TW202019537A - Method for solvent purification - Google Patents
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Abstract
Description
本發明係關於用以減少溶劑中所包含之微粒子之溶劑的純化方法。The present invention relates to a purification method of a solvent for reducing fine particles contained in a solvent.
在進行半導體器件的製造或清洗時，會使用微粒子等雜質經減少的溶劑。於是，專利文獻1中，已提案有具備已備有過濾器的過濾手段與金屬吸附手段之有機溶劑的純化裝置，作為用以去除有機溶劑中之金屬雜質的裝置。When manufacturing or cleaning semiconductor devices, a solvent with reduced impurities such as fine particles is used. Therefore, Patent Document 1 has proposed a purification device for an organic solvent provided with a filtering means equipped with a filter and a metal adsorption means as a device for removing metal impurities in the organic solvent.
並且，就減少環境負荷的觀點而言，包含氟系溶劑的有機溶劑會使用在於上已述之半導體器件的製造或清洗。而且，專利文獻2中，已提案有利用由不具氟原子之材料而成的過濾器將氟系溶劑過濾之氟系溶劑的純化方法。根據此純化方法，可有效去除粒徑200 nm以上的微粒子。In addition, from the viewpoint of reducing the environmental load, the organic solvent containing a fluorine-based solvent is used in the manufacture or cleaning of the semiconductor device described above. Furthermore,
『專利文獻』
《專利文獻1》：日本專利公開第2016-73922號公報
《專利文獻2》：日本專利公開第2005-239615號公報"Patent Literature"
"Patent Document 1": Japanese Patent Publication No. 2016-73922
"
然而，在上述以往之純化裝置或純化方法中，由於利用過濾器過濾以將溶劑純化，故有來自過濾器的溶出物混入經純化的溶劑，而由此在溶劑中生成微粒子之虞。是故，要求不使用過濾器即減少溶劑中的微粒子之溶劑的純化方法。並且，用於半導體器件之製造或清洗的溶劑，在減少該溶劑中所包含之微粒子──具體而言係粒徑100 nm以下的微粒子──這點上，有改善的餘地。However, in the above-described conventional purification device or purification method, since the solvent is purified by filtering with a filter, there is a possibility that fine particles are generated in the solvent by mixing the eluate from the filter with the purified solvent. Therefore, a purification method of a solvent that reduces particulates in the solvent without using a filter is required. In addition, the solvent used in the manufacture or cleaning of semiconductor devices has room for improvement in reducing fine particles contained in the solvent—specifically, fine particles having a particle diameter of 100 nm or less.
於是，本發明之目的在於提供係為不使用過濾器即將溶劑純化的方法，且係用以減少該溶劑中的微粒子之溶劑的純化方法。Therefore, an object of the present invention is to provide a method for purifying a solvent without using a filter, and a method for purifying a solvent for reducing fine particles in the solvent.
本發明人等為能解決上述問題而潛心進行研究。然後，本發明人等發現，若使用構成蒸餾設備之各構成部件之液體接觸面及氣體接觸面的表面為指定粗糙度的蒸餾設備，且在指定氣體流速下將溶劑蒸餾，則可將溶劑中所包含之微粒子──尤其係粒徑30 nm以上且100 nm以下的微粒子──有效去除，進而完成本發明。The inventors have made intensive studies to solve the above problems. Then, the inventors found that if the surface of the liquid contact surface and the gas contact surface of each component constituting the distillation apparatus is a distillation apparatus of a specified roughness, and the solvent is distilled at a specified gas flow rate, the solvent can be The contained microparticles—particularly those with a particle size of 30 nm or more and 100 nm or less—are effectively removed, thereby completing the present invention.
亦即，此發明係以順利解決上述問題為目的者，本發明之溶劑的純化方法之特徵在於，其係利用包含蒸餾器的蒸餾設備將溶劑蒸餾而獲得純化溶劑之溶劑的純化方法，其中將構成前述蒸餾設備之各構成部件之液體接觸面及氣體接觸面的表面之中心平均粗糙度（Ra）做成1 μm以下，且將蒸餾前述溶劑時的氣體流速定為100 mm／秒鐘以下。如此，若將構成蒸餾設備之各構成部件之液體接觸面及氣體接觸面的表面之中心平均粗糙度（Ra）做成1 μm以下，且將蒸餾溶劑時的氣體流速定為100 mm／秒鐘以下，則可獲得微粒子──尤其係粒徑100 nm以下之微粒子──經減少的純化溶劑。That is, this invention is for the purpose of smoothly solving the above-mentioned problems. The method for purifying a solvent of the present invention is characterized in that it is a method for purifying a solvent to obtain a purified solvent by distilling the solvent using a distillation apparatus including a distiller. The center roughness (Ra) of the surface of the liquid contact surface and the gas contact surface constituting each component of the distillation equipment is 1 μm or less, and the gas flow rate during the distillation of the solvent is set to 100 mm/sec or less. In this way, if the center average roughness (Ra) of the surface of the liquid contact surface and the gas contact surface constituting each component of the distillation apparatus is made 1 μm or less, and the gas flow rate when distilling the solvent is set to 100 mm/sec Below, you can obtain fine particles-especially those with a particle size of less than 100 nm-reduced purification solvent.
此外，在本說明書中，所謂「液體接觸面」，係謂「係構成蒸餾設備之構成部件的表面，並得與液狀之溶劑或經液化之溶劑接觸」的表面。並且，所謂「氣體接觸面」，係謂「係構成蒸餾設備之構成部件的表面，並得與經汽化之溶劑接觸」的表面。In addition, in this specification, the "liquid contact surface" refers to a surface that "composes the surface of the component parts of the distillation apparatus and comes into contact with a liquid solvent or a liquefied solvent." In addition, the so-called "gas contact surface" refers to the "surface that constitutes the component parts of the distillation equipment and must be in contact with the vaporized solvent".
並且，在本發明中，「中心平均粗糙度（Ra）」係表示表面之粗糙度的指標，由日本工業標準JIS B0601:2013所規定。In addition, in the present invention, the "center average roughness (Ra)" is an index indicating the roughness of the surface and is prescribed by the Japanese Industrial Standard JIS B0601:2013.
而且，在本發明中，「氣體流速」可依據下述式求得。 氣體流速（mm／秒鐘）＝［每單位時間自蒸餾器減少之溶劑的液體量（mm3 ／秒鐘）／蒸餾器之液面面積（mm2 ）］Furthermore, in the present invention, the "gas flow rate" can be obtained according to the following formula. Gas flow rate (mm/sec) = [the amount of solvent liquid reduced from the distiller per unit time (mm 3 /sec) / liquid area of the distiller (mm 2 )]
於此，在本發明之溶劑的純化方法中，以前述溶劑包含選自由烴類、醇類、醚類、酮類、醯胺類、酯類、腈類、氫氟碳類、氫氟醚類、全氟碳類及氫氟烯烴類而成之群組之1種以上為佳。若溶劑包含選自於上已述之群組之1種以上，則可將藉由本發明之純化方法獲得之純化溶劑合適作為用於細微之半導體器件之製造或清洗的溶劑來使用。Here, in the method for purifying a solvent of the present invention, the aforementioned solvent contains a hydrocarbon, alcohol, ether, ketone, amide, ester, nitrile, hydrofluorocarbon, hydrofluoroether , Perfluorocarbons and hydrofluoroolefins are preferred. If the solvent contains one or more kinds selected from the above-mentioned group, the purified solvent obtained by the purification method of the present invention can be suitably used as a solvent for the manufacture or cleaning of fine semiconductor devices.
而且，本發明之溶劑的純化方法，以前述溶劑包含1,1,2,2,3,3,4-七氟環戊烷為佳。1,1,2,2,3,3,4-七氟環戊烷為不燃性，且為低毒性，在水存在下的穩定性優異，臭氧耗竭潛勢為零，於作為溶劑操作方面具有適度的沸點。因此，若使用1,1,2,2,3,3,4-七氟環戊烷作為溶劑，則藉由本發明之溶劑的純化方法，可有效率獲得環境負荷經減少的純化溶劑。Furthermore, in the method for purifying the solvent of the present invention, it is preferred that the aforementioned solvent contains 1,1,2,2,3,3,4-heptafluorocyclopentane. 1,1,2,2,3,3,4-heptafluorocyclopentane is non-combustible, low toxicity, excellent stability in the presence of water, ozone depletion potential is zero, and has the ability to operate as a solvent Moderate boiling point. Therefore, if 1,1,2,2,3,3,4-heptafluorocyclopentane is used as a solvent, the solvent purification method of the present invention can efficiently obtain a purified solvent with reduced environmental load.
再者，本發明之溶劑的純化方法，以前述溶劑為共沸組成物或類共沸組成物為佳。若溶劑為共沸組成物或類共沸組成物，則溶劑的組成不因蒸餾而變化，故可較有效率進行溶劑的純化。Furthermore, in the method for purifying the solvent of the present invention, it is preferable that the aforementioned solvent is an azeotropic composition or azeotrope-like composition. If the solvent is an azeotropic composition or an azeotrope-like composition, the composition of the solvent does not change due to distillation, so the solvent can be purified more efficiently.
此外，在本發明中，所謂「共沸組成物」，意謂處於與液相平衡之氣相顯示出與液相相同之組成的混合物，所謂「類共沸組成物」，意謂處於與液相平衡之氣相顯示出與液相類似之組成的混合物。In addition, in the present invention, the so-called "azeotropic composition" means a mixture in which the gas phase in equilibrium with the liquid phase shows the same composition as the liquid phase, and the so-called "azeotrope-like composition" means that The gas phase in equilibrium shows a mixture with a composition similar to the liquid phase.
而且，本發明之溶劑的純化方法，以前述共沸組成物包含氫氟碳類與醇類為佳，以包含1,1,2,2,3,3,4-七氟環戊烷與三級戊醇為較佳。若使用包含氫氟碳類與醇類的共沸組成物，則可較穩定進行溶劑的純化。再者，包含1,1,2,2,3,3,4-七氟環戊烷與三級戊醇的共沸組成物為不燃性。是故，若使用包含1,1,2,2,3,3,4-七氟環戊烷與三級戊醇的共沸組成物作為溶劑，則可更穩定進行溶劑的純化。Moreover, the method for purifying the solvent of the present invention is preferably such that the aforementioned azeotropic composition contains hydrofluorocarbons and alcohols, and contains 1,1,2,2,3,3,4-heptafluorocyclopentane and tri Grade pentanol is preferred. If an azeotropic composition containing hydrofluorocarbons and alcohols is used, the solvent can be purified more stably. In addition, the azeotropic composition containing 1,1,2,2,3,3,4-heptafluorocyclopentane and tertiary amyl alcohol is nonflammable. Therefore, if an azeotropic composition containing 1,1,2,2,3,3,4-heptafluorocyclopentane and tertiary amyl alcohol is used as a solvent, the purification of the solvent can be performed more stably.
根據本發明之溶劑的純化方法，可不使用過濾器即獲得微粒子經減少的純化溶劑。According to the method for purifying a solvent of the present invention, a purified solvent with reduced fine particles can be obtained without using a filter.
以下依據圖式詳細說明本發明之溶劑的純化方法。The method for purifying the solvent of the present invention will be described in detail based on the drawings.
於此，本發明之溶劑的純化方法係利用蒸餾設備將溶劑純化而獲得純化溶劑的方法，可用於包含微粒子之溶劑的純化。而且，藉由本發明之溶劑的純化方法獲得之純化溶劑，並無特別受限，舉例而言，可合適作為用於半導體器件之製造或清洗的溶劑來使用。此外，本發明之溶劑的純化方法通常係在無塵室內實施者。Here, the solvent purification method of the present invention is a method of obtaining a purified solvent by purifying the solvent using a distillation apparatus, and can be used for purification of a solvent containing fine particles. Furthermore, the purified solvent obtained by the solvent purification method of the present invention is not particularly limited, and for example, it can be suitably used as a solvent for manufacturing or cleaning semiconductor devices. In addition, the solvent purification method of the present invention is usually carried out in a clean room.
（溶劑的純化方法）(Solvent purification method)
本發明之溶劑的純化方法中，將構成蒸餾設備之各構成部件之液體接觸面及氣體接觸面的表面做成指定粗糙度，並使用該蒸餾設備在指定氣體流速下將溶劑蒸餾而獲得純化溶劑。In the solvent purification method of the present invention, the surfaces of the liquid contact surface and the gas contact surface of each component constituting the distillation equipment are made to a specified roughness, and the distillation equipment is used to distill the solvent at a specified gas flow rate to obtain a purified solvent .
〈蒸餾設備〉<Distillation equipment>
於此，圖1繪示在本發明之溶劑的純化方法中得使用之蒸餾設備的概略結構。Here, FIG. 1 illustrates a schematic structure of a distillation apparatus used in the solvent purification method of the present invention.
圖1所示之蒸餾設備10具備：將溶劑加熱而汽化的蒸餾器1、將已汽化之溶劑冷卻而液化的冷凝器2、儲存已液化之溶劑的接收器3、將蒸餾器1與冷凝器2接續的第1配管及第1接頭（皆未繪示）、將冷凝器2與接收器3接續的第2配管及第2接頭（皆未繪示）、設於蒸餾器1與冷凝器2之間以調節往冷凝器2之已汽化之溶劑之流動的第1閥（未繪示），以及設於冷凝器2與接收器3之間以調節往接收器3之已液化之溶劑之流動的第2閥（未繪示），作為構成蒸餾設備10的構成部件。The
而且，蒸餾器1、冷凝器2、接收器3、第1配管及第2配管、第1接頭及第2接頭、第1閥及第2閥皆以液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）為1 μm以下為必要。再者，液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）以0.7 μm以下為佳，以0.5 μm以下為較佳，並且，以0.001 μm以上為佳，以0.002 μm以上為較佳。如此，若構成蒸餾設備10之各構成部件之液體接觸面及氣體接觸面的表面之中心平均粗糙度（Ra）為1 μm以下，則可抑制吸附於各構成部件之液體接觸面及氣體接觸面之表面的雜質或粒子混入已汽化之溶劑或已液化之溶劑中。In addition, the distiller 1, the
此外，作為得構成液體接觸面及氣體接觸面的材質，只要係能藉由表面處理將中心平均粗糙度（Ra）調整為1 μm以下的材質，即不特別受限，可列舉例如：不鏽鋼、含鋁不鏽鋼、鋁合金、鋁、銅等。而且，作為不鏽鋼，可列舉例如：沃斯田鐵系、亞鐵酸鹽系、沃斯田鐵―亞鐵酸鹽系及麻田散鐵系不鏽鋼等。再者，作為沃斯田鐵系之不鏽鋼，合適使用例如SUS（stainless steel）304、SUS304L、SUS316、SUS316L、SUS317、SUS317L等。In addition, the material constituting the liquid contact surface and the gas contact surface is not particularly limited as long as it can adjust the center average roughness (Ra) to 1 μm or less by surface treatment, and examples include stainless steel, Aluminum-containing stainless steel, aluminum alloy, aluminum, copper, etc. Furthermore, examples of the stainless steel include, for example, Vostian iron-based, ferrite-based, Vostian iron-ferrite-based, and Matian loose-iron-based stainless steel. Furthermore, as the stainless steel of the Vostian iron system, for example, SUS (stainless steel) 304, SUS304L, SUS316, SUS316L, SUS317, SUS317L, etc. are suitably used.
並且，作為用以獲得中心平均粗糙度（Ra）為1 μm以下之液體接觸面及氣體接觸面的表面處理方法，並不特別受限，可合適使用例如酸洗、機械研磨、帶式研磨、滾筒研磨、擦光（buff）研磨、磨料流動研磨、研光（lap）研磨、壓光（burnish）研磨、化學研磨、電解研磨、電解複合研磨等。其中，就「藉由較為降低液體接觸面及氣體接觸面的表面之中心平均粗糙度（Ra）之值，而較為抑制吸附於液體接觸面及氣體接觸面之表面的雜質或粒子混入已汽化或已液化的溶劑中」的觀點而言，以電解研磨或電解複合研磨作為表面處理方法為佳。In addition, as a surface treatment method for obtaining a liquid contact surface and a gas contact surface with a center average roughness (Ra) of 1 μm or less, it is not particularly limited, and for example, pickling, mechanical grinding, belt grinding, Barrel grinding, buff grinding, abrasive flow grinding, lap grinding, burnish grinding, chemical grinding, electrolytic grinding, electrolytic compound grinding, etc. Among them, "by reducing the value of the center average roughness (Ra) of the surface of the liquid contact surface and the gas contact surface, it is more suppressed that the impurities or particles adsorbed on the surface of the liquid contact surface and the gas contact surface are mixed into the vaporized or From the viewpoint of "liquefied solvent", electrolytic polishing or electrolytic composite polishing is preferred as the surface treatment method.
此外，在構成蒸餾設備10之各構成部件中，液體接觸面及氣體接觸面的表面與液體接觸面及氣體接觸面之表面以外的其他部分可由彼此相異之材質構成，亦可由相同之材質構成。In addition, among the constituent parts constituting the
再者，在液體接觸面及氣體接觸面的表面亦可形成氧化物鈍態膜。於此，氧化物鈍態膜並不特別受限，但以由選自由氧化鋁、氧化鉻、氧化鈦、氧化釔及氧化鎂而成之群組之至少1種氧化物而成為佳，以由氧化鋁、氧化鉻而成為較佳。藉由在液體接觸面及氣體接觸面的表面形成氧化物鈍態膜，而更降低液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）之值，可更抑制吸附於液體接觸面及氣體接觸面之表面的雜質或粒子混入已汽化或已液化之溶劑中，同時可提升液體接觸面及氣體接觸面之表面的耐蝕性。Furthermore, an oxide passive film can also be formed on the surface of the liquid contact surface and the gas contact surface. Here, the oxide passive film is not particularly limited, but it is preferably made of at least one oxide selected from the group consisting of aluminum oxide, chromium oxide, titanium oxide, yttrium oxide, and magnesium oxide. Alumina and chromium oxide are preferred. By forming an oxide passive film on the surface of the liquid contact surface and the gas contact surface, the value of the center average roughness (Ra) of the surface of the liquid contact surface and the gas contact surface is further reduced, and the adsorption on the liquid contact surface can be more suppressed The impurities or particles on the surface of the gas contact surface are mixed into the vaporized or liquefied solvent, and at the same time, the corrosion resistance of the surface of the liquid contact surface and the gas contact surface can be improved.
於此，在構成部件之液體接觸面及氣體接觸面的表面形成氧化物鈍態膜的方法，並不特別受限，可舉出例如使氧化性氣體接觸於構成部件之液體接觸面及氣體接觸面的表面並進行熱處理的方法，具體而言，可舉出例如國際專利公開第2005/088185號所記載之方法。Here, the method of forming an oxide passive film on the surfaces of the liquid contact surface and the gas contact surface of the component is not particularly limited, and examples thereof include contacting the oxidizing gas with the liquid contact surface and the gas contact of the component The method of performing heat treatment on the surface of the surface, specifically, for example, the method described in International Patent Publication No. 2005/088185.
此外，在本發明之溶劑的純化方法中使用之蒸餾設備只要至少包含蒸餾器，且構成蒸餾設備之各構成部件之液體接觸面及氣體接觸面的表面之中心平均粗糙度（Ra）為1 μm以下，即不特別受限。因此，蒸餾設備除了圖1所示之構成部件之外，得更包含例如液體接觸面及氣體接觸面的表面之中心平均粗糙度（Ra）為1 μm以下的壓力計、液位計、溫度計等。In addition, the distillation equipment used in the solvent purification method of the present invention only needs to include at least a distiller, and the center average roughness (Ra) of the surfaces of the liquid contact surface and the gas contact surface constituting each component of the distillation equipment is 1 μm The following is not particularly restricted. Therefore, in addition to the components shown in FIG. 1, the distillation equipment further includes, for example, a pressure gauge, a liquid level gauge, a thermometer, etc. whose center average roughness (Ra) of the surface of the liquid contact surface and the gas contact surface is 1 μm or less .
〈溶劑〉<Solvent>
而且，本發明之溶劑的純化方法中使用之溶劑通常係包含微粒子者。於此，溶劑並不特別受限，但以包含選自由例如烴類、醇類、醚類、酮類、醯胺類、酯類、腈類、氫氟碳類、氫氟醚類、全氟碳類及氫氟烯烴類而成之群組之1種以上為佳。若使用包含選自於上已述之群組之1種以上的溶劑，則可將藉由本發明之純化方法獲得的純化溶劑合適作為用於細微之半導體器件之製造或清洗的溶劑來使用。In addition, the solvent used in the solvent purification method of the present invention usually contains fine particles. Here, the solvent is not particularly limited, but may be selected from hydrocarbons, alcohols, ethers, ketones, amides, esters, nitriles, hydrofluorocarbons, hydrofluoroethers, perfluoro One or more of the group consisting of carbons and hydrofluoroolefins is preferred. If one or more solvents selected from the group described above are used, the purified solvent obtained by the purification method of the present invention can be suitably used as a solvent for the manufacture or cleaning of fine semiconductor devices.
而且，作為烴類，可列舉例如：己烷、環己烷、苯、甲苯、二甲苯等。In addition, examples of the hydrocarbons include hexane, cyclohexane, benzene, toluene, and xylene.
並且，作為醇類，可列舉例如：環戊醇、丁醇、異丙醇、2-丁醇、甲基丁醇、三級戊醇、丙醇、庚醇、己醇、癸醇、壬醇等脂族醇類，或苄醇、甲基苄醇、乙基苄醇、甲氧基苄醇、乙氧基苄醇、羥基苄醇、3-苯丙醇、異丙苯醇、糠醇、苯乙醇、甲氧基苯乙醇、乙氧基苯乙醇等芳族醇類等。In addition, examples of alcohols include cyclopentanol, butanol, isopropanol, 2-butanol, methylbutanol, tertiary amyl alcohol, propanol, heptanol, hexanol, decanol, and nonanol. Aliphatic alcohols such as benzyl alcohol, methyl benzyl alcohol, ethyl benzyl alcohol, methoxy benzyl alcohol, ethoxy benzyl alcohol, hydroxy benzyl alcohol, 3-phenylpropanol, cumene alcohol, furfuryl alcohol, benzene Aromatic alcohols such as ethanol, methoxyphenethyl alcohol, ethoxyphenethyl alcohol, etc.
並且，作為醚類，可列舉例如：環戊基甲基醚、丙二醇一甲基醚、二丙二醇一丙基醚、二丙二醇一甲基醚、二丙二醇一丁基醚、3-甲氧基-3-甲基丁醇等二元醇醚類等。In addition, examples of the ethers include cyclopentyl methyl ether, propylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, and 3-methoxy- Glycol ethers such as 3-methylbutanol.
而且，作為酮類，可列舉例如：環戊酮、甲基乙基酮、甲基異丁基酮、環己酮等。Moreover, examples of the ketones include cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
並且，作為醯胺類，可列舉例如：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、六甲基磷三醯胺、N-甲基吡咯啶酮等。In addition, examples of the amides include N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoramide, and N-methylpyrrolidone.
而且，作為酯類，可列舉例如：乙酸丁酯、乙酸異丙酯、丙酸丁酯、己酸甲酯、己酸丁酯等。In addition, examples of the esters include butyl acetate, isopropyl acetate, butyl propionate, methyl caproate, and butyl caproate.
並且，作為腈類，可列舉例如：乙腈、苄腈等。In addition, examples of the nitriles include acetonitrile and benzonitrile.
而且，作為氫氟碳類，可列舉例如：由下述式（1）或下述式（2）所示之氫氟碳類。Furthermore, examples of the hydrofluorocarbons include hydrofluorocarbons represented by the following formula (1) or the following formula (2).
Cn Hm F2n ＋ 2 － m ・・・（1） Cn Hm F2n － m ・・・（2）C n H m F 2n ＋ 2 － m・・・(1) C n H m F 2n － m・・・(2)
上述式（1）及（2）中，n皆為4以上且6以下，m皆為1以上並以3以上為佳。In the above formulas (1) and (2), n is 4 or more and 6 or less, and m is 1 or more and preferably 3 or more.
並且，作為由上述式（1）所示之氫氟碳類，並非特別受限者，但以1,1,1,3,3-五氟丁烷為佳。In addition, the hydrofluorocarbons represented by the above formula (1) are not particularly limited, but 1,1,1,3,3-pentafluorobutane is preferred.
而且，作為由上述式（2）所示之氫氟碳類，可列舉例如：1,1,2,2,3-五氟環丁烷、1,1,2,2,3,3,4-七氟環戊烷、1,1,2,2,3,3,4,4,5-九氟環己烷等。Furthermore, examples of the hydrofluorocarbons represented by the above formula (2) include, for example, 1,1,2,2,3-pentafluorocyclobutane, 1,1,2,2,3,3,4 -Heptafluorocyclopentane, 1,1,2,2,3,3,4,4,5-nonafluorocyclohexane, etc.
並且，作為氫氟醚類，可列舉例如：甲基全氟丁基醚、甲基全氟異丁基醚、甲基全氟戊基醚、乙基全氟丁基醚、乙基全氟異丁基醚等。In addition, examples of the hydrofluoroethers include methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, methyl perfluoropentyl ether, ethyl perfluorobutyl ether, and ethyl perfluoroisobutyl ether. Butyl ether and so on.
而且，作為全氟碳類，可列舉例如：全氟己烷、全氟庚烷等。Moreover, examples of the perfluorocarbons include perfluorohexane and perfluoroheptane.
並且，作為氫氟烯烴類，可舉出例如：1-氯-3,3,3-三氟丙烯等。In addition, examples of the hydrofluoroolefins include 1-chloro-3,3,3-trifluoropropene and the like.
而且，在於上已述之溶劑之中，以使用氫氟碳類為較佳。氫氟碳類為不燃性，在水存在下之穩定性優異，低毒性，且臭氧耗竭潛勢為零。是故，若溶劑為氫氟碳類，則可合適使用藉由本發明之溶劑的純化方法獲得之純化溶劑作為環境負荷經減少的溶劑。再者，氫氟碳類以環狀之氫氟碳類為較佳，就於作為溶劑操作方面具有適度之沸點的觀點而言，以1,1,2,2,3,3,4-七氟環戊烷為更佳。Among the solvents mentioned above, the use of hydrofluorocarbons is preferred. Hydrofluorocarbons are non-combustible, have excellent stability in the presence of water, have low toxicity, and have zero ozone depletion potential. Therefore, if the solvent is a hydrofluorocarbon, the purified solvent obtained by the solvent purification method of the present invention can be suitably used as a solvent with reduced environmental load. Furthermore, the hydrofluorocarbons are preferably cyclic hydrofluorocarbons, and from the viewpoint of having a moderate boiling point when operating as a solvent, 1,1,2,2,3,3,4-seven Fluorocyclopentane is better.
此外，於上已述之溶劑，可單獨使用1種或混合2種以上使用。In addition, the solvents described above can be used alone or in combination of two or more.
再者，本發明之溶劑的純化方法中使用的溶劑以共沸組成物或類共沸組成物為更佳。若溶劑為共沸組成物或類共沸組成物，則溶劑的組成不因蒸餾而變化，故可較有效率進行溶劑的純化。Furthermore, the solvent used in the solvent purification method of the present invention is more preferably an azeotropic composition or an azeotrope-like composition. If the solvent is an azeotropic composition or an azeotrope-like composition, the composition of the solvent does not change due to distillation, so the solvent can be purified more efficiently.
此外，共沸組成物或類共沸組成物可藉由適當組合種類或濃度等相異之2種以上的溶劑來製備。In addition, the azeotropic composition or azeotrope-like composition can be prepared by appropriately combining two or more kinds of solvents having different types or concentrations.
於此，共沸組成物或類共沸組成物，並不特別受限，但以包含氫氟碳類與醇類為較佳。若使用包含氫氟碳類與醇類的共沸組成物，則可較穩定進行溶劑的純化。而且，共沸組成物以包含1,1,2,2,3,3,4-七氟環戊烷與三級戊醇為更佳。包含1,1,2,2,3,3,4-七氟環戊烷與三級戊醇的共沸組成物為不燃性。是故，若使用包含1,1,2,2,3,3,4-七氟環戊烷與三級戊醇的共沸組成物作為溶劑，則可更穩定進行溶劑的純化。Here, the azeotropic composition or azeotrope-like composition is not particularly limited, but it is preferably composed of hydrofluorocarbons and alcohols. If an azeotropic composition containing hydrofluorocarbons and alcohols is used, the solvent can be purified more stably. Furthermore, the azeotropic composition preferably includes 1,1,2,2,3,3,4-heptafluorocyclopentane and tertiary amyl alcohol. The azeotropic composition containing 1,1,2,2,3,3,4-heptafluorocyclopentane and tertiary amyl alcohol is nonflammable. Therefore, if an azeotropic composition containing 1,1,2,2,3,3,4-heptafluorocyclopentane and tertiary amyl alcohol is used as a solvent, the purification of the solvent can be performed more stably.
而且，共沸組成物中所包含之1,1,2,2,3,3,4-七氟環戊烷與三級戊醇的質量比，並不特別受限，但1,1,2,2,3,3,4-七氟環戊烷與三級戊醇的質量比（1,1,2,2,3,3,4-七氟環戊烷／三級戊醇）以94～98／6～2為佳，以95～97／5～3為較佳，以得形成共沸組成物之質量比的95.8／4.2為更佳。Moreover, the mass ratio of 1,1,2,2,3,3,4-heptafluorocyclopentane to tertiary amyl alcohol contained in the azeotropic composition is not particularly limited, but 1,1,2 , The mass ratio of 2,2,3,3,4-heptafluorocyclopentane to tertiary amyl alcohol (1,1,2,2,3,3,4-heptafluorocyclopentane/tertiary amyl alcohol) is 94 It is preferably ~98/6-6~2, preferably 95~97/5~3, and more preferably 95.8/4.2 for forming the mass ratio of the azeotropic composition.
〈氣體流速〉<Gas flow rate>
而且，本發明之溶劑的純化方法中，以「使用於上已述之蒸餾設備，亦即至少包含蒸餾器且構成蒸餾設備之各構成部件之液體接觸面及氣體接觸面的表面之中心平均粗糙度（Ra）為1 μm以下的蒸餾設備，將溶劑在氣體流速100 mm／秒鐘以下蒸餾」為必要。於此，氣體流速以50 mm／秒鐘以下為佳，以30 mm／秒鐘以下為較佳，並且，以0.1 mm／秒鐘以上為佳，以1 mm／秒鐘以上為較佳。藉由使用於上已述之蒸餾設備且將溶劑在氣體流速100 mm／秒鐘以下蒸餾，可抑制溶劑中所包含之微粒子伴隨已汽化的溶劑，故就結果而言，可獲得微粒子經減少的純化溶劑。Furthermore, in the method for purifying the solvent of the present invention, the average of the center of the surface of the liquid contact surface and the gas contact surface of each component part of the distillation device used in the above-mentioned distillation equipment, that is, at least including a distiller For distillation equipment with a degree (Ra) of 1 μm or less, it is necessary to distill the solvent at a gas flow rate of 100 mm/sec or less.” Here, the gas flow rate is preferably 50 mm/sec or less, preferably 30 mm/sec or less, and more preferably 0.1 mm/sec or more, and preferably 1 mm/sec or more. By using the distillation equipment described above and distilling the solvent at a gas flow rate of 100 mm/sec or less, the particles contained in the solvent can be suppressed along with the vaporized solvent, so as a result, reduced particles can be obtained Purify the solvent.
此外，氣體流速的調整，可藉由調整蒸餾溫度或蒸餾器的尺寸等來進行。In addition, the gas flow rate can be adjusted by adjusting the distillation temperature or the size of the distiller.
而且，進行蒸餾時的餾出率，因應使用之溶劑的種類等而適當調整即可，但通常為1質量%以上且99.5質量%以下。In addition, the distillation rate during distillation may be appropriately adjusted according to the type of solvent to be used, etc., but it is usually 1% by mass or more and 99.5% by mass or less.
此外，「餾出率」可依照本說明書之實施例記載的方法求得。In addition, the "distillation rate" can be obtained according to the method described in the examples of the present specification.
並且，蒸餾壓力可為加壓、常壓、減壓，但通常為−0.102 MPaG以上且1 MPaG以下，以−0.09 MPaG以上且0.8 MPaG以下為佳。In addition, the distillation pressure may be pressurized, normal pressure, or reduced pressure, but it is usually −0.102 MPaG or more and 1 MPaG or less, preferably −0.09 MPaG or more and 0.8 MPaG or less.
根據本發明之溶劑的純化方法，可有效減少溶劑中所包含之粒徑100 nm以下的微粒子。而且，將溶劑純化而獲得之純化溶劑中所包含之粒徑30 nm以上的微粒子以100個／mL以下為佳，以95個／mL以下為較佳。According to the solvent purification method of the present invention, it is possible to effectively reduce the particles contained in the solvent with a particle diameter of 100 nm or less. Furthermore, fine particles having a particle diameter of 30 nm or more included in the purified solvent obtained by purifying the solvent are preferably 100 particles/mL or less, and preferably 95 particles/mL or less.
此外，溶劑中所包含之「微粒子數」可依照本說明書之實施例記載的方法量測。In addition, the "number of fine particles" contained in the solvent can be measured according to the method described in the examples of the present specification.
而且，藉由本發明之溶劑的純化方法獲得之純化溶劑，得合適作為例如用於半導體器件之製造或清洗的溶劑來使用。Furthermore, the purified solvent obtained by the solvent purification method of the present invention can be suitably used as a solvent used for manufacturing or cleaning of semiconductor devices, for example.
『實施例』『Examples』
以下依據實施例具體說明本發明，但本發明並非受限於此等實施例者。此外，在以下說明中，表示量之「%」除非特別註記，否則為質量基準。The present invention will be specifically described below based on embodiments, but the present invention is not limited to those embodiments. In addition, in the following description, "%" of the indicated quantity is a quality standard unless otherwise noted.
於此，在實施例及比較例中，氣體流速、餾出率及微粒子數利用下述方法量測。Here, in Examples and Comparative Examples, the gas flow rate, the distillation rate, and the number of fine particles were measured by the following method.
〈氣體流速〉<Gas flow rate>
氣體流速依據下述式算出。 氣體流速（mm／秒鐘）＝［每單位時間自蒸餾器減少之溶劑的液體量（mm3 ／秒鐘）／蒸餾器之液面面積（mm2 ）］The gas flow rate is calculated according to the following formula. Gas flow rate (mm/sec) = [the amount of solvent liquid reduced from the distiller per unit time (mm 3 /sec) / liquid area of the distiller (mm 2 )]
〈餾出率〉<Distillation rate>
依據下述式算出餾出率。 餾出率（%）＝（已餾出之溶劑之量／已置入蒸餾器之溶劑之量）×100The distillation rate was calculated according to the following formula. Distillation rate (%) = (amount of solvent that has been distilled/amount of solvent that has been placed in the distiller) × 100
〈微粒子數〉<number of particles>
使用液中微粒子計數器（RION公司製「KS-19F」），在溫度23℃量測置入液（溶劑）中及餾分（純化溶劑）中所包含之粒徑30 nm以上且100 nm以下的微粒子數。Using a liquid particle counter ("KS-19F" manufactured by RION Corporation), at a temperature of 23°C, the particles with a particle diameter of 30 nm or more and 100 nm or less contained in the liquid (solvent) and the fraction (purified solvent) are measured. number.
（實施例1）(Example 1)
〈蒸餾設備的結構〉<Structure of distillation equipment>
準備液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）已藉由電解研磨調整為0.4 μm以下的蒸餾器、冷凝器及接收器。然後，將蒸餾器及冷凝器以及冷凝器及接收器分別藉由配管及UPG接頭或ICF法蘭盤接續。此時，使用在液體接觸面及氣體接觸面之表面形成由氧化鉻而成之氧化物鈍態膜且液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）已調整為0.7 μm以下的配管（A）作為配管。並且，使用液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）已藉由電解研磨調整為0.7 μm以下者作為UPG接頭。而且，使用液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）已調整為1 μm以下者作為ICF法蘭盤。再者，在蒸餾器與冷凝器之間及冷凝器與接收器之間，設置液體接觸面及氣體接觸面之表面沒有滑動部並已將靜滯區極小化之電解研磨規格的隔膜閥（Fujikin公司製「NEW MEGA系列」，隔膜閥之液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）：0.1 μm以下），構成蒸餾設備。Prepare the distiller, condenser and receiver where the center average roughness (Ra) of the surface of the liquid contact surface and the gas contact surface has been adjusted to 0.4 μm or less by electrolytic polishing. Then, the distiller and condenser and the condenser and receiver are respectively connected by piping and UPG joints or ICF flanges. At this time, the oxide passivation film made of chromium oxide is formed on the surface of the liquid contact surface and the gas contact surface and the center average roughness (Ra) of the surface of the liquid contact surface and the gas contact surface has been adjusted to 0.7 μm or less The piping (A) is used as piping. In addition, the center average roughness (Ra) of the surface of the liquid contact surface and the gas contact surface has been adjusted to 0.7 μm or less by electrolytic polishing as a UPG joint. Furthermore, the center roughness (Ra) of the surface of the liquid contact surface and the gas contact surface has been adjusted to 1 μm or less as the ICF flange. In addition, between the distiller and the condenser and between the condenser and the receiver, the liquid contact surface and the gas contact surface are provided with no sliding parts on the surface, and the electrolytic grinding specification diaphragm valve (Fujikin The "NEW MEGA series" manufactured by the company, the average roughness (Ra) of the center of the liquid contact surface of the diaphragm valve and the surface of the gas contact surface (Ra below 0.1 μm), constitutes the distillation equipment.
〈溶劑的蒸餾〉<Distillation of Solvent>
將作為溶劑之1,1,2,2,3,3,4-七氟環戊烷（1,1,2,2,3,3,4-七氟環戊烷中所包含之粒徑30 nm以上且100 nm以下的微粒子數：2420個／mL，沸點：82.5℃）置入蒸餾器作為置入液。然後，以蒸餾壓力呈−50 kPaG的減壓下，1,1,2,2,3,3,4-七氟環戊烷的氣體流速呈10 mm／秒鐘，餾出液溫度呈66℃的方式將蒸餾器加熱而蒸餾。然後，使1,1,2,2,3,3,4-七氟環戊烷餾出而獲得純化溶劑作為餾分。此時之餾出率揭示於表1。然後，量測餾分（純化溶劑）中所包含之粒徑30 nm以上且100 nm以下的微粒子數。結果揭示於表1。The particle size of 1,1,2,2,3,3,4-heptafluorocyclopentane (1,1,2,2,3,3,4-heptafluorocyclopentane as the solvent is 30 The number of fine particles above nm and below 100 nm: 2420 particles/mL, boiling point: 82.5°C) was placed in a distiller as an inlet liquid. Then, under a reduced pressure of −50 kPaG at the distillation pressure, the gas flow rate of 1,1,2,2,3,3,4-heptafluorocyclopentane was 10 mm/sec, and the temperature of the distillate was 66°C Heating the distiller to distill. Then, 1,1,2,2,3,3,4-heptafluorocyclopentane was distilled off to obtain a purified solvent as a fraction. The distillation rate at this time is shown in Table 1. Then, the number of fine particles with a particle size of 30 nm or more and 100 nm or less contained in the fraction (purification solvent) is measured. The results are shown in Table 1.
（實施例2）(Example 2)
除了將氣體流速改變為100 mm／秒鐘以外，比照實施例1操作將溶劑蒸餾，使1,1,2,2,3,3,4-七氟環戊烷餾出作為餾分。然後，量測獲得之餾分中所包含之粒徑30 nm以上且100 nm以下的微粒子數。結果揭示於表1。Except that the gas flow rate was changed to 100 mm/sec, the solvent was distilled as in Example 1, and 1,1,2,2,3,3,4-heptafluorocyclopentane was distilled off as a fraction. Then, the number of fine particles with a particle diameter of 30 nm or more and 100 nm or less contained in the obtained fraction is measured. The results are shown in Table 1.
（實施例3）(Example 3)
除了使用包含1,1,2,2,3,3,4-七氟環戊烷與三級戊醇的共沸組成物（以質量比（1,1,2,2,3,3,4-七氟環戊烷／三級戊醇）計為95.8／4.2，共沸組成物中所包含之粒徑30 nm以上的微粒子數：4350個／mL，共沸組成物的沸點：82℃）作為溶劑，以溶劑之餾出液溫度呈65℃的方式將蒸餾器加熱以外，比照實施例1操作將溶劑蒸餾，使包含1,1,2,2,3,3,4-七氟環戊烷與三級戊醇的共沸組成物餾出作為餾分。此時之餾出率揭示於表1。然後，量測所獲得之餾分中所包含之粒徑30 nm以上且100 nm以下的微粒子數。結果揭示於表1。In addition to using an azeotropic composition containing 1,1,2,2,3,3,4-heptafluorocyclopentane and tertiary amyl alcohol (in mass ratio (1,1,2,2,3,3,4 -Heptafluorocyclopentane/tertiary amyl alcohol) 99.8/4.2, the number of fine particles with a particle size of 30 nm or more included in the azeotropic composition: 4350/mL, boiling point of the azeotropic composition: 82°C) As a solvent, except that the distiller was heated so that the temperature of the distillate of the solvent was 65°C, the solvent was distilled as in Example 1 to contain 1,1,2,2,3,3,4-heptafluorocyclopentane The azeotropic composition of alkane and tertiary amyl alcohol is distilled off as a fraction. The distillation rate at this time is shown in Table 1. Then, the number of fine particles having a particle diameter of 30 nm or more and 100 nm or less included in the obtained fraction is measured. The results are shown in Table 1.
（實施例4）(Example 4)
除了使用環戊酮（環戊酮中所包含之粒徑30 nm以上的微粒子數：5325個／mL，沸點：130.6℃）代替1,1,2,2,3,3,4-七氟環戊烷作為溶劑，以蒸餾壓力呈−82 kPaG的減壓下，溶劑之餾出液溫度呈80℃的方式將蒸餾器加熱以外，比照實施例1操作將溶劑蒸餾，使環戊酮餾出作為餾分。此時之餾出率揭示於表1。然後，量測所獲得之餾分中所包含之粒徑30 nm以上且100 nm以下的微粒子數。結果揭示於表1。In addition to using cyclopentanone (the number of fine particles with a particle diameter of 30 nm or more included in cyclopentanone: 5325 particles/mL, boiling point: 130.6°C) instead of 1,1,2,2,3,3,4-heptafluoro ring Pentane was used as the solvent, except that the distillation pressure was reduced to −82 kPaG and the distillate temperature of the solvent was 80°C. The solvent was distilled in accordance with Example 1 to distill the cyclopentanone as Distillate. The distillation rate at this time is shown in Table 1. Then, the number of fine particles having a particle diameter of 30 nm or more and 100 nm or less included in the obtained fraction is measured. The results are shown in Table 1.
（實施例5）(Example 5)
除了使用環戊醇（環戊醇中所包含之粒徑30 nm以上的微粒子數：7890個／mL，環戊醇的沸點：140.85℃）代替1,1,2,2,3,3,4-七氟環戊烷作為溶劑，以蒸餾壓力呈−88 kPaG的減壓下，溶劑之餾出液溫度呈86℃的方式將蒸餾器加熱以外，比照實施例1操作將溶劑蒸餾，使環戊醇餾出作為餾分。此時之餾出率揭示於表1。然後，量測所獲得之餾分中所包含之粒徑30 nm以上且100 nm以下的微粒子數。結果揭示於表1。In addition to using cyclopentanol (the number of fine particles with a particle diameter of 30 nm or more included in cyclopentanol: 7890 particles/mL, the boiling point of cyclopentanol: 140.85°C) instead of 1,1,2,2,3,3,4 -Heptafluorocyclopentane was used as the solvent, except that the distillation pressure was reduced to −88 kPaG and the distillate temperature of the solvent was 86°C, except that the distiller was heated, and the solvent was distilled in accordance with Example 1 to obtain cyclopentane. The alcohol is distilled off as a fraction. The distillation rate at this time is shown in Table 1. Then, the number of fine particles having a particle diameter of 30 nm or more and 100 nm or less included in the obtained fraction is measured. The results are shown in Table 1.
（實施例6）(Example 6)
除了使用環戊基甲基醚（環戊基甲基醚中所包含之粒徑30 nm以上的微粒子數：7570個／mL，環戊基甲基醚的沸點：106℃）代替1,1,2,2,3,3,4-七氟環戊烷作為溶劑，以蒸餾壓力呈−48 kPaG的減壓下，溶劑之餾出液溫度呈85℃的方式將蒸餾器加熱以外，比照實施例1操作將溶劑蒸餾，使環戊基甲基醚餾出作為餾分。此時之餾出率揭示於表1。然後，量測所獲得之餾分中所包含之粒徑30 nm以上且100 nm以下的微粒子數。結果揭示於表1。In addition to the use of cyclopentyl methyl ether (cyclopentyl methyl ether particles with a particle size of 30 nm or more: 7570 particles/mL, the boiling point of cyclopentyl methyl ether: 106°C) instead of 1,1, 2,2,3,3,4-heptafluorocyclopentane was used as the solvent, except that the distiller was heated under a reduced pressure of −48 kPaG and the distillate temperature of the solvent was 85°C. 1 Operation Distill the solvent to distill cyclopentyl methyl ether as a fraction. The distillation rate at this time is shown in Table 1. Then, the number of fine particles having a particle diameter of 30 nm or more and 100 nm or less included in the obtained fraction is measured. The results are shown in Table 1.
（實施例7）(Example 7)
除了使用N-甲基吡咯啶酮（N-甲基吡咯啶酮中所包含之粒徑30 nm以上的微粒子數：9800個／mL，N-甲基吡咯啶酮的沸點：202℃）代替1,1,2,2,3,3,4-七氟環戊烷作為溶劑，以蒸餾壓力呈−100 kPaG的減壓下，溶劑之餾出液溫度呈85℃的方式將蒸餾器加熱以外，比照實施例1操作將溶劑蒸餾，使N-甲基吡咯啶酮餾出作為餾分。此時之餾出率揭示於表1。然後，量測所獲得之餾分中所包含之粒徑30 nm以上且100 nm以下的微粒子數。結果揭示於表1。In addition to using N-methylpyrrolidone (number of fine particles with a particle size of 30 nm or more included in N-methylpyrrolidone: 9800 particles/mL, boiling point of N-methylpyrrolidone: 202°C) instead of 1 ,1,2,2,3,3,4-heptafluorocyclopentane as a solvent, the distiller is heated except that the distillation pressure is reduced to −100 kPaG and the temperature of the distillate of the solvent is 85°C. The solvent was distilled as in Example 1 to distill N-methylpyrrolidone as a fraction. The distillation rate at this time is shown in Table 1. Then, the number of fine particles having a particle diameter of 30 nm or more and 100 nm or less included in the obtained fraction is measured. The results are shown in Table 1.
（比較例1）(Comparative example 1)
除了將氣體流速改變為300 mm／秒鐘以外，比照實施例1操作將溶劑蒸餾，使1,1,2,2,3,3,4-七氟環戊烷餾出作為餾分。此時之餾出率揭示於表1。然後，量測所獲得之餾分中所包含之粒徑30 nm以上且100 nm以下的微粒子數。結果揭示於表1。Except that the gas flow rate was changed to 300 mm/sec, the solvent was distilled as in Example 1, and 1,1,2,2,3,3,4-heptafluorocyclopentane was distilled off as a fraction. The distillation rate at this time is shown in Table 1. Then, the number of fine particles having a particle diameter of 30 nm or more and 100 nm or less included in the obtained fraction is measured. The results are shown in Table 1.
（比較例2）(Comparative example 2)
〈蒸餾設備的結構〉<Structure of distillation equipment>
除了具備配管（B）（液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）為3～4.5 μm程度之不鏽鋼BA管（輝面退火管））代替配管（A）作為配管以外，使用具有與實施例1同樣結構的蒸餾設備。而且，除了使用此蒸餾設備及將溶劑的氣體流速定為300 mm／秒鐘以外，比照實施例1將溶劑蒸餾，使1,1,2,2,3,3,4-七氟環戊烷餾出作為餾分。此時之餾出率揭示於表1。然後，量測所獲得之餾分中所包含之粒徑30 nm以上且100 nm以下的微粒子數。結果揭示於表1。In addition to piping (B) (stainless steel BA pipe (glow surface annealed pipe) with a center average roughness (Ra) of the surface of the liquid contact surface and gas contact surface of 3 to 4.5 μm) instead of the piping (A) as the piping, A distillation apparatus having the same structure as Example 1 was used. Furthermore, except using this distillation equipment and setting the gas flow rate of the solvent to 300 mm/sec, distill the solvent according to Example 1 to make 1,1,2,2,3,3,4-heptafluorocyclopentane Distillate as a fraction. The distillation rate at this time is shown in Table 1. Then, the number of fine particles having a particle diameter of 30 nm or more and 100 nm or less included in the obtained fraction is measured. The results are shown in Table 1.
『表1』
此外，表1中， 「溶劑A」表示1,1,2,2,3,3,4-七氟環戊烷， 「溶劑B」表示包含1,1,2,2,3,3,4-七氟環戊烷與三級戊醇的共沸組成物（以質量比（1,1,2,2,3,3,4-七氟環戊烷／三級戊醇）計為95.8／4.2）， 「溶劑C」表示環戊酮， 「溶劑D」表示環戊醇， 「溶劑E」表示環戊基甲基醚， 「溶劑F」表示N-甲基吡咯啶酮。In addition, in Table 1, "Solvent A" means 1,1,2,2,3,3,4-heptafluorocyclopentane, "Solvent B" means an azeotropic composition containing 1,1,2,2,3,3,4-heptafluorocyclopentane and tertiary amyl alcohol (in mass ratio (1,1,2,2,3, 3,4-heptafluorocyclopentane/tertiary amyl alcohol) is calculated as 95.8/4.2), "Solvent C" means cyclopentanone, "Solvent D" means cyclopentanol, "Solvent E" means cyclopentyl methyl ether, "Solvent F" means N-methylpyrrolidone.
由實施例1～7可知，若使用具備液體接觸面及氣體接觸面的表面之中心平均粗糙度（Ra）已調整為1 μm以下之構成部件的蒸餾設備，並以氣體流速100 mm／秒鐘以下將溶劑蒸餾，則可充分減少粒徑30 nm以上的微粒子。It can be seen from Examples 1 to 7 that if the distillation equipment with components whose center average roughness (Ra) of the surface having the liquid contact surface and the gas contact surface has been adjusted to 1 μm or less is used, and the gas flow rate is 100 mm/sec When the solvent is distilled below, fine particles with a particle diameter of 30 nm or more can be sufficiently reduced.
相對於此，由比較例1可知，即使構成蒸餾設備之各構成部件的液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）為1 μm以下，若以大於100 mm／秒鐘之氣體流速將溶劑蒸餾，則無法充分減少粒徑30 nm以上的微粒子。In contrast to this, it is known from Comparative Example 1 that even if the center average roughness (Ra) of the surface of the liquid contact surface and gas contact surface of each component constituting the distillation apparatus is 1 μm or less, if it is greater than 100 mm/sec Distilling the solvent with the gas flow rate cannot sufficiently reduce fine particles with a particle diameter of 30 nm or more.
並且，由比較例2可知，若使用具備液體接觸面及氣體接觸面之表面之中心平均粗糙度（Ra）大於1 μm之構成部件的蒸餾設備，並以大於100 mm／秒鐘之氣體流速將溶劑蒸餾，則幾乎無法減少粒徑30 nm以上且100 nm以下的微粒子。Also, as can be seen from Comparative Example 2, if a distillation apparatus having a component having a center average roughness (Ra) of more than 1 μm on the surface of the liquid contact surface and the gas contact surface is used, and the gas flow rate is greater than 100 mm/sec. Solvent distillation can hardly reduce fine particles with a particle size of 30 nm or more and 100 nm or less.
藉由本發明之溶劑的純化方法獲得之純化溶劑，可作為使用於半導體器件之製造或清洗的溶劑來使用。The purified solvent obtained by the solvent purification method of the present invention can be used as a solvent used in the manufacture or cleaning of semiconductor devices.
1:蒸餾器 2:冷凝器 3:接收器 10:蒸餾設備1: still 2: condenser 3: receiver 10: Distillation equipment
〈圖1〉係繪示在本發明之溶劑的純化方法中得使用之蒸餾設備的概略結構圖。<FIG. 1> is a schematic structural diagram showing a distillation apparatus used in the method for purifying a solvent of the present invention.
1:蒸餾器 1: still
2:冷凝器 2: condenser
3:接收器 3: receiver
10:蒸餾設備 10: Distillation equipment
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| KR (1) | KR20210053873A (en) |
| CN (1) | CN112189002A (en) |
| TW (1) | TW202019537A (en) |
| WO (1) | WO2020044825A1 (en) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788043A (en) * | 1985-04-17 | 1988-11-29 | Tokuyama Soda Kabushiki Kaisha | Process for washing semiconductor substrate with organic solvent |
| JPS61239628A (en) * | 1985-04-17 | 1986-10-24 | Tokuyama Soda Co Ltd | Cleaning of semiconductor substrate |
| JP2633277B2 (en) * | 1988-01-12 | 1997-07-23 | 三菱化学株式会社 | Prevention of polymerization in the purification of unsaturated carboxylic acids and their esters. |
| JP2005239615A (en) | 2004-02-25 | 2005-09-08 | Nippon Zeon Co Ltd | Method for refining fluorine-based solvent |
| KR20080053411A (en) * | 2004-03-10 | 2008-06-12 | 제온 코포레이션 | Apparatus for producing gas, vessel for supplying gas and gas for use in manufacturing electronic device |
| JP2008081477A (en) * | 2006-09-29 | 2008-04-10 | Nippon Zeon Co Ltd | Container-infilled oxygen-containing fluorine compound, method of storing oxygen-containing fluorine compound and plasma etching method |
| DE102013020400A1 (en) * | 2013-12-10 | 2015-06-11 | Merck Patent Gmbh | cleaning device |
| JP2016073922A (en) | 2014-10-07 | 2016-05-12 | 信越化学工業株式会社 | Refining apparatus of organic solvent |
| JPWO2017188209A1 (en) * | 2016-04-28 | 2019-02-14 | 富士フイルム株式会社 | Purification apparatus, purification method, manufacturing apparatus, chemical manufacturing method, container, and chemical container |
| KR102008566B1 (en) * | 2016-05-24 | 2019-08-07 | 가부시키가이샤 스크린 홀딩스 | Substrate processing apparatus and substrate processing method |
| JP6780998B2 (en) * | 2016-09-26 | 2020-11-04 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing equipment and substrate processing method |
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2019
- 2019-07-16 CN CN201980034550.6A patent/CN112189002A/en active Pending
- 2019-07-16 JP JP2020540128A patent/JPWO2020044825A1/en active Pending
- 2019-07-16 WO PCT/JP2019/027945 patent/WO2020044825A1/en active Application Filing
- 2019-07-16 KR KR1020217000832A patent/KR20210053873A/en not_active Application Discontinuation
- 2019-08-21 TW TW108129834A patent/TW202019537A/en unknown
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| JPWO2020044825A1 (en) | 2021-08-26 |
| KR20210053873A (en) | 2021-05-12 |
| CN112189002A (en) | 2021-01-05 |
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