JPS6222978B2 - - Google Patents
Info
- Publication number
- JPS6222978B2 JPS6222978B2 JP2477581A JP2477581A JPS6222978B2 JP S6222978 B2 JPS6222978 B2 JP S6222978B2 JP 2477581 A JP2477581 A JP 2477581A JP 2477581 A JP2477581 A JP 2477581A JP S6222978 B2 JPS6222978 B2 JP S6222978B2
- Authority
- JP
- Japan
- Prior art keywords
- ion exchange
- metal ions
- exchange resin
- ppm
- group
- 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.)
- Expired
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000003456 ion exchange resin Substances 0.000 claims description 23
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 23
- 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 20
- 238000000034 method Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 11
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 229910021654 trace metal Inorganic materials 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 description 25
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 20
- 239000003513 alkali Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- -1 quaternary ammonium ions Chemical class 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910021655 trace metal ion Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 241001550224 Apha Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Description
本発明は、ポリアクリルゲル系の弱酸性イオン
交換樹脂を用いて、有機アルカリ溶液中に溶存せ
る微量金属イオンを選択的に除去することを特徴
とする有機アルカリ溶液の精製方法に関するもの
である。
最近の電子工業の発展は目覚しく、IS、LSI、
更には、超LSIへと推移してきている。これにと
もない、技術面においても、加工精度の向上微細
化への方向をたどつている。これに関連して解像
力に優れているポジ型レジストが注目を浴びてき
た。本発明は、このポジ型レジスト等の用に供す
るメタルフリーの有機アルカリ溶液からなる現象
液を提供することにある。有機アルカリ現像液に
要求されることは、不純物イオンが極力少ないこ
と、特にアルカリ金属、アルカリ土類金属が少な
いことが要求される。然るに有機アルカリ溶液中
には、カリウム、ナトリウム、鉄、亜鉛、カルシ
ウム、マグネシウム、ニツケル、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情である。これら金属イオン
の混入原因は種々である。有機アルカリの原料中
から、又は、製造装置からの溶出により、あるい
は、処理過程中に、大気からの塵埃による汚染、
保存容器からの溶出等、原因により、汚染イオン
の種類もさまざまである。然し、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、これら金属イオンは、ウエハ内に
拡散し、ウエハの電気的特性の劣化等の弊害を及
ぼす。このことは良く知られている事実である。
以上の理由から無機アルカリ現像液にかわつて、
〓〓〓〓〓
有機アルカリ現像液が脚光を浴びてきた。然し、
尚且つ微量金属イオンが数ppm以上存在して問
題にされており、これを1ppm以上迄除去するこ
とが望まれてきた。現在迄にも、金属イオンの少
ない有機アルカリ現像液の製造法に関する提案は
なされてきてはいる。特開昭52−3008号公報は第
４級アンモニウム塩化物と、NH4OHとから、第
４級アンモニウム水酸化物を製造する方法である
が、この方法では、金属イオンを数ppm以下に
することは、不可能である。原料中、装置からの
溶出、容器からの溶出等により、一般的には、数
＋ppm以上となる。
又特開昭52−3009号公報は、第４級アンモニウ
ム塩化物を陰イオン交換樹脂で処理することによ
り、第４級アンモニウム水酸化物を得る方法であ
る。然し、この方法の欠点は、陰イオン交換樹脂
の交換容量が極めて小さい為、多量の第４級アン
モニウム水酸化物を得る為には、多量の陰イオン
交換樹脂を必要とし、再生に際しても、第４級ア
ンモニウム水酸化物の損失をひきおこし、経済性
に問題がある。又この方法では、原料中、装置上
からの溶出金属イオンの除去は出来ないという問
題がある。又特開昭51−54505号公報は、コロイ
ド状シリカ等の着色防止法に関するものであり、
こうした添加物を含有せしめることは、着色防止
は可能としても、レジスト用等の現像液として
は、固形物が存在するので好ましくない。本発明
者等は、上記欠点を克服すべく種々検討した結
果、テトラアルキルアンモニウムクロライドを、
アルコール溶液中で、水酸化ナトリウム又は水酸
化カリウム等のアルカリ剤と反応させ、第４級ア
ンモニウム水酸化物と沈澱NaCl又はKClを得た
のち、過等の方法で、沈澱生成物を分離するこ
とにより、大部分のアルカリ金属を除去した後、
特定のイオン交換樹脂を使用することにより、溶
解している微量の金属イオンを、第４級アンモニ
ウム水酸化物の変質もなく、効率よく、且つ、経
済的に除去する方法を見い出し、本発明を完成さ
れるに致つた。すなわち、本発明の方法によれ
ば、有機アルカリ現像液等にとつて好ましくない
アルカリ金属、アルカリ土類金属等の金属イオン
を、従来の製造法によれば、数ppm〜数万ppm
であつたものを、1ppm以下にすることが出来る
と同時に、経日的な変質並びに着色を防止出来る
ばかりでなく、特定イオン交換樹脂を使用するこ
とによつて、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、且つ再生迄の期間が長い
為、有機アルカリの損失が少なくて済み、極めて
経済的な処理法である。
本発明でいう有機アルカリとは、
一般式
（但し、R1、R2、R3及びR4はアルキル基、アラル
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。）で表わされる第４級アンモ
ニウム水酸化物をいう。従つて有機アルカリ溶液
とは該有機アルカリを溶媒に溶解させたものであ
る。本発明に適用し得る有機アルカリ溶液の溶媒
は、メタノール、エタノール、イソプロピルアル
コール、プロピルアルコール、ブチルアルコー
ル、tert−ブチルアルコール等のアルコールもし
くは水が好ましいが、特にこれらに限定されるも
のではない。本発明で使用し得る特定のイオン交
換樹脂は、ポリアクリル系の交換基がカルボキシ
ル基である弱酸性イオン交換樹脂であり、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。例えば、フエノール系、ポリスチレンのマ
クロポーラス系、ポリスチレンゲル系の交換基が
スルフオン酸基である強酸性のイオン交換樹脂
は、有機アルカリの第４級アンモニウムイオン
と、イオン交換し、金属イオンを十分除去するこ
とが出来ない。従つて金属イオンは1ppm以下に
はならない。数百ppmの金属イオンが存在する
場合には、20ppm以下迄除去することは困難で
ある。これに対してポリアクリルマクロポーラス
系で交換基が、カルボキシル基の弱酸性のイオン
交換樹脂を使用すると、意外にも第４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。最も好ましいイオン交換樹脂は、ポリアク
リルゲル系の交換基がカルボキシル基である弱酸
性型のものである。この場合には、金属イオンを
1ppm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４級アン
〓〓〓〓〓
モニウムイオンは、イオン半径が大きく立体障害
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、イオン交
換樹脂の酸度が小さい程、選択性は顕著になるか
らであると思われる。
本発明の実施に際しては、イオン交換樹脂の一
般的使用法に基いて行なうことが出来る。先に塩
基性イオン交換樹脂により陰イオンを除去した
後、本発明の方法を使用することも、又その逆に
おいても、本発明単独と同じように金属イオンを
1ppm以下迄除去することが出来る。一般的に
は、カラム方式で、通液することにより実施され
る。
以上の説明から明らかな如く、本発明の特徴
は、有機アルカリ溶液中に存在する少量の金属イ
オンを、有機アルカリの変質並びに吸着損失を極
力抑制し、選択的に1ppm以下迄除去し得ること
にある。特に多量のイオンが存在する系から、少
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、除去が困難であつた。これらの除去は、
キレート樹脂を使用するのが一般的であるが高価
なキレート樹脂を使用しても、重金属類について
は、ある程度除去し得ても、アルカリ金属、アル
カリ土類金属は、満足に除去し得なかつた。然る
に、本発明は、水酸化第４級アンモニウム塩の特
質をいかし、汎用のイオン交換樹脂を使用して、
アルカリ金属、アルカリ土類金属を0.1ppm以下
迄、経済的に除去し得た訳で、有機アルカリ現像
液の安価な工業的製造法といえる。以下本発明に
ついて具体的に説明するが、これによつて本発明
は制限されるものではない。
実施例 １
窒素置換した１オートクレーブに、メタノー
ル750部、トリメチルアミン260部を仕込み、反応
系内温度を70℃に保ちながら、塩化メチル720部
を連続的にフイード反応させ、塩化テトラメチル
アンモニウムのメタノール溶液を作り、次にこれ
に水酸化カリウム250部、メタノール620部よりな
るアルカリ溶液を添加反応させ、同時に生成した
塩化カリウムを過分離し、水酸化テトラメチル
アンモニウムのメタノール溶液を製造した。更
に、メタノールを蒸発乾固し、蒸留水8020部を加
え、水酸化テトラメチルアンモニウム水溶液とし
た。調整液中の水酸化テトラメチルアンモニウム
濃度は、5.0wt％で、カリウムイオン濃度
1208ppm、ナトリウムイオン濃度4.5ppm、鉄イ
オン濃度0.41ppm、亜鉛イオン濃度0.32ppm、ア
ルミニウムイオン濃度は0.27ppmであつた。
ポリアクリルゲル系で交換基がカルボキシル基
である弱酸性イオン交換樹脂（商品名：住友化学
デユオライトＣ−433）375ｇをイオン交換カラム
に充填し、NaOH、HCl水溶液を用い、Ｈ型イオ
ン交換樹脂にコンデイシヨニングし、洗浄液中の
ナトリウムイオン、塩素イオンが、各々、
0.01ppm以下となる迄水洗をくり返した。イオン
交換樹脂の総交換容量は、4.1meｇ／ml−樹脂で
あつた。これに、上記水酸化テトラメチルアンモ
ニウム水溶液10を、SV12.6hr-1で通液した。
結果を第１表に示した。金属イオンを1ppm以下
迄除去することが出来た。
The present invention relates to a method for purifying an organic alkaline solution, which is characterized by selectively removing trace metal ions dissolved in the organic alkaline solution using a polyacrylic gel-based weakly acidic ion exchange resin. Recent developments in the electronics industry have been remarkable, including IS, LSI,
Furthermore, there is a shift towards super LSI. Along with this, in terms of technology, there is a trend towards improved processing accuracy and miniaturization. In this regard, positive resists with excellent resolution have attracted attention. The object of the present invention is to provide a phenomenon liquid consisting of a metal-free organic alkaline solution for use in positive resists and the like. The organic alkaline developer is required to contain as few impurity ions as possible, especially alkali metals and alkaline earth metals. However, the reality is that metal ions such as potassium, sodium, iron, zinc, calcium, magnesium, nickel, chromium, aluminum, copper, etc. are mixed into the organic alkaline solution to a greater or lesser extent. There are various causes for the contamination of these metal ions. Contamination by dust from the atmosphere due to organic alkali raw materials or elution from manufacturing equipment, or during the processing process.
The types of contaminating ions vary depending on the cause, such as elution from storage containers. However, if these metal ions are present, when the photoresist is exposed and developed with a developer, these metal ions will diffuse into the wafer, causing adverse effects such as deterioration of the electrical characteristics of the wafer. This is a well-known fact.
For the above reasons, instead of inorganic alkaline developer,
〓〓〓〓〓
Organic alkaline developers have been in the spotlight. However,
Moreover, the presence of trace metal ions of several ppm or more has been a problem, and it has been desired to remove these to 1 ppm or more. Until now, proposals have been made regarding methods for producing organic alkaline developers containing few metal ions. JP-A No. 52-3008 discloses a method for producing quaternary ammonium hydroxide from quaternary ammonium chloride and NH 4 OH, but in this method, metal ions are reduced to several ppm or less. That is impossible. Generally, it is several ppm or more due to elution from raw materials, equipment, containers, etc. Furthermore, JP-A-52-3009 discloses a method for obtaining quaternary ammonium hydroxide by treating quaternary ammonium chloride with an anion exchange resin. However, the disadvantage of this method is that the exchange capacity of the anion exchange resin is extremely small, so in order to obtain a large amount of quaternary ammonium hydroxide, a large amount of anion exchange resin is required. This causes loss of quaternary ammonium hydroxide and is economically problematic. Furthermore, this method has a problem in that it is not possible to remove metal ions eluted from the raw material or from the apparatus. Furthermore, JP-A-51-54505 relates to a method for preventing coloring of colloidal silica, etc.
Although it is possible to prevent coloring by including such additives, it is not preferable for developing solutions for resists and the like because they contain solids. As a result of various studies to overcome the above-mentioned drawbacks, the present inventors discovered that tetraalkylammonium chloride,
After reacting with an alkaline agent such as sodium hydroxide or potassium hydroxide in an alcohol solution to obtain quaternary ammonium hydroxide and precipitated NaCl or KCl, the precipitated product is separated by a suitable method. After removing most of the alkali metals by
By using a specific ion exchange resin, we have discovered a method for efficiently and economically removing trace amounts of dissolved metal ions without deterioration of quaternary ammonium hydroxide, and have achieved the present invention. It was completed. That is, according to the method of the present invention, metal ions such as alkali metals and alkaline earth metals, which are undesirable for organic alkaline developers, are reduced from several ppm to several tens of thousands of ppm according to conventional production methods.
It is possible to reduce the amount of metal ions to 1 ppm or less, and at the same time prevent deterioration and discoloration over time, and by using a specific ion exchange resin, metal ions can be selectively removed. For,
The number of playbacks can be greatly improved. That is, since only a small amount of ion exchange resin is required and the period until regeneration is long, the loss of organic alkali is small, making it an extremely economical treatment method. The organic alkali referred to in the present invention has the general formula (However, R 1 , R 2 , R 3 and R 4 represent an alkyl group, an aralkyl group, an alkenyl group, a benzyl group, or a hydroxyalkyl group). Therefore, an organic alkaline solution is one in which the organic alkali is dissolved in a solvent. The solvent for the organic alkaline solution applicable to the present invention is preferably alcohol such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butyl alcohol, tert-butyl alcohol, or water, but is not particularly limited thereto. The specific ion exchange resin that can be used in the present invention is a weakly acidic ion exchange resin whose polyacrylic exchange group is a carboxyl group, and preferred results cannot be obtained with other ion exchange resins. For example, strongly acidic ion exchange resins such as phenol type, polystyrene macroporous type, and polystyrene gel type in which the exchange group is a sulfonic acid group perform ion exchange with the quaternary ammonium ion of an organic alkali, and sufficiently remove metal ions. I can't do it. Therefore, metal ions cannot fall below 1 ppm. When several hundred ppm of metal ions are present, it is difficult to remove them to 20 ppm or less. On the other hand, when using a weakly acidic ion exchange resin in which the exchange group is a carboxyl group in a polyacrylic macroporous system, the degree of ion exchange of quaternary ammonium ions surprisingly decreases, giving priority to metal ions. It is removed by ion exchange. The most preferred ion exchange resin is a weakly acidic type in which the exchange group of the polyacrylic gel type is a carboxyl group. In this case, metal ions
It can be sufficiently removed down to 1ppm or less. The reason for this is not clear, but it is probably
Monium ions have a large ionic radius and cause steric hindrance, and metal ions with a small ionic radius are thought to participate selectively in ion exchange, and the lower the acidity of the ion exchange resin, the more pronounced the selectivity. Seem. The present invention can be carried out based on the general usage of ion exchange resins. The method of the present invention can be used after first removing anions with a basic ion exchange resin, or vice versa, as in the case of the present invention alone, metal ions can be removed.
Can be removed down to 1ppm or less. Generally, this is carried out by passing a liquid through a column. As is clear from the above description, the feature of the present invention is that it is possible to selectively remove a small amount of metal ions present in an organic alkaline solution down to 1 ppm or less while minimizing deterioration and adsorption loss of the organic alkali. be. In particular, it has been thought that it is extremely difficult to selectively remove small amounts of ionic species from systems in which a large amount of ions are present, and it has been particularly difficult to remove alkali metals and the like. These removals are
It is common to use chelate resins, but even if expensive chelate resins are used, heavy metals can be removed to some extent, but alkali metals and alkaline earth metals cannot be removed satisfactorily. . However, the present invention takes advantage of the characteristics of quaternary ammonium hydroxide salt and uses a general-purpose ion exchange resin.
Since it was possible to economically remove alkali metals and alkaline earth metals to 0.1 ppm or less, it can be said to be an inexpensive industrial manufacturing method for organic alkaline developers. The present invention will be specifically explained below, but the present invention is not limited thereby. Example 1 750 parts of methanol and 260 parts of trimethylamine were charged into a nitrogen-substituted autoclave, and while the temperature inside the reaction system was kept at 70°C, 720 parts of methyl chloride was continuously fed and reacted to form a methanol solution of tetramethylammonium chloride. Next, an alkaline solution consisting of 250 parts of potassium hydroxide and 620 parts of methanol was added to the solution, and the potassium chloride produced at the same time was over-separated to produce a methanol solution of tetramethylammonium hydroxide. Furthermore, methanol was evaporated to dryness, and 8020 parts of distilled water was added to obtain a tetramethylammonium hydroxide aqueous solution. The concentration of tetramethylammonium hydroxide in the adjustment solution is 5.0wt%, and the concentration of potassium ion
1208 ppm, sodium ion concentration 4.5 ppm, iron ion concentration 0.41 ppm, zinc ion concentration 0.32 ppm, and aluminum ion concentration 0.27 ppm. Fill an ion exchange column with 375 g of a weakly acidic ion exchange resin (trade name: Sumitomo Chemical Duolite C-433), which is a polyacrylic gel type and whose exchange group is a carboxyl group, and convert it into an H-type ion exchange resin using an aqueous solution of NaOH and HCl. After conditioning, the sodium ions and chlorine ions in the cleaning solution are
Washing with water was repeated until the concentration was 0.01 ppm or less. The total exchange capacity of the ion exchange resin was 4.1 meg/ml-resin. The above tetramethylammonium hydroxide aqueous solution 10 was passed through this at a SV of 12.6 hr -1 .
The results are shown in Table 1. It was possible to remove metal ions to less than 1 ppm.
【表】
実施例 ２
実施例１の方法で、水酸化テトラメチルアンモ
ニウムのメタノール溶液を製造し、これにメタノ
ールを加えて水酸化テトラメチルアンモニウムの
濃度を5.0wt％になるように調整した。この溶液
のカリカムイオン濃度は、1229ppm、ナトリウ
ムイオン濃度1.2ppm、亜鉛イオン濃度
0.29ppm、アルミニウムイオン濃度0.11ppm、鉄
〓〓〓〓〓
イオン濃度0.53ppmであつた。この10を実施例
１と全く同じ方法で、イオン交換樹脂カラムに通
液した。表−２に示す結果を得た。金属イオンを
1ppm以下迄除去することが出来た。[Table] Example 2 A methanol solution of tetramethylammonium hydroxide was produced by the method of Example 1, and methanol was added thereto to adjust the concentration of tetramethylammonium hydroxide to 5.0 wt%. The concentration of potassium ions in this solution is 1229 ppm, the concentration of sodium ions is 1.2 ppm, and the concentration of zinc ions is
0.29ppm, aluminum ion concentration 0.11ppm, iron
The ion concentration was 0.53 ppm. This solution No. 10 was passed through an ion exchange resin column in exactly the same manner as in Example 1. The results shown in Table 2 were obtained. metal ions
We were able to remove it down to 1ppm or less.
【表】
実施例 ３
金属イオンを含有する各種有機アルカリ水溶液
を使用して、実施例１と同じ方法で金属イオンの
除去を行つた。イオン交換樹脂処理前と処理後の
第４級アンモニウム水酸化物、金属イオン含有量
の結果を表３に示した。[Table] Example 3 Metal ions were removed in the same manner as in Example 1 using various organic alkali aqueous solutions containing metal ions. Table 3 shows the results of quaternary ammonium hydroxide and metal ion contents before and after ion exchange resin treatment.
【表】
実施例 ４
実施例１において、調製、イオン交換樹脂処理
した水酸化テトラメチルアンモニウム水溶液とイ
オン交換樹脂処理しない水酸化テトラメチルアン
モニウム水溶液とを用い、常温で、空気雰囲気下
室内に静置し時間経過による着色度APHA
（ASTM Ｄ−102の法による）を測定した。その
結果を表４に示す。本発明の方法により製造した
水酸化テトラメチルアンモニウムな長期間にわた
り着色しない事がわかる。[Table] Example 4 In Example 1, a tetramethylammonium hydroxide aqueous solution prepared and treated with an ion exchange resin and a tetramethylammonium hydroxide aqueous solution not treated with an ion exchange resin were used, and left standing in a room under an air atmosphere at room temperature. Coloration degree APHA over time
(according to ASTM D-102 method). The results are shown in Table 4. It can be seen that the tetramethylammonium hydroxide produced by the method of the present invention does not become colored for a long period of time.
【表】
比較例 １
実施例１と同様にして製造した水酸化テトラメ
チルアンモニウム水溶液10を、ポリスチレンマ
クロポーラス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（商品名：住友化学デユオラ
イトＣ−25D）を用いて、実施例１の方法にて通
液した。結果を表５に示した。金属イオンは殆ん
ど除去されなかつた。
〓〓〓〓〓
[Table] Comparative Example 1 Aqueous tetramethylammonium hydroxide solution 10 produced in the same manner as in Example 1 was mixed with a strongly acidic ion exchange resin (product name: Sumitomo Chemical Duolite C) in which the exchange group of polystyrene macroporous system is a sulfonic acid group. -25D) in the same manner as in Example 1. The results are shown in Table 5. Almost no metal ions were removed. 〓〓〓〓〓
【表】
〓〓〓〓〓
[Table] 〓〓〓〓〓
Claims (1)
を用いて、 一般式 （但しR1、R2、R3及びR4はアルキル基、アルケニ
ル基、ベンジル基、ヒドロキシアルキル基を示
す。） で表わされる第４級アンモニウム水酸化物を含有
する溶液中に溶存せ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有機アルカリ溶液の精
製方法。 ２ 有機アルカリ溶液の溶媒が、水、メタノー
ル、エタノール又はイソプロピルアルコールであ
る特許請求の範囲第１項記載の有機アルカリ溶液
の精製方法。[Claims] 1 Using a polyacrylic gel-based weakly acidic ion exchange resin, the general formula (However, R 1 , R 2 , R 3 and R 4 represent an alkyl group, an alkenyl group, a benzyl group, and a hydroxyalkyl group.) A trace metal dissolved in a solution containing a quaternary ammonium hydroxide represented by A method for purifying an organic alkaline solution, characterized by selectively removing ions. 2. The method for purifying an organic alkaline solution according to claim 1, wherein the solvent of the organic alkaline solution is water, methanol, ethanol, or isopropyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2477581A JPS57139042A (en) | 1981-02-20 | 1981-02-20 | Preparation of metal-free organic alkali solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2477581A JPS57139042A (en) | 1981-02-20 | 1981-02-20 | Preparation of metal-free organic alkali solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57139042A JPS57139042A (en) | 1982-08-27 |
| JPS6222978B2 true JPS6222978B2 (en) | 1987-05-20 |
Family
ID=12147542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2477581A Granted JPS57139042A (en) | 1981-02-20 | 1981-02-20 | Preparation of metal-free organic alkali solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57139042A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69703428T2 (en) * | 1996-07-23 | 2001-04-19 | Tokuyama Corp | METHOD FOR PRODUCING AQUEOUS SOLUTIONS OF TETRAALKYLAMMONIUM HYDROXIDES |
| 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 |
-
1981
- 1981-02-20 JP JP2477581A patent/JPS57139042A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57139042A (en) | 1982-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3664870A (en) | Removal and separation of metallic oxide scale | |
| US20090145850A1 (en) | Method of removing and recovering contaminants from solutions with modified anion exchange materials having metal inside the materials | |
| JPH05212382A (en) | Method for removing heavy metal ion from waste liquid stream | |
| JPH06128321A (en) | Selected chelate resins and their use for removing polyvalent metallic impurities from resist component | |
| US2954276A (en) | Hydrometallurgical process | |
| US2559529A (en) | Process for removing sulfate and bicarbonate ions from water | |
| CA2424110C (en) | Process for recovering onium hydroxides from solutions containing onium compounds | |
| US4872989A (en) | Selective removal of nitrate ions from salt solutions | |
| USRE29680E (en) | Regeneration of anion exchange resins | |
| US2789036A (en) | Purification of concentrated alkali metal hydroxide by ion exchange | |
| JPS6222978B2 (en) | ||
| US4266045A (en) | Etherified phenolic chelate resin, process for its production, and method for adsorption treatment | |
| US3342730A (en) | Method for producing soft water | |
| JPH03167160A (en) | Purification of aqueous solution of quaternary ammonium hydroxide | |
| US3321521A (en) | Regeneration of chelating solutions | |
| JP2003048716A (en) | Method for recovering molybdate | |
| JP2000319233A (en) | Purification of halogenated quaternary ammonium salt solution | |
| US3931004A (en) | Method of treating waste liquids from photographic processings | |
| JPH05192592A (en) | Treatment of strongly basic anion exchange resin | |
| JPH0460700B2 (en) | ||
| US3043867A (en) | Method for the purification of aminocarboxylic acids | |
| US3382277A (en) | Process for recovering an alkali metal styrene sulfonate from an aqueous medium | |
| US3127443A (en) | Decolorization of amino acids | |
| CN116419798A (en) | Method and apparatus for purifying liquid to be treated containing tetraalkylammonium ion | |
| JPS60219598A (en) | Method and device for removing chlorine ion in radioactive waste liquor |