JP4438077B2 - Method for preparing gas-dissolved water for cleaning electronic materials - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、ガス溶解水の調製方法に関する。さらに詳しくは、本発明は、半導体用シリコン基板、液晶用ガラス基板などの電子材料などのウェット洗浄に用いられる所望濃度のガス溶解水を、短時間で効率的に調製することができるガス溶解水の調製方法に関する。
【０００２】
【従来の技術】
半導体用シリコン基板、液晶用ガラス基板、フォトマスク用石英基板などの電子材料の表面から、微粒子、有機物、金属などを除去することは、製品の品質、歩留まりを確保する上で極めて重要である。この目的のために、いわゆるＲＣＡ洗浄法と呼ばれる過酸化水素をベースとする濃厚薬液による高温でのウェット洗浄が行われ、アンモニアと過酸化水素水の混合溶液（ＡＰＭ）や塩酸と過酸化水素水の混合溶液（ＨＰＭ）などが用いられていた。これらの洗浄法を採用した場合の多大な薬液コスト、リンス用の超純水コスト、廃液処理コスト、薬品蒸気を排気し新たに清浄空気を調製する空調コストなどを低減し、さらに水の大量使用、薬物の大量廃棄、排ガスの放出などの環境への負荷を低減するために、近年ウェット洗浄工程の見直しが進められている。
本発明者らは、先に特定のガスを超純水に溶解し、必要に応じて微量の薬品を添加して調製する、薬品の使用量が極めて少なく、しかも優れた洗浄効果を発揮する機能性洗浄水を開発した。この機能性洗浄水は、省資源性と環境保全性が高く評価され、高濃度薬液に代わって使用されるようになった。機能性洗浄水に用いられるガスとしては、水素ガス、酸素ガス、オゾンガス、希ガス、炭酸ガスなどがある。これらのガスを溶解した機能性洗浄水は、純水に近い性質を維持しつつ、従来から使用されていた高濃度の薬液洗浄に匹敵する洗浄効果を発揮する。特に、アンモニアを極微量添加した水素ガス溶解水、酸素ガス溶解水、アルゴンなどの希ガス溶解水は、超音波を併用した洗浄工程で使用すると、極めて高い微粒子除去効果を発揮する。
ガス溶解水の製造にあたっては、精度のよいガス流量コントローラーなどを採用することによって、再現性よく、比較的高濃度の特定ガスを溶解した水が得られる。しかし、特定ガスを溶解した機能性洗浄水の使用が広がるにつれて、より短時間で効率的に特定のガスの溶解を行うことができるガス溶解水の調製方法が求められるようになった。
【０００３】
【発明が解決しようとする課題】
本発明は、半導体用シリコン基板、液晶用ガラス基板などの電子材料などのウェット洗浄に用いられる所望濃度のガス溶解水を、短時間で効率的に調製することができるガス溶解水の調製方法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】
本発明者は、上記の課題を解決すべく鋭意研究を重ねた結果、ガスを溶解させる水を低い温度又は高い圧力に調整して所望濃度のガスを溶解したのち、得られたガス溶解水を所定温度又は所定圧力に戻すことにより、短時間で効率的にガスを溶解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）所定温度、所定圧力における所望濃度のガス溶解水を得る方法であって、ガスを溶解させる水をあらかじめ脱気して溶存ガスの飽和度を低下させた後、該所定温度より低い温度に温度調整した水に、該所望濃度に相当する量のガスを気体溶解膜モジュールに供給して該ガスを温度調整した水に溶解したのち、得られたガス溶解水を所定温度まで加温することを特徴とする電子材料洗浄用ガス溶解水の調製方法、
（２）所定温度、所定圧力における所望濃度のガス溶解水を得る方法であって、ガスを溶解させる水をあらかじめ脱気して溶存ガスの飽和度を低下させた後、ガスを溶解させる水を該所定圧力より高い圧力に圧力調整した水に、該所望濃度に相当する量のガスを気体溶解膜モジュールに供給して該ガスを圧力調整した水に溶解したのち、得られたガス溶解水を所定圧力まで減圧することを特徴とする電子材料洗浄用ガス溶解水の調製方法、及び、
（３）ガスが水素であり、ガス溶解水が水素溶解水である第(１)項又は第(２)項記載の電子材料洗浄用ガス溶解水の調製方法、
を提供するものである。
【０００５】
【発明の実施の形態】
本発明のガス溶解水の調製方法は、所定温度、所定圧力における所望濃度のガス溶解水を得る方法であって、ガスを溶解させる水を、該所定温度より低い温度に温度調整し、又は、該所定圧力より高い圧力に圧力調整し、温度調整又は圧力調整した水に、該所望濃度に相当する量のガスを供給して溶解したのち、得られたガス溶解水を所定温度まで加温し、又は、所定圧力まで減圧するガス溶解水の調製方法である。本発明方法は、半導体用シリコン基板、液晶用ガラス基板、フォトマスク用石英基板などの電子材料の表面を洗浄して、表面に付着した微粒子、有機物、金属などを除去するために用いられる、水素ガス、酸素ガス、オゾンガス、希ガスなどを溶解したガス溶解超純水の調製に好適に用いることができる。
多くのガスは、温度が低いほど飽和溶解度が大きく、圧力が高いほど飽和溶解度が大きく、また、水中へのガスの溶解速度も、温度が低く、圧力が高いほど大きい。したがって、ガスを溶解させる水を、所定温度より低い温度に温度調整し、又は、所定圧力より高い圧力に圧力調整したのち、ガスを溶解させることにより、ガスの溶解速度を高め、効率的にガス溶解水を調製することができる。ガス溶解水の溶存ガス濃度は、ガス溶解装置への通水量とガス供給量によって制御することができる。ガス供給量の制御方式に特に制限はなく、例えば、ガス流量計と調整弁の組み合わせ、マスフローコントローラーなどを挙げることができる。本発明方法により調製するガス溶解水の溶存ガス濃度は、所定温度、所定圧力における飽和溶解度以下であることが好ましい。本発明方法においては、ガスを溶解させる水の温度のみを調整することができ、圧力のみを調整することもでき、あるいは、温度と圧力を同時に調整することもできる。
【０００６】
本発明方法においては、ガスを溶解させる水をあらかじめ脱気して溶存ガスの飽和度を低下させ、ガス溶解キャパシティーに空きをつくったのち、ガスを溶解させることが好ましい。本発明において、ガスの飽和度とは、水中に溶解しているガスの量を、温度２５℃、圧力０.１MPaにおけるガスの溶解量で除した値である。例えば、水が温度２５℃、圧力０.１MPaで窒素ガスと接して平衡状態にあるとき、水への窒素ガスの溶解量は１７.６mg／リットルであるので、水中に溶解しているガスが窒素ガスのみであって、その溶解量が１７.６mg／リットルである水の飽和度は１.０倍であり、水中に溶解しているガスが窒素ガスのみであって、その溶解量が８.８mg／リットルである水の飽和度は０.５倍である。また、温度２５℃、圧力０.１MPaで空気と接して平衡状態にある水は、窒素ガス１３.７mg／リットル及び酸素ガス８.１mg／リットルを溶解して飽和度１.０倍の状態となっているので、脱気によりガスの溶解量を窒素ガス２.７mg／リットル、酸素ガス１.６mg／リットルとした水の飽和度は０.２倍である。
飽和度０.５倍の水は、ガス溶解キャパシティーに飽和度０.５倍に相当する空きがあるので、飽和度０.５倍に相当する量の他のガスを容易かつ迅速に溶解することができる。また、飽和度０.２倍の水は、ガス溶解キャパシティーに飽和度０.８倍に相当する空きがあるので、飽和度０.８倍に相当する量の他のガスを容易かつ迅速に溶解することができる。本発明方法によりガス溶解水を調製するに際して、水の脱気処理方法に特に制限はなく、例えば、真空脱気、減圧膜脱気などによることができる。また、水に、ガスを溶解させる方法に特に制限はなく、例えば、バブリングや、水を透過させずにガスのみを容易に透過させる気体透過膜モジュールを用いる溶解などによることができる。
【０００７】
電子材料などの洗浄水として用いられるガス溶解超純水は、常温で用いられる場合が多いので、超純水を常温以下に冷却したのちガスを溶解させ、次いでガス溶解水の温度を常温まで上げることにより、所望濃度のガス溶解水を得ることができる。水を冷却してガスを溶解したのち加温する方法は、常温より水温が低いほど飽和溶解度が高くなる水素ガス、酸素ガス、オゾンガス、ネオンガス、アルゴンガス、クリプトンガス、キセノンガスなどに適用することができる。ガスを溶解させる水の温度が、ガス溶解水の使用温度より低い場合には、ガスを溶解させる水の冷却工程を省略することができる。
電子材料などの洗浄水として用いられるガス溶解超純水は、常圧で用いられる場合が多いので、超純水が保有される密閉環境を常圧以上の加圧状態にしたのちガスを溶解させ、次いでガス溶解水の環境を常圧に戻すことにより、所望濃度のガス溶解水を得ることができる。水が保有される密閉環境を加圧条件下に保ちつつガスを溶解させたのち、ガス溶解水の環境を常圧に戻す方法は、水素ガス、酸素ガス、オゾンガス、ヘリウムガス、ネオンガス、アルゴンガス、クリプトンガス、キセノンガスなど、ほとんどすべてのガスに適用することができる。
本発明方法を超純水に適用し、得られたガス溶解超純水を電子材料などの洗浄水として用いる場合、原水として使用する超純水は、温度２５℃における電気抵抗率が１８ＭΩ・cm以上であり、有機体炭素が１０μｇ／リットル以下であり、金属分の含有量が２０ｎｇ／リットル以下であり、微粒子が１０,０００個／リットル以下であることが好ましい。
本発明方法によりガス溶解超純水を調製して電子材料などの洗浄に用いる場合、温度調整又は圧力調整に伴う水質の悪化は避けなければならないので、温度調整又は圧力調整を行う機器の接液部材は、フッ素樹脂などの水質悪化を招くおそれのない部材とすることが好ましい。例えば、フッ素樹脂製のチューブを複数本束ねて容器に入れ、チューブの内側又は外側にガスを溶解する水を流し、チューブ壁面を介して逆の側に冷却媒体又は加温媒体を通水あるいは保持する構造を有する熱交換器などを用いることができる。冷却及び加温の媒体としては、水などの液体のほかに気体も適用することができるが、温度調整効果の面からは熱容量の大きい液体を用いることが好ましい。
本発明方法によれば、水へのガス溶解速度を高め、効率よく短時間で所望濃度のガス溶解水を調製することができるので、小型のガス溶解装置を用い、高いガス溶解効率で、経済的にガス溶解水を製造することができる。
【０００８】
【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１
直径２.５インチの気体透過膜モジュール［セルガード製、保有水量４００ml］を用いて、水素ガス溶解水を調製した。なお、気体溶解膜モジュールの気相系には圧力調整弁をつけ、一定量の水素ガスを供給して水素ガス圧力が上昇する場合は、水素ガスが圧力調整弁を通じて放出され、一定の圧力に保持される機構とした。
脱気済みの超純水をテフロン製熱交換器を通して温度１５℃に冷却したのち、気体溶解膜モジュールの液相側に、圧力０.１MPa、流量２.０リットル／分で通水した。気体溶解膜モジュール内の超純水の滞留時間は、１２.０秒である。気体溶解膜モジュールの気相側には、水素ガスを、圧力０.１MPa、供給量２７Ｎml／分で供給した。気体溶解膜モジュールより流出する水素ガス溶解水の溶存水素ガス濃度は１.２mg／リットルであり、水素ガスの溶解効率は１００％であった。
次いで、温度１５℃に調製した脱気済みの超純水の流量を３.５リットル／分、水素ガスの供給量を４７Ｎml／分に増加して水素ガス溶解水の調製を行った。気体溶解膜モジュール内の超純水の滞留時間は、６.９秒である。気体溶解膜モジュールより流出する水素ガス溶解水の溶存水素ガス濃度は１.２mg／リットルであり、水素ガスの溶解効率は１００％であった。
さらに、温度１５℃に調製した脱気済みの超純水の流量を５.０リットル／分、水素ガスの供給量を６８Ｎml／分に増加して水素ガス溶解水の調製を行った。気体溶解膜モジュール内の超純水の滞留時間は、４.８秒である。気体溶解膜モジュールより流出する水素ガス溶解水の溶存水素ガス濃度は１.１mg／リットルであり、水素ガスの溶解効率は９１％であった。
実施例２
脱気済みの超純水を温度２５℃のまま用い、通水圧と水素ガス供給圧をともに高めた以外は、実施例１と同様にして水素ガス溶解水を調製した。
脱気済みの超純水を気体溶解膜モジュールの液相側に、圧力０.２MPa、流量２.０リットル／分で通水し、気相側には、水素ガスを、圧力０.２MPa、供給量２７Ｎml／分で供給した。気体溶解膜モジュールより流出する水素ガス溶解水の溶存水素ガス濃度は１.２mg／リットルであり、水素ガスの溶解効率は１００％であった。
次いで、脱気済みの超純水の流量を３.５リットル／分、水素ガスの供給量を４７Ｎml／分に増加して水素ガス溶解水の調製を行った。気体溶解膜モジュールより流出する水素ガス溶解水の溶存水素ガス濃度は１.２mg／リットルであり、水素ガスの溶解効率は１００％であった。
さらに、脱気済みの超純水の流量を５.０リットル／分、水素ガスの供給量を６８Ｎml／分に増加して水素ガス溶解水の調製を行った。気体溶解膜モジュールより流出する水素ガス溶解水の溶存水素ガス濃度は１.１mg／リットルであり、水素ガスの溶解効率は９１％であった。
比較例１
脱気済みの超純水を温度２５℃のまま用い、通水圧と水素ガス供給圧をともに常圧とし、実施例１と同様にして水素ガス溶解水を調製した。
脱気済みの超純水を気体溶解膜モジュールの液相側に、圧力０.１MPa、流量２.０リットル／分で通水し、気相側には、水素ガスを、圧力０.１MPa、供給量２７Ｎml／分で供給した。気体溶解膜モジュールより流出する水素ガス溶解水の溶存水素ガス濃度は１.２mg／リットルであり、水素ガスの溶解効率は１００％であった。
次いで、脱気済みの超純水の流量を３.５リットル／分、水素ガスの供給量を４７Ｎml／分に増加して水素ガス溶解水の調製を行った。気体溶解膜モジュールより流出する水素ガス溶解水の溶存水素ガス濃度は１.０mg／リットルであり、水素ガスの溶解効率は８３％であった。
さらに、脱気済みの超純水の流量を５.０リットル／分、水素ガスの供給量を６８Ｎml／分に増加して水素ガス溶解水の調製を行った。気体溶解膜モジュールより流出する水素ガス溶解水の溶存水素ガス濃度は０.７mg／リットルであり、水素ガスの溶解効率は５８％であった。
実施例１〜２及び比較例１の結果を、第１表に示す。
【０００９】
【表１】
第１表に見られるように、気体透過膜モジュールへの超純水の通水量を２.０リットル／分、水素ガス供給量を２７Ｎml／分とした場合は、実施例、比較例ともに、超純水に供給された水素ガスが完全に溶解して、溶存水素ガス濃度１.２mg／リットルの水素ガス溶解水が得られている。しかし、通水量を３.５リットル／分、水素ガス供給量を４７Ｎml／分に増加すると、水温を下げた実施例１と、処理圧力を上げた実施例２では、溶存水素ガス濃度１.２mg／リットルの水素ガス溶解水が得られ、水素ガス溶解効率１００％が保たれているのに対して、常温、常圧で処理している比較例１では、溶存水素ガス濃度が１.０mg／リットル、水素ガス溶解効率が８３％に低下し、供給した水素ガスの１７％が失われている。さらに、通水量を５.０リットル／分、水素ガス供給量を６８Ｎml／分に増加すると、実施例１と実施例２では、溶存水素ガス濃度１.１mg／リットル、水素ガス溶解効率９１％となるが、比較例１では、溶存水素ガス濃度が０.７mg／リットル、水素ガス溶解効率が５８％まで低下する。
すなわち、気体溶解膜モジュールにおいて、ガスを溶解させる水を低い温度又は高い圧力に調製することにより、常温、常圧で処理する場合に比べて、ガスの溶解速度とガス溶解効率を高め、短時間で効率的に、所望濃度のガス溶解水を製造することができる。
なお、実施例１及び実施例２で得られた水素ガス溶解水は、常温、常圧に戻したのちは、常温、常圧で水素ガスを溶解する従来法で製造された同一濃度の水素ガス溶解水となんら違いがなく、ウェット洗浄の効果においても全く同じであった。
【００１１】
【発明の効果】
本発明方法により、特定のガスを溶解させる水の温度又は圧力を、ガスの溶解度が増加する方向に調製してガスを供給すると、ガス溶解効率が著しく向上するとともに、気体透過膜モジュールなどのガス溶解装置の単位時間あたりの処理量を増加させることができ、効率よく経済的にガス溶解水を調製することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for preparing gas-dissolved water. More specifically, the present invention relates to gas-dissolved water that can efficiently prepare gas-dissolved water having a desired concentration used for wet cleaning of electronic materials such as silicon substrates for semiconductors and glass substrates for liquid crystals in a short time. It relates to the preparation method.
[0002]
[Prior art]
Removing fine particles, organic substances, metals, and the like from the surface of electronic materials such as a semiconductor silicon substrate, a liquid crystal glass substrate, and a photomask quartz substrate is extremely important for ensuring product quality and yield. For this purpose, wet cleaning at a high temperature with a concentrated chemical solution based on hydrogen peroxide called the so-called RCA cleaning method is performed, and a mixed solution (APM) of ammonia and hydrogen peroxide solution or hydrochloric acid and hydrogen peroxide solution. A mixed solution (HPM) or the like was used. Reduces the cost of chemicals when using these cleaning methods, the cost of ultrapure water for rinsing, the cost of waste liquid treatment, the air conditioning cost of exhausting chemical vapor and newly preparing clean air, and the use of large amounts of water In recent years, the wet cleaning process has been reviewed in order to reduce environmental burdens such as mass disposal of drugs and emission of exhaust gas.
The present inventors previously dissolved a specific gas in ultrapure water and prepared by adding a small amount of chemical as needed, a function that uses an extremely small amount of chemical and exhibits an excellent cleaning effect Water was developed. This functional wash water has been highly evaluated for its resource saving and environmental conservation, and has come to be used in place of high-concentration chemicals. Examples of the gas used for the functional cleaning water include hydrogen gas, oxygen gas, ozone gas, rare gas, and carbon dioxide gas. Functional cleaning water in which these gases are dissolved exhibits a cleaning effect comparable to that of conventionally used high-concentration chemical liquid cleaning while maintaining properties close to pure water. In particular, hydrogen gas-dissolved water, oxygen gas-dissolved water, and rare gas-dissolved water such as argon to which a very small amount of ammonia is added exhibit an extremely high particulate removal effect when used in a cleaning process using ultrasonic waves.
In the production of gas-dissolved water, by using an accurate gas flow controller or the like, water in which a specific gas having a relatively high concentration is dissolved can be obtained with good reproducibility. However, as the use of functional cleaning water in which a specific gas is dissolved spreads, a method for preparing a gas-dissolved water that can efficiently dissolve a specific gas in a shorter time has come to be demanded.
[0003]
[Problems to be solved by the invention]
The present invention provides a method for preparing gas-dissolved water that can efficiently prepare gas-dissolved water having a desired concentration used for wet cleaning of electronic materials such as silicon substrates for semiconductors and glass substrates for liquid crystals in a short time. It was made for the purpose of providing.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor adjusted the water for dissolving the gas to a low temperature or a high pressure to dissolve the gas having a desired concentration, and then obtained the gas-dissolved water. It has been found that the gas can be efficiently dissolved in a short time by returning to the predetermined temperature or the predetermined pressure, and the present invention has been completed based on this finding.
That is, the present invention
(1) A method for obtaining a gas-dissolved water having a desired concentration at a predetermined temperature and a predetermined pressure, wherein after degassing water for dissolving the gas in advance to lower the saturation of the dissolved gas, the temperature lower than the predetermined temperature After supplying the gas whose amount is equivalent to the desired concentration to the gas-dissolved membrane module and dissolving the gas in the temperature-adjusted water , the obtained gas-dissolved water is heated to a predetermined temperature. A method for preparing a gas-dissolved water for cleaning electronic materials,
(2) A method for obtaining a gas-dissolved water having a desired concentration at a predetermined temperature and a predetermined pressure, wherein the water for dissolving the gas is degassed in advance to reduce the saturation of the dissolved gas, and then the water for dissolving the gas is added. An amount of gas corresponding to the desired concentration is supplied to the gas-dissolving membrane module in water adjusted to a pressure higher than the predetermined pressure, and the gas is dissolved in the pressure-adjusted water. A method for preparing a gas-dissolved water for electronic material cleaning, characterized by reducing pressure to a predetermined pressure, and
( 3 ) The method for preparing a gas-dissolved water for electronic material cleaning according to (1) or (2) , wherein the gas is hydrogen and the gas-dissolved water is hydrogen-dissolved water,
Is to provide.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The method for preparing gas-dissolved water according to the present invention is a method for obtaining gas-dissolved water having a desired concentration at a predetermined temperature and a predetermined pressure, and adjusting the temperature of water for dissolving gas to a temperature lower than the predetermined temperature, or After adjusting the pressure to a pressure higher than the predetermined pressure and dissolving the temperature-adjusted or pressure-adjusted water by supplying an amount of gas corresponding to the desired concentration, the obtained gas-dissolved water is heated to the predetermined temperature. Or a method for preparing gas-dissolved water that is depressurized to a predetermined pressure. The method of the present invention is used to clean the surface of an electronic material such as a silicon substrate for a semiconductor, a glass substrate for a liquid crystal, or a quartz substrate for a photomask to remove fine particles, organic substances, metals, etc. attached to the surface. It can be suitably used for the preparation of gas-dissolved ultrapure water in which gas, oxygen gas, ozone gas, rare gas and the like are dissolved.
Many gases have higher saturation solubility at lower temperatures and higher saturation solubility at higher pressures, and the rate of gas dissolution into water is higher at lower temperatures and higher pressures. Therefore, by adjusting the temperature of water for dissolving the gas to a temperature lower than the predetermined temperature or adjusting the pressure to a pressure higher than the predetermined pressure, the gas is dissolved to increase the gas dissolution rate and efficiently Dissolved water can be prepared. The dissolved gas concentration of the gas dissolved water can be controlled by the amount of water flow to the gas dissolving apparatus and the gas supply amount. There is no particular limitation on the gas supply amount control method, and examples thereof include a combination of a gas flow meter and a regulating valve, a mass flow controller, and the like. The dissolved gas concentration of the gas-dissolved water prepared by the method of the present invention is preferably not more than the saturation solubility at a predetermined temperature and a predetermined pressure. In the method of the present invention, only the temperature of water for dissolving the gas can be adjusted, only the pressure can be adjusted, or the temperature and pressure can be adjusted simultaneously.
[0006]
In the method of the present invention, it is preferable to degas the water in which the gas is dissolved in advance to lower the degree of saturation of the dissolved gas and make the gas dissolution capacity empty, and then dissolve the gas. In the present invention, the gas saturation is a value obtained by dividing the amount of gas dissolved in water by the amount of gas dissolved at a temperature of 25 ° C. and a pressure of 0.1 MPa. For example, when water is in equilibrium with nitrogen gas at a temperature of 25 ° C. and a pressure of 0.1 MPa, the amount of nitrogen gas dissolved in water is 17.6 mg / liter. The saturation of water, which is only nitrogen gas and its dissolution amount is 17.6 mg / liter, is 1.0 times, and the gas dissolved in water is only nitrogen gas, and its dissolution amount is 8 The saturation of water, which is 0.8 mg / liter, is 0.5 times. In addition, water in contact with air at a temperature of 25 ° C. and a pressure of 0.1 MPa is in a state of equilibrium of 1.0 times by dissolving 13.7 mg / liter of nitrogen gas and 8.1 mg / liter of oxygen gas. Therefore, the degree of saturation of water with the amount of dissolved gas of 2.7 mg / liter of nitrogen gas and 1.6 mg / liter of oxygen gas by degassing is 0.2 times.
Water having a saturation level of 0.5 times has an empty space corresponding to a saturation level of 0.5 times in the gas dissolution capacity, so that other gases corresponding to a saturation level of 0.5 times can be easily and quickly dissolved. be able to. In addition, since water having a saturation degree of 0.2 times has an empty space corresponding to a saturation degree of 0.8 times in the gas dissolution capacity, another gas corresponding to a saturation degree of 0.8 times can be easily and quickly discharged. Can be dissolved. In preparing the gas-dissolved water by the method of the present invention, there is no particular limitation on the water degassing treatment method, and for example, vacuum degassing, reduced-pressure membrane degassing and the like can be used. Moreover, there is no restriction | limiting in particular in the method of dissolving gas in water, For example, it can be based on bubbling or the melt | dissolution which uses the gas permeation membrane module which permeate | transmits only gas without permeate | transmitting water.
[0007]
Gas-dissolved ultrapure water used as cleaning water for electronic materials is often used at room temperature, so after cooling ultrapure water below room temperature, dissolve the gas, and then raise the temperature of the gas-dissolved water to room temperature. Thus, gas-dissolved water having a desired concentration can be obtained. The method of heating after dissolving the gas by cooling the water is applicable to hydrogen gas, oxygen gas, ozone gas, neon gas, argon gas, krypton gas, xenon gas, etc. whose saturation solubility increases as the water temperature is lower than normal temperature Can do. When the temperature of the water for dissolving the gas is lower than the use temperature of the gas-dissolved water, the step of cooling the water for dissolving the gas can be omitted.
Gas-dissolved ultrapure water used as cleaning water for electronic materials, etc. is often used at normal pressure, so the gas is dissolved after the sealed environment in which ultrapure water is held is brought to a pressurized state higher than normal pressure. Then, the gas-dissolved water having a desired concentration can be obtained by returning the environment of the gas-dissolved water to normal pressure. After dissolving the gas while maintaining the sealed environment where water is held under pressure, the method of returning the environment of the gas dissolved water to normal pressure is hydrogen gas, oxygen gas, ozone gas, helium gas, neon gas, argon gas. It can be applied to almost all gases such as krypton gas and xenon gas.
When the method of the present invention is applied to ultrapure water and the obtained gas-dissolved ultrapure water is used as cleaning water for electronic materials, the ultrapure water used as raw water has an electrical resistivity of 18 MΩ · cm at a temperature of 25 ° C. The organic carbon is preferably 10 μg / liter or less, the metal content is 20 ng / liter or less, and the fine particles are preferably 10,000 particles / liter or less.
When gas-dissolved ultrapure water is prepared by the method of the present invention and used for cleaning electronic materials and the like, deterioration of water quality associated with temperature adjustment or pressure adjustment must be avoided. The member is preferably a member that does not cause deterioration of water quality such as a fluororesin. For example, bundle multiple tubes made of fluororesin into a container, let water that dissolves gas flow inside or outside the tube, and pass or hold cooling medium or heating medium on the opposite side through the tube wall A heat exchanger or the like having a structure to be used can be used. As the cooling and heating medium, a gas other than a liquid such as water can be applied, but it is preferable to use a liquid having a large heat capacity in terms of the temperature adjustment effect.
According to the method of the present invention, the gas dissolution rate in water can be increased and gas dissolution water having a desired concentration can be efficiently prepared in a short time. Thus, gas-dissolved water can be produced.
[0008]
【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.
Example 1
Hydrogen gas-dissolved water was prepared using a gas permeable membrane module having a diameter of 2.5 inches [manufactured by Celgard, 400 ml of retained water]. In addition, a pressure control valve is attached to the gas phase system of the gas dissolution membrane module, and when a certain amount of hydrogen gas is supplied and the hydrogen gas pressure rises, the hydrogen gas is released through the pressure control valve and is kept at a constant pressure. The mechanism is held.
The deaerated ultrapure water was cooled to a temperature of 15 ° C. through a Teflon heat exchanger, and then passed through the liquid phase side of the gas dissolution membrane module at a pressure of 0.1 MPa and a flow rate of 2.0 liters / minute. The residence time of ultrapure water in the gas dissolution membrane module is 12.0 seconds. Hydrogen gas was supplied to the gas phase side of the gas-dissolving membrane module at a pressure of 0.1 MPa and a supply amount of 27 Nml / min. The dissolved hydrogen gas concentration of the hydrogen gas-dissolved water flowing out from the gas-dissolving membrane module was 1.2 mg / liter, and the dissolution efficiency of hydrogen gas was 100%.
Next, hydrogen gas-dissolved water was prepared by increasing the flow rate of degassed ultrapure water prepared at a temperature of 15 ° C. to 3.5 liters / minute and the supply amount of hydrogen gas to 47 Nml / minute. The residence time of ultrapure water in the gas dissolution membrane module is 6.9 seconds. The dissolved hydrogen gas concentration of the hydrogen gas-dissolved water flowing out from the gas-dissolving membrane module was 1.2 mg / liter, and the dissolution efficiency of hydrogen gas was 100%.
Furthermore, hydrogen gas-dissolved water was prepared by increasing the flow rate of degassed ultrapure water prepared at a temperature of 15 ° C. to 5.0 liters / minute and the supply amount of hydrogen gas to 68 Nml / minute. The residence time of ultrapure water in the gas dissolution membrane module is 4.8 seconds. The dissolved hydrogen gas concentration of the hydrogen gas-dissolved water flowing out from the gas-dissolving membrane module was 1.1 mg / liter, and the dissolution efficiency of hydrogen gas was 91%.
Example 2
Hydrogen gas-dissolved water was prepared in the same manner as in Example 1 except that degassed ultrapure water was used at a temperature of 25 ° C., and both the water flow pressure and the hydrogen gas supply pressure were increased.
Ultrapure water that has been degassed is passed through the liquid phase side of the gas-dissolving membrane module at a pressure of 0.2 MPa and a flow rate of 2.0 liters / min. Hydrogen gas is supplied to the gas phase side at a pressure of 0.2 MPa, It was fed at a feed rate of 27 Nml / min. The dissolved hydrogen gas concentration of the hydrogen gas-dissolved water flowing out from the gas-dissolving membrane module was 1.2 mg / liter, and the dissolution efficiency of hydrogen gas was 100%.
Next, hydrogen gas-dissolved water was prepared by increasing the flow rate of degassed ultrapure water to 3.5 liters / minute and the supply amount of hydrogen gas to 47 Nml / minute. The dissolved hydrogen gas concentration of the hydrogen gas-dissolved water flowing out from the gas-dissolving membrane module was 1.2 mg / liter, and the dissolution efficiency of hydrogen gas was 100%.
Furthermore, hydrogen gas-dissolved water was prepared by increasing the flow rate of degassed ultrapure water to 5.0 liters / minute and the supply amount of hydrogen gas to 68 Nml / minute. The dissolved hydrogen gas concentration of the hydrogen gas-dissolved water flowing out from the gas-dissolving membrane module was 1.1 mg / liter, and the dissolution efficiency of hydrogen gas was 91%.
Comparative Example 1
Hydrogen gas-dissolved water was prepared in the same manner as in Example 1, using degassed ultrapure water at a temperature of 25 ° C., setting both the water flow pressure and the hydrogen gas supply pressure to normal pressure.
Ultrapure water that has been degassed is passed through the liquid phase side of the gas dissolution membrane module at a pressure of 0.1 MPa and a flow rate of 2.0 liters / minute, and hydrogen gas is supplied to the gas phase side at a pressure of 0.1 MPa, It was fed at a feed rate of 27 Nml / min. The dissolved hydrogen gas concentration of the hydrogen gas-dissolved water flowing out from the gas-dissolving membrane module was 1.2 mg / liter, and the dissolution efficiency of hydrogen gas was 100%.
Next, hydrogen gas-dissolved water was prepared by increasing the flow rate of degassed ultrapure water to 3.5 liters / minute and the supply amount of hydrogen gas to 47 Nml / minute. The dissolved hydrogen gas concentration of hydrogen gas-dissolved water flowing out from the gas-dissolving membrane module was 1.0 mg / liter, and the dissolution efficiency of hydrogen gas was 83%.
Furthermore, hydrogen gas-dissolved water was prepared by increasing the flow rate of degassed ultrapure water to 5.0 liters / minute and the supply amount of hydrogen gas to 68 Nml / minute. The dissolved hydrogen gas concentration of the hydrogen gas-dissolved water flowing out from the gas-dissolving membrane module was 0.7 mg / liter, and the dissolution efficiency of hydrogen gas was 58%.
The results of Examples 1 and 2 and Comparative Example 1 are shown in Table 1.
[0009]
[Table 1]
As shown in Table 1, when the flow rate of ultrapure water to the gas permeable membrane module was 2.0 liter / min and the hydrogen gas supply rate was 27 Nml / min, both the examples and comparative examples Hydrogen gas supplied to pure water is completely dissolved, and hydrogen gas-dissolved water having a dissolved hydrogen gas concentration of 1.2 mg / liter is obtained. However, when the water flow rate is increased to 3.5 liters / minute and the hydrogen gas supply rate is increased to 47 Nml / minute, the dissolved hydrogen gas concentration is 1.2 mg in Example 1 where the water temperature is lowered and in Example 2 where the treatment pressure is raised. / Liter of hydrogen gas-dissolved water is obtained and the hydrogen gas dissolution efficiency is maintained at 100%, whereas in Comparative Example 1 where the treatment is performed at normal temperature and normal pressure, the dissolved hydrogen gas concentration is 1.0 mg / liter. Liters, the hydrogen gas dissolution efficiency is reduced to 83%, and 17% of the supplied hydrogen gas is lost. Further, when the water flow rate is increased to 5.0 liters / minute and the hydrogen gas supply amount is increased to 68 Nml / minute, in Examples 1 and 2, the dissolved hydrogen gas concentration is 1.1 mg / liter and the hydrogen gas dissolution efficiency is 91%. However, in Comparative Example 1, the dissolved hydrogen gas concentration is 0.7 mg / liter, and the hydrogen gas dissolution efficiency is reduced to 58%.
That is, in the gas dissolution membrane module, by adjusting the water for dissolving the gas to a low temperature or a high pressure, the gas dissolution rate and the gas dissolution efficiency are increased compared with the case of treating at normal temperature and normal pressure, and the time is shortened. Thus, gas-dissolved water having a desired concentration can be produced efficiently.
The hydrogen gas-dissolved water obtained in Example 1 and Example 2 is the same concentration of hydrogen gas produced by the conventional method of dissolving hydrogen gas at normal temperature and normal pressure after returning to normal temperature and normal pressure. There was no difference from the dissolved water, and the wet cleaning effect was exactly the same.
[0011]
【The invention's effect】
According to the method of the present invention, when the temperature or pressure of water for dissolving a specific gas is adjusted so as to increase the solubility of the gas and the gas is supplied, the gas dissolution efficiency is remarkably improved, and the gas such as a gas permeable membrane module The throughput per unit time of the dissolution apparatus can be increased, and gas dissolution water can be prepared efficiently and economically.
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| JP2003334433A (en) | 2002-05-16 | 2003-11-25 | Kurita Water Ind Ltd | Continuous dissolving device, continuous dissolving method and apparatus for supplying gas-dissolved water |
| JP2004230370A (en) * | 2002-12-05 | 2004-08-19 | Wataru Murota | Reduced water and manufacturing method therefor |
| JP4470101B2 (en) * | 2004-03-24 | 2010-06-02 | 栗田工業株式会社 | Nitrogen-dissolved ultrapure water production method |
| CA2601814A1 (en) * | 2005-03-28 | 2006-10-05 | Wataru Murota | Oxygen-containing reductive aqueous beverage and process for production of the same |
| WO2006120747A1 (en) * | 2005-05-13 | 2006-11-16 | Wataru Murota | Process and apparatus for producing oxygen-containing reducing aqueous beverage |
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| JPH01130785A (en) * | 1987-11-18 | 1989-05-23 | Ishikawajima Harima Heavy Ind Co Ltd | Ozonized water sterilizer |
| JPH0338198U (en) * | 1989-08-24 | 1991-04-12 | ||
| JPH0458527A (en) * | 1990-06-28 | 1992-02-25 | Ebara Res Co Ltd | Cleaning method |
| JP2751943B2 (en) * | 1992-04-03 | 1998-05-18 | 仁蔵 長廣 | High concentration ozone water production method and high concentration ozone water production device |
| US5464480A (en) * | 1993-07-16 | 1995-11-07 | Legacy Systems, Inc. | Process and apparatus for the treatment of semiconductor wafers in a fluid |
| JPH0889771A (en) * | 1994-09-19 | 1996-04-09 | Dainippon Ink & Chem Inc | Gas dissolver and gas dissolving method |
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