JP3871036B2 - Method and apparatus for reducing elution of long chain amines in high purity water - Google Patents
Method and apparatus for reducing elution of long chain amines in high purity water Download PDFInfo
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- 150000001412 amines Chemical class 0.000 title claims description 120
- 239000012498 ultrapure water Substances 0.000 title claims description 69
- 238000010828 elution Methods 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 29
- 239000012528 membrane Substances 0.000 claims description 117
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 102
- 238000005406 washing Methods 0.000 claims description 72
- 238000000926 separation method Methods 0.000 claims description 62
- 238000000108 ultra-filtration Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
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- 229920003002 synthetic resin Polymers 0.000 claims description 10
- 238000001471 micro-filtration Methods 0.000 claims description 9
- 238000001223 reverse osmosis Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000013032 photocatalytic reaction Methods 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
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- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
- Cleaning By Liquid Or Steam (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、高純度水中への長鎖アミンの溶出低減方法及び溶出低減装置に関する。さらに詳しくは、本発明は、半導体、液晶などの電子部品製造工場、医薬用水、原子力発電所などで広く使用されている高純度水中への長鎖アミンの溶出を効果的に低減し、純度の極めて高い高純度水を供給することができる高純度水中への長鎖アミンの溶出低減方法及び溶出低減装置に関する。
【０００２】
【従来の技術】
半導体、液晶などの電子部品の製造においては、多量の純水や超純水が用いられている。超純水は、２５℃において１８.２４ＭΩ・cmという理論純水の比抵抗に極めて近い比抵抗値を有する。図１は、超純水供給装置の一例の系統図である。超純水供給装置では、市水、工業用水、井水などを原水とし、前処理装置、一次純水装置及び二次純水装置で処理されて、超純水が製造される。前処理装置では、ろ過、凝集沈殿、精密ろ過膜などによる前処理が施される。一次純水装置では、イオン交換、膜分離、ガス放散、紫外線照射などが行われ、原水の水質と、要求される処理水の水質に合わせて、各装置が適宜組み合わされる。二次純水装置では、一次純水中に残存する極微量のイオン、シリカ、有機物、微粒子などを除去するために、さらに紫外線照射、イオン交換、限外ろ過膜などを組み合わせて最終的に処理され、超純水が得られる。製造された超純水は、電子部品の洗浄工程などのユースポイントに送られて使用される。ユースポイントでは、濃厚排水、希薄排水、使用されなかった純水が発生する。濃厚排水は、排水処理されたのち、放流又は排水処理系で回収再利用される。希薄排水は排水回収装置で処理され、純水は純水回収装置で処理されて、それぞれ一次純水装置に供給され、再利用される。
このような超純水供給装置を用いて、有機体炭素、無機塩類、菌、溶存ガスが極力除去され、理論的な水質面では、超純水はほぼ満足する水準に達している。しかし、電子部品の製造現場、特に半導体製品の製造現場においては、製品不良の発生がしばしば経験されている。この原因について本発明者らが鋭意検討したところ、超純水中の長鎖アミンが、製品不良の原因物質であるという結論にいたった。また、その発生源を特定したところ一次純水装置や二次純水装置に使用される精密ろ過膜、限外ろ過膜、逆浸透膜などのポッティング材料や、接着剤から長鎖アミンが溶出することをつきとめた。このために、高純度水中の不純物としてこれまで注目されていた無機イオンとは別に、長鎖アミンの溶出を低減する方法及び装置の開発が緊急の課題となった。
【０００３】
【発明が解決しようとする課題】
本発明は、半導体、液晶などの電子部品製造工場、医薬用水、原子力発電所などで広く使用されている高純度水中への長鎖アミンの溶出を効果的に低減し、純度の極めて高い高純度水を供給することができる高純度水中への長鎖アミンの溶出低減方法及び溶出低減装置を提供することを目的としてなされたものである。
【０００４】
【課題を解決するための手段】
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、分離膜を用いた高純度水製造装置からの高純度水を得るために、長鎖アミンを除去する手段又は長鎖アミンを分解する手段を用いることにより、高純度水中への長鎖アミンの溶出を効果的に低減し得ることを見いだし、この知見に基づいて本発明を完成するに至った。
すなわち、本発明は、
（１）分離膜を用いた高純度水製造装置からの高純度水中への炭素数８〜３０の長鎖アミンの溶出低減方法であって、洗浄水で予め分離膜を加圧下に洗浄し、洗浄中に断続的に逆洗することにより、分離膜に含まれる炭素数８〜３０の長鎖アミンを除去することを特徴とする高純度水中への長鎖アミンの溶出低減方法、
（２）分離膜が、精密ろ過膜、限外ろ過膜、逆浸透膜又は脱気膜である第１項記載の高純度水中への長鎖アミンの溶出低減方法、
（３）分離膜を、加温条件下に洗浄水で洗浄する第１項記載の高純度水中への長鎖アミンの溶出低減方法、
（４）洗浄水が、有機溶剤を含有する第１項記載の高純度水中への長鎖アミンの溶出低減方法、
（５）洗浄によって分離膜に含まれる炭素数８〜３０の長鎖アミンを除去する装置であって、洗浄水を貯めておくタンクと；その洗浄水をタンクから送出させる手段と；分離膜を配置する分離膜洗浄部と；分離膜の洗浄後の洗浄水をタンクに戻す手段と；そして、分離膜から洗浄中に溶出した炭素数８〜３０の長鎖アミンを除去または分解する手段とを有し、さらに、前記分離膜を加圧下で洗浄する洗浄水の加圧手段と、前記分離膜の洗浄中に断続的に逆洗する逆洗手段を有することを特徴とする高純度水中への長鎖アミンの溶出低減装置、
（６）分離膜が、精密ろ過膜、限外ろ過膜、逆浸透膜又は脱気膜である第５項記載の高純度水中への長鎖アミンの溶出低減装置、
（７）洗浄水の加温手段を有する第５項記載の高純度水中への長鎖アミンの溶出低減装置、
（８）長鎖アミンを除去する手段が、合成樹脂又はイオン交換体である第５項記載の高純度水中への長鎖アミンの溶出低減装置、及び、
（９）長鎖アミンを分解する手段が、紫外線酸化分解又は光触媒反応である第５項記載の高純度水中への長鎖アミンの溶出低減装置、
を提供するものである。
【０００５】
【発明の実施の形態】
本発明方法は、分離膜を用いた高純度水製造装置からの高純度水中への長鎖アミンの溶出低減方法であって、洗浄水で予め分離膜を洗浄して、分離膜に含まれる長鎖アミン除去する方法である。本発明装置は、洗浄によって分離膜に含まれる長鎖アミンを除去する装置であって、洗浄水を貯めておくタンクと；その洗浄水をタンクから送出させる手段と；分離膜を配置する分離膜洗浄部と；分離膜の洗浄後の洗浄水をタンクに戻す手段と；そして、分離膜から洗浄中に溶出した長鎖アミンを除去または分解する手段を有する装置である。
本発明においては、炭素数８〜３０の炭化水素基を有する長鎖アミンを対象とすることができる。本発明の対象とする長鎖アミンの種別に特に制限はなく、例えば、第一級アミン、第二級アミン、第三級アミン、第四級アンモニウム塩などや、モノアミン、ジアミン、トリアミンなどを挙げることができる。炭素数８〜３０の炭化水素基を有する長鎖アミンとしては、例えば、オクチルアミンからトリアコンチルアミンまでの直鎖状脂肪族モノアミン、デカメチレンジアミンなどの直鎖状脂肪族ジアミン、２,２,４−トリメチルヘキサメチレンジアミンなどの側鎖を有する脂肪族ジアミン、メンテンジアミン、イソホロンジアミン、ジアミノジシクロヘキシルメタンなどの脂環式構造を有するジアミン、ｍ−キシリレンジアミン、ｐ,ｐ'−ジアミノジフェニルメタンなどの芳香族環を有するジアミンなどを挙げることができる。第二級アミン、第三級アミン及び第四級アンモニウム塩においては、窒素原子に結合する炭化水素基の１個以上が炭素数８〜３０であれば、本発明装置の対象とすることができる。
【０００６】
長鎖アミンは界面活性作用を有するので、高純度水中に長鎖アミンが存在すると、長鎖アミン自体が不純物となるばかりでなく、長鎖アミンの数十ないし数百重量倍の他の不純物を界面活性作用により溶解し、水質を低下させる原因となる。また、半導体材料などを、高純度水を用いて洗浄などの処理をするとき、高純度水中に長鎖アミンが存在すると、長鎖アミンの疎水基が疎水性材料の表面に吸着されて、製品不良が発生する原因となる。高純度水中への長鎖アミンの溶出量を低減することにより、水質の良好な高純度水として、工程を安定化することができる。炭化水素基の炭素数が７以下であるアミンと、炭化水素基の炭素数が３１以上である長鎖アミンは、界面活性作用が弱く、表面吸着性も小さいので、本発明による除去の対象とする必要は少ない。
本発明の対象とする高純度水製造装置の分離膜に特に制限はなく、例えば、精密ろ過膜、限外ろ過膜、逆浸透膜、脱気膜などを挙げることができる。分離膜の材質に特に制限はなく、例えば、セルロースエステル、ポリアミド、ポリアクリロニトリル、ボリエーテルスルホンなどを挙げることができる。分離膜の形状にも特に制限はなく、例えば、平面膜、スパイラル、管型、中空糸、モノリス型などを挙げることができる。
本発明の目的は、高純度水を製造するに際し、用いられる分離膜を通常運転に先立って予め洗浄水により十分洗浄することにより達せられる。
本発明装置は、洗浄水の加圧手段を有することが好ましい。加圧手段に特に制限はないが、洗浄水を大気圧以上３MPa未満に加圧し得る手段であることが好ましい。本発明方法においては、分離膜を加圧下に洗浄水で洗浄することが好ましく、大気圧以上３MPa未満の圧力で洗浄することがより好ましく、１００kPa〜２MPaの圧力で洗浄することがさらに好ましい。洗浄水を加圧して分離膜を洗浄することにより、長鎖アミンの溶出量をより低減することができる。洗浄水の圧力は、分離膜の濃縮水の圧力として測定することができる。洗浄水の圧力を、大気圧未満の減圧にすることによる利点は見いだされない。洗浄水の圧力を３MPa以上にするためには、装置に大きい耐圧性が必要となり、設備費が嵩むおそれがある。
【０００７】
本発明装置は、洗浄水の加温手段を有することが好ましい。加温手段に特に制限はないが、洗浄水を２０〜１００℃に加温し得る手段であることが好ましい。本発明方法においては、分離膜を、加温条件下に洗浄水で洗浄することが好ましく、２０〜１００℃の洗浄水で洗浄することがより好ましく、２５〜７０℃の洗浄水で洗浄することがさらに好ましい。洗浄水を加温して分離膜を洗浄することにより、長鎖アミンの溶出量をより低減することができる。洗浄水の温度が２０℃未満であると、長鎖アミンの溶出低減効果が十分に発現しないおそれがある。洗浄水の温度が１００℃を超えると、分離膜が損傷を受けるおそれがある。加温手段の設置場所に特に制限はないが、加圧手段と分離膜洗浄部の間に設置することが好ましい。加圧手段と分離膜洗浄部の間に加温手段を設置することにより、装置部材への熱放散を抑えて熱消費を節減することができる。
本発明装置は、逆洗手段を有することが好ましい。本発明方法においては、分離膜の洗浄水による洗浄中に、断続的に逆洗することが好ましい。逆洗手段を設けて、分離膜の透過水側から、濃縮水側へ、さらに吸水側へ洗浄水を通水して洗浄することにより、長鎖アミンの溶出量をより低減することができる。
本発明方法においては、洗浄水に有機溶剤を含有させることができる。洗浄水に含有させる有機溶剤は、水溶性の有機溶剤であることが好ましい。水溶性の有機溶剤としては、例えば、メチルアルコール、エチルアルコール、イソプロピルアルコール、アセトン、ジアセトンアルコール、エチルセロソルブ、ブチルセロソルブ、ジオキサン、テトラヒドロフラン、ジメチルホルムアミドなどを挙げることができる。洗浄水に有機溶剤を含有させることにより、洗浄後の長鎖アミンの溶出量をより低減することができる。
【０００８】
本発明において、長鎖アミンを除去する手段に特に制限はないが、合成樹脂又はイオン交換体を好適に用いることができる。使用する合成樹脂は、疎水性を有する合成樹脂であることが好ましい。疎水性を有する合成樹脂としては、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン系樹脂や、ポリテトラフルオロエチレン、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体などのフッ素系樹脂などを挙げることができる。これらの中で、ポリエチレンは長鎖アミンの除去性能が良好なので、特に好適に用いることができる。疎水性の合成樹脂の形状に特に制限はないが、取り扱いの容易さと形態の安定性から、球状であることが好ましい。洗浄水中に含まれる長鎖アミンは、その炭化水素基が疎水性の合成樹脂に吸着され、洗浄水から除去される。
本発明に使用するイオン交換体の交換形態に特に制限はなく、例えば、カチオン交換、アニオン交換、キレート交換、静電吸着などを挙げることができる。イオン交換体の形状にも特に制限はなく、例えば、ポーラス型イオン交換樹脂、ゲル型イオン交換樹脂、膜表面に担持させたイオン交換膜、繊維状イオン交換体などを挙げることができる。イオン交換樹脂、キレート樹脂などは、単体として使用することができ、あるいは、混合体として使用することもできる。混合体として使用するとき、その混合比についても特に制限はない。ただし、イオン交換膜については、ポッティング材料や接着剤に長鎖アミン系材料を使用しているものと、過酸化水素殺菌洗浄によりイオン交換能が低下するものを避けることが好ましい。
本発明装置において、長鎖アミンを除去する装手段は、加圧手段の前段に設置することが好ましい。また、吸着破過及び充填材の交換を考慮して、並行に少なくとも２基以上の長鎖アミンを除去する手段と、ブローするラインと、これらの装置をバイパスするラインを設置することが好ましい。
本発明装置において、長鎖アミンを除去する手段の装置構成に特に制限はないが、合成樹脂、イオン交換樹脂又はキレート樹脂の場合は、例えば、合成樹脂、イオン交換樹脂又はキレート樹脂が充填された耐圧性の容器、イオン交換膜の場合は、例えば、イオン交換膜を充填した耐圧性の容器などを好適に用いることができる。通水条件についても特に制限はないが、例えば、イオン交換樹脂を用いた長鎖アミンを除去する手段の場合、上向流で空間速度５０ｈ-1以上、差圧１４７kPa以下であることが好ましい。
【０００９】
本発明において、長鎖アミンを分解する手段に特に制限はないが、紫外線酸化分解又は光触媒反応を好適に用いることができる。紫外線酸化分解の装置構成に特に制限はないが、波長３００ｎｍ（約４ｅＶ）以下の紫外線を使用することが好ましい。長鎖アミンを構成する炭化水素基における炭素原子間の結合は一定の結合エネルギーを有し、それよりも高いエネルギーを有する紫外線を長鎖アミンに照射することにより、炭素間の結合が切断されて、長鎖の炭化水素基が短くなり、シリコンウェーハなどの表面に影響を与えない化合物に変化する。また、炭化水素基における炭素原子間の結合エネルギーは３.５８ｅＶ、アミンなどの炭素−窒素原子間の結合エネルギーは３.１５ｅＶであり、波長１８５ｎｍの紫外線は６.６８ｅＶのエネルギーを有する。したがって、長鎖アミンを含む高純度水に波長３００ｎｍ（約４ｅＶ）以下の紫外線を照射することにより、水中の長鎖アミンを分解することができる。
光触媒反応は、酸化チタン、酸化亜鉛などの酸化物半導体触媒や、半導体に金属を担持した半導体光触媒を用いて、不均一光触媒反応により長鎖アミンを分解することが好ましい。長鎖アミンは光を吸収することなく、光触媒が現象的に光を吸収して、そのエネルギーにより長鎖アミンを分解することができる。
【００１０】
本発明においては、高純度水製造装置に用いられる分離膜を、洗浄水を用いて予め洗浄して、分離膜に含まれる長鎖アミンを溶出させて除去し、分離膜からもはや長鎖アミンが溶出しない状態としたのち、高純度水製造装置に組み込んで用いる。このように洗浄された分離膜を用いた高純度水製造装置から得られる高純度水には、長鎖アミンが含まれるおそれがない。分離膜から溶出する長鎖アミンは、分離膜のポッティング材料や、接着剤に起因する場合が多い。長鎖アミンは分離膜から溶出しにくいので、分離膜から長鎖アミンがもはや溶出しない状態とするためには、分離膜を長時間にわたって洗浄する必要がある。このために、分離膜を洗浄して溶出した微量の長鎖アミンを含む洗浄水を、長鎖アミンを除去する手段又は分解する手段で処理し、長鎖アミンを含まない洗浄水として循環使用することが好ましい。
図２は、本発明装置の一態様の工程系統図である。タンク１に貯留された高純度の洗浄水が、ポンプ２により長鎖アミンを除去する手段３に送られる。長鎖アミンを除去する手段の代わりに、同じ位置に長鎖アミンを分解する手段を設置することもできる。長鎖アミンを除去する手段から流出する洗浄水は、加圧手段４において加圧され、加温手段５において加熱され、分離膜洗浄部に配置された高純度水製造装置に装着されるべき分離膜６を洗浄する。分離膜は、逆洗手段７からの信号によるバルブ作動により、断続的に逆洗される。洗浄後の洗浄水はタンク１に返送して循環使用する。
本発明の高純度水中への長鎖アミンの溶出低減方法及び溶出低減装置によれば、高純度水製造装置で使用される精密ろ過膜、限外ろ過膜、逆浸透膜などのポッティング材料や接着剤から水中に溶出する長鎖アミンを、効率よく低減することができる。これにより、無機イオンなどにとどまらず、長鎖アミンによる水質低下と、それによる影響を未然に防止して、電子産業などに多大な貢献をすることができる。
【００１１】
【実施例】
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
実施例においては、図２に示す装置の分離膜ユニットに、有効膜面積６.３ｍ2、公称分画分子量２０,０００、透過水量１.７ｍ3／ｈ以上の限外ろ過膜を設置し、洗浄効果を評価した。なお、圧力１９６kPaの超純水を、カチオン交換樹脂５０Ｌを充填したステンレス鋼製の容器に５ｍ3／ｈで通水して処理した洗浄水を用いた。また、満水時のブロー配管を有する受けタンク、濃縮水圧力と透過水圧力の信号でインバータ制御したポンプからなる加圧手段、熱交換プレートを用いた加温手段、圧空バルブを組み合せた制御装置からなる逆洗手段を用いた。さらに、ポリ塩化ビニルからなる配管を用いた。
参考例１
洗浄水温度２５℃、濃縮水圧力１４７kPa、膜面差圧４９kPaに制御して、限外ろ過膜の洗浄を４２日間行った。
４２日後、洗浄した限外ろ過膜の透過水を１ｍ3のステンレス鋼製の容器に貯め、この透過水を用いて、容量１５Ｌの石英洗浄槽に設置したあらかじめ疎水表面処理を施したシリコンウェーハに対し、水量２０Ｌ／minのオーバフローリンス洗浄し、それを７日間行った。次いで、シリコンウェーハ表面に吸着した長鎖アミンを、昇温脱離装置［GL Sciences Inc.製、ＳＷＡ−２５６］を付帯したガスクロマトグラフ／質量分析計［日本電子データム(株)、ＡＭＳＵＭ３００］を用いて分析した。長鎖アミンの信号のカウント数は、１５２,２３７であった。
参考例２
洗浄水温度２５℃、濃縮水圧力２９４kPa、膜面差圧１４７kPaに制御した以外は、参考例１と同様にして、限外ろ過膜を４２日間洗浄し、その透過水を用いて疎水表面処理を施したシリコンウェーハを７日間洗浄し、シリコンウェーハ表面に吸着した長鎖アミンを分析した。長鎖アミンの信号のカウント数は、６０,９１１であった。
参考例３
洗浄水温度５０℃、濃縮水圧力２９４kPa、膜面差圧１４７kPaに制御した以外は、参考例１と同様にして、限外ろ過膜を４２日間洗浄し、その透過水を用いて疎水表面処理を施したシリコンウェーハを７日間洗浄し、シリコンウェーハ表面に吸着した長鎖アミンを分析した。長鎖アミンの信号のカウント数は、１２,１８２であった。
実施例１
洗浄水温度５０℃、濃縮水圧力２９４kPa、膜面差圧１４７kPaに制御し、１日に１回１時間５０℃の洗浄水を用いて逆洗した以外は、参考例１と同様にして、限外ろ過膜を４２日間洗浄し、その透過水を用いて疎水表面処理を施したシリコンウェーハを７日間洗浄し、シリコンウェーハ表面に吸着した長鎖アミンを分析した。長鎖アミンの信号のカウント数は、６,０９２であった。
参考例１〜３、及び実施例１の結果を、第１表に示す。
【００１２】
【表１】
第１表に見られるように、予め長鎖アミンを除去した限外ろ過膜を用いて得られた透過水でシリコンウェーハを洗浄すると、参考例１のようにシリコンウェーハに吸着された長鎖アミンの量は十分に低下している。濃縮水圧力を２倍に上げた参考例２では、長鎖アミンの吸着量は４０％に減少し、洗浄水の温度を５０℃に上昇して参考例３では、長鎖アミンの吸着量は２０％に激減し、さらに逆洗を行った実施例１では、長鎖アミンの吸着量は半減している。
参考例４
水道水を原水とし、前処理装置、逆浸透膜装置及びイオン交換装置からなる一次純水装置、並びに、紫外線照射装置、イオン交換樹脂カートリッジ及び限外ろ過膜からなる二次純水装置の最終段の限外ろ過膜に、参考例１で示した方法で４２日間洗浄した限外ろ過膜を適用し、定格運転を行った。運転開始２日目から、透過水にシリコンウェーハを３日間浸漬したのち、参考例１と同様にして、シリコンウェーハ表面に吸着した長鎖アミンを、昇温脱離装置を付帯したガスクロマトグラフ／質量分析計を用いて分析した。長鎖アミンの信号のカウント数は、５２,４６２であった。
比較例１
限外ろ過膜として、新品の限外ろ過膜を適用した以外は、参考例４と同様にして、透過水にシリコンウェーハを浸漬し、表面に吸着した長鎖アミンを分析した。長鎖アミンの信号のカウント数は、１４５,３８８であった。
参考例４及び比較例１の結果を、第２表に示す。
【００１４】
【表２】
第２表に見られるように、長鎖アミンを除去した洗浄水を用いて４２日間洗浄した限外ろ過膜を適用した超純水製造装置から得られる超純水で洗浄したシリコンウェーハに吸着された長鎖アミンの量は、新品の限外ろ過膜を適用した超純水製造装置から得られる超純水で洗浄したシリコンウェーハに吸着された長鎖アミンの量の約３分の１である。この結果から、予め洗浄した限外ろ過膜を使用することにより、製造される超純水の水質が向上し、シリコンウェーハの汚染が低減されることが分かる。
【００１６】
【発明の効果】
本発明の高純度水中への長鎖アミンの溶出低減方法及び溶出低減装置によれば、高純度水製造装置に使用する分離膜から溶出する長鎖アミンの量を効率よく低減することができる。さらに、精密ろ過膜、限外ろ過膜、逆浸透膜などの部品交換後も、これらの部品からの長鎖アミンの溶出を抑制することができる。これにより、無機イオンなどにとどまらず、長鎖アミンによる水質低下とその影響を未然に防止して、電子産業などに大いに貢献することができる。
【図面の簡単な説明】
【図１】図１は、超純水供給装置の一例の系統図である。
【図２】図２は、本発明装置の一態様の工程系統図である。
【符号の説明】
１ タンク
２ ポンプ
３ 長鎖アミンを除去する手段
４ 加圧手段
５ 加温手段
６ 高純度水製造装置の分離膜
７ 逆洗手段[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an elution reduction method and elution reduction apparatus for long-chain amines in high-purity water. More specifically, the present invention effectively reduces the elution of long-chain amines into high-purity water widely used in factories for electronic parts such as semiconductors and liquid crystals, pharmaceutical water, and nuclear power plants. The present invention relates to an elution reduction method and elution reduction apparatus for long-chain amines in high-purity water that can supply extremely high-purity water.
[0002]
[Prior art]
In the manufacture of electronic parts such as semiconductors and liquid crystals, a large amount of pure water or ultrapure water is used. Ultrapure water has a specific resistance value very close to the specific resistance of theoretical pure water of 18.24 MΩ · cm at 25 ° C. FIG. 1 is a system diagram of an example of an ultrapure water supply apparatus. In the ultrapure water supply apparatus, city water, industrial water, well water, and the like are used as raw water and processed by a pretreatment apparatus, a primary pure water apparatus, and a secondary pure water apparatus to produce ultrapure water. In the pretreatment device, pretreatment by filtration, coagulation sedimentation, microfiltration membrane or the like is performed. In the primary pure water device, ion exchange, membrane separation, gas diffusion, ultraviolet irradiation, and the like are performed, and each device is appropriately combined according to the quality of raw water and the required quality of treated water. In the secondary pure water device, in order to remove trace amounts of ions, silica, organic matter, fine particles, etc. remaining in the primary pure water, the final treatment is performed by further combining ultraviolet irradiation, ion exchange, ultrafiltration membrane, etc. And ultrapure water is obtained. The manufactured ultrapure water is sent to a use point such as a cleaning process for electronic parts and used. At the point of use, concentrated drainage, diluted drainage, and pure water that has not been used are generated. Concentrated wastewater is drained and then discharged or recovered and reused in a wastewater treatment system. The diluted waste water is processed by the waste water recovery device, and the pure water is processed by the pure water recovery device, and each is supplied to the primary pure water device and reused.
Using such an ultrapure water supply device, organic carbon, inorganic salts, bacteria, and dissolved gas are removed as much as possible, and in terms of theoretical water quality, ultrapure water has almost reached a satisfactory level. However, the occurrence of product defects is often experienced in electronic component manufacturing sites, particularly semiconductor product manufacturing sites. When the present inventors diligently investigated the cause, it was concluded that a long-chain amine in ultrapure water is a causative substance for product defects. In addition, when the source was identified, long-chain amines eluted from potting materials such as microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, and adhesives used in primary and secondary pure water devices. I found out. For this reason, apart from inorganic ions that have been attracting attention as impurities in high-purity water, the development of methods and devices that reduce elution of long-chain amines has become an urgent issue.
[0003]
[Problems to be solved by the invention]
The present invention effectively reduces the elution of long-chain amines into high-purity water widely used in semiconductor, liquid crystal and other electronic component manufacturing factories, pharmaceutical water, nuclear power plants, etc. The object of the present invention is to provide a method and an apparatus for reducing elution of a long-chain amine in high-purity water that can supply water.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained means for removing long-chain amines or long-chains in order to obtain high-purity water from a high-purity water production apparatus using a separation membrane. It has been found that elution of long-chain amines into high-purity water can be effectively reduced by using a means for decomposing amines, and the present invention has been completed based on this finding.
That is, the present invention
(1) A method for reducing elution of a long-chain amine having 8 to 30 carbon atoms into high-purity water from a high-purity water production apparatus using a separation membrane, wherein the separation membrane is previously washed with water under pressure , A method for reducing the elution of long-chain amines in high-purity water, wherein the long-chain amines having 8 to 30 carbon atoms contained in the separation membrane are removed by backwashing intermittently during washing ,
(2) The method for reducing the elution of long-chain amines in high-purity water according to item 1, wherein the separation membrane is a microfiltration membrane, an ultrafiltration membrane, a reverse osmosis membrane or a degassing membrane,
(3) The method for reducing elution of long-chain amines in high-purity water according to item 1, wherein the separation membrane is washed with washing water under heating conditions,
( 4 ) The method for reducing elution of long-chain amines in high-purity water according to item 1, wherein the washing water contains an organic solvent,
( 5 ) An apparatus for removing long-chain amines having 8 to 30 carbon atoms contained in the separation membrane by washing, a tank for storing washing water; means for sending the washing water from the tank; and a separation membrane a separation membrane washing unit to place; and means for returning to the tank washing water after washing of the separation membrane; and a removing or decomposing means a long-chain amine having a carbon number of 8-30 eluted during the wash from the separation membrane And further comprising a pressurizing means for washing water for washing the separation membrane under pressure, and a backwashing means for backwashing intermittently during washing of the separation membrane . Long chain amine elution reduction device,
( 6 ) The apparatus for reducing elution of long-chain amines into high-purity water according to
( 7 ) The apparatus for reducing elution of long-chain amines into high-purity water according to
( 8 ) The elution reducing device for long-chain amines in high-purity water according to
( 9 ) The apparatus for reducing elution of long-chain amines in high-purity water according to
Is to provide.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention is a method for reducing the elution of long-chain amines into high-purity water from a high-purity water production apparatus using a separation membrane. This is a method for removing a chain amine. The apparatus of the present invention is an apparatus for removing long-chain amines contained in a separation membrane by washing, a tank for storing washing water; means for sending out the washing water from the tank; and a separation membrane in which the separation membrane is arranged A washing unit; means for returning washing water after washing of the separation membrane to the tank; and means for removing or decomposing long-chain amines eluted during washing from the separation membrane.
In the present invention, a long-chain amine having a hydrocarbon group having 8 to 30 carbon atoms can be targeted. There is no restriction | limiting in particular in the kind of long-chain amine made into the object of this invention, For example, a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium salt etc., a monoamine, diamine, a triamine etc. are mentioned. be able to. Examples of the long chain amine having a hydrocarbon group having 8 to 30 carbon atoms include linear aliphatic monoamines from octylamine to triacontylamine, linear aliphatic diamines such as decamethylenediamine, 2,2, Aliphatic diamines having side chains such as 4-trimethylhexamethylenediamine, menthendiamine, isophoronediamine, diamines having an alicyclic structure such as diaminodicyclohexylmethane, m-xylylenediamine, p, p'-diaminodiphenylmethane, etc. Examples thereof include diamines having an aromatic ring. In the secondary amine, the tertiary amine, and the quaternary ammonium salt, if one or more of the hydrocarbon groups bonded to the nitrogen atom have 8 to 30 carbon atoms, the apparatus of the present invention can be used. .
[0006]
Since long-chain amines have a surface-active action, when long-chain amines are present in high-purity water, not only long-chain amines themselves become impurities, but also other impurities that are tens to hundreds of times the weight of long-chain amines. It dissolves due to the surface active action and causes water quality to deteriorate. In addition, when semiconductor materials are treated with high-purity water, such as washing, if long-chain amines are present in the high-purity water, the hydrophobic groups of the long-chain amines are adsorbed on the surface of the hydrophobic material, resulting in a product. It becomes a cause of occurrence of defects. By reducing the elution amount of long-chain amines in high-purity water, the process can be stabilized as high-purity water with good water quality. An amine having a hydrocarbon group having 7 or less carbon atoms and a long-chain amine having a hydrocarbon group having 31 or more carbon atoms have a weak surface activity and a low surface adsorptivity. There is little need to do.
There is no restriction | limiting in particular in the separation membrane of the high purity water manufacturing apparatus made into the object of this invention, For example, a microfiltration membrane, an ultrafiltration membrane, a reverse osmosis membrane, a deaeration membrane etc. can be mentioned. There is no restriction | limiting in particular in the material of a separation membrane, For example, a cellulose ester, polyamide, polyacrylonitrile, polyethersulfone etc. can be mentioned. There is no restriction | limiting in particular also in the shape of a separation membrane, For example, a plane membrane, a spiral, a tube type, a hollow fiber, a monolith type etc. can be mentioned.
The object of the present invention is achieved by sufficiently washing the separation membrane to be used with washing water prior to normal operation when producing high-purity water.
The apparatus of the present invention preferably has a means for pressurizing cleaning water. Although there is no restriction | limiting in particular in a pressurization means, It is preferable that it is a means which can pressurize washing water to atmospheric pressure or more and less than 3 MPa. In the method of the present invention, the separation membrane is preferably washed with washing water under pressure, more preferably at a pressure of from atmospheric pressure to less than 3 MPa, and more preferably from 100 kPa to 2 MPa. By washing the separation membrane by pressurizing the washing water, the elution amount of the long chain amine can be further reduced. The pressure of the washing water can be measured as the pressure of the concentrated water in the separation membrane. No advantage is found by reducing the pressure of the wash water to less than atmospheric pressure. In order to increase the pressure of the washing water to 3 MPa or more, the apparatus needs to have a large pressure resistance, which may increase the equipment cost.
[0007]
The apparatus of the present invention preferably has a means for warming cleaning water. Although there is no restriction | limiting in particular in a heating means, It is preferable that it is a means which can heat wash water to 20-100 degreeC. In the method of the present invention, the separation membrane is preferably washed with washing water under heating conditions, more preferably washed with washing water at 20 to 100 ° C., and washing with washing water at 25 to 70 ° C. Is more preferable. By washing the separation membrane by heating the washing water, the elution amount of the long chain amine can be further reduced. If the temperature of the washing water is less than 20 ° C, the elution reduction effect of the long-chain amine may not be sufficiently exhibited. If the temperature of the washing water exceeds 100 ° C, the separation membrane may be damaged. Although there is no restriction | limiting in particular in the installation place of a heating means, It is preferable to install between a pressurization means and a separation membrane washing | cleaning part. By installing a heating unit between the pressurizing unit and the separation membrane cleaning unit, heat dissipation to the apparatus member can be suppressed and heat consumption can be reduced.
The apparatus of the present invention preferably has backwashing means. In the method of the present invention, it is preferable to intermittently backwash the separation membrane during washing with the washing water. The amount of elution of long-chain amines can be further reduced by providing backwashing means and washing by passing wash water from the permeate side of the separation membrane to the concentrated water side and further to the water absorption side.
In the method of the present invention, the washing water can contain an organic solvent. The organic solvent to be contained in the washing water is preferably a water-soluble organic solvent. Examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, diacetone alcohol, ethyl cellosolve, butyl cellosolve, dioxane, tetrahydrofuran, dimethylformamide and the like. By containing an organic solvent in the washing water, the elution amount of the long-chain amine after washing can be further reduced.
[0008]
In the present invention, the means for removing the long-chain amine is not particularly limited, but a synthetic resin or an ion exchanger can be preferably used. The synthetic resin used is preferably a hydrophobic synthetic resin. Examples of the synthetic resin having hydrophobicity include polyolefin resins such as polyethylene and polypropylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and the like. Fluorine resin can be used. Among these, polyethylene is particularly suitable because it has a good long-chain amine removal performance. The shape of the hydrophobic synthetic resin is not particularly limited, but is preferably spherical from the viewpoint of ease of handling and shape stability. The long-chain amine contained in the wash water has its hydrocarbon group adsorbed on the hydrophobic synthetic resin and removed from the wash water.
There is no restriction | limiting in particular in the exchange form of the ion exchanger used for this invention, For example, cation exchange, anion exchange, chelate exchange, electrostatic adsorption etc. can be mentioned. The shape of the ion exchanger is not particularly limited, and examples thereof include porous ion exchange resins, gel ion exchange resins, ion exchange membranes supported on the membrane surface, and fibrous ion exchangers. An ion exchange resin, a chelate resin, etc. can be used as a simple substance, or can also be used as a mixture. When used as a mixture, the mixing ratio is not particularly limited. However, it is preferable to avoid ion exchange membranes that use long-chain amine materials for potting materials and adhesives and those that have reduced ion exchange capacity due to hydrogen peroxide sterilization cleaning.
In the apparatus of the present invention, it is preferable that the device for removing the long-chain amine is installed in front of the pressurizing unit. In consideration of adsorption breakthrough and replacement of the filler, it is preferable to install a means for removing at least two or more long-chain amines, a line for blowing, and a line for bypassing these devices in parallel.
In the apparatus of the present invention, there is no particular limitation on the apparatus configuration of the means for removing the long chain amine, but in the case of a synthetic resin, an ion exchange resin or a chelate resin, for example, a synthetic resin, an ion exchange resin or a chelate resin is filled. In the case of a pressure-resistant container or ion exchange membrane, for example, a pressure-resistant container filled with an ion exchange membrane can be preferably used. Although there are no particular restrictions on the water flow conditions, for example, in the case of means for removing a long-chain amine using an ion exchange resin, it is preferable that the upward flow has a space velocity of 50 h −1 or more and a differential pressure of 147 kPa or less.
[0009]
In the present invention, the means for decomposing a long-chain amine is not particularly limited, but ultraviolet oxidative decomposition or photocatalytic reaction can be preferably used. Although there is no restriction | limiting in particular in the apparatus structure of ultraviolet oxidative decomposition, It is preferable to use the ultraviolet-ray with a wavelength of 300 nm (about 4 eV) or less. The bond between carbon atoms in the hydrocarbon group constituting the long chain amine has a constant bond energy. By irradiating the long chain amine with ultraviolet light having a higher energy, the bond between the carbon atoms is broken. The long-chain hydrocarbon group becomes shorter and changes to a compound that does not affect the surface of a silicon wafer or the like. In addition, the bond energy between carbon atoms in the hydrocarbon group is 3.58 eV, the bond energy between carbon-nitrogen atoms such as amines is 3.15 eV, and ultraviolet light having a wavelength of 185 nm has an energy of 6.68 eV. Therefore, long-chain amines in water can be decomposed by irradiating high-purity water containing long-chain amines with ultraviolet rays having a wavelength of 300 nm (about 4 eV) or less.
In the photocatalytic reaction, it is preferable to decompose long-chain amines by heterogeneous photocatalytic reaction using an oxide semiconductor catalyst such as titanium oxide or zinc oxide, or a semiconductor photocatalyst in which a metal is supported on a semiconductor. The long-chain amine does not absorb light, and the photocatalyst absorbs light in a phenomenon, and the long-chain amine can be decomposed by the energy.
[0010]
In the present invention, the separation membrane used in the high-purity water production apparatus is washed in advance with washing water to elute and remove the long-chain amine contained in the separation membrane. After making it into a state where it does not elute, it is incorporated into a high-purity water production device. The high-purity water obtained from the high-purity water production apparatus using the washed separation membrane does not contain a long-chain amine. The long-chain amine eluted from the separation membrane is often caused by the potting material of the separation membrane or the adhesive. Since long-chain amines are difficult to elute from the separation membrane, it is necessary to wash the separation membrane for a long time in order to make the long-chain amines no longer elute from the separation membrane. For this purpose, washing water containing a trace amount of long-chain amines eluted by washing the separation membrane is treated with means for removing or decomposing long-chain amines, and recycled as washing water containing no long-chain amines. It is preferable.
FIG. 2 is a process flow diagram of one embodiment of the apparatus of the present invention. High-purity washing water stored in the tank 1 is sent to the means 3 for removing long-chain amines by the pump 2. Instead of the means for removing the long chain amine, a means for decomposing the long chain amine can be installed at the same position. The washing water flowing out from the means for removing the long-chain amine is pressurized in the pressurizing means 4 and heated in the heating means 5 and separated to be attached to the high purity water production apparatus disposed in the separation membrane washing section. The membrane 6 is washed. The separation membrane is intermittently backwashed by a valve operation by a signal from the backwashing means 7. The washed water after washing is returned to the tank 1 for circulation.
According to the elution reduction method and elution reduction device for long chain amines in high purity water of the present invention, potting materials such as microfiltration membranes, ultrafiltration membranes and reverse osmosis membranes used in high purity water production devices and adhesion The long chain amine eluting from the agent into water can be efficiently reduced. As a result, not only inorganic ions but also water quality deterioration due to long-chain amines and the influences thereof can be prevented, thereby making a great contribution to the electronics industry and the like.
[0011]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the Examples, an ultrafiltration membrane having an effective membrane area of 6.3 m 2 , a nominal molecular weight cut off of 20,000, and a permeate flow rate of 1.7 m 3 / h or more is installed in the separation membrane unit of the apparatus shown in FIG. The cleaning effect was evaluated. Washing water was used which was treated by passing ultrapure water with a pressure of 196 kPa through a stainless steel container filled with 50 L of cation exchange resin at 5 m 3 / h. Also, from a control unit that combines a receiving tank having a blow pipe when full of water, pressurizing means comprising a pump controlled by an inverter with signals of concentrated water pressure and permeate pressure, heating means using a heat exchange plate, and a pneumatic valve The following backwashing means was used. Furthermore, piping made of polyvinyl chloride was used.
Reference example 1
The ultrafiltration membrane was washed for 42 days under the control of a washing water temperature of 25 ° C., a concentrated water pressure of 147 kPa, and a membrane surface differential pressure of 49 kPa.
42 days later, the permeated water of the washed ultrafiltration membrane was stored in a 1 m 3 stainless steel container, and this permeated water was used to pre-hydrophobic surface-treated silicon wafers installed in a quartz washing tank with a capacity of 15 L. On the other hand, it was washed with an overflow rinse with a water amount of 20 L / min and carried out for 7 days. Next, the long-chain amine adsorbed on the silicon wafer surface was analyzed using a gas chromatograph / mass spectrometer [JEOL Datum Co., Ltd., AMSUM300] equipped with a temperature programmed desorption device [manufactured by GL Sciences Inc., SWA-256]. And analyzed. The long chain amine signal count was 152,237.
Reference example 2
The ultrafiltration membrane was washed for 42 days in the same manner as in Reference Example 1 except that the washing water temperature was 25 ° C., the concentrated water pressure was 294 kPa, and the membrane surface differential pressure was 147 kPa. Hydrophobic surface treatment was performed using the permeated water. The applied silicon wafer was washed for 7 days, and the long-chain amine adsorbed on the silicon wafer surface was analyzed. The signal count of the long chain amine was 60,911.
Reference example 3
The ultrafiltration membrane was washed for 42 days in the same manner as in Reference Example 1 except that the washing water temperature was controlled at 50 ° C., the concentrated water pressure was 294 kPa, and the membrane differential pressure was 147 kPa. Hydrophobic surface treatment was performed using the permeated water. The applied silicon wafer was washed for 7 days, and the long-chain amine adsorbed on the silicon wafer surface was analyzed. The signal count of the long chain amine was 12,182.
Example 1
In the same manner as in Reference Example 1 , except that the cleaning water temperature was controlled to 50 ° C., the concentrated water pressure was 294 kPa, and the membrane differential pressure was 147 kPa, and back washing was performed once a day using 50 ° C. cleaning water for 1 hour. The outer filtration membrane was washed for 42 days, and the silicon wafer subjected to the hydrophobic surface treatment using the permeated water was washed for 7 days, and the long-chain amine adsorbed on the silicon wafer surface was analyzed. The signal count of the long chain amine was 6,092.
The results of Reference Examples 1 to 3 and Example 1 are shown in Table 1.
[0012]
[Table 1]
As seen in Table 1, when the silicon wafer was washed with permeated water obtained using an ultrafiltration membrane from which long-chain amine had been removed in advance, the long-chain amine adsorbed on the silicon wafer as in Reference Example 1 The amount of is sufficiently reduced. In Reference Example 2 where the concentrated water pressure was doubled, the long-chain amine adsorption amount decreased to 40%, and the temperature of the wash water was increased to 50 ° C. In Reference Example 3 , the long-chain amine adsorption amount was In Example 1 , which was drastically reduced to 20% and further backwashed, the amount of adsorbed long chain amine was halved.
Reference example 4
The final stage of the primary pure water device comprising tap water as raw water and comprising a pretreatment device, a reverse osmosis membrane device and an ion exchange device, and a secondary pure water device comprising an ultraviolet irradiation device, an ion exchange resin cartridge and an ultrafiltration membrane. The ultrafiltration membrane washed for 42 days by the method shown in Reference Example 1 was applied to the ultrafiltration membrane, and rated operation was performed. Gas chromatograph / mass with attached thermal desorption device for long-chain amine adsorbed on the silicon wafer surface in the same manner as in Reference Example 1 after dipping the silicon wafer in the permeated water for 3 days from the second day of operation. Analysis was performed using an analyzer. The signal count of the long chain amine was 52,462.
Comparative Example 1
A long-chain amine adsorbed on the surface was analyzed by immersing a silicon wafer in permeated water in the same manner as in Reference Example 4 except that a new ultrafiltration membrane was used as the ultrafiltration membrane. The signal count of the long chain amine was 145,388.
The results of Reference Example 4 and Comparative Example 1 are shown in Table 2.
[0014]
[Table 2]
As can be seen in Table 2, it is adsorbed on a silicon wafer washed with ultrapure water obtained from an ultrapure water production apparatus to which an ultrafiltration membrane washed with wash water from which long chain amines have been removed for 42 days is applied. The amount of the long-chain amine is about one third of the amount of the long-chain amine adsorbed on the silicon wafer washed with ultrapure water obtained from the ultrapure water production apparatus to which a new ultrafiltration membrane is applied. . From this result, it can be seen that the quality of the ultrapure water produced is improved and the contamination of the silicon wafer is reduced by using a pre-cleaned ultrafiltration membrane.
[0016]
【The invention's effect】
According to the elution reduction method and elution reduction apparatus for long-chain amines in high-purity water of the present invention, the amount of long-chain amines eluted from the separation membrane used in the high-purity water production apparatus can be efficiently reduced. Furthermore, elution of long chain amines from these components can be suppressed even after replacement of components such as microfiltration membranes, ultrafiltration membranes, and reverse osmosis membranes. As a result, not only inorganic ions, but also water quality deterioration due to long-chain amines and their effects can be prevented in advance, which can greatly contribute to the electronics industry and the like.
[Brief description of the drawings]
FIG. 1 is a system diagram of an example of an ultrapure water supply apparatus.
FIG. 2 is a process flow diagram of one embodiment of the apparatus of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Tank 2 Pump 3 Means to remove long-chain amine 4 Pressurizing means 5 Heating means 6
Claims (9)
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