EP0445438A1 - Azeotrope-like solvents mixture and process for cleaning electronic components using them - Google Patents

Azeotrope-like solvents mixture and process for cleaning electronic components using them Download PDF

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Publication number
EP0445438A1
EP0445438A1 EP90125837A EP90125837A EP0445438A1 EP 0445438 A1 EP0445438 A1 EP 0445438A1 EP 90125837 A EP90125837 A EP 90125837A EP 90125837 A EP90125837 A EP 90125837A EP 0445438 A1 EP0445438 A1 EP 0445438A1
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EP
European Patent Office
Prior art keywords
azeotrope
weight
mixture
methanol
electronic components
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90125837A
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German (de)
French (fr)
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EP0445438B1 (en
Inventor
Horst Robeck
Hans-Matthias Dr. Deger
Klaus Dr. Raab
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Solvay SA
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Hoechst AG
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • C11D7/5036Azeotropic mixtures containing halogenated solvents
    • C11D7/5068Mixtures of halogenated and non-halogenated solvents
    • C11D7/5077Mixtures of only oxygen-containing solvents
    • C11D7/5081Mixtures of only oxygen-containing solvents the oxygen-containing solvents being alcohols only
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02803Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing fluorine

Definitions

  • 1,4-dihydroperfluorobutane (CHF2-CF2-CF2-CHF2) forms an azeotrope-like solvent mixture with methanol, which is outstandingly suitable for cleaning electronic components, in particular soldered printed circuit boards or printed circuits, especially for removing soldering flux .
  • the invention relates to an azeotrope-like mixture which contains about 3-5% by weight of methanol and about 95-97% by weight of 1,4-dihydroperfluorobutane.
  • the mixture preferably contains 3.2-4.0% by weight of methanol, in particular 3.4-3.6% by weight of methanol, the remainder being 1,4-dihydroperfluorobutane in each case.
  • Another object of the invention is a method for cleaning electronic components, in particular soldered circuit boards or printed circuits, which is characterized in that the components are washed with an azeotrope-like mixture which contains about 3-5% by weight of methanol and 95-97 Wt .-% 1,4-dihydroperfluorobutane contains.
  • a mixture is preferably used which contains 3.2-4.0% by weight of methanol, in particular 3.4-3.6% by weight of methanol, the remainder being essentially 1,4-dihydroperfluorobutane.
  • a particularly preferred solvent mixture contains 96.5% by weight of 1,4-dihydroperfluorobutane and 3.5% by weight of methanol and has a boiling point of 40.5 ° C. at 1 bar.
  • the composition of the vapor is identical or essentially identical to the composition of the liquid, ie the composition of the mixture does not change or does not change significantly during evaporation.
  • the solvent mixture according to the invention has the further advantage that it contains no chlorine and therefore does not cause any damage to the ozone layer. Besides, it is not flammable and can be used in the usual ultrasonic, immersion and brush washing systems.
  • a glass-fiber-reinforced base material for printed circuit boards based on polyester was coated with a commercially available soldering flux (Zeva C20-200 from Zevatron, main component rosin, also activators) and dried in a drying cabinet at 60 ° C. for 18 hours. The material was then washed with a mixture of 1,4-dihydroperfluorobutane (96.5% by weight) and methanol (3.5% by weight) using ultrasound. The exposure time was 5 seconds, the flux was completely removed.
  • a commercially available soldering flux Zeva C20-200 from Zevatron, main component rosin, also activators
  • Example 2 The procedure was as in Example 1, except that another soldering flux was used (Zeva C 30-300 from Zevatron), which in turn contained rosin as the main constituent in addition to activators.
  • the flux was completely removed after an exposure time of 10 seconds.
  • the treatment times are between 60 and 90 seconds, depending on the flux.
  • ionic residues can be removed more easily with the azeotrope than with the conventional mixtures.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Detergent Compositions (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

Die Erfindung betrifft ein azeotropartiges Gemisch, das etwa 3 - 5 Gew.-% Methanol und etwa 95 - 97 Gew.-% 1,4-Dihydroperfluorbutan enthält, sowie ein Verfahren zur Reinigung von elektronischen Bauteilen, insbesondere gelöteten Leiterplatten oder gedruckten Schaltungen mit Hilfe dieses Gemisches.The invention relates to an azeotrope-like mixture which contains about 3-5% by weight of methanol and about 95-97% by weight of 1,4-dihydroperfluorobutane, and a method for cleaning electronic components, in particular soldered printed circuit boards or printed circuits, with the aid this mixture.

Description

Es ist Stand der Technik, zum Reinigen von gelöteten Leiterplatten und anderen elektronischen Bauteilen Gemische aus 1,1,2-Trichlor-1,2,2-trifluorethan (R 113) und Alkoholen wie Methanol, Ethanol oder 2-Propanol einzusetzen (GB-PS 1 026 003, GB-PS 1 399 867). Aus US-PS 3 960 746 ist eine azeotropartige Mischung aus R 113, Methanol und Nitromethan für denselben Zweck bekannt. Da jedoch die FCKW im Verdacht stehen, die Ozonschicht zu schädigen, ist es notwendig, auf diese Stoffklasse zu verzichten.It is state of the art to use mixtures of 1,1,2-trichloro-1,2,2-trifluoroethane (R 113) and alcohols such as methanol, ethanol or 2-propanol for cleaning soldered circuit boards and other electronic components (GB- PS 1 026 003, GB-PS 1 399 867). An azeotrope-like mixture of R 113, methanol and nitromethane for the same purpose is known from US Pat. No. 3,960,746. However, since CFCs are suspected of damaging the ozone layer, it is necessary to dispense with this class of substances.

Für den Bereich der Elektronik-Industrie, insbesondere zum Reinigen von Leiterplatten nach dem Lötvorgang, werden zur Zeit verschiedene Systeme auf wäßriger Basis und auf Basis nichthalogenierter organischer Lösemittel diskutiert. Bei wäßrigen Reinigungsmitteln ist es jedoch schwierig, die richtige Tensid/Komplexbildner-Kombination zu finden. Auch muß das System an die mechanische Behandlung wie Spülen, Bürsten, Dampfstrahl, Ultraschall angepaßt werden. Bei der SMT (Surface Mount Technology)-Technik scheiden wäßrige Reinigungssysteme häufig aus, da sich das Wasser nur schwer wieder entfernen läßt.Various systems based on water and non-halogenated organic solvents are currently being discussed for the electronics industry, especially for cleaning printed circuit boards after the soldering process. With aqueous cleaning agents, however, it is difficult to find the right surfactant / complexing agent combination. The system must also be adapted to mechanical treatment such as rinsing, brushing, steam jet, ultrasound. With the SMT (Surface Mount Technology) technology, aqueous cleaning systems are often ruled out because the water is difficult to remove.

Bei Einsatz nichthalogenierter organischer Lösemittel, wie Benzin, Alkohole, Terpene oder Ester ist aufgrund der Brennbarkeit und der Explosivität dieser Substanzen eine explosionsgeschützte Ausführung der Anlage erforderlich, so daß aus ökonomischen Gründen eine Verwendung in Oberflächenbehandlungsanlagen nur in wenigen Fällen infrage kommt.When using non-halogenated organic solvents, such as gasoline, alcohols, terpenes or esters, the flammability and explosiveness of these substances necessitates an explosion-proof design of the system, so that use in surface treatment systems is only possible in a few cases for economic reasons.

Überraschenderweise wurde nun gefunden, daß 1,4-Dihydroperfluorbutan (CHF₂-CF₂-CF₂-CHF₂) mit Methanol ein azeotropartiges Lösungsmittelgemisch bildet, welches hervorragend zur Reinigung von elektronischen Bauteilen, insbesondere gelöteten Leiterplatten oder gedruckten Schaltungen, vor allem zur Entfernung von Lötflußmitteln geeignet ist.Surprisingly, it has now been found that 1,4-dihydroperfluorobutane (CHF₂-CF₂-CF₂-CHF₂) forms an azeotrope-like solvent mixture with methanol, which is outstandingly suitable for cleaning electronic components, in particular soldered printed circuit boards or printed circuits, especially for removing soldering flux .

Ein Gegenstand der Erfindung ist ein azeotropartiges Gemisch, das etwa 3 - 5 Gew.-% Methanol und etwa 95 - 97 Gew.-% 1,4-Dihydroperfluorbutan enthält. Vorzugsweise enthält das Gemisch 3,2 - 4,0 Gew.-% Methanol, insbesondere 3,4 - 3,6 Gew.-% Methanol, wobei der Rest jeweils 1,4-Dihydroperfluorbutan ist. Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Reinigung von elektronischen Bauteilen, insbesondere gelöteten Leiterplatten oder gedruckten Schaltungen, das dadurch gekennzeichnet ist, daß man die Bauteile mit einem azeotropartigen Gemisch wäscht, das etwa 3 - 5 Gew.-% Methanol und 95 - 97 Gew.-% 1,4-Dihydroperfluorbutan enthält. Vorzugsweise verwendet man ein Gemisch, das 3,2 - 4,0 Gew.-% Methanol, insbesondere 3,4 - 3,6 Gew.-% Methanol enthält, wobei der Rest jeweils im wesentlichen 1,4-Dihydroperfluorbutan ist.The invention relates to an azeotrope-like mixture which contains about 3-5% by weight of methanol and about 95-97% by weight of 1,4-dihydroperfluorobutane. The mixture preferably contains 3.2-4.0% by weight of methanol, in particular 3.4-3.6% by weight of methanol, the remainder being 1,4-dihydroperfluorobutane in each case. Another object of the invention is a method for cleaning electronic components, in particular soldered circuit boards or printed circuits, which is characterized in that the components are washed with an azeotrope-like mixture which contains about 3-5% by weight of methanol and 95-97 Wt .-% 1,4-dihydroperfluorobutane contains. A mixture is preferably used which contains 3.2-4.0% by weight of methanol, in particular 3.4-3.6% by weight of methanol, the remainder being essentially 1,4-dihydroperfluorobutane.

Ein besonders bevorzugtes Lösungsmittelgemisch enthält 96,5 Gew.-% 1,4-Dihydroperfluorbutan und 3,5 Gew.-% Methanol und hat einen Siedepunkt bei 1 bar von 40,5°C.A particularly preferred solvent mixture contains 96.5% by weight of 1,4-dihydroperfluorobutane and 3.5% by weight of methanol and has a boiling point of 40.5 ° C. at 1 bar.

Bei dem erfindungsgemäßen Gemisch ist die Zusammensetzung des Dampfes identisch oder im wesentlichen identisch mit der Zusammensetzung der Flüssigkeit, d.h. beim Verdampfen ändert sich die Zusammensetzung des Gemisches nicht oder nicht wesentlich. Das erfindungsgemäße Lösemittelgemisch hat den weiteren Vorteil, daß es kein Chlor enthält, und damit keine Ozonschädigung bewirkt. Außerdem ist es nicht brennbar und kann in den üblichen Ultraschall-, Tauch- und Bürstenwaschanlagen eingesetzt werden.In the mixture according to the invention, the composition of the vapor is identical or essentially identical to the composition of the liquid, ie the composition of the mixture does not change or does not change significantly during evaporation. The solvent mixture according to the invention has the further advantage that it contains no chlorine and therefore does not cause any damage to the ozone layer. Besides, it is not flammable and can be used in the usual ultrasonic, immersion and brush washing systems.

Beispiel 1: Example 1 :

Ein glasfaserverstärktes Basismaterial für Leiterplatten auf Polyesterbasis wurde mit einem handelsüblichen Lötflußmittel (Zeva C20-200 der Firma Zevatron, Hauptbestandteil Kolophonium, daneben Aktivatoren) bestrichen und 18 Stunden bei 60°C im Trockenschrank getrocknet. Anschließend wurde das Material mit einem Gemisch aus 1,4-Dihydroperfluorbutan (96,5 Gew.-%) und Methanol (3,5 Gew.-%) unter Anwendung von Ultraschall gewaschen. Die Einwirkzeit betrug 5 Sekunden, das Flußmittel wurde vollständig entfernt.A glass-fiber-reinforced base material for printed circuit boards based on polyester was coated with a commercially available soldering flux (Zeva C20-200 from Zevatron, main component rosin, also activators) and dried in a drying cabinet at 60 ° C. for 18 hours. The material was then washed with a mixture of 1,4-dihydroperfluorobutane (96.5% by weight) and methanol (3.5% by weight) using ultrasound. The exposure time was 5 seconds, the flux was completely removed.

Beispiel 2: Example 2 :

Man ging vor wie in Beispiel 1, nur daß man ein anderes Lötflußmittel benutzte (Zeva C 30-300 der Firma Zevatron), welches wiederum als Hauptbestandteil Kolophonium neben Aktivatoren enthielt. Nach einer Einwirkzeit von 10 Sekunden war das Flußmittel vollständig entfernt. Bei den herkömmlichen Gemischen aus 1,1,2-Trichlor-1,2,2-trifluorethan mit Methanol, Ethanol oder 2-Propanol betragen die Behandlungszeiten dagegen je nach Flußmittel zwischen 60 und 90 Sekunden. Außerdem lassen sich ionische Rückstände mit dem Azeotrop besser entfernen als mit den herkömmlichen Gemischen.The procedure was as in Example 1, except that another soldering flux was used (Zeva C 30-300 from Zevatron), which in turn contained rosin as the main constituent in addition to activators. The flux was completely removed after an exposure time of 10 seconds. In contrast, with conventional mixtures of 1,1,2-trichloro-1,2,2-trifluoroethane with methanol, ethanol or 2-propanol, the treatment times are between 60 and 90 seconds, depending on the flux. In addition, ionic residues can be removed more easily with the azeotrope than with the conventional mixtures.

Claims (6)

Azeotropartiges Gemisch, das etwa 3 - 5 Gew.-% Methanol und etwa 95 - 97 Gew.-% 1,4-Dihydroperfluorbutan enthält.Azeotrope-like mixture containing about 3-5% by weight of methanol and about 95-97% by weight of 1,4-dihydroperfluorobutane. Azeotropartiges Gemisch nach Anspruch 1, das etwa 3,2 - 4,0 Gew.-% Methanol und etwa 96,0 - 96,8 Gew.-% 1,4-Dihydroperfluorbutan enthält.The azeotrope-like mixture of claim 1, which contains about 3.2-4.0 weight percent methanol and about 96.0-96.8 weight percent 1,4-dihydroperfluorobutane. Azeotropartiges Gemisch nach Anspruch 1, das etwa 3,4 - 3,6 Gew.-% Methanol, und 96,4 - 96,6 Gew.-% 1,4-Dihydroperfluorbutan enthält.An azeotrope-like mixture according to claim 1, which contains about 3.4-3.6% by weight of methanol and 96.4-96.6% by weight of 1,4-dihydroperfluorobutane. Verfahren zur Reinigung von elektronischen Bauteilen, insbesondere gelöteten Leiterplatten oder gedruckten Schaltungen, dadurch gekennzeichnet, daß man die Bauteile mit einem azeotropartigen Gemisch nach einem der Ansprüche 1 bis 3 wäscht.Process for cleaning electronic components, in particular soldered circuit boards or printed circuits, characterized in that the components are washed with an azeotrope-like mixture according to one of Claims 1 to 3. Verfahren zur Entfernung von Lötflußmitteln, gekennzeichnet durch eine Wäsche mit einem azeotropartigen Gemisch nach einem der Ansprüche 1 bis 3.Process for removing soldering flux, characterized by washing with an azeotrope-like mixture according to one of Claims 1 to 3.
EP90125837A 1990-01-25 1990-12-31 Azeotrope-like solvents mixture and process for cleaning electronic components using them Expired - Lifetime EP0445438B1 (en)

Applications Claiming Priority (2)

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DE4002120 1990-01-25
DE4002120A DE4002120A1 (en) 1990-01-25 1990-01-25 NEW AZEOTROPARTY SOLVENT MIXTURE AND METHOD FOR CLEANING ELECTRONIC COMPONENTS WITH THE HELP OF THE SAME

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EP0445438A1 true EP0445438A1 (en) 1991-09-11
EP0445438B1 EP0445438B1 (en) 1996-06-05

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US (1) US5073291A (en)
EP (1) EP0445438B1 (en)
JP (1) JP2812369B2 (en)
DE (2) DE4002120A1 (en)
DK (1) DK0445438T3 (en)
ES (1) ES2088953T3 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0519432A2 (en) * 1991-06-21 1992-12-23 Hoechst Aktiengesellschaft Azeotrope-like mixture of 2-propanol and 1H-perfluorohexane
EP0519431A2 (en) * 1991-06-21 1992-12-23 Hoechst Aktiengesellschaft Azeotrope-like mixture of methanol and 1H-perfluorohexane
WO1993008240A1 (en) * 1991-10-18 1993-04-29 E.I. Du Pont De Nemours And Company Azeotropic compositions of 1,1,2,2,3,3,4,4-octafluorobutane and alcohols or ketones
WO1993020177A1 (en) * 1992-04-02 1993-10-14 E.I. Du Pont De Nemours And Company Ternary azeotropic compositions

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US5531916A (en) * 1990-10-03 1996-07-02 E. I. Du Pont De Nemours And Company Hydrofluorocarbon cleaning compositions
FR2676066B1 (en) * 1991-05-02 1993-07-23 Atochem COMPOSITION BASED ON 1,1-DICHLORO-1-FLUOROETHANE, 1,1,1,3,3-PENTAFLUOROBUTANE AND METHANOL, FOR CLEANING AND / OR DRYING SOLID SURFACES.
FR2676067B1 (en) * 1991-05-02 1993-07-23 Atochem COMPOSITION BASED ON 1,1,1,3,3-PENTAFLUOROBUTANE AND METHANOL, FOR CLEANING AND / OR DRYING SOLID SURFACES.
US5219488A (en) * 1992-03-16 1993-06-15 Allied-Signal Inc. Azeotrope-like compositions of 2-trifluoromethyl-1,1,1,2-tetrafluorobutane and ethanol or isopropanol
WO1993009216A1 (en) * 1991-10-31 1993-05-13 Daikin Industries, Ltd. Cleaning solvent composition and cleaning method
US6355113B1 (en) 1991-12-02 2002-03-12 3M Innovative Properties Company Multiple solvent cleaning system
US5194170A (en) * 1992-04-02 1993-03-16 E. I. Du Pont De Nemours And Company Binary azeotropic compositions of 1,1,2,2,3,3,4,4-octafluorobutane and either tran-1,2-dichloroethylene, cis 1,2-dichloroethylene, or 1-1 dichloroethane
US5219490A (en) * 1992-04-27 1993-06-15 Allied-Signal Inc. Azeotrope-like compositions of 1,1,2,3,3-pentafluoropropane
US5696307A (en) * 1994-01-21 1997-12-09 Alliedsignal Inc. Hydrofluoroalkanes as cleaning and degreasing solvents
FR2740469B1 (en) * 1995-10-31 1997-12-05 Atochem Elf Sa CLEANING COMPOSITIONS BASED ON 1,1,1,2,2,4,4, - HEPTAFLUOROBUTANE AND ALCOHOLS
US5730894A (en) * 1996-04-16 1998-03-24 E. I. Du Pont De Nemours And Company 1,1,2,2,3,3,4,4-octafluorobutane azeotropic (like) compositions
US5769935A (en) 1996-11-26 1998-06-23 Alliedsignal Inc. Use of fluorocarbons as a fusing agent for toners in laser printers

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0519432A2 (en) * 1991-06-21 1992-12-23 Hoechst Aktiengesellschaft Azeotrope-like mixture of 2-propanol and 1H-perfluorohexane
EP0519431A2 (en) * 1991-06-21 1992-12-23 Hoechst Aktiengesellschaft Azeotrope-like mixture of methanol and 1H-perfluorohexane
EP0519432A3 (en) * 1991-06-21 1993-05-05 Hoechst Aktiengesellschaft Azeotrope-like mixture of 2-propanol and 1h-perfluorohexane
EP0519431A3 (en) * 1991-06-21 1993-05-05 Hoechst Aktiengesellschaft Azeotrope-like mixture of methanol and 1h-perfluorohexane
US5266231A (en) * 1991-06-21 1993-11-30 Hoechst Aktiengesellschaft Azeotrope-like mixture of 2-propanol and 1H-perfluorohexane
US5266232A (en) * 1991-06-21 1993-11-30 Hoechst Aktiengesellschaft Azeotrope-like mixture of methanol and 1H-perfluorohexane
WO1993008240A1 (en) * 1991-10-18 1993-04-29 E.I. Du Pont De Nemours And Company Azeotropic compositions of 1,1,2,2,3,3,4,4-octafluorobutane and alcohols or ketones
EP0697452A1 (en) * 1991-10-18 1996-02-21 E.I. Du Pont De Nemours And Company Azeotropic compositions of 1,1,2,2,3,3,4,4-octafluorobutane and alcohols or ketones
WO1993020177A1 (en) * 1992-04-02 1993-10-14 E.I. Du Pont De Nemours And Company Ternary azeotropic compositions

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Publication number Publication date
JPH04213397A (en) 1992-08-04
JP2812369B2 (en) 1998-10-22
ES2088953T3 (en) 1996-10-01
EP0445438B1 (en) 1996-06-05
DE4002120A1 (en) 1991-08-01
DK0445438T3 (en) 1996-11-04
US5073291A (en) 1991-12-17
DE59010360D1 (en) 1996-07-11

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