率可使用下述算式算出。 含水率(質量%)=((以乾燥機進行了加熱處理的樹脂之質量(g)-以加熱乾燥式水分計完全乾燥之樹脂的質量(g))/以乾燥機進行了加熱處理之樹脂的質量(g))×100 As another pretreatment method for suppressing elution of water from the resin, a method of setting a heat-resistant container filled with an ion exchange resin in a drier and performing a heat (dry) treatment for several hours is mentioned. Drying conditions can be set according to the type of ion exchange resin, and the appropriate temperature and time can be set between 50°C~120°C and 1 hour~24 hours. By performing this treatment, the water content in the ion exchange resin can be reduced to 10% by mass or less. The drying method may be any one of normal pressure, reduced pressure and vacuum drying, and from the viewpoint of short drying time and good efficiency, reduced pressure or vacuum drying is preferable. In addition, the water content of the ion exchange resin can be calculated using the following formula. Moisture content (mass %)=((mass of resin heat-treated with a dryer (g)-mass of resin completely dried with a heat-drying moisture meter (g))/resin heat-treated with a dryer Mass (g))×100
此處,上述式中,以乾燥機進行了加熱處理的樹脂,可藉由如上述將樹脂進行加熱處理來獲得(含水率為10質量%以下)。然後,在以加熱乾燥式水分計測量該以乾燥機進行了加熱處理的樹脂之前,以避免來自空氣中的水分混入的方式進行保管、移動。然後,在加熱乾燥式水分計上設置該樹脂,進一步於105℃使樹脂完全乾燥數分鐘~數十分鐘,藉此得到經加熱乾燥式水分計完全乾燥的樹脂。加熱乾燥式水分計,例如可使用A&D公司製的MX-50(商品名稱)。另外,為了提高測量的正確性,取用5g以上的乾燥前之樹脂進行測量。Here, in the above formula, the resin heat-treated with a dryer can be obtained by heat-treating the resin as described above (moisture content is 10% by mass or less). Then, the resin heat-treated in a dryer was stored and moved so as not to mix in moisture from the air until the heat-drying type moisture meter was used to measure the resin. Then, the resin was set on a heat-drying moisture meter, and the resin was completely dried at 105° C. for several minutes to tens of minutes to obtain a resin completely dried by the heat-drying moisture meter. As the heat drying type moisture meter, for example, MX-50 (trade name) manufactured by A&D Co., Ltd. can be used. In addition, in order to improve the accuracy of measurement, more than 5g of resin before drying is used for measurement.
使水解性有機溶劑接觸離子交換樹脂的方法並未特別限制,可列舉批次處理方法及以管柱所進行的連續通液處理方法。其中從操作性及效率的觀點來看,宜為連續通液處理方法。The method of bringing the hydrolyzable organic solvent into contact with the ion exchange resin is not particularly limited, and examples thereof include a batch treatment method and a continuous liquid-passing treatment method using a column. Among them, the continuous liquid flow treatment method is preferable from the viewpoint of operability and efficiency.
連續通液處理方法中,離子交換樹脂填充於管柱等精製塔。精製塔的樹脂填充層高度並未特別限定,例如可為100~1500mm。接著,例如以SV(空間速度,h -1)2~20通入2~100BV的水解性有機溶劑。此處,BV(Bed volume)表示通入之溶劑相對於樹脂量的流量倍數。水解性有機溶劑的通液,從去除金屬的觀點來看,宜以SV2~20進行,更佳係以SV5~10進行。通液的方向可為向下流或向上流的任一種。藉由如此進行通液,可使水解性有機溶劑中的金屬雜質吸附於離子交換樹脂而將其去除。 In the continuous liquid treatment method, the ion exchange resin is filled in a purification column such as a column. The height of the resin packed bed in the refining tower is not particularly limited, and may be, for example, 100 to 1500 mm. Next, for example, 2-100 BV of a hydrolyzable organic solvent is introduced at a SV (space velocity, h -1 ) of 2-20. Here, BV (Bed volume) represents the flow rate of the solvent that is passed through relative to the amount of resin. From the standpoint of metal removal, the flow of the hydrolyzable organic solvent should be carried out at SV2~20, more preferably at SV5~10. The direction of the liquid flow can be either downflow or upflow. By passing the liquid in this way, metal impurities in the hydrolyzable organic solvent can be adsorbed to the ion exchange resin and removed.
接著說明批次處理方法。首先在具備攪拌機的反應槽內填入離子交換樹脂。然後,將水解性有機溶劑填充至該反應槽內。容積比並未特別限定,相對於樹脂量1,宜為有機溶劑2~200。之後,例如放置0.5~24小時左右。放置後使攪拌機運作,將樹脂與有機溶劑均勻地混合。攪拌速度及攪拌時間可根據反應槽的尺寸及處理量等適當決定。攪拌結束後進行過濾等,將樹脂與水解性有機溶劑分離,藉此去除金屬雜質,可得到經精製的水解性有機溶劑。Next, the batch processing method will be described. First, the ion exchange resin is filled in the reaction tank equipped with a stirrer. Then, the hydrolyzable organic solvent is filled in this reaction tank. The volume ratio is not particularly limited, but is preferably 2 to 200 of the organic solvent relative to the resin amount of 1. After that, it is left to stand, for example, for about 0.5 to 24 hours. After standing, run the mixer to mix the resin and the organic solvent evenly. The stirring speed and stirring time can be appropriately determined according to the size of the reaction tank, the processing capacity, and the like. After the stirring is completed, filter or the like is performed to separate the resin from the hydrolyzable organic solvent, thereby removing metal impurities and obtaining a refined hydrolyzable organic solvent.
另外,關於離子交換樹脂,在用於精製水解性有機溶劑之前實施上述用以抑制從樹脂溶出水分之前處理的情況,可直接使用前處理中所使用的管柱等容器進行使離子交換樹脂接觸水解性有機溶劑以進行精製的步驟。In addition, regarding the ion exchange resin, before it is used to purify the hydrolyzable organic solvent, the above-mentioned pretreatment for suppressing the elution of water from the resin can be carried out, and the ion exchange resin can be contacted and hydrolyzed directly using the container such as the column used in the pretreatment. Non-toxic organic solvents are used for refining steps.
本發明之精製方法,主要係以連續運轉進行水解性有機溶劑的精製,亦即在精製步驟中,在開始精製對象之水解性有機溶劑的精製(通液)後到精製結束前途中不停止通液而連續進行。然而,亦可以間歇性運轉來進行水解性有機溶劑的精製。以間歇性運轉來進行水解性有機溶劑之精製的情況,在試驗系內部,可能會因為來自外部的水分或來自樹脂的官能基導致有機溶劑進行水解而產生水分及酸。因此,以間歇性運轉進行的情況中,本發明之精製方法宜具有排放步驟,其係在精製步驟的開始後,以固定時間使從填充有陽離子交換樹脂、任意的螯合樹脂及任意的陰離子交換樹脂的精製塔之出口溶出的該水解性有機溶劑排出至用以儲存精製後之該水解性有機溶劑的儲存槽外。例如,在精製步驟開始後停止通入水解性有機溶劑30分鐘以上的情況中,作為排放步驟,使相對於離子交換樹脂(陽離子交換樹脂、任意的螯合樹脂及任意的陰離子交換樹脂)量為0.5BV以上的從精製塔之出口溶出的該水解性有機溶劑排出至儲存槽外之後,再開始精製步驟。藉由設置排放步驟,可減少停止運轉的過程中產生的水分及酸。排放步驟中的排放量(排出至系外之水解性有機溶劑的量)亦可根據運轉停止時間、精製塔出口中的水解性有機溶劑中的水分量、酸濃度及電阻率等預先設定。或是亦可以線上監控進行設定,在到達預先設定之電阻率時自動停止排放步驟並切換至精製步驟。另外,以連續運轉來進行水解性有機溶劑之精製的情況中,亦可因應需求實施上述排放步驟。The refining method of the present invention mainly carries out the refining of the hydrolyzable organic solvent with continuous operation, that is, in the refining step, after the refining (fluiding) of the hydrolyzable organic solvent to be refined is started, the flow is not stopped until the end of the refining process. liquid and continuously. However, it is also possible to refine the hydrolyzable organic solvent by intermittent operation. When the purification of the hydrolyzable organic solvent is carried out by intermittent operation, in the test system, the organic solvent may be hydrolyzed by external moisture or functional groups from the resin to generate moisture and acid. Therefore, in the case of intermittent operation, the refining method of the present invention preferably has a discharge step, which is to discharge the cation exchange resin, any chelating resin, and any anion from the cation exchange resin, any chelating resin, and any anion for a fixed period of time after the start of the refining step. The hydrolyzable organic solvent eluted from the outlet of the purification tower for exchanging resin is discharged to the outside of the storage tank for storing the purified hydrolyzable organic solvent. For example, in the case of stopping the introduction of the hydrolyzable organic solvent for more than 30 minutes after the start of the purification step, as a discharge step, the amount relative to the ion exchange resin (cation exchange resin, any chelating resin, and any anion exchange resin) is After 0.5 BV or more of the hydrolyzable organic solvent eluted from the outlet of the purification tower is discharged to the outside of the storage tank, the purification step is started again. Water and acid generated during shutdown can be reduced by providing a drain step. The discharge amount (amount of hydrolyzable organic solvent discharged outside the system) in the discharge step can also be set in advance according to the stop time of operation, the water content in the hydrolyzable organic solvent in the outlet of the refining tower, the acid concentration, and the resistivity. Or it can also be set by online monitoring, and automatically stop the discharge step and switch to the refining step when the preset resistivity is reached. In addition, in the case where the purification of the hydrolyzable organic solvent is carried out by continuous operation, the above-mentioned discharge step may be implemented as required.
根據本發明之精製方法,因為抑制從水解性有機溶劑生成酸,可將精製步驟後的水解性有機溶劑之pH保持在中性附近。具體而言,可使精製步驟後的水解性有機溶劑之pH為5~7。然而,根據水解性有機溶劑的種類,亦具有pH例如為4以下的情況。According to the purification method of the present invention, since acid generation from the hydrolyzable organic solvent is suppressed, the pH of the hydrolyzable organic solvent after the purification step can be kept near neutral. Specifically, the pH of the hydrolyzable organic solvent after the purification step can be adjusted to 5-7. However, depending on the type of the hydrolyzable organic solvent, the pH may be, for example, 4 or less.
根據本發明之精製方法,在精製步驟中,可將水解性有機溶劑中的各金屬濃度降低70質量%以上,宜為80質量%以上。另外,水解性有機溶劑中包含的金屬雜質可列舉例如:Li、Na、Mg、Al、K、Ca、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、As、Sr、Ag、Cd、Sn、Ba、Pb等。According to the refining method of the present invention, in the refining step, the concentration of each metal in the hydrolyzable organic solvent can be reduced by at least 70% by mass, preferably at least 80% by mass. In addition, the metal impurities contained in the hydrolyzable organic solvent include, for example: Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Ag , Cd, Sn, Ba, Pb, etc.
以下藉由實施例具體說明本發明,但本發明不限於此等實施例。 [實施例] The following examples illustrate the present invention in detail, but the present invention is not limited to these examples. [Example]
金屬濃度、乙酸濃度及水分濃度的測量方法如下所述。The measurement methods of metal concentration, acetic acid concentration and moisture concentration are as follows.
(金屬濃度) 金屬濃度(ng/L)係使用Agilent 8900 三段式四極ICP-MS(商品名稱,Agilent Technologies股份有限公司製)進行測量。 (metal concentration) The metal concentration (ng/L) was measured using an Agilent 8900 three-stage quadrupole ICP-MS (trade name, manufactured by Agilent Technologies Co., Ltd.).
(乙酸濃度) 乙酸濃度(質量ppm)係使用毛細管電泳系統(商品名稱:Agilent 7100,大塚電子股份有限公司製)進行測量。 (acetic acid concentration) The acetic acid concentration (ppm by mass) was measured using a capillary electrophoresis system (trade name: Agilent 7100, manufactured by Otsuka Electronics Co., Ltd.).
(水分濃度) 水分濃度係使用卡爾費雪容量法水分計(商品名稱:Aquacounter AQ-2200,平沼產業股份有限公司製)以卡爾費雪法進行測量。 (moisture concentration) The water concentration was measured by the Karl Fisher method using a Karl Fisher volumetric moisture meter (trade name: Aquacounter AQ-2200, manufactured by Hiranuma Sangyo Co., Ltd.).
(離子交換樹脂) 下例中所使用的各種離子交換樹脂之詳情如下。 ・ORLITE(註冊商標) DS-21(商品名稱,奧璐佳瑙股份有限公司製):螯合樹脂,螯合基:胺基甲基磷酸基 ・ORLITE(註冊商標) DS-4(商品名稱,奧璐佳瑙股份有限公司製):MR型的強酸性陽離子交換樹脂,離子交換基:磺酸基 ・ORLITE(註冊商標) DS-1(商品名稱,奧璐佳瑙股份有限公司製):凝膠型的強酸性陽離子交換樹脂,離子交換基:磺酸基,交聯度:標準 ・AMBERLITE(註冊商標) CR99 K/350(商品名稱,杜邦公司製):凝膠型的強酸性陽離子交換樹脂,交聯度:低 ・AMBERLITE(註冊商標) IRN99H(商品名稱,杜邦公司製):凝膠型的強酸性陽離子交換樹脂,交聯度:高 ・ORLITE(註冊商標) DS-6(商品名稱,奧璐佳瑙股份有限公司製):MR型的弱鹼性陰離子交換樹脂 (ion exchange resin) The details of the various ion exchange resins used in the following examples are as follows. ・ORLITE (registered trademark) DS-21 (trade name, manufactured by ORLITE Co., Ltd.): chelating resin, chelating group: aminomethylphosphonic group ・ORLITE (registered trademark) DS-4 (trade name, manufactured by ORLITE Co., Ltd.): MR type strongly acidic cation exchange resin, ion exchange group: sulfonic acid group ・ORLITE (registered trademark) DS-1 (trade name, manufactured by ORLITE Co., Ltd.): gel-type strongly acidic cation exchange resin, ion exchange group: sulfonic acid group, degree of crosslinking: standard ・AMBERLITE (registered trademark) CR99 K/350 (trade name, manufactured by DuPont): gel-type strongly acidic cation exchange resin, degree of cross-linking: low ・AMBERLITE (registered trademark) IRN99H (trade name, manufactured by DuPont): gel-type strongly acidic cation exchange resin, degree of cross-linking: high ・ORLITE (registered trademark) DS-6 (trade name, manufactured by Orlite Co., Ltd.): MR type weakly basic anion exchange resin
[比較例1、實施例1~5:混合床比例的比較] (PGMEA的精製) 在PFA樹脂製管柱(內徑:16mm,高度:300mm)中,按表1所示的陽離子交換樹脂的混合床比例(體積比),以總計成為36mL的方式,分別填充係螯合樹脂的ORLITE(註冊商標) DS-21及係MR型強酸性陽離子交換樹脂的ORLITE(註冊商標) DS-4。另外,確認了在按體積比25倍量使濃度3質量%的鹽酸通過上述螯合樹脂時溶出的總金屬雜質量為5μg/mL-R以下。作為前處理,以SV5對其通入PGMEA(商品名稱:PM Thinner,東京應化工業股份有限公司製),直到PGMEA中的水分濃度在管柱入口與管柱出口成為相同等級為止,以去除樹脂中的水分。另外,亦確認了在上述前處理中通入在25℃中的相對介電常數大於PGMEA的例如甲醇以代替PGMEA可去除樹脂中的水分。 然後以SV5使20BV的PGMEA通入進行前處理之後的樹脂,以進行精製步驟。收集精製前的PGMEA(原液)及精製後的管柱出口的PGMEA,測量Cr濃度、乙酸濃度及水分濃度。結果顯示於表1。另外,關於產生的乙酸,到5mg/L(絕對值)為止皆在測量誤差範圍內,亦即可視為幾乎未產生乙酸。又,各例中,原液中的Cr及乙酸濃度不同,此為原液批號不同所致。 [Comparative Example 1, Examples 1 to 5: Comparison of Mixed Bed Ratio] (refinement of PGMEA) In a column made of PFA resin (inner diameter: 16 mm, height: 300 mm), the mixed bed ratio (volume ratio) of the cation exchange resin shown in Table 1 was filled with chelating resin so that the total amount was 36 mL. ORLITE (registered trademark) DS-21 and ORLITE (registered trademark) DS-4 which is an MR type strongly acidic cation exchange resin. In addition, it was confirmed that the total amount of metal impurities eluted when the hydrochloric acid with a concentration of 3% by mass was passed through the above-mentioned chelate resin in an amount of 25 times the volume ratio was 5 μg/mL-R or less. As a pretreatment, pass SV5 into PGMEA (trade name: PM Thinner, manufactured by Tokyo Ohka Industry Co., Ltd.) until the water concentration in PGMEA becomes the same level at the column inlet and column outlet to remove the resin moisture in. In addition, it was also confirmed that the water in the resin can be removed by passing, for example, methanol, which has a relative dielectric constant greater than PGMEA at 25° C., instead of PGMEA during the above pretreatment. Then, 20BV of PGMEA was passed through the pretreated resin at SV5 to perform a refining step. Collect the PGMEA (stock solution) before refining and the PGMEA at the outlet of the column after refining, and measure the Cr concentration, acetic acid concentration and water concentration. The results are shown in Table 1. In addition, the generated acetic acid was within the measurement error range up to 5 mg/L (absolute value), that is, it can be considered that almost no acetic acid was generated. In addition, in each example, the concentration of Cr and acetic acid in the stock solution is different, which is due to the difference in batch numbers of the stock solution.
[表1]
如表1所示,陽離子交換樹脂的混合床比例為10%~100%的實施例1~5中,精製後的PGMEA中的Cr濃度小於15ng/L,一方面抑制了乙酸的生成,一方面以良好效率去除金屬。尤其是以混合床使用螯合樹脂與陽離子交換樹脂的實施例1~4中,大致上抑制了乙酸的產生。另一方面,在陽離子交換樹脂的混合床比例為0%、亦即僅使用螯合樹脂的比較例1中,精製後的PGMEA中的Cr去除率為55%,可知其並未充分去除金屬。As shown in Table 1, in Examples 1 to 5 where the mixed bed ratio of the cation exchange resin is 10% to 100%, the Cr concentration in the refined PGMEA is less than 15ng/L, which on the one hand suppresses the generation of acetic acid, on the one hand Removes metals with good efficiency. Especially in the embodiment 1~4 that uses chelating resin and cation exchange resin with mixed bed, substantially suppressed the generation of acetic acid. On the other hand, in Comparative Example 1 in which the mixed bed ratio of the cation exchange resin was 0%, that is, only the chelating resin was used, the Cr removal rate in the purified PGMEA was 55%, which shows that it did not sufficiently remove the metal.
[實施例6~7:根據強酸性陽離子交換樹脂的種類比較Cr的去除性能] 作為與螯合樹脂混合的強酸性陽離子交換樹脂(混合床比例:25體積%),分別使用ORLITE(註冊商標) DS-1(凝膠型的強酸性陽離子交換樹脂,交聯度:標準)及AMBERLITE(註冊商標) CR99 K/350(凝膠型的強酸性陽離子交換樹脂,交聯度:低,將K形轉換成H形而成者),除此之外,以與實施例3相同的方法進行PGMEA的精製。採樣精製前的PGMEA(原液)及精製後的管柱出口之PGMEA,測量Cr濃度及水分濃度。結果與實施例3一併顯示於表2。 [Example 6~7: According to the kind of strongly acidic cation exchange resin, the removal performance of Cr is compared] As the strongly acidic cation exchange resin mixed with the chelating resin (mixed bed ratio: 25% by volume), ORLITE (registered trademark) DS-1 (gel-type strongly acidic cation exchange resin, degree of crosslinking: standard) and AMBERLITE (registered trademark) CR99 K/350 (the strongly acidic cation exchange resin of gel type, degree of cross-linking: low, the person that the K form is converted into H form), in addition, with embodiment 3 identical Methods for the purification of PGMEA. Sampling of PGMEA (stock solution) before refining and PGMEA at the outlet of the column after refining, and measuring Cr concentration and water concentration. The results are shown in Table 2 together with Example 3.
[表2]
如表2所示,可知係MR型之強酸性陽離子交換樹脂的DS-4,相較於係凝膠型之強酸性陽離子交換樹脂的DS-1、係凝膠型之小粒徑強酸性陽離子交換樹脂的CR99 K/350,去除金屬的性能特別優良。As shown in Table 2, it can be seen that DS-4, which is an MR-type strongly acidic cation exchange resin, is compared with DS-1, which is a gel-type strongly acidic cation-exchange resin, and a gel-type small particle size strongly acidic cation The exchange resin CR99 K/350 has particularly good metal removal performance.
[實施例8~10:根據交聯度的不同比較乙酸的產生] 作為與螯合樹脂混合的凝膠型之強酸性陽離子交換樹脂(混合床比例:25體積%),分別使用AMBERLITE(註冊商標)IRN99H(交聯度:高)、ORLITE(註冊商標)DS-1(交聯度:標準)及AMBERLITE(註冊商標)CR99 K/350(交聯度:低,將K形轉換成H形),除此之外,以與實施例3相同的方法進行PGMEA的精製。採樣精製前的PGMEA(原液)及精製後的管柱出口之PGMEA,測量乙酸濃度及水分濃度。結果顯示於表3。 [Embodiments 8-10: According to the difference of cross-linking degree, compare the generation of acetic acid] As a gel-type strongly acidic cation exchange resin mixed with a chelating resin (mixed bed ratio: 25% by volume), AMBERLITE (registered trademark) IRN99H (crosslinking degree: high) and ORLITE (registered trademark) DS-1 were used respectively. (Degree of cross-linking: standard) and AMBERLITE (registered trademark) CR99 K/350 (degree of cross-linking: low, K-shape converted to H-shape), in addition to the purification of PGMEA in the same manner as in Example 3 . Sampling of PGMEA (stock solution) before refining and PGMEA at the outlet of the column after refining to measure acetic acid concentration and water concentration. The results are shown in Table 3.
[表3]
如表3所示,可知在凝膠型的強酸性陽離子交換樹脂之中,使用高交聯樹脂的情況,可確實抑制乙酸的產生。As shown in Table 3, it can be seen that among gel-type strongly acidic cation exchange resins, when a highly cross-linked resin is used, the generation of acetic acid can be reliably suppressed.
[參考例1:藉由陰離子交換樹脂減少乙酸] 作為樹脂,僅使用係MR型之弱鹼性陰離子交換樹脂的ORLITE(註冊商標)DS-6,除此之外,以與實施例3相同的方法進行PGMEA的精製。採樣精製前的PGMEA(原液)及精製後的管柱出口之PGMEA,測量乙酸濃度。結果顯示於表4。 [Reference Example 1: Reduction of acetic acid by anion exchange resin] Purification of PGMEA was performed in the same manner as in Example 3 except that only ORLITE (registered trademark) DS-6, which is an MR-type weakly basic anion exchange resin, was used as the resin. Sampling the PGMEA (stock solution) before refining and PGMEA at the outlet of the column after refining to measure the concentration of acetic acid. The results are shown in Table 4.
[表4]
如表4所示,得知藉由使用陰離子交換樹脂,可去除原液中所包含的乙酸。因此明白藉由對於本發明之陽離子交換樹脂及任意的螯合樹脂進一步組合使用陰離子交換樹脂,可進行確實抑制乙酸產生的水解性有機溶劑之精製。As shown in Table 4, it was found that acetic acid contained in the stock solution can be removed by using an anion exchange resin. Therefore, it was found that by further using an anion exchange resin in combination with the cation exchange resin of the present invention and an optional chelate resin, purification of a hydrolyzable organic solvent that reliably suppresses the generation of acetic acid can be performed.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-061044 | 2021-03-31 | ||
JP2021061044 | 2021-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW202302499A true TW202302499A (en) | 2023-01-16 |
Family
ID=83458822
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW111111264A TW202302499A (en) | 2021-03-31 | 2022-03-25 | Method for refining hydrolyzable organic solvent, and method for producing resin for refining hydrolyzable organic solvent |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPWO2022209392A1 (en) |
TW (1) | TW202302499A (en) |
WO (1) | WO2022209392A1 (en) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3768549B2 (en) * | 1993-02-25 | 2006-04-19 | ローム・アンド・ハース・エレクトロニック・マテリアルズ,エル.エル.シー. | Method for producing high-purity photosensitive resin composition |
DE10024313A1 (en) * | 2000-05-17 | 2001-11-22 | Basf Ag | Removal of alkali metal ions (production catalyst residues) from alkoxylates uses cation exchangers to give products sufficiently pure and combustible for use as fuel additives |
JP2004181351A (en) * | 2002-12-03 | 2004-07-02 | Japan Organo Co Ltd | Method for refining non-aqueous liquid material |
JP4441472B2 (en) * | 2005-10-24 | 2010-03-31 | オルガノ株式会社 | Method for reducing the amount of metal impurities contained in a cation exchange resin |
JP5785000B2 (en) * | 2011-06-21 | 2015-09-24 | 野村マイクロ・サイエンス株式会社 | Operation method of pure water device and pure water device |
-
2022
- 2022-02-17 WO PCT/JP2022/006402 patent/WO2022209392A1/en active Application Filing
- 2022-02-17 JP JP2023510631A patent/JPWO2022209392A1/ja active Pending
- 2022-03-25 TW TW111111264A patent/TW202302499A/en unknown
Also Published As
Publication number | Publication date |
---|---|
JPWO2022209392A1 (en) | 2022-10-06 |
WO2022209392A1 (en) | 2022-10-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4441472B2 (en) | Method for reducing the amount of metal impurities contained in a cation exchange resin | |
TWI773881B (en) | Production method and production device for chelate resin, and method for refining liquid to be processed | |
CA3009750C (en) | Purification process for hydrolysable organic solvent | |
TWI827592B (en) | Method for removing metals in liquid, and anion exchange resin-mixed h-type chelating resin | |
TW202225131A (en) | Method for purifying organic solvent | |
JP2004181352A (en) | Method for refining non-aqueous liquid material | |
JP2004181351A (en) | Method for refining non-aqueous liquid material | |
TW202302499A (en) | Method for refining hydrolyzable organic solvent, and method for producing resin for refining hydrolyzable organic solvent | |
TW202311217A (en) | Processes for purifying glycol ethers | |
TW202402370A (en) | Organic solvent purification method and purification device | |
JP2022545155A (en) | Process for purifying organic solvents | |
JP4081503B2 (en) | Mixed bed type ion exchange resin | |
TW202306646A (en) | Refining method and refining device for non-aqueous liquid, and production method and pretreatment device for ion exchange resin | |
WO2015016230A1 (en) | Preparation method of aqueous tetraalkyl ammonium salt solution | |
JPH02163130A (en) | Purification of highly purified nonelectrolytic polymer aqueous solution for semiconductor | |
WO2022209233A1 (en) | Dry ion exchange resin manufacturing method and manufacturing device, and treated liquid purifying method and purifying device | |
JP2534861B2 (en) | Method for producing high-purity hydrazine hydrate | |
JP2003334550A (en) | Ultrapure water and production method therefor | |
JP2007075720A (en) | Method for treating strong basic anion exchange resin and strong basic anion exchange resin obtained thereby | |
JP2023137717A (en) | Preparation method of mixed bed ion exchanger for purifying hydrogen peroxide water, and purification method of purifying hydrogen peroxide water | |
JPH04271848A (en) | Recovery method for anion exchange resin | |
TW202229176A (en) | Method and device for refining liquid to be processed containing tetraalkylammonium ions | |
BR112021026674B1 (en) | PROCESS AND PROCESS FOR REMOVING IONIC CONTAMINANTS FROM AN ORGANIC SOLVENT | |
JP2023009492A (en) | Adjustment method of anion exchange resin | |
JPH01119344A (en) | Method for decreasing eluate of cation-exchange resin of high acidity |