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JP2005239615A - Method for refining fluorine-based solvent - Google Patents

Method for refining fluorine-based solvent Download PDF

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JP2005239615A
JP2005239615A JP2004050294A JP2004050294A JP2005239615A JP 2005239615 A JP2005239615 A JP 2005239615A JP 2004050294 A JP2004050294 A JP 2004050294A JP 2004050294 A JP2004050294 A JP 2004050294A JP 2005239615 A JP2005239615 A JP 2005239615A
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fluorine
based solvent
filter
fine particles
less
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Masahiro Nakamura
昌洋 中村
Masami Togo
正美 東郷
Hiroko Yuasa
裕子 湯浅
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Zeon Corp
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Nippon Zeon Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To obtain a fluorine-based solvent containing few microparticles and suitable for cleansing devices. <P>SOLUTION: The fluorine-based solvent containing few microparticles is obtained by filtering a fluorine-based solvent such as a hydrofluorocarbon with a filter made of a fluorine atom-free material. This fluorine-based solvent is effectively usable as a cleansing liquid for producing devices. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は弗素系溶剤の精製方法に関し、詳しくは、デバイス製造で使用される洗浄剤に好適な、微粒子が低減された弗素系溶剤を得るための弗素系溶剤の精製方法に関するものである。   The present invention relates to a method for purifying a fluorine-based solvent, and more particularly to a method for purifying a fluorine-based solvent for obtaining a fluorine-based solvent with reduced fine particles, which is suitable for a cleaning agent used in device manufacturing.

半導体デバイス、ディスプレイデバイス、メディカルデバイス、オプティカルデバイスなどのデバイス製造では、樹脂組成物や洗浄液など液状材料が広く用いられている。このデバイス製造に用いられる液状材料には、溶剤が使用される。そして、この溶剤として、近年、その疎水性の高さから、弗素系溶剤が注目されている。たとえば、ハイドロフルオロエーテルは、化学的機械的研磨などの基板表面処理用の溶剤として用いられている(特開2002−124504号公報)。また、ハイドロフルオロカーボンは、レジスト、ソルダーペーストなどの各種有機材料を除去するための洗浄成分として有用であることが知られている(特開平10−316596号公報)。
デバイスは、より高密度化、微細化が要求され、これに伴いデバイス製造に用いる液状材料には、微粒子の低減が求められている。したがって、液状材料を構成する成分の多くを占める溶剤に対する微粒子の低減が重要となっている。
In the manufacture of devices such as semiconductor devices, display devices, medical devices, and optical devices, liquid materials such as resin compositions and cleaning liquids are widely used. A solvent is used for the liquid material used for manufacturing the device. In recent years, a fluorine-based solvent has attracted attention as the solvent because of its high hydrophobicity. For example, hydrofluoroether is used as a solvent for substrate surface treatment such as chemical mechanical polishing (Japanese Patent Laid-Open No. 2002-124504). Hydrofluorocarbons are known to be useful as cleaning components for removing various organic materials such as resists and solder pastes (Japanese Patent Laid-Open No. 10-316596).
Devices are required to have higher density and miniaturization, and accordingly, liquid materials used for device manufacturing are required to reduce fine particles. Therefore, it is important to reduce fine particles with respect to the solvent that occupies most of the components constituting the liquid material.

特開2002−124504号公報JP 2002-124504 A 特開平10−316596号公報JP-A-10-316596

従来から、液状材料や溶剤の微粒子低減のために、フィルタろ過が採用されている。ろ過用のフィルタとしては、ポリテトラフルオロエチレン(PTFE)製フィルタがもっとも広く使用されている。しかし、本発明者らが検討した結果、汎用されているPTFE製フィルタでは、十分に微粒子を除去するのが困難であることが判った。
かかる知見に基づき、本発明者らが、ハイドロフルオロエーテルやハイドロフルオロカーボンなどの弗素系溶剤の微粒子を低減するべく鋭意検討した結果、ポリオレフィン製フィルタやポリアミド製フィルタなどの弗素原子を有しないフィルタを用いると、きわめて効率よく微粒子が除去できることを見出し、本発明の完成に至った。
Conventionally, filter filtration has been employed to reduce fine particles of liquid materials and solvents. As a filter for filtration, a filter made of polytetrafluoroethylene (PTFE) is most widely used. However, as a result of studies by the present inventors, it has been found that it is difficult to sufficiently remove fine particles with a widely used PTFE filter.
Based on this knowledge, the present inventors have intensively studied to reduce the fine particles of fluorine-based solvents such as hydrofluoroethers and hydrofluorocarbons. As a result, filters that do not have fluorine atoms such as polyolefin filters and polyamide filters are used. The inventors have found that the fine particles can be removed very efficiently, and have completed the present invention.

かくして本発明によれば、弗素系溶剤を、弗素原子を有しない材料からなるフィルタでろ過することを特徴とする弗素系溶剤の精製方法が提供される。この精製方法は、弗素系溶剤がハイドロフルオロカーボンのときに、著効を示す。
また、本発明によれば、0.2μm以上の微粒子の含有量が500個/ml以下である弗素系溶剤が提供される。この弗素系溶剤は、本発明の精製方法により容易に得ることができる。
Thus, according to the present invention, there is provided a method for purifying a fluorine-based solvent, wherein the fluorine-based solvent is filtered with a filter made of a material having no fluorine atoms. This purification method is particularly effective when the fluorine-based solvent is hydrofluorocarbon.
In addition, according to the present invention, there is provided a fluorine-based solvent in which the content of fine particles of 0.2 μm or more is 500 / ml or less. This fluorine-based solvent can be easily obtained by the purification method of the present invention.

本発明に用いる弗素系溶剤は、常圧、常温で液体の弗素原子を含有する化合物であり、たとえば、ハイドロフルオロカーボンやハイドロフルオロエーテルが挙げられ、ハイドロフルオロカーボンが本発明の精製方法に特に好適である。
ハイドロフルオロカーボン(以下、「HFC」ということがある)は、部分弗素化炭化水素であり、常温での操作性が良好であるため、特に環構造を有する環状のものが好ましい。
The fluorine-based solvent used in the present invention is a compound containing a fluorine atom that is liquid at normal pressure and room temperature, and examples thereof include hydrofluorocarbons and hydrofluoroethers. Hydrofluorocarbons are particularly suitable for the purification method of the present invention. .
Hydrofluorocarbons (hereinafter sometimes referred to as “HFCs”) are partially fluorinated hydrocarbons and have good operability at room temperature, and therefore cyclic hydrocarbons having a ring structure are particularly preferable.

ハイドロフルオロカーボンの具体例としては、式(I−a)や式(I−b)で表されるハイドロフルオロカーボンが挙げられる。特に式(I−b)で表されるものがより好ましく、式(I−b)で表されるHFCの中でも環状のHFCが特に好ましい。   Specific examples of the hydrofluorocarbon include hydrofluorocarbons represented by the formula (Ia) and the formula (Ib). In particular, those represented by the formula (Ib) are more preferred, and among the HFCs represented by the formula (Ib), a cyclic HFC is particularly preferred.

Figure 2005239615
Figure 2005239615

(いずれも、nは4以上6以下、mは1以上である) (In each case, n is 4 or more and 6 or less, and m is 1 or more)

式(I−a)で表されるHFCであって、常圧での沸点が50℃以上100℃以下であるものとして、例えば、CFCFHCFHCFCF、CFCFCHCHF、CHFCFCFCHF、CFCHFCHCF、CFCFCHFCHCF、CFCFCHCHFCF、CFCHFCHFCFCF、CFCFCFCHFCHCF、CFCFCFCHCHFCF、CFCFCHCHFCFなどが挙げられ、中でもCFCFCHFCHCFやCFCFCHCHFCFが好ましい As HFC represented by the formula (Ia), the boiling point at normal pressure is 50 ° C. or more and 100 ° C. or less. For example, CF 3 CFHCHFCF 2 CF 3 , CF 3 CF 2 CH 2 CH 2 F , CHF 2 CF 2 CF 2 CHF 2 , CF 3 CHFCH 2 CF 3 , CF 3 CF 2 CHFCH 2 CF 3 , CF 3 CF 2 CH 2 CHFCF 3 , CF 3 CHFCHFCF 2 CF 3 , CF 3 CF 2 CF 2 CFF CH 2 CF 3 , CF 3 CF 2 CF 2 CH 2 CHFCF 3 , CF 3 CF 2 CH 2 CHFCF 2 F 3 and the like are mentioned, among which CF 3 CF 2 CHFCH 2 CF 3 and CF 3 CF 2 CH 2 CHFCF 3 are preferable.

式(I−b)で表されるHFCであって、常圧での沸点が50℃以上100℃以下であるものとして、例えば、1,1,2,2,3−ペンタフルオロシクロブタン、1,1,2,2,3,3,4−ヘプタフルオロシクロペンタン、1,1,2,2,3,3,4,4,5−ノナフルオロシクロシクロヘキサンなど環状のハイドロフルオロカーボンが好ましい例として挙げられ、中でも1,1,2,2,3,3,4−ヘプタフルオロシクロペンタンが、本発明の方法によるろ過に好適である。   As an HFC represented by the formula (Ib) having a boiling point of 50 ° C. or more and 100 ° C. or less at normal pressure, for example, 1,1,2,2,3-pentafluorocyclobutane, Preferred examples include cyclic hydrofluorocarbons such as 1,2,2,3,3,4-heptafluorocyclopentane and 1,1,2,2,3,3,4,4,5-nonafluorocyclocyclohexane. Among them, 1,1,2,2,3,3,4-heptafluorocyclopentane is suitable for filtration by the method of the present invention.

HFCのような弗素系溶剤は、不燃性で、水存在下での安定性に優れ、無毒であり、オゾン破壊係数がゼロであることから、デバイス製造における洗浄剤成分としてなど、大量に使用する場合であっても、地球環境にやさしく、その回収、廃棄に対する処理コストも軽減できるという利点もある。   Fluorine-based solvents such as HFC are nonflammable, have excellent stability in the presence of water, are non-toxic, and have a zero ozone depletion coefficient. Even in this case, there is an advantage that it is friendly to the global environment and the processing cost for the recovery and disposal can be reduced.

この弗素化溶剤中の微粒子を除去する目的で、フィルタろ過を行う。フィルタの形状は特に制限されず、ろ過装置に合った市販のフィルタを採用すればよい。
本発明においては、このフィルタろ過に用いるフィルタとして、弗素原子を有しない材料からなるものを使用する。
弗素原子を有しない材料としては、ポリエチレンやポリプロピレンなどのポリオレフィン;ナイロン6、ナイロン66などのポリアミド;ポリスルホン;などの樹脂が挙げられる。これらの材料を用いたフィルタの具体例としては、日本マイクロリス社製超高分子量ポリエチレンフィルタ「オプチマイザー」シリーズ、「マイクロガード」シリーズ、KITZ社製ポリプロピレンフィルタ「ポリフィックス」シリーズ、日本ポール社製ナイロン66フィルタ「P−ナイロン」シリーズなどが挙げられる。
フィルタとして、カートリッジタイプのものを用いる場合、Oリングなどフィルタ以外のカートリッジ部材に弗素原子を有する材料が用いられたものであっても、フィルタのろ過機能を妨げないため、本発明の精製方法に用いることができる。
フィルタは1つだけ用いても、2つ以上を組み合わせて用いても良い。
フィルタを1つだけ使用してろ過する場合、フィルタの孔径は、通常0.1μm以下、好ましくは0.05μm以下、より好ましくは0.04μm以下である。2つ以上を組み合わせて用いる場合、フィルタの孔径はやや大きめの孔径でも十分な微粒子除去効果が得られるため、通常0.2μm以下、好ましくは0.1μm以下、より好ましくは0.05μm以下である。
Filter filtration is performed for the purpose of removing fine particles in the fluorinated solvent. The shape of the filter is not particularly limited, and a commercially available filter suitable for the filtration device may be adopted.
In the present invention, a filter made of a material having no fluorine atoms is used as the filter used for the filter filtration.
Examples of the material having no fluorine atom include resins such as polyolefins such as polyethylene and polypropylene; polyamides such as nylon 6 and nylon 66; and polysulfones. Specific examples of filters using these materials include ultra-high molecular weight polyethylene filters “Optimizer” series, “MicroGuard” series manufactured by Japan Microlith, polypropylene filters “Polyfix” series manufactured by KITZ, and manufactured by Pall Japan Nylon 66 filter “P-nylon” series and the like.
When a cartridge type filter is used, even if a material having fluorine atoms is used for a cartridge member other than a filter such as an O-ring, the filter does not interfere with the filtration function of the filter. Can be used.
Only one filter may be used, or two or more filters may be used in combination.
When filtering using only one filter, the pore size of the filter is usually 0.1 μm or less, preferably 0.05 μm or less, more preferably 0.04 μm or less. When two or more are used in combination, a sufficient fine particle removal effect can be obtained even if the pore diameter of the filter is slightly larger, so it is usually 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.05 μm or less. .

ろ過は、一般的な液体のろ過装置を用いることができる。また、薬液供給装置などの工業ライン上で、薬液となる弗素系溶剤が通過する個所にフィルタを設置することでろ過してもよい。
ろ過に当たっては生産性を向上させる観点から、加圧条件にて行うことができる。加える圧力は、用いるフィルタの孔径やろ過速度などを考慮して任意に設定すればよいが、通常0.001〜0.5MPa、好ましくは0.01〜0.3MPaである。
ろ過時の温度は、ろ過する弗素系溶剤の沸点を考慮して、任意に設定することができるが、その上限は、弗素系溶剤の沸点より、通常10℃以上低い温度、好ましくは15℃以上低い温度、より好ましくは20℃以上低い温度であって、その下限は、弗素系溶剤の凝固点より、通常5℃以上高い温度、好ましくは10℃以上高い温度、より好ましくは15℃以上高い温度である。
For the filtration, a general liquid filtration device can be used. Moreover, you may filter by installing a filter in the location where the fluorine-type solvent used as a chemical | medical solution passes on industrial lines, such as a chemical | medical solution supply apparatus.
Filtration can be performed under pressure from the viewpoint of improving productivity. The pressure to be applied may be arbitrarily set in consideration of the pore size of the filter to be used, the filtration speed, etc., but is usually 0.001 to 0.5 MPa, preferably 0.01 to 0.3 MPa.
The temperature at the time of filtration can be arbitrarily set in consideration of the boiling point of the fluorine-based solvent to be filtered, but the upper limit is usually 10 ° C. or more lower than the boiling point of the fluorine-based solvent, preferably 15 ° C. or more. A lower temperature, more preferably a temperature lower by 20 ° C. or more, and the lower limit thereof is a temperature that is usually 5 ° C. or higher, preferably a temperature higher by 10 ° C., more preferably a temperature higher by 15 ° C. is there.

本発明の方法によりろ過することで、弗素系溶剤の微粒子数を顕著に低減することができる。ハイドロフルオロカーボン(HFC)、特に環状のHFC、とりわけ1,1,2,2,3,3,4−ヘプタフルオロシクロペンタンは、その製造工程で多くの微粒子を含有する場合が多く、本発明の方法でろ過すれば、粒径が0.2μm以上の微粒子数を500個/ml以下、好ましくは100個/ml以下、より好ましくは50個/ml以下、特に好ましくは10個/ml以下、とりわけ好ましくは5個/ml以下に低減することができる。   By filtering by the method of the present invention, the number of fine particles of the fluorine-based solvent can be remarkably reduced. Hydrofluorocarbons (HFCs), especially cyclic HFCs, especially 1,1,2,2,3,3,4-heptafluorocyclopentane, often contain many fine particles in the production process, and the method of the present invention. The number of fine particles having a particle size of 0.2 μm or more is 500 / ml or less, preferably 100 / ml or less, more preferably 50 / ml or less, particularly preferably 10 / ml or less, particularly preferably. Can be reduced to 5 pieces / ml or less.

このような微粒子数の少ない弗素系溶剤をデバイス製造用の洗浄剤として用いる場合、弗素系溶剤のほかに界面活性剤、他の有機溶剤、オゾン、水、錯化剤などを併用することができる。これらの成分を弗素系溶剤に添加する時期は、弗素系溶剤のろ過前でもろ過後でもよいが、弗素系溶剤以外の成分からの微粒子除去が可能であることから、これらの成分を弗素系溶剤に添加してから、本発明のろ過を行うのが好ましい。
界面活性剤としては、特に、弗素系溶剤との相溶性が良好で、優れた洗浄性を容易に与えられることから、非イオン性界面活性剤が好ましく、特に、大日本インキ化学工業社製の界面活性剤メガファックシリーズ(F−177、F−443、F−470、F−472SF、R−08、R−30等)、三菱マテリアル社製EFシリーズ(122C、351、352、802等)、ネオス社製フタージェントシリーズ(250、251等)、ネオス社製FTXシリーズ(209F、208G、204D、207X等)等の弗素原子を含有する非イオン性の界面活性剤が好ましい。
これら界面活性剤の使用量は、洗浄液全量の通常10重量%以下、好ましくは0.00001〜5重量%、特に好ましくは0.0001〜1重量%である。
When such a fluorine-based solvent having a small number of fine particles is used as a cleaning agent for device production, a surfactant, other organic solvent, ozone, water, a complexing agent, etc. can be used in addition to the fluorine-based solvent. . The timing of adding these components to the fluorine-based solvent may be before or after the filtration of the fluorine-based solvent. However, since it is possible to remove fine particles from components other than the fluorine-based solvent, these components are added to the fluorine-based solvent. It is preferable to perform the filtration of the present invention after adding to the above.
As the surfactant, a nonionic surfactant is particularly preferable since it has good compatibility with a fluorine-based solvent and can easily provide excellent detergency, and particularly, manufactured by Dainippon Ink & Chemicals, Inc. Surfactant mega-fac series (F-177, F-443, F-470, F-472SF, R-08, R-30, etc.), Mitsubishi Materials Corporation EF series (122C, 351, 352, 802, etc.), Nonionic surfactants containing fluorine atoms, such as Neos's footgent series (250, 251, etc.), Neos FTX series (209F, 208G, 204D, 207X, etc.) are preferred.
The amount of these surfactants to be used is usually 10% by weight or less, preferably 0.00001 to 5% by weight, particularly preferably 0.0001 to 1% by weight, based on the total amount of the cleaning liquid.

本発明の洗浄液には、界面活性剤の弗素系溶剤への溶解性を良好にする目的で、有機溶剤を添加することができる。添加する有機溶剤としては、操作性の観点から常圧での沸点が好ましくは70〜250℃、より好ましくは75〜200℃、特に好ましくは80〜150℃のものを使用するのが良い。特に、イソプロパノール(沸点83℃)、2−ブタノール(沸点100℃)、メチルブタノール(沸点102℃)、プロピレングリコールモノメチルエーテル(120℃)、酢酸イソプロピル(沸点89℃)、シクロペンタノン(沸点131℃)、アセチルアセトン(沸点140℃)等が、乾燥効率の観点から好ましい。有機溶剤は単独で使用しても、2種以上を組み合わせて用いてもよい。添加量は、洗浄液全量に対して、0.1〜25重量%、好ましくは1〜20重量%である。この範囲であれば、引火性も低く、低表面張力が維持できるので好ましい。   An organic solvent can be added to the cleaning liquid of the present invention for the purpose of improving the solubility of the surfactant in the fluorine-based solvent. As an organic solvent to be added, an organic solvent having a boiling point at normal pressure of preferably 70 to 250 ° C., more preferably 75 to 200 ° C., particularly preferably 80 to 150 ° C. may be used from the viewpoint of operability. In particular, isopropanol (boiling point 83 ° C), 2-butanol (boiling point 100 ° C), methylbutanol (boiling point 102 ° C), propylene glycol monomethyl ether (120 ° C), isopropyl acetate (boiling point 89 ° C), cyclopentanone (boiling point 131 ° C) ), Acetylacetone (boiling point 140 ° C.) and the like are preferable from the viewpoint of drying efficiency. The organic solvent may be used alone or in combination of two or more. The addition amount is 0.1 to 25% by weight, preferably 1 to 20% by weight, based on the total amount of the cleaning liquid. If it is this range, since flammability is also low and low surface tension can be maintained, it is preferable.

洗浄液は、各成分を混合して、溶解させることによって調製される。調製方法に格別な制限はなく、各成分を同時に容器へ投入しても、任意の順番で投入しても良い。   The cleaning liquid is prepared by mixing and dissolving each component. There is no particular limitation on the preparation method, and the components may be charged simultaneously into the container or in any order.

この洗浄剤を用いてデバイスを洗浄する方法は、上述した洗浄液を基板表面に接触させることを特徴とする。本発明の洗浄液を基板表面に接触させる方法に格別な制限はなく、通常の基板洗浄方法と同様の方法を採用することができる。例えば、基板を洗浄液に浸漬する方法や、基板表面にスプレー等で噴霧する方法がある。物理的除去効果を付与するため、ブラシスクラブ洗浄や、高圧ジェット洗浄、二流体ノズル洗浄、メガソニック洗浄などを併用してもよい。
本発明の洗浄方法に用いる洗浄液の温度に格別な制限はないが、弗素系溶剤の融点や沸点を考慮して調整すればよく、通常は20℃以上、好ましくは25℃〜70℃、より好ましくは25〜60℃である。この範囲であれば、蒸発ロスと汚染物の除去性能とをバランスさせることができる。
A method of cleaning a device using this cleaning agent is characterized in that the above-described cleaning liquid is brought into contact with the substrate surface. There is no particular limitation on the method of bringing the cleaning liquid of the present invention into contact with the substrate surface, and a method similar to a normal substrate cleaning method can be employed. For example, there are a method of immersing the substrate in a cleaning liquid and a method of spraying the substrate surface with a spray or the like. In order to provide a physical removal effect, brush scrub cleaning, high-pressure jet cleaning, two-fluid nozzle cleaning, megasonic cleaning, or the like may be used in combination.
The temperature of the cleaning liquid used in the cleaning method of the present invention is not particularly limited, but may be adjusted in consideration of the melting point and boiling point of the fluorine-based solvent, and is usually 20 ° C. or higher, preferably 25 ° C. to 70 ° C., more preferably Is 25-60 ° C. Within this range, the evaporation loss and the contaminant removal performance can be balanced.

ここで基板は、半導体デバイス、ディスプレイデバイス、メディカルデバイス、オプティカルデバイスなどのデバイス製造に用いる基板である。デバイス製造工程における化学的機械的研磨などの表面処理によって、基板に由来する金属(その酸化物等を含む)や絶縁材料等からなる微小汚染物、又は、研磨剤成分に含まれる微小金属不純物などの研磨剤残渣などが基板表面に付着するため、これを除去するために本発明の弗素系溶剤を洗浄剤として用いることができる。   Here, the substrate is a substrate used for manufacturing a device such as a semiconductor device, a display device, a medical device, or an optical device. Surface contamination such as chemical mechanical polishing in the device manufacturing process, minute contaminants composed of metals (including oxides) and insulating materials derived from the substrate, or minute metal impurities contained in the abrasive component, etc. In order to remove the abrasive residue and the like of the substrate, the fluorine-based solvent of the present invention can be used as a cleaning agent.

以下の実施例を用いて、本発明を具体的に説明するが、本発明の内容がこれらに限定されるものではない。   The present invention will be specifically described with reference to the following examples, but the contents of the present invention are not limited thereto.

(実施例1〜5及び比較例1)
1,1,2,2,3,3,4−ヘプタフルオロシクロペンタン(粒径0.2μm以上の微粒子数は4059個/ml)を、23℃で、表1記載のフィルタを備えた加圧濾過装置を用い、表1記載のろ過圧力とフィルタ段数でろ過した後、粒径0.2μm以上の微粒子数を液中微粒子カウンター「KL−11A」(RION社製)を用いて測定した。
(Examples 1-5 and Comparative Example 1)
1,1,2,2,3,3,4-heptafluorocyclopentane (the number of fine particles having a particle size of 0.2 μm or more is 4059 / ml) at 23 ° C. under pressure equipped with the filter described in Table After filtration using a filtration device with the filtration pressure and the number of filter stages shown in Table 1, the number of fine particles having a particle size of 0.2 μm or more was measured using an in-liquid fine particle counter “KL-11A” (manufactured by RION).

Figure 2005239615
Figure 2005239615

この結果から、弗素原子を有しない材料からなるフィルタを用いると、ポリテトラフルオロエチレンのような弗素原子を有する材料からなるフィルタを用いた場合と比べ、弗素系溶剤の微粒子を顕著に低減することができることがわかる。
特に0.04μm以下のフィルタを用いると、2μm以上の微粒子数が1個と激減させられることがわかる(実施例2〜4)。
また、フィルタを2段に組み合わせて用いると、0.2μm以上の微粒子を実質的に完全に除去できることがわかる(実施例2)。
From this result, the use of a filter made of a material not containing fluorine atoms significantly reduces the fine particles of the fluorine-based solvent compared to the case where a filter made of a material containing fluorine atoms such as polytetrafluoroethylene is used. You can see that
In particular, it can be seen that when a filter of 0.04 μm or less is used, the number of fine particles of 2 μm or more is drastically reduced to 1 (Examples 2 to 4).
Further, it can be seen that when the filters are used in combination in two stages, the fine particles of 0.2 μm or more can be substantially completely removed (Example 2).

Claims (8)

弗素系溶剤を、弗素原子を有しない材料からなるフィルタでろ過することを特徴とする弗素系溶剤の精製方法。 A method for purifying a fluorine-based solvent, comprising filtering the fluorine-based solvent with a filter made of a material having no fluorine atoms. 弗素系溶剤が、ハイドロフルオロカーボンである請求項1記載の弗素系溶剤の精製方法。 2. The method for purifying a fluorine-based solvent according to claim 1, wherein the fluorine-based solvent is hydrofluorocarbon. 弗素原子を有しない材料が、ポリオレフィン又はポリアミドである請求項1記載の弗素系溶剤の精製方法。 2. The method for purifying a fluorine-based solvent according to claim 1, wherein the material having no fluorine atom is polyolefin or polyamide. フィルタが、0.05μm以下の孔径のものである請求項1記載の弗素系溶剤の精製方法。 The method for purifying a fluorine-based solvent according to claim 1, wherein the filter has a pore size of 0.05 μm or less. 0.2μm以上の微粒子の含有量が500個/ml以下である弗素系溶剤。 A fluorine-based solvent having a content of fine particles of 0.2 μm or more of 500 particles / ml or less. 弗素系溶剤が、ハイドロフルオロカーボンである請求項5記載の弗素化溶剤。 6. The fluorinated solvent according to claim 5, wherein the fluorinated solvent is hydrofluorocarbon. 請求項1〜4のいずれかの方法により精製されたものである請求項5記載の弗素系溶剤。 The fluorine-based solvent according to claim 5, which has been purified by the method according to any one of claims 1 to 4. 請求項5記載の弗素系溶剤を含んでなるデバイス製造用洗浄液。
A cleaning liquid for device production comprising the fluorine-based solvent according to claim 5.
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Cited By (4)

* Cited by examiner, † Cited by third party
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WO2007029767A1 (en) * 2005-09-09 2007-03-15 Tokyo Ohka Kogyo Co., Ltd. Washing agent for photolithography and method of forming photoresist pattern using the same
WO2020031732A1 (en) * 2018-08-10 2020-02-13 日本ゼオン株式会社 Method for refining fluorine-based-solvent-containing article, and refined fluorine-based-solvent-containing article
KR20210053873A (en) 2018-08-31 2021-05-12 니폰 제온 가부시키가이샤 Solvent purification method
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007029767A1 (en) * 2005-09-09 2007-03-15 Tokyo Ohka Kogyo Co., Ltd. Washing agent for photolithography and method of forming photoresist pattern using the same
WO2020031732A1 (en) * 2018-08-10 2020-02-13 日本ゼオン株式会社 Method for refining fluorine-based-solvent-containing article, and refined fluorine-based-solvent-containing article
CN112236216A (en) * 2018-08-10 2021-01-15 日本瑞翁株式会社 Method for purifying fluorine-containing solvent-containing substance and purified product of fluorine-containing solvent
KR20210035800A (en) 2018-08-10 2021-04-01 니폰 제온 가부시키가이샤 Fluorine-based solvent-containing material purification method and fluorine-based solvent-containing purified product
JPWO2020031732A1 (en) * 2018-08-10 2021-09-24 日本ゼオン株式会社 Fluorine-based solvent-containing purification method and fluorine-based solvent-containing refined product
KR20210053873A (en) 2018-08-31 2021-05-12 니폰 제온 가부시키가이샤 Solvent purification method
WO2022004217A1 (en) * 2020-06-30 2022-01-06 富士フイルムエレクトロニクスマテリアルズ株式会社 Method for producing treatment liquid
JP7438357B2 (en) 2020-06-30 2024-02-26 富士フイルム株式会社 Processing liquid manufacturing method

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