JPH03167160A - Purification of aqueous solution of quaternary ammonium hydroxide - Google Patents
Purification of aqueous solution of quaternary ammonium hydroxideInfo
- Publication number
- JPH03167160A JPH03167160A JP1303640A JP30364089A JPH03167160A JP H03167160 A JPH03167160 A JP H03167160A JP 1303640 A JP1303640 A JP 1303640A JP 30364089 A JP30364089 A JP 30364089A JP H03167160 A JPH03167160 A JP H03167160A
- Authority
- JP
- Japan
- Prior art keywords
- quaternary ammonium
- aqueous solution
- ammonium hydroxide
- exchange resin
- metal ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 36
- 125000001453 quaternary ammonium group Chemical group 0.000 title claims abstract description 32
- 239000000908 ammonium hydroxide Substances 0.000 title claims abstract description 31
- 238000000746 purification Methods 0.000 title description 3
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 26
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 26
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 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 abstract description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 12
- 229910021655 trace metal ion Inorganic materials 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 3
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 125000000304 alkynyl group Chemical group 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 18
- 230000002378 acidificating effect Effects 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 10
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- -1 Lzinc Chemical compound 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000001143 conditioned effect Effects 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LJBWEZVYRBKOCI-UHFFFAOYSA-N 2,4,6-triaminoquinazoline Chemical compound N1=C(N)N=C(N)C2=CC(N)=CC=C21 LJBWEZVYRBKOCI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100127285 Drosophila melanogaster unc-104 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DVUVKWLUHXXIHK-UHFFFAOYSA-N tetraazanium;tetrahydroxide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[OH-].[OH-].[OH-].[OH-] DVUVKWLUHXXIHK-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、第四級アンモニウム塩から高純度の水酸化第
四級アンモニウムを得る新規な精製方法に関する
［従来の技術〕
水酸化第四級アンモニウム水溶液は、金属イオンを含ま
ない有機系アルカリ剤として、例えばＩＣ。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a novel purification method for obtaining highly pure quaternary ammonium hydroxide from a quaternary ammonium salt. [Prior Art] Quaternary hydroxide The ammonium aqueous solution is an organic alkaline agent that does not contain metal ions, such as IC.
ＬＳＩ、超ＬＳＩ等の半導体装置の製造におけるポジ型
レジストの現像液、半導体基板の洗浄剤、レジストの剥
離剤等への用途が広がりつつある。特に、最近の電子工
業の発展は目覚ましく、半導体装置の高集積化に伴い、
不純物イオンが極めて少ない、特にアルカリ金属、アル
カリ土類金属の少ない水酸化第四級アンモニウム水溶液
が要求される。Applications are expanding for positive resist developers, semiconductor substrate cleaning agents, resist stripping agents, etc. in the manufacture of semiconductor devices such as LSIs and VLSIs. In particular, the recent development of the electronics industry is remarkable, and with the increasing integration of semiconductor devices,
An aqueous quaternary ammonium hydroxide solution containing extremely few impurity ions, especially alkali metals and alkaline earth metals, is required.
一方、水酸化第四級アンモニウムの製造方法として、陽
イオン交換膜を隔膜とする電解槽を用いて第四級アンモ
ニウムクロライド、第四級アンモニウム硫酸塩等の第四
級アンモニウム塩水溶液を電気分解して、水酸化第四級
アンモニウムを製造する方法が知られている。On the other hand, as a method for producing quaternary ammonium hydroxide, an aqueous solution of quaternary ammonium salts such as quaternary ammonium chloride and quaternary ammonium sulfate is electrolyzed using an electrolytic cell with a cation exchange membrane as a diaphragm. A method for producing quaternary ammonium hydroxide is known.
しかしながら、このような隔膜電解槽を用いた製造方法
においても、カリウム、ナトリウム、カルシウム、マグ
ネシウム、Ｌ 亜鉛、＝ッケル、クロム、アルミニウム
、銅、等の金属イオンは、多かれ少なかれ混入してくる
のが実状である。これらの金属イオンの混入原因は、原
料の第四級アンモニウム塩の不純物、製造装置からの溶
出、あるいは、処理過程における大気からの塵埃による
汚染、保存容器からの溶出等種々であり、又、汚染イオ
ンの種類もさまざまである。しかし、これら金属イオン
が存在すると、ホトレジストに露光後、現像液で現像す
る際、又は、半導体基板の洗浄等の際、半導体基板内に
拡散し、半導体基板の電気的特性の劣化等の弊害を及ぼ
す。そこで、半導体装置の高集積化に伴い、微量金属イ
オンが数１０ｐｐｂ存在しても問題にされ、これを数ｐ
ｆ）ｂ以下塩除去することが望まれてきた。However, even in the manufacturing method using such a diaphragm electrolytic cell, metal ions such as potassium, sodium, calcium, magnesium, Lzinc, chromium, aluminum, copper, etc. are more or less mixed in. This is the actual situation. There are various causes of contamination of these metal ions, such as impurities in the raw quaternary ammonium salt, elution from manufacturing equipment, contamination by dust from the atmosphere during the processing process, elution from storage containers, etc. There are also various types of ions. However, if these metal ions are present, they will diffuse into the semiconductor substrate when the photoresist is exposed to light, developed with a developer, or when the semiconductor substrate is cleaned, causing harmful effects such as deterioration of the electrical characteristics of the semiconductor substrate. affect Therefore, as semiconductor devices become more highly integrated, even the presence of several tens of ppb of trace metal ions becomes a problem.
f) It has been desired to remove salts below b.
金属イオンの少ない水酸化第四級アンモニウムの製造方
法に関して、従来種々提案がなされてきてきた。Various proposals have been made regarding methods for producing quaternary ammonium hydroxide containing few metal ions.
例えば、特公昭４５−２８５６４号公報、特公昭４６−
１４８８５号公報、特開昭６０−１００６９０号公報、
特開昭６０−２６３１４８号公報、特開昭６２−１４２
７９２号公報、および、特開昭６３−２１３６８６号公
報等があるが、すべて基本的には、陽イオン交換膜によ
って陽極室と陰極室に区画された電解槽を使用して、陽
極室に第四級アンモニウム塩水溶液、または、水酸化第
四級アンモニウム水溶液を供給し、陰極室に水を供給し
て電極間に直流電流を通電することにより陰極室から水
酸化第四級アンモニウムを得る方法であり、それぞれ、
第四級アンモニウム塩の種類、イオン交換膜、及び、電
解槽の改善がされている。しかしながら、いずれの方法
においても、全ての金属イオンを安定して数ｐＨｂ以下
にまで除去することは困難である。又、特公昭６２−２
２９７８号公報には、第四級アンモニウムクロライドを
、アルコール溶液中で、水酸化ナトリウムまたは水酸化
カリウム等のアルカリ剤と反応させ、水酸化第四級アン
モニウムと沈殿ＮａＣ１またはＫＣＩを得たのち、ろ過
等の方法で、沈殿生成物を分離除去した後、ポリアクリ
ル系の弱酸性イオン交換樹脂で処理する方法が記載され
ている。しかし、この方法は、ナトリウムの除去性が悪
＜５ｐｐｂが限度であると同時にアルカリ剤の一部が溶
存するため、イオン交換樹脂の再生頻度が多くなり、再
生に際して、水酸化第四級アンモニウムの損失をひきお
こし、経済性に問題がある。For example, Japanese Patent Publication No. 45-28564, Japanese Patent Publication No. 46-
No. 14885, Japanese Patent Application Laid-Open No. 1983-100690,
JP-A-60-263148, JP-A-62-142
No. 792 and Japanese Patent Application Laid-open No. 63-213686, etc., but all of them basically use an electrolytic cell divided into an anode chamber and a cathode chamber by a cation exchange membrane, and A method of supplying a quaternary ammonium salt aqueous solution or a quaternary ammonium hydroxide aqueous solution, supplying water to the cathode chamber, and passing a direct current between the electrodes to obtain quaternary ammonium hydroxide from the cathode chamber. Yes, each
Improvements have been made in the types of quaternary ammonium salts, ion exchange membranes, and electrolytic cells. However, in either method, it is difficult to stably remove all metal ions to a pH of several b or less. Also, special public service 1986-2
No. 2978 discloses that quaternary ammonium chloride is reacted with an alkaline agent such as sodium hydroxide or potassium hydroxide in an alcohol solution to obtain quaternary ammonium hydroxide and precipitated NaCl or KCI, and then filtered. A method is described in which the precipitated product is separated and removed using a method such as the above, and then treated with a polyacrylic weakly acidic ion exchange resin. However, with this method, the ability to remove sodium is poor and the limit is <5 ppb, and at the same time, a portion of the alkaline agent is dissolved, so the ion exchange resin must be regenerated more frequently, and during regeneration, quaternary ammonium hydroxide must be removed. This causes losses and is economically unsatisfactory.
このように、多種のイオンが存在する系から、微量のイ
オン種を選択的に除去することは極めて困難と従来から
考えられており、特に、アルカリ金属等は、除去が困難
であった。これらの除去は、イオン交換樹脂の酸性度が
小さいポリアクリルゲル系の弱酸性イオン交換樹脂を使
用しても、２価以上の陽イオンについては、除去し得る
が、アルカリ金属特にナトリウムは、満足に除去し得な
かった。As described above, it has been conventionally considered that it is extremely difficult to selectively remove trace amounts of ion species from a system in which many types of ions exist, and it has been particularly difficult to remove alkali metals and the like. Even if a polyacrylic gel-based weakly acidic ion exchange resin with low acidity is used, divalent or higher cations can be removed, but alkali metals, especially sodium, cannot be removed satisfactorily. could not be removed.
かかる現状に鑑み、本発明は多種類のイオンが存在する
水酸化第四級アンモニウム水溶液から、選択的に微量金
属イオンを除去して高純度の水酸化第四級アンモニウム
水溶液を得ることを目的とする。In view of the current situation, the present invention aims to selectively remove trace metal ions from a quaternary ammonium hydroxide aqueous solution containing many types of ions to obtain a highly pure quaternary ammonium hydroxide aqueous solution. do.
［課題を解決するための手段］
第四級アンモニウム塩水溶液を電気分解して水酸化第四
級アンモニウム水溶液を得た後、特定のイオン交換樹脂
と接触させることにより、極めて効率よく全金属イオン
が除去され、高純度の水酸化第四級アンモニウムを得ら
れることを見い出し、本発明を完成するに至った。すな
わち、本発明の方法は、第四級アンモニウム塩水溶液を
隔膜法電解槽で電気分解して得られた水酸化第四級アン
モニウム水溶液をジビニルベンゼン含有量ＩＱｗｔ％以
上の高架橋度のポリスチレン系スルホン酸イオン交換樹
脂を用いて、
一般式
（但し、Ｒ＋ 、Ｒ２、Ｒ３ふよびＲ４は同一であって
も異なってもよく、アルキル基、アルケニル基、ベンジ
ル基、ヒドロキシアルキル基を示す。）で表される水酸
化第四級アンモニウムを含有する水溶液中に存在する微
量金属イオンを選択的に除去することを特徴とする水酸
化第四級アンモニウム水溶液の精製方法である。[Means for solving the problem] All metal ions can be removed extremely efficiently by electrolyzing a quaternary ammonium salt aqueous solution to obtain a quaternary ammonium hydroxide aqueous solution and then contacting it with a specific ion exchange resin. The present inventors have discovered that highly pure quaternary ammonium hydroxide can be obtained by removing the hydroxide, and have completed the present invention. That is, in the method of the present invention, a quaternary ammonium hydroxide aqueous solution obtained by electrolyzing a quaternary ammonium salt aqueous solution in a diaphragm electrolytic cell is converted into a polystyrene-based sulfonic acid having a high degree of crosslinking and having a divinylbenzene content of IQwt% or more. Using an ion exchange resin, the following formula is used: A method for purifying a quaternary ammonium hydroxide aqueous solution, which is characterized by selectively removing trace metal ions present in an aqueous solution containing quaternary ammonium hydroxide.
本発明でいう水酸化第四級アンモニウムとは一般式
（但し、Ｒ＋ 、Ｒ２、ＲｓおよびＲ４は同一であって
も異なってもよく、アルキル基、アルケニル基、ベンジ
ル基、ヒドロキシアルキル基を示す。）で表される水酸
化第四級アンモニウムをいう。The quaternary ammonium hydroxide referred to in the present invention has the general formula (wherein R+, R2, Rs and R4 may be the same or different, and represent an alkyl group, an alkenyl group, a benzyl group, or a hydroxyalkyl group). ) Quaternary ammonium hydroxide.
原料に用いる水酸化第四級アンモニウムは、第四級アン
モニウム塩水溶液を隔膜法電解槽で電気分解した場合に
得られる通常の不純物イオン濃度を有する水酸化第四級
アンモニウム水溶液を用いるのが望ましい。As the quaternary ammonium hydroxide used as a raw material, it is desirable to use an aqueous quaternary ammonium hydroxide solution having a normal impurity ion concentration obtained when a quaternary ammonium salt aqueous solution is electrolyzed in a diaphragm electrolytic cell.
本発明で使用し得る特定のイオン交換樹脂は、ポリスチ
レン系の交換基がスルホン酸基である強酸性イオン交換
樹脂の内、ジビニルベンゼン含有量ＩＱｗｔ％以上の高
架橋度樹脂であり、これ以外のイオン交換樹脂では、好
ましい結果が得られない。The specific ion exchange resin that can be used in the present invention is a highly crosslinked resin with a divinylbenzene content of IQwt% or more among polystyrene-based strongly acidic ion exchange resins in which the exchange group is a sulfonic acid group, and other ion exchange resins. Exchange resins do not give favorable results.
例えば、フェノール系の強酸性イオン交換樹脂や、ジビ
ニルベンゼン含有量８ｗｔ％以下のポリスチレン系の交
換基がスルホン酸基である強酸性のイオン交換樹脂は、
水酸化第四級アンモニウムの第四級アンモニウムイオン
と、イオン交換してしまい、特にす） ＩＪウムイオン
の除去が困難である。従ってこのような方法では、ナト
リウムイオンは１ｐｐｂ以下にはならない。これに対し
て、ポリスチレン系の交換基がスルホン酸基である強酸
性イオン交換樹脂の内、ジビニルベンゼン含有量ＩＱｗ
ｔ％以上の高架橋度樹脂を使用すると、意外にも第四級
アンモニウムイオンは、イオン交換される度合いが減少
し、金属イオンが優先的にイオン交換され除去されるこ
とが判った。最も好ましいイオン交換樹脂は、ジビニル
ベンゼン含有量ＩＱｗｔ％以上のポリスチレン系で交換
基がスルホン酸基である強酸性型のものである。この場
合には、金属イオンを１ ｐｐｂ以下迄充分に除去可能
である。この理由については、明らかではないが、恐ら
く第四級アンモニウムイオンはイオン半径が大きく、ジ
ビニルベンゼン含有量の多い高架橋品は立体障害をおこ
し、イオン半径の小さい金属イオンが選択的にイオン交
換に関与すると考えられる。For example, phenol-based strongly acidic ion-exchange resins and polystyrene-based ion-exchange resins whose exchange groups are sulfonic acid groups with a divinylbenzene content of 8 wt% or less,
It exchanges ions with the quaternary ammonium ions of quaternary ammonium hydroxide, making it particularly difficult to remove IJium ions. Therefore, in such a method, the sodium ion concentration does not fall below 1 ppb. On the other hand, among strongly acidic ion exchange resins whose exchange groups are sulfonic acid groups, the divinylbenzene content IQw
It has been found that when a highly crosslinked resin of t% or more is used, the degree to which quaternary ammonium ions are ion-exchanged is surprisingly reduced, and metal ions are preferentially ion-exchanged and removed. The most preferred ion exchange resin is a polystyrene type resin having a divinylbenzene content of IQwt% or more, and a strongly acidic type resin in which the exchange group is a sulfonic acid group. In this case, metal ions can be sufficiently removed to 1 ppb or less. The reason for this is not clear, but it is probably because quaternary ammonium ions have a large ionic radius, and highly crosslinked products with a high divinylbenzene content cause steric hindrance, and metal ions with a small ionic radius selectively participate in ion exchange. It is thought that then.
本発明の実施に際しては、イオン交換樹脂の一般的使用
法に基づいて行うことができる。先に塩基性イオン交換
樹脂により陰イオン特に塩素イオンを除去した後、本発
明の方法を使用することも、その逆においても、又本発
明単独に実施しても金属イオンを１ ｐｐｂ以下迄除去
することができる。The present invention can be carried out based on the general usage of ion exchange resins. After first removing anions, especially chloride ions, with a basic ion exchange resin, metal ions can be removed to 1 ppb or less by using the method of the present invention, vice versa, or by carrying out the present invention alone. can do.
通液は一般的には、カラム方式で実施される。Liquid passage is generally performed using a column method.
［実施例コ
以下、本発明を具体的に説明すため、実施例および比較
例を示すが、本発明はこれに限定されるものではない。[Examples] Examples and comparative examples will be shown below to specifically explain the present invention, but the present invention is not limited thereto.
各実施例における、イオン濃度の分析は以下の方法によ
った。In each example, the ion concentration was analyzed by the following method.
（１）塩素イオン：ＪＩＳ−０１０１（工業用水試験方
法）の２５−１チオシアン酸第二水銀吸光光度法によっ
た。(1) Chlorine ion: According to JIS-0101 (industrial water test method) 25-1 mercuric thiocyanate absorption spectrophotometry.
（２）水酸化テトラアンモニウム：試料２０〜３０ｇ
ラフエノールフタレインを指示薬として、ｌＮ−ＨＣｌ
で滴定した。(2) Tetraammonium hydroxide: sample 20-30g
1N-HCl using roughenolphthalein as an indicator.
It was titrated with
（３） 金属イオン：試料１００ｇを白金蒸発皿で蒸発
乾固し、３００℃で分解灰化後、３％硝酸２ｍｌ に溶
解して、ＩＣＰ（Ｉｎｄｕｃｔｉｖｉｔｙ Ｃｏｕｐｌ
ｅｄ Ｐｌａｓｍａ）−発光分析装置（島原製作所ＩＣ
ＰＱ−１０００型）にて分析した。(3) Metal ions: 100 g of the sample was evaporated to dryness in a platinum evaporating dish, decomposed and incinerated at 300°C, then dissolved in 2 ml of 3% nitric acid, and inducted into ICP (Inductivity Couple).
ed Plasma)-Emission spectrometer (Shimabara Manufacturing IC
PQ-1000 model).
実施例−１
陽イオン交換膜（商品名：デュポン製ナフィオン９０１
） 、陰イオン交換膜（商品名：徳山ソーダー製ネオ
セブタＡＣＨ−４５Ｔ）を隔膜とした３室型電解槽（陽
極Ｔｉ／Ｐｔ 、陰極５ｔｌＳ３１６） （７）塩基ニ
１５％テトラメチルアンモニウムクロライド水溶液を、
陽極室に０．ＩＮ塩酸水溶液を、更に陰極室には０．５
％水酸化テトラメチルアンモニウム水溶液を、各々循環
供給して、ＩＯＡ／ｄｍ”で通電した所、次第に陰極室
の濃度が上昇し、約５％水酸化テトラメチルアンモニウ
ム水溶液が得られた所で電気分解を終了した。得られた
約５％水酸化テトラメチルアンモニウム水溶液は、ナト
リウムイオン濃度３７ｐｐｂ 、カリウムイオン濃度２
ｐｐｂ、カルシウムイオン濃度１９ｐｐｂ 、マグネシ
ウムイオン濃度４ｐｐｂ、鉄イオン濃度２ｐｐｂ、アル
ミニウムイオン濃度４ ｐｐｂであった。一方、ジビニ
ルベンゼン含有量１２ＩＩｉｔ％のポリスチレン系強酸
性イオン交換樹脂（商品名：住友化学デュオライ） Ｃ
−２６以下樹脂Ａとする）２０ｍ１をカラム（テフロン
製、内径１５ｍｍ、長さ５００ｍｍ）に充填し、Ｎａ叶
、ＨＣ１水溶液を用い、Ｈ型イオン交換樹脂にコンディ
ショニングし、超純水（比抵抗１５ＭΩ以上）で、洗浄
液中のす） ＩＪウムイオンが１ ｐｐｂ以下、塩素イ
オンが１ ｐｐｍ以下となる迄水洗を繰り返した。この
カラムに、上記水酸化テトラメチルアンモニウム水溶液
１０ ｆ ヲ、Ｓｖ５、Ｑｈｒ−’で通液した。結果を
第１表に示した。金属イオンを１ ｐｐｂ以下に除去す
ることができた。Example-1 Cation exchange membrane (product name: DuPont Nafion 901
), a three-chamber electrolytic cell (anode Ti/Pt, cathode 5tlS316) using an anion exchange membrane (trade name: Neosebta ACH-45T manufactured by Tokuyama Soder) as a diaphragm (7) A 15% aqueous solution of tetramethylammonium chloride in base di,
0 in the anode chamber. IN hydrochloric acid aqueous solution, and further 0.5 in the cathode chamber.
% tetramethylammonium hydroxide aqueous solution was circulated and supplied with electricity at IOA/dm, the concentration in the cathode chamber gradually increased, and when an approximately 5% tetramethylammonium hydroxide aqueous solution was obtained, electrolysis started. The obtained approximately 5% aqueous tetramethylammonium hydroxide solution had a sodium ion concentration of 37 ppb and a potassium ion concentration of 2.
ppb, calcium ion concentration 19 ppb, magnesium ion concentration 4 ppb, iron ion concentration 2 ppb, and aluminum ion concentration 4 ppb. On the other hand, a polystyrene-based strongly acidic ion exchange resin with a divinylbenzene content of 12IIt% (product name: Sumitomo Chemical Duoly) C
-26 or less Resin A) was packed into a column (made of Teflon, inner diameter 15 mm, length 500 mm), conditioned to H-type ion exchange resin using Na leaf and HC1 aqueous solution, and ultrapure water (specific resistance 15 MΩ Washing with water was repeated until the IJium ions in the cleaning solution were 1 ppb or less and the chlorine ions were 1 ppm or less. Through this column, 10 f, Sv5, Qhr-' of the above tetramethylammonium hydroxide aqueous solution was passed. The results are shown in Table 1. Metal ions could be removed to 1 ppb or less.
実施例−２
ジビニルベンゼン含有１１０ｗｔ％以上のポリスチレン
系強酸性イオン交換樹脂（商品名：住友化学イマックＣ
１６Ｐ 以下樹脂Ｂとする）を、実施例−１と同じ方
法でコンディショニングし、水洗後、実施例−１の電解
法で得た水酸化テトラメチルアンモニウム水溶液を、実
施例−１と同じ方法で通液した。結果を第１表に示した
。金属イオンを１ｐｐｂ以下に除去することができた。Example-2 Polystyrene-based strongly acidic ion exchange resin containing 110 wt% or more of divinylbenzene (product name: Sumitomo Chemical Imac C
16P (hereinafter referred to as resin B) was conditioned in the same manner as in Example-1, washed with water, and then passed through the tetramethylammonium hydroxide aqueous solution obtained by the electrolysis method in Example-1 in the same manner as in Example-1. It liquefied. The results are shown in Table 1. Metal ions could be removed to 1 ppb or less.
実施例−３
ジビニルベンゼン含有１２０ｗｔ％のポリスチレン系強
酸性イオン交換樹脂（商品名：住友化学デュオライ）
Ｃ−２６５以下樹脂Ｃとする）を、実施例−１と同じ方
法でコンディショニングし、水洗後、実施例−１の電解
法で得た水酸化テトラメチルアンモニウム水溶液を、実
施例−１と同じ方法で通液した。結果を第１表に示した
。金属イオンを２ｐｐｂ以下まで除去することができた
。Example-3 Polystyrene-based strongly acidic ion exchange resin containing 120 wt% divinylbenzene (product name: Sumitomo Chemical Duoly)
C-265 (hereinafter referred to as resin C) was conditioned in the same manner as in Example-1, and after washing with water, the tetramethylammonium hydroxide aqueous solution obtained by the electrolysis method in Example-1 was treated in the same manner as in Example-1. The liquid was passed through. The results are shown in Table 1. Metal ions could be removed to 2 ppb or less.
比較例−１
ポリアクリルゲル系弱酸性イオン交換樹脂（商品名：住
友化学デニオライ） Ｃ−４３３以下樹脂りとする）を
、実施例−１と同じ方法でコンディショニングし、水洗
後、実施例−１の電解法で得た水酸化テトラメチルアン
モニウム水溶液を、実施例−１と同じ方法で通液した。Comparative Example-1 A polyacrylic gel-based weakly acidic ion-exchange resin (trade name: Sumitomo Chemical Deniolai C-433 hereinafter referred to as resin) was conditioned in the same manner as in Example-1, and after washing with water, Example-1 The tetramethylammonium hydroxide aqueous solution obtained by the electrolytic method was passed in the same manner as in Example-1.
結果を第１表に示した。ナトリウムイオンが８ ｐｐｂ
で除去が不充分であった。The results are shown in Table 1. Sodium ion is 8 ppb
The removal was insufficient.
比較例−２
ジビニルベンゼン含有１３ｗｔ％のポリスチレン系強酸
性イオン交換樹脂（商品名：住友化学デュオライ） Ｃ
−２０以下樹脂Ｅとする）を、実施例−１と同じ方法で
コンディショニングし、水洗後、実施例−１の電解法で
得た水酸化テトラメチルアンモニウム水溶液を、実施例
−１と同じ方法で通液した。結果を第１表に示した。ナ
トリウムイオンが、全く除去されなかった。Comparative Example-2 Polystyrene-based strongly acidic ion exchange resin containing 13 wt% divinylbenzene (product name: Sumitomo Chemical Duoly) C
-20 (hereinafter referred to as Resin E) was conditioned in the same manner as in Example-1, and after washing with water, the tetramethylammonium hydroxide aqueous solution obtained by the electrolysis method in Example-1 was added in the same manner as in Example-1. The liquid was passed through. The results are shown in Table 1. No sodium ions were removed.
比較例−３
ポリフェノール系強酸性イオン交換樹脂（商品名：住友
化学デュオライトＣ−６６３以下樹脂Ｆとする）を、実
施例−１と同じ方法でコンディショニングし、水洗後、
実施例−１の電解法で得た水酸化テトラメチルアンモニ
ウム水溶液を、実施例−１と同じ方法で通液した。結果
を第１表に示した。Comparative Example-3 A polyphenol-based strongly acidic ion exchange resin (trade name: Sumitomo Chemical Duolite C-663 hereinafter referred to as Resin F) was conditioned in the same manner as in Example-1, and after washing with water,
The tetramethylammonium hydroxide aqueous solution obtained by the electrolytic method of Example-1 was passed in the same manner as in Example-1. The results are shown in Table 1.
ナトリウムイオンが、全く除去されなかった。No sodium ions were removed.
［発明の効果］
以上の説明より理解される如く、本発明の方法によれば
、第四級アンモニウム塩を原料とした水酸化第四級アン
モニウム水溶液の電解合成においても、微量混入する金
属イオンを効率よく除去し、高度に精製された水酸化第
四級アンモニウム水溶液を高収率で得ることが可能であ
る。[Effects of the Invention] As understood from the above explanation, according to the method of the present invention, even in the electrolytic synthesis of a quaternary ammonium hydroxide aqueous solution using a quaternary ammonium salt as a raw material, trace amounts of metal ions can be eliminated. It is possible to remove it efficiently and obtain a highly purified quaternary ammonium hydroxide aqueous solution in high yield.
したがって、レジスト現像液等にとって好ましくないア
ルカリ金属、アルカリ土類金属等の金属イオンを、従来
の製造方法による、数ｆｌｆｌｂ〜数１０ｐｐ数置０ｐ
ｐｂ
２〜１ ｐｐｂ以下にすることができる。また、特定イ
オン交換樹脂を使用することによって、選択的に金属イ
オンを除去する為、再生回数を大巾に改善し得る。すな
わち、イオン交換樹脂は少量で良く、且つ、再生比の期
間が長い為、水酸化第四級アンモニウムの損失が少なく
て済み、
極めて経済
的な精製方法である。Therefore, metal ions such as alkali metals and alkaline earth metals, which are undesirable for resist developers, etc., can be removed from several flflb to several tens of pp and several tens of pp by conventional manufacturing methods.
pb 2 to 1 ppb or less. Further, by using a specific ion exchange resin, metal ions are selectively removed, so the number of regenerations can be greatly improved. In other words, only a small amount of ion exchange resin is required, and the regeneration ratio period is long, so the loss of quaternary ammonium hydroxide is small, making it an extremely economical purification method.
Claims (1)
気分解して得られた水酸化第四級アンモニウム水溶液を
ジビニルベンゼン含有量１０ｗｔ％以上の高架橋度のポ
リスチレン系スルホン酸イオン交換樹脂を用いて、 一般式 ▲数式、化学式、表等があります▼ （但し、Ｒ＿１、Ｒ＿２、Ｒ＿３およびＲ＿４は同一で
あっても異なってもよく、アルキル基、アルケニル基、
ベンジル基、ヒドロキシアルキル基を示す。）で表され
る水酸化第四級アンモニウムを含有する水溶液中に存在
する微量金属イオンを選択的に除去することを特徴とす
る水酸化第四級アンモニウム水溶液の精製方法。(1) A quaternary ammonium hydroxide aqueous solution obtained by electrolyzing a quaternary ammonium salt aqueous solution in a diaphragm electrolytic cell is used with a highly crosslinked polystyrene-based sulfonic acid ion exchange resin with a divinylbenzene content of 10 wt% or more. Therefore, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc.
Indicates a benzyl group and a hydroxyalkyl group. ) A method for purifying a quaternary ammonium hydroxide aqueous solution, the method comprising selectively removing trace metal ions present in an aqueous solution containing quaternary ammonium hydroxide represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1303640A JPH03167160A (en) | 1989-11-22 | 1989-11-22 | Purification of aqueous solution of quaternary ammonium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1303640A JPH03167160A (en) | 1989-11-22 | 1989-11-22 | Purification of aqueous solution of quaternary ammonium hydroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03167160A true JPH03167160A (en) | 1991-07-19 |
Family
ID=17923431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1303640A Pending JPH03167160A (en) | 1989-11-22 | 1989-11-22 | Purification of aqueous solution of quaternary ammonium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03167160A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06142649A (en) * | 1992-11-10 | 1994-05-24 | Tama Kagaku Kogyo Kk | Treatment of organic quaternary ammonium hydroxide-containing waste liquid |
| WO1998003466A1 (en) * | 1996-07-23 | 1998-01-29 | Tokuyama Corporation | Process for the preparation of aqueous solutions of tetraalkylammonium hydroxides |
| JP2006341253A (en) * | 2006-09-07 | 2006-12-21 | Rohm & Haas Co | Hydrogen ion type strongly acidic cation exchange resin |
| JP2007530593A (en) * | 2004-03-26 | 2007-11-01 | アルベマール・コーポレーシヨン | Method for exchanging anions of tetraalkylammonium salts |
| JP2008536809A (en) * | 2005-03-04 | 2008-09-11 | ハネウェル・インターナショナル・インコーポレーテッド | Method for purifying quaternary onium salts |
| JP2009506972A (en) * | 2005-09-02 | 2009-02-19 | サッチェム， インコーポレイテッド | Removal of metal ions from onium hydroxide and onium salt solutions |
| WO2014208509A1 (en) * | 2013-06-24 | 2014-12-31 | 株式会社トクヤマ | Method for producing high-concentration tetraalkylammonium salt solution |
| CN112999694A (en) * | 2021-03-24 | 2021-06-22 | 沧州信联化工有限公司 | Raw material refining device for processing tetramethylammonium hydroxide and use method thereof |
| WO2023166999A1 (en) * | 2022-03-03 | 2023-09-07 | 株式会社トクヤマ | Method for manufacturing purified quaternary ammonium compound aqueous solution |
-
1989
- 1989-11-22 JP JP1303640A patent/JPH03167160A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06142649A (en) * | 1992-11-10 | 1994-05-24 | Tama Kagaku Kogyo Kk | Treatment of organic quaternary ammonium hydroxide-containing waste liquid |
| WO1998003466A1 (en) * | 1996-07-23 | 1998-01-29 | Tokuyama Corporation | Process for the preparation of aqueous solutions of tetraalkylammonium hydroxides |
| US5929280A (en) * | 1996-07-23 | 1999-07-27 | Tokuyama Corporation | Process for the preparation of aqueous solutions of tetraalkylammonium hydroxides |
| JP2007530593A (en) * | 2004-03-26 | 2007-11-01 | アルベマール・コーポレーシヨン | Method for exchanging anions of tetraalkylammonium salts |
| JP2008536809A (en) * | 2005-03-04 | 2008-09-11 | ハネウェル・インターナショナル・インコーポレーテッド | Method for purifying quaternary onium salts |
| JP2012232993A (en) * | 2005-03-04 | 2012-11-29 | Honeywell Internatl Inc | Method of purifying quaternary onium salt |
| JP2009506972A (en) * | 2005-09-02 | 2009-02-19 | サッチェム， インコーポレイテッド | Removal of metal ions from onium hydroxide and onium salt solutions |
| JP2006341253A (en) * | 2006-09-07 | 2006-12-21 | Rohm & Haas Co | Hydrogen ion type strongly acidic cation exchange resin |
| JP4511500B2 (en) * | 2006-09-07 | 2010-07-28 | ローム アンド ハース カンパニー | Hydrogen ion type strongly acidic cation exchange resin |
| WO2014208509A1 (en) * | 2013-06-24 | 2014-12-31 | 株式会社トクヤマ | Method for producing high-concentration tetraalkylammonium salt solution |
| CN112999694A (en) * | 2021-03-24 | 2021-06-22 | 沧州信联化工有限公司 | Raw material refining device for processing tetramethylammonium hydroxide and use method thereof |
| WO2023166999A1 (en) * | 2022-03-03 | 2023-09-07 | 株式会社トクヤマ | Method for manufacturing purified quaternary ammonium compound aqueous solution |
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