JP4996172B2 - Method for producing high purity alkali metal hydroxide - Google Patents
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- JP4996172B2 JP4996172B2 JP2006227408A JP2006227408A JP4996172B2 JP 4996172 B2 JP4996172 B2 JP 4996172B2 JP 2006227408 A JP2006227408 A JP 2006227408A JP 2006227408 A JP2006227408 A JP 2006227408A JP 4996172 B2 JP4996172 B2 JP 4996172B2
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- alkali metal
- metal hydroxide
- ion exchange
- exchange resin
- alkaline earth
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- 150000008044 alkali metal hydroxides Chemical class 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 29
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 29
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 26
- 239000003456 ion exchange resin Substances 0.000 claims description 26
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000013522 chelant Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Treatment Of Water By Ion Exchange (AREA)
Description
この発明は、粗水酸化アルカリ金属中のアルカリ土類金属を効果的に除去することができる高純度水酸化アルカリ金属の製造方法に関するものである。 The present invention relates to a method for producing a high-purity alkali metal hydroxide capable of effectively removing an alkaline earth metal in a crude alkali metal hydroxide.
例えば半導体ウェーハやカラーフィルター等の電子部品の製造においては、ウェーハ表面のエッチングによる平面化、レジスト材の除去、あるいは表面を洗浄するためなどに水酸化アルカリ金属が使用されている。これら電子部品の製造に使用される水酸化アルカリ金属は、半導体ウェーハの劣化、半導体デバイスの特性の低下等を防ぐため、ニッケル、クロム、鉄、および銅等の金属不純物を含まない高純度の水酸化アルカリ金属を用いることが要求されている。またこの他、医療用や化粧品等においてもこのような不純物を含まない薬剤の要求が高まっている。 For example, in the manufacture of electronic components such as semiconductor wafers and color filters, an alkali metal hydroxide is used to planarize the wafer surface by etching, remove the resist material, or clean the surface. Alkali metal hydroxide used in the manufacture of these electronic components is a high-purity water that does not contain metal impurities such as nickel, chromium, iron, and copper in order to prevent deterioration of semiconductor wafers and deterioration of semiconductor device characteristics. It is required to use an alkali metal oxide. In addition, there is an increasing demand for drugs that do not contain such impurities in medical use and cosmetics.
高純度の水酸化アルカリ金属の製法としては、イオン交換膜により水酸化アルカリを精製する製造方法が挙げられる（例えば、特許文献１参照）。この方法は精製精度は十分に高いものの設備化に比較的手間がかかり、どこでも簡単に高度精製された水酸化アルカリが得られない状況であった。また、活性炭により水酸化カリウム中のニッケルを除去する方法（例えば、特許文献２参照）、活性炭にて水酸化ナトリウム中の鉄やニッケルを除去する方法（例えば、特許文献３参照）が開示されている。これらは比較的簡単な設備で対応でき高度な精製が可能であるが精製可能な金属種が少ない状況であった。また、ここから一部溶出する金属種もありこの前処理に労力がかかる場合がある。 As a method for producing high-purity alkali metal hydroxide, a production method for purifying alkali hydroxide with an ion exchange membrane can be mentioned (for example, see Patent Document 1). Although this method has a sufficiently high refining accuracy, it takes a relatively long time to install equipment, and it is difficult to obtain highly purified alkali hydroxide anywhere. Also disclosed are a method for removing nickel in potassium hydroxide with activated carbon (for example, see Patent Document 2) and a method for removing iron and nickel in sodium hydroxide with activated carbon (for example, see Patent Document 3). Yes. These can be handled with relatively simple equipment and can be highly purified, but there are few metal species that can be purified. In addition, some metal species are eluted from here, and this pretreatment may take effort.
一方、キレート樹脂やイオン交換樹脂にて金属類を補足し被接触溶液等を精製、もしくは金属類を回収することが知られている。これら樹脂による水酸化アルカリの精製例としては、特定構造を有するキレート樹脂による精製が開示されている（例えば、特許文献４参照）。これらは鉄等の重金属を除去し精製することができるが、更なる高処理については開示されていないことと、取扱いの濃度で例えば苛性ソーダ濃度で１５０〜５００ｇ／ｌが好適例として挙げられているが、これよりも高濃度の領域でも高度な精製を満足するものではなかった。また、水酸化アルカリ中の重金属分析では、キレート樹脂（代表的にはイミノ二酢酸系）にて水酸化アルカリ中重金属を吸着しアルカリ金属と分離してから金属分を脱着して測定する方法が用いられている。しかし、金属類の捕捉効率を上げるため、例えば水酸化ナトリウムの分析では数重量％以下（以降％）の濃度に薄める必要がある（例えば、非特許文献１参照）。一方市場に流通している水酸化アルカリは、代表的な水酸化ナトリウム及び水酸化カリウムの両者とも４８％（液温度にもよるが、水酸化ナトリウム、水酸化カリウムの両者とも７３０ｇ／ｌ）付近が多く、使用段階ではさまざまであるが、仮保存の形態も含め２０〜６０％の範囲で保存や使用がされている場合が多い。従って、これまでに知られている方法では、一般的に流通及び使用されている高濃度の領域をカバーし、かつ高度の精製をあわせ持ったものができるものではなかった。 On the other hand, it is known to supplement a metal with a chelate resin or an ion exchange resin to purify a solution to be contacted or recover a metal. As examples of the purification of alkali hydroxide by these resins, purification by a chelate resin having a specific structure is disclosed (for example, see Patent Document 4). These can be purified by removing heavy metals such as iron, but further high treatment is not disclosed, and 150 to 500 g / l as a caustic soda concentration is mentioned as a preferable example at a handling concentration. However, even in the region of higher concentration than this, high-level purification was not satisfied. In addition, in the analysis of heavy metals in alkali hydroxide, there is a method in which a heavy metal in alkali hydroxide is adsorbed with a chelate resin (typically iminodiacetic acid) and separated from the alkali metal, and then the metal content is desorbed and measured. It is used. However, in order to increase the capture efficiency of metals, for example, in the analysis of sodium hydroxide, it is necessary to dilute to a concentration of several weight percent or less (hereinafter%) (for example, see Non-Patent Document 1). On the other hand, the alkali hydroxide on the market is around 48% for both typical sodium hydroxide and potassium hydroxide (depending on the solution temperature, both sodium hydroxide and potassium hydroxide are around 730 g / l). There are many cases, and there are many cases in the stage of use, but there are many cases where they are stored and used in a range of 20 to 60% including a temporary storage form. Therefore, the methods known so far have not been able to cover a high concentration region which is generally distributed and used and have a high degree of purification.
本発明は、粗水酸化アルカリ金属水溶液を高濃度の状態のままで、この中に含まれるアルカリ土類金属を除去することができる高純度水酸化アルカリ金属水溶液の製造方法を提供するものである。 The present invention provides a method for producing a high-purity alkali metal hydroxide aqueous solution capable of removing an alkaline earth metal contained in a crude alkali metal hydroxide aqueous solution in a high concentration state. .
市場に流通されている様な濃度で粗水酸化アルカリ金属水溶液中のアルカリ土類金属の除去を鋭意検討した結果、アミジノ基を有するイオン交換樹脂により粗水酸化アルカリ金属中のアルカリ土類金属を除去できることを見出し、本発明を完成させたのである。即ち、本発明は具体的に、
（１）官能基としてアミジノ基を有するイオン交換樹脂を用いて粗水酸化アルカリ金属水溶液中のアルカリ土類金属を除去することを特徴とする高純度水酸化アルカリ金属の製造方法であり、
（２）アミジノ基を有するイオン交換樹脂が下記式（１）で表されるイオン交換樹脂である前記１記載の高純度水酸化アルカリの製造方法であり、
Ａ−Ｃ（＝ＮＲ1）−ＮＨＲ2 （１）
（式（１）において、Ａはスチレン系樹脂であり、Ｒ1は水素原子、水酸基または炭素数１〜３のアルキル基であり、Ｒ2は水素原子、水酸基または炭素数１〜３のアルキル基である。）
（３）前記の粗水酸化アルカリ金属水溶液の濃度が２０〜６０重量％であることを特徴とする前記１または２に記載の高純度水酸化アルカリ金属の製造方法である。
また、
（４）アミジノ基誘導体を有するイオン交換樹脂を用いる水酸化アルカリ金属中からのアルカリ土類金属を除去する方法である。
As a result of intensive investigations on the removal of alkaline earth metal in the aqueous solution of crude alkali metal hydroxide at a concentration that has been distributed in the market, the alkaline earth metal in the crude alkali metal hydroxide was reduced by an ion exchange resin having an amidino group. The present inventors have found that it can be removed and completed the present invention. That is, the present invention specifically includes
(1) A method for producing a high-purity alkali metal hydroxide characterized by removing an alkaline earth metal in a crude alkali metal hydroxide aqueous solution using an ion exchange resin having an amidino group as a functional group,
(2) The method for producing a high-purity alkali hydroxide according to 1 above, wherein the ion-exchange resin having an amidino group is an ion-exchange resin represented by the following formula (1):
AC (= NR 1 ) -NHR 2 (1)
(In Formula (1), A is a styrene resin, R 1 is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and R 2 is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. .)
(3) The method for producing a high-purity alkali metal hydroxide as described in 1 or 2 above, wherein the concentration of the crude alkali metal hydroxide aqueous solution is 20 to 60% by weight.
Also,
(4) A method of removing an alkaline earth metal from an alkali metal hydroxide using an ion exchange resin having an amidino group derivative.
本発明の製造方法により、高濃度の粗水酸化アルカリ金属水溶液からでもアルカリ土類金属を除去できることから、濃縮操作等を行うことなくアルカリ土類金属の含有量が低い高純度水酸化アルカリ金属を提供することができる。 According to the production method of the present invention, alkaline earth metal can be removed even from a high-concentration crude aqueous alkali metal hydroxide solution. Can be provided.
本発明において取扱う粗水酸化アルカリ金属としては、水酸化ナトリウム及び水酸化カリウムが好ましい種類として挙げられる。そして、水酸化カリウムが効率良く重金属の除去処理ができるので特に好ましい。
本発明において粗水酸化アルカリ金属水溶液の濃度は、どのような濃度でもアルカリ土類金属の低減効果が望めるが、輸送効率、保管効率や、その後の取扱で高濃度に煮詰める等の余計な操作をしない意味で、２０％以上が好ましく、固形化しない範囲として６０％以下が好ましく、より好ましくは３５％以上５５％以下であり、４０％以上５３％以下が特に好ましい。
Examples of the crude alkali metal hydroxide handled in the present invention include sodium hydroxide and potassium hydroxide. Further, potassium hydroxide is particularly preferable because it can efficiently remove heavy metals.
In the present invention, the concentration of the crude alkali metal hydroxide aqueous solution can be expected to reduce alkaline earth metal at any concentration, but it is necessary to carry out unnecessary operations such as transportation efficiency, storage efficiency, and subsequent simmering to a high concentration by handling. 20% or more is preferable, and 60% or less is preferable as a range not to be solidified, more preferably 35% or more and 55% or less, and particularly preferably 40% or more and 53% or less.
また、使用する粗水酸化アルカリ金属はイオン交換膜法にて作られるものが専らではあるが、この中に含まれる不純物としての金属類としては、カルシウム、マグネシウム、ストロンチウム、バリウム、鉄、ニッケル、銅、亜鉛、鉛、カドミウム、マンガン、コバルト、バナジウム、モリブデン、クロム、ジルコニウム、銀、錫、アルミニウム、水銀、アンチモン、チタン、ビスマス、ガリウム、タリウム等が挙げられ、これを極力少なくすることが望ましい。更には特定の金属においては少量の含有でも製品の品質に対して影響が大きく、カルシウムやマグネシウムは更に低レベルまで低減できることから好ましい。 In addition, although the crude alkali hydroxide metal used is exclusively produced by the ion exchange membrane method, the metals as impurities contained therein are calcium, magnesium, strontium, barium, iron, nickel, Examples include copper, zinc, lead, cadmium, manganese, cobalt, vanadium, molybdenum, chromium, zirconium, silver, tin, aluminum, mercury, antimony, titanium, bismuth, gallium, and thallium. It is desirable to reduce this as much as possible. . Furthermore, even if a specific metal is contained in a small amount, the quality of the product is greatly affected, and calcium and magnesium can be further reduced to a low level.
本発明において高純度水酸化アルカリ金属中のカルシウムまたはマグネシウム等のアルカリ土類金属は５００ｐｐｂ以下であり、好ましくは５０ｐｐｂ以下であり、より好ましくは３０ｐｐｂ以下であり、１ｐｐｂ以上である。 In the present invention, the alkaline earth metal such as calcium or magnesium in the high purity alkali metal hydroxide is 500 ppb or less, preferably 50 ppb or less, more preferably 30 ppb or less, and 1 ppb or more.
なお、本方法に適した粗水酸化アルカリ金属水溶液としては、含有しているアルカリ土類金属により異なる。例えば不純物除去後の濃度が２０ｐｐｂ以下である場合、除去前として混入していても差し支えない濃度としては１０重量ｐｐｍ以下（以降ｐｐｍ）が好ましく、より好ましくは３ｐｐｍ以下である。なお、粗水酸化アルカリ金属水溶液において含有しているアルカリ土類金属の下限量は、上記高純度水酸化アルカリ金属におけるアルカリ土類金属の含有量より多いものである。 Note that the crude alkali metal hydroxide aqueous solution suitable for this method varies depending on the alkaline earth metal contained. For example, when the concentration after impurity removal is 20 ppb or less, the concentration that may be mixed before removal is preferably 10 ppm by weight (hereinafter ppm), more preferably 3 ppm or less. In addition, the minimum amount of alkaline earth metal contained in the crude alkali metal hydroxide aqueous solution is larger than the content of alkaline earth metal in the high-purity alkali metal hydroxide.
本発明の製造方法は、例えば充填塔に該アミジノ基を有するイオン交換樹脂を充填し、そこに粗水酸化アルカリ金属水溶液を通液することにより、該溶液中のアルカリ土類金属を手軽に除去することができる。またタンク等に粗水酸化アルカリ金属溶液をためておき、樹脂を加え攪拌する等バッチ操作によりアルカリ土類金属を低減することも可能である。
本発明にてアルカリ土類金属が吸着したアミジノ基を有するイオン交換樹脂は、超純水等による洗浄や逆洗浄操作、更に塩酸や硝酸等の酸により処理した後、水で洗浄する等の、公知の脱アルカリ土類金属操作による再生方法を使用することができる。そして、このようにして再生したアミジノ基を有するイオン交換樹脂は、本発明の製造方法に使用できる。
In the production method of the present invention, for example, the ion exchange resin having the amidino group is packed in a packed tower, and a crude alkali metal hydroxide aqueous solution is passed therethrough to easily remove the alkaline earth metal in the solution. can do. It is also possible to reduce alkaline earth metal by batch operation such as storing a crude alkali metal hydroxide solution in a tank or the like, adding a resin and stirring.
In the present invention, an ion exchange resin having an amidino group adsorbed with an alkaline earth metal is washed with ultrapure water or the like, backwashed, further treated with an acid such as hydrochloric acid or nitric acid, and then washed with water. Known regeneration methods by dealkalizing earth metal operations can be used. The ion exchange resin having an amidino group regenerated in this way can be used in the production method of the present invention.
本発明に用いるアミジノ基を有するイオン交換樹脂は、官能基としてアミジノ基を有するものであれば如何様なものでも使用することができる。更に、上記式（１）で表されるイオン交換樹脂が粗水酸化アルカリ金属水溶液中からアルカリ土類金属を容易に除去できることから好ましいものとして例示できる。 Any ion exchange resin having an amidino group for use in the present invention can be used as long as it has an amidino group as a functional group. Furthermore, the ion exchange resin represented by the above formula (1) can be exemplified as a preferable one because alkaline earth metals can be easily removed from the crude aqueous alkali metal hydroxide solution.
本発明の式（１）において、Ａは、スチレン系樹脂が例示でき、ポリスチレン、ポリスチレン−ジビニルベンゼン共重合体またはフェノール樹脂等が好ましく、スチレン・ジビニルベンゼン共重合体のものがより好ましい。
本発明の式（１）において、Ｒ1は水素原子、水酸基または炭素数１〜３のアルキル基であり、好ましくは水素原子または水酸基である。
本発明の式（１）において、Ｒ2は水素原子、水酸基または炭素数１〜３のアルキル基であり、好ましくは水素原子または炭素数１〜３のアルキル基であり、より好ましくは水素原子である。
本発明の式（１）としては、Ｒ1が水酸基で、そしてＲ2が水素原子のものが好ましいものとして例示できる。
本発明においてアミジノ基を有するイオン交換樹脂としては、Muromac XMS-5713（官能基 アミドオキシム基、ムロマチテクノス(株)製）等が例示できる。
In the formula (1) of the present invention, A may be a styrene resin, preferably polystyrene, polystyrene-divinylbenzene copolymer or phenol resin, and more preferably styrene / divinylbenzene copolymer.
In the formula (1) of the present invention, R 1 is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a hydroxyl group.
In the formula (1) of the present invention, R 2 is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom. is there.
The formula (1) of the present invention is preferably exemplified by those in which R 1 is a hydroxyl group and R 2 is a hydrogen atom.
Examples of the ion exchange resin having an amidino group in the present invention include Muromac XMS-5713 (functional group, amidooxime group, manufactured by Muromachi Technos Co., Ltd.).
本発明において、該イオン交換樹脂の使用量は、粗水酸化アルカリ金属中のアルカリ土類金属の含有量により決定すればよい。
本発明において、該イオン交換樹脂に対する接触時間は、粗水酸化アルカリ金属中のアルカリ土類金属の含有量により決定すればよい。例えば充填塔で吸着させる場合は空塔速度（以下ＳＶと表記）で、ＳＶ＝０．１〜５［１／ｈ］、更に好ましくはＳＶ＝０．２〜４［１／ｈ］、特に好ましくはＳＶ＝０．３〜３［１／ｈ］で接触させることにより効率良くアルカリ土類金属を吸着する事ができる。この範囲であると効率良くアルカリ土類金属を除去することができることから好ましい。
In this invention, what is necessary is just to determine the usage-amount of this ion exchange resin by content of the alkaline-earth metal in crude alkali hydroxide.
In the present invention, the contact time with the ion exchange resin may be determined by the content of alkaline earth metal in the crude alkali metal hydroxide. For example, when adsorbing in a packed tower, the superficial velocity (hereinafter referred to as SV) is SV = 0.1-5 [1 / h], more preferably SV = 0.2-4 [1 / h], particularly preferably. Can adsorb alkaline earth metals efficiently by contact at SV = 0.3-3 [1 / h]. This range is preferable because the alkaline earth metal can be efficiently removed.
本発明の製造方法において、操作温度は０℃から６０℃程度であり、好ましくは５℃から５０℃であり、より好ましくは１０℃から４５℃である。該イオン交換樹脂との接触温度がこの範囲であると粗水酸化アルカリ金属中のアルカリ土類金属を効率よく除去することができるので好ましい。 In the production method of the present invention, the operating temperature is about 0 ° C to 60 ° C, preferably 5 ° C to 50 ° C, more preferably 10 ° C to 45 ° C. When the contact temperature with the ion exchange resin is within this range, it is preferable because the alkaline earth metal in the crude alkali metal hydroxide can be efficiently removed.
例えば、粗水酸化アルカリ金属水溶液をカラムにつめた該イオン交換樹脂と０℃から６０℃の間の温度で、上記ＳＶで流してアルカリ土類金属を除去して、高純度水酸化アルカリ金属水溶液を製造することができる。または、粗水酸化アルカリ金属水溶液と該イオン交換樹脂とをバッチで０℃から６０℃の間の温度で例えば２時間接触させてアルカリ土類金属を除去して、高純度水酸化アルカリ金属水溶液を製造することができる。 For example, a high-purity alkali metal hydroxide aqueous solution is obtained by removing the alkaline earth metal by flowing in the SV at a temperature between 0 ° C. and 60 ° C. with the ion exchange resin packed in a column with a crude alkali metal hydroxide aqueous solution. Can be manufactured. Alternatively, a crude alkali metal hydroxide aqueous solution and the ion exchange resin are contacted in batches at a temperature between 0 ° C. and 60 ° C. for 2 hours, for example, to remove alkaline earth metal, and a high-purity alkali metal hydroxide aqueous solution is obtained. Can be manufactured.
本発明の製造方法を用いて製造した高純度水酸化アルカリ金属水溶液は、用途により濃度を調整して使用することができる。 The high-purity alkali metal hydroxide aqueous solution produced using the production method of the present invention can be used after adjusting the concentration depending on the application.
本発明の製造方法を用いて製造した高純度水酸化アルカリ金属は、半導体ウェーハやカラーフィルター等の電子部品の製造、ウェーハ表面エッチングによる平面化、レジスト材の除去、あるいは表面を洗浄するものなどに使用することができる。
本発明の精製方法を用いることにより、半導体ウェーハやカラーフィルター等の電子部品の製造、ウェーハ表面エッチングによる平面化、レジスト材の除去、あるいは表面を洗浄するものなどに使用する高純度水酸化アルカリ金属を提供することができる。
○実施態様
アミジノ基誘導体を有するイオン交換樹脂を用いて粗水酸化アルカリ金属水溶液中のアルカリ土類金属を除去する方法。
式（１）を有するイオン交換樹脂を用いて粗水酸化アルカリ金属水溶液中のアルカリ土類金属を除去する方法。
アミジノ基誘導体を有するイオン交換樹脂を用いて粗水酸化アルカリ金属水溶液中のカルシウムおよび／またはマグネシウムを除去する方法。
濃度が２０〜６０重量％の粗水酸化アルカリ金属水溶液中のアルカリ土類金属をアミジノ基誘導体を有するイオン交換樹脂を用いて除去する方法。
High-purity alkali metal hydroxide manufactured using the manufacturing method of the present invention is used for manufacturing electronic parts such as semiconductor wafers and color filters, planarizing by wafer surface etching, removing resist material, or cleaning the surface. Can be used.
By using the purification method of the present invention, high-purity alkali metal hydroxide used for manufacturing electronic components such as semiconductor wafers and color filters, planarizing by wafer surface etching, removing resist material, or cleaning the surface, etc. Can be provided.
Embodiment A method for removing an alkaline earth metal in a crude aqueous alkali metal hydroxide solution using an ion exchange resin having an amidino group derivative.
A method for removing an alkaline earth metal in a crude alkali metal hydroxide aqueous solution by using an ion exchange resin having the formula (1).
A method for removing calcium and / or magnesium in a crude alkali metal hydroxide aqueous solution using an ion exchange resin having an amidino group derivative.
A method of removing an alkaline earth metal in a crude alkali metal hydroxide aqueous solution having a concentration of 20 to 60% by weight using an ion exchange resin having an amidino group derivative.
○実施例
以下、実施例を用いて本発明を説明するが、これらの本発明が限定されるものではない。なお、％は重量％を、ｐｐｍは重量ｐｐｍを、ｐｐｂは重量ｐｐｂを表す。
Examples Hereinafter, the present invention will be described using examples, but the present invention is not limited thereto. In addition,% represents weight%, ppm represents weight ppm, and ppb represents weight ppb.
１００ｇの４８％粗水酸化カリウム水溶液とＭｕｒｏｍａｃ ＸＭＳ−５７１３（商品名、官能基 アミドオキシム基、ムロマチテクノス（株）製）２０ｃｍ3とをポリテトラフルオロエチレンポリ四フッ化エチレン（ＰＴＦＥ）製の容器に入れた。この溶液を２時間攪拌した後、溶液の一部を採取し、カルシウムおよびマグネシウムの分析を行った。これらの分析結果とアミジノ基を有するイオン交換樹脂と未接触の原液とを表１（ｐｐｂ）に示した。 A container made of polytetrafluoroethylene polytetrafluoroethylene (PTFE) of 100 g of 48% crude potassium hydroxide aqueous solution and Muromac XMS-5713 (trade name, functional group, amidooxime group, manufactured by Muromachi Technos Co., Ltd.) 20 cm 3 Put it in. After the solution was stirred for 2 hours, a part of the solution was collected and analyzed for calcium and magnesium. These analysis results, the ion exchange resin having an amidino group, and the uncontacted stock solution are shown in Table 1 (ppb).
○カルシウム、マグネシウムの分析方法
採取した試料に蒸留水を用いてメスアップし供試液とした。これをＩＣＰ発光分析装置で測定し、検量線法によりカルシウムおよびマグネシウム濃度を求めた。
○ Analytical method of calcium and magnesium The collected sample was diluted with distilled water to make a test solution. This was measured with an ICP emission analyzer, and the calcium and magnesium concentrations were determined by the calibration curve method.
４８％水酸化カリウム水溶液の代わりに４８％水酸化ナトリウム水溶液を用いた以外は実施例１と同様に操作し、カルシウムおよびマグネシウムを測定した。この結果を表１に記載した。 Calcium and magnesium were measured in the same manner as in Example 1 except that a 48% sodium hydroxide aqueous solution was used instead of the 48% potassium hydroxide aqueous solution. The results are shown in Table 1.
＜比較例１＞
Ｍｕｒｏｍａｃ ＸＭＳ−５７１３（商品名）の代わりにムロキレートＢ−１（商品名、官能基 イミノジ酢酸基、ムロマチテクノス（株）製）を用いた以外は実施例１と同様に操作し、カルシウムおよびマグネシウムを測定した。この結果を表２（ｐｐｂ）に記載した。
<Comparative Example 1>
The same procedure as in Example 1 was carried out except that Murochel B-1 (trade name, functional group, iminodiacetic acid group, manufactured by Muromachi Technos Co., Ltd.) was used instead of Muromax XMS-5713 (trade name). It was measured. The results are shown in Table 2 (ppb).
＜比較例２＞
Ｍｕｒｏｍａｃ ＸＭＳ−５７１３（商品名）の代わりにムロキレートＢ−１（商品名、官能基 イミノジ酢酸基、ムロマチテクノス（株）製）を用いた以外は実施例２と同様に操作し、カルシウムおよびマグネシウムを測定した。この結果を表２（ｐｐｂ）に記載した。
The same procedure as in Example 2 was performed except that Murochel B-1 (trade name, functional group, iminodiacetic acid group, manufactured by Muromachi Technos Co., Ltd.) was used instead of Muromac XMS-5713 (trade name), and calcium and magnesium were used. It was measured. The results are shown in Table 2 (ppb).
本発明は水酸化アルカリ金属中のアルカリ土類金属を除去精製することができるため、半導体ウェーハ研磨等の電子材料向け、医薬品、化粧品等あらゆる分野に適用でき、水酸化アルカリ金属製造時、出荷時、受け入れ時、使用時等のいずれの場合でも手軽に適用することができる。 Since the present invention can remove and refine alkaline earth metals in alkali metal hydroxides, it can be applied to various fields such as electronic materials such as semiconductor wafer polishing, pharmaceuticals, and cosmetics. It can be easily applied at any time of acceptance or use.
Claims (4)
Ａ−Ｃ（＝ＮＲ1）−ＮＨＲ2 （１）
（式（１）において、Ａはスチレン系樹脂であり、Ｒ1は水素原子、水酸基または炭素数１〜３のアルキル基であり、Ｒ2は水素原子、水酸基または炭素数１〜３のアルキル基である。） The method for producing a high purity alkali hydroxide according to claim 1, wherein the ion exchange resin having an amidino group is an ion exchange resin represented by the following formula (1).
AC (= NR 1 ) -NHR 2 (1)
(In Formula (1), A is a styrene resin, R 1 is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and R 2 is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. .)
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