EP0160854B1 - Azeotropähnliche Zusammensetzungen aus Trichlortrifluoräthan, Aceton, Nitromethan und Hexan - Google Patents

Azeotropähnliche Zusammensetzungen aus Trichlortrifluoräthan, Aceton, Nitromethan und Hexan Download PDF

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Publication number
EP0160854B1
EP0160854B1 EP85104402A EP85104402A EP0160854B1 EP 0160854 B1 EP0160854 B1 EP 0160854B1 EP 85104402 A EP85104402 A EP 85104402A EP 85104402 A EP85104402 A EP 85104402A EP 0160854 B1 EP0160854 B1 EP 0160854B1
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EP
European Patent Office
Prior art keywords
azeotrope
hexane
weight percent
composition
acetone
Prior art date
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.)
Expired - Lifetime
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EP85104402A
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English (en)
French (fr)
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EP0160854A1 (de
Inventor
Earl E. A. Lund
David Paul Wilson
Rajat Subhra Basu
Hang Thanh Pham
Eugene Francis Szafranski
Francis John Figiel
Aaron Colbert
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Honeywell International Inc
Original Assignee
AlliedSignal Inc
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Filing date
Publication date
Priority claimed from US06/685,871 external-priority patent/US4790955A/en
Application filed by AlliedSignal Inc filed Critical AlliedSignal Inc
Publication of EP0160854A1 publication Critical patent/EP0160854A1/de
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Publication of EP0160854B1 publication Critical patent/EP0160854B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/509—Mixtures of hydrocarbons and oxygen-containing solvents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning 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
    • C23G5/02809—Cleaning 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 chlorine and fluorine
    • C23G5/02812—Perhalogenated hydrocarbons
    • C23G5/02816—Ethanes
    • C23G5/02819—C2Cl3F3

Definitions

  • This invention relates to azeotrope-like mixtures of trichlorotrifluoroethane, acetone, nitromethane and hexane. These mixtures are useful in a variety of vapor degreasing or solvent cleaning applications including defluxing.
  • Vapor degreasing and solvent cleaning with fluorocarbon based solvents have found widespread use in industry for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.
  • vapor degreasing or solvent cleaning consists of exposing a room-temperature object to be cleaned to the vapors of a boiling solvent. Vapors condensing on the object provide clean distilled solvent to wash away grease or other contamination. Final evaporation of solvent from the object leaves behind no residue as would be the case where the object is simply washed in liquid solvent.
  • the conventional operation of a vapor degreaser consists of immersing the part to be cleaned in a sump of boiling solvent which removes the bulk of the soil, thereafter immersing the part in a sump containing freshly distilled solvent near room temperature, and finally exposing the part to solvent vapors over the boiling sump which condense on the cleaned part.
  • the part can also be sprayed with distilled solvent before final rinsing.
  • Vapor degreasers suitable in the above-described operations are well known in the art.
  • Sherliker et al. in US-A-3 085 918 disclose such suitable vapor degreasers comprising a boiling sump, a clean sump, a water separator, and other ancillary equipment.
  • Fluorocarbon solvents such as trichlorotrifluoroethane
  • Trichlorotrifluoroethane in particular has been found to have satisfactory solvent power for greases, oils, waxes and the like. It has therefore found widespread use for cleaning electric motors, compressors, heavy metal parts, delicate precision metal parts, printed circuit boards, gyroscopes, guidance systems, aerospace and missile hardware, aluminum parts and the like.
  • trichlorofrifluoroethane alone may have insufficient solvent power. Since trichlorotrifluoroethane is non-polar, it does not remove polar contaminants well.
  • trichlorotrifluoroethane has been mixed with polar components such as aliphatic alcohols or chlorocarbons such as methylene chloride.
  • polar components such as aliphatic alcohols or chlorocarbons such as methylene chloride.
  • US-A-3881949 discloses the use of mixtures of 1,1,2 trichloro - 1,2,2 - trifluoroethane and ethanol as solvents for vapor degreasers.
  • azeotropic compositions including the desired fluorocarbon components, such as trichlorotrifluoroethane, which include components which contribute additionally desired characteristics, such as polar functionality, increased solvency power, and stabilizers.
  • Azeotropic compositions are desired because they exhibit a minimum boiling point and do not fractionate upon boiling. This is desirable because in the previously described vapor degreasing equipment with which these solvents are employed, redistilled material is generated for final rinse-cleaning. Thus, the vapor degreasing system acts as a still.
  • solvent composition exhibits a constant boiling point, i.e., is an azeotrope or is azeotrope-like, fractionation will occur and undesirable solvent distribution may act to upset the cleaning and safety of processing.
  • Preferential evaporation of the more volatile components of the solvent mixtures which would be the case if they were not azeotrope or azeotrope-like, would result in mixtures with changed compositions which may have less desirable properties, such as lower solvency towards soils, less inertness towards metal, plastic or elastomer components, and increased flammability and toxicity.
  • US-A-2999815 discloses the azeotrope of 1,1,2 - trichloro - 1,2,2 - trifluoroethane and acetone
  • US-A-3573213 discloses the azeotrope of 1,1,2 - trichloro - 1,2,2 - trifluoroethane and nitromethane
  • US-A-4045366 discloses ternary azeotropic-like mixtures which contain 1,1,2 - trichlorotrifluoroethane, nitromethane and azetone
  • US-A-4279664 discloses an azeotrope-like composition consisting of trichlorotrifluoroethane, acetone, and hexane.
  • Another object of the invention is to provide novel constant boiling or essentially constant boiling solvents which are liquid at room temperature, will not fractionate under conditions of use and also have the foregoing advantages.
  • a further object is to provide azeotrope-like compositions which are relatively nontoxic and nonflammable both in the liquid phase and the vapour phase.
  • novel azeotrope-like compositions comprising 1,1,2 - trichloro - 1,2,2 - trifluoroethane, acetone, nitromethane and a hexane, having a boiling point of 44.0 ⁇ 0.2°C at 0.10132 MPa (760 mm Hg).
  • the preferred azeotrope-like compositions comprise from 72.7 to 87.8 weight percent of 1,1,2 - trichloro - 1,2,2 - trifluoroethane, from 10.0 to 16.6 weight percent of acetone, from 0.005 to 1.5 weight percent of nitromethane, and from 0.2 to 10.6 weight percent of a hexane.
  • the azeotrope-like compositions comprise from 77.9 to 87.6 weight percent of 1,1,2 - trichloro - 1,2,2 - trifluoroethane; from 10.0 to 14.2 weight percent of acetone; from 0.05 to 0.9 weight percent of nitromethane, and from 1.0 to 7.9 weight percent of a hexane.
  • Such compositions possess constant or essentially constant boiling points of about 44.0°C at 760 mm Hg (0.10132 MPa).
  • the precise azeotrope composition has not yet been determined but has been ascertained to be within the above ranges. Regardless of where the true azeotrope lies, all compositions within the indicated ranges, as well as certain compositions outside the indicated ranges, are azeotrope-like, as defined more particularly below.
  • these azeotrope-like compositions are stable, safe to use and that the preferred compositions of the invention are nonflammable (exhibit no flash point when tested by the Tag Open Cup test method-ASTM D1 310-16) and exhibit excellent solvency power.
  • These compositions have been found to be particularly effective when employed in conventional degreasing units for the dissolution of lubricating and machine cutting oils and the cleaning of such oils from solid surfaces.
  • azeotrope-like composition means that the composition behaves like a true azeotrope in terms of its constant boiling characteristics or tendency not to fractionate. upon boiling or evaporation. Such a composition may or may not be a true azeotrope.
  • the composition of the vapour formed during boiling or evaporation is identical or substantially identical to the original liquid composition.
  • the liquid' composition if it changes at all, changes only to a minimal or negligible extent. That is to be contrasted to non-azeotrope-like compositions in which during boiling or evaporation, the liquid composition changes to a substantial degree.
  • azeotrope-like compositions As is well known in the this art, another characteristic of azeotrope-like compositions is that there is a range of compositions containing the same components in varying proportions which are azeotrope-like. All such compositions are intended to be covered by the term azeotrope-like as used herein. As an example, it is well known that at differing pressures, the composition of a given azeotrope will vary at least slightly and changes in distillation pressures also change, at least slightly, the distillation temperatures. Thus, an azeotrope of A and B represents a unique type of relationship but with a variable composition depending on temperature and/or pressure.
  • the 1,1,2-trichloro-1,2,2-trifluoroethane, acetone, nitromethane, and hexane components of the novel solvent azeotrope-like compositions of the invention are all commercially available. Preferably they should be used in sufficiently high purity so as to avoid the introduction of adverse influences upon the solvency properties or constant boiling properties of the system.
  • a suitable grade of 1,1,2-trichloro-1,2,2-trifluoroethane, for example, is sold by Allied Corporation under the trade name "GENESOLV O D".
  • hexane is used herein as to mean any C 6 paraffin hydrocarbon (C 6 H 14 ) (see Ralphh's Chemical Dictionary, 3 rd Ed., McGraw Hill Book Co. (1944) p. 408).
  • hexane includes n-hexane,2 - methyl pentane, 3 - methylpentane, 2,2 - dimethyl butane, 2,3 - dimethylbutane and any and all mixtures thereof.
  • isohexane typically contains from about 35 to about 100 weight percent of 2 - methylpentane admixed with other hexane isomers.
  • each hexane isomer separately and in combination with other hexane isomers, form azeotrope-like compositions with 1,1,2 - trichloro - 1,2,2 - trifluoroethane, acetone, and nitromethane in accordance with the invention.
  • a solvent mixture containing about 84 weight percent of 1,1,2 - trichloro - 1,2,2 - trifluoroethane, about 12 weight percent of acetone, about 2 weight percent of n-hexane and about 1 weight percent nitromethane based on the total weight of the mixture.
  • This mixture was distilled utilizing a five liter, three-necked distillation flask containing a four plate column, a distillation head and a ASTM calibrated thermometer. The distillation process consisted of refluxing the solvent mixture for about one hour, and collecting eight distillation cuts.
  • Example 2 The procedure of Example 1 was repeated with a solvent mixture containing about 84 weight percent 1,1,2 - trichloro - 1,2,2 - trifluoroethane, about 12 weight percent of acetone, about 2 weight percent of n-hexane and about 1 weight percent nitromethane. All weight percents are based on the total weight of the mixture.
  • the barometric pressure was about 744.4 mm Hg (0.09924 MPa).
  • the distillation rate was about 20 ml/minute, and the distillation temperature was about 43.8°C.
  • the specific gravity was about 1.368 g/ml at (74°F) 23°C.
  • the four fractions were analyzed by gas chromatograph, and the results are set forth in the following Table II.
  • composition of this invention was evaluated in a stability test.
  • the analysis of the composition employed in this test is set forth in the following Table IV.
  • the above-referenced composition was refluxed at autogenous pressure in the presence of zinc and aluminum metal for a period of 48 hours. The composition was then analyzed for the presence of chloride ion. The greater the amount of chloride ion, the greater the amount of solvent breakdown.
  • a similar test and analysis were conducted using an azeotrope composition containing from about 83 to about 85 weight percent 1,1,2 - trichloro - 1,2,2 - trifluoroethane, from about 12.5 to about 13.5 weight percent acetone and from about 2.5 to about 3.5 weight percent n - hexane which is manufactured and sold by Allied Corporation under the trade name "GENESOLV° 404".
  • the azeotrope-like compositions of the invention may be determined through the use of distillation techniques designed to provide higher rectification of the distillate than found in the most demanding vapor degreaser systems.
  • distillation techniques designed to provide higher rectification of the distillate than found in the most demanding vapor degreaser systems.
  • a five theoretical plate Oldershaw distillation column was used with a cold water condensed, manual liquid dividing head. Typically, approximately 350 cc of liquid were charged to the distillation pot.
  • the liquid was a mixture comprised of various combinations of 1,1,2 - trichloro - 1,2,2 - trifluoroethane, acetone, nitromethane and hexane.
  • the mixture was heated at total reflux for about one hour to ensure equilibration.
  • the distillate was obtained using a 2:1 reflux ratio at a boil-up rate of 400-500 grams per hr. Approximately 300 cc of product were distilled and 6 approximately equivalent sized overhead cuts were collected. The vapor temperature (of the distillate), pot temperature, and barometric pressure were monitored. A constant boiling fraction was collected and analyzed by gas chromatography to determine the weight percentages of its components. A mixture was then made up according to the approximate compositions of the constant boiling fraction and was redistilled at the same conditions. Compositions of distillate and residue were compared by chromatographic analysis to verify the constant-boiling nature of the mixture.
  • Table VIII The constant boiling mixture obtained according to the present invention through the above described distillation techniques is shown in Table VIII.
  • each hexane isomer exhibits its own unique compositional identity in azeotrope-like mixtures with 1,1,2 - trichloro - 1,2,2 - trifluoroethane, acetone, and nitromethane and that each hexane isomer and mixtures thereof form azeotrope-like constant boiling mixtures thereof form azeotrope-like constant boiling mixtures at about 44.0 ⁇ 0.2°C with such components.
  • the hexane isomers and their boiling points are shown in the following Table IX.
  • constant boiling or essentially constant boiling for the purposes of this invention means constant boiling or essentially constant boiling in the environment of a vapour degreaser system such as utilized in the art. All such mixtures in accordance with the invention which are constant boiling or essentially constant boiling are "azeotrope-like" within the meaning of this invention.
  • a vapour phase degreasing machine was charged with a preferred azeotrope-like mixture in accordance with the invention comprising about 81.3 weight percent 1,1,2 - trichloro - 1,2,2 - trifluoroethane (FC-113), about 13.1 weight percent acetone, about 5.4 weight percent of commercial isohexane, and about 0.2 weight percent nitromethane.
  • FC-113 1,1,2 - trichloro - 1,2,2 - trifluoroethane
  • FC-113 1,1,2 - trichloro - 1,2,2 - trifluoroethane
  • the mixture was evaluated for its constant boiling or non-segregating characteristics.
  • Solvents were tested in a Baron Blakeslee refrigeration cooled 3 sump VPD (Series 5000 machine-Model No. MLR-216).
  • the solvent charge was brought to reflux and the individual sump compositions were determined with a Hewlett Packard 5890 Gas Chromatograph. Refluxing was continued for 21 hours and sump compositions were monitored throughout this time. A mixture was considered constant boiling or non-segregating if the maximum concentration difference between sumps for any mixture component was less than 0.3%.
  • This example illustrates the use of the preferred azeotrope-like composition of the invention to clean metal parts.
  • the metal coupons were sanded to give a totally clean, freshly exposed surface. Following a deionized water rinse, the coupons were rinsed in followed by methanol and air dried for 10 minutes. Four identical coupons were then dipped into each of the metal working fluids. Cleaning tests were run on two of these coupons shortly after dipping into the metal working fluids. The other two coupons were tested after standing for 24 hours. For cleaning, the parts were placed on racks in a stainless steel wire mesh basket. In a first step, this assembly was immersed in the work sump for two minutes, then transferred to the rinse sump for two minutes, followed by a two minute solvent distillate spray in the vapor zone. The final step was a one minute hold in the vapor zone.
  • the treated coupons were visually inspected for evidence of soil residue.
  • a water-break test was also applied wherein the coupons were immersed in water and allowed to drain for 10 seconds. The coupon surface was examined for breaks in the water film over the 10 second draining period. A coupon was considered totally clean if no soil residues or breaks in the water film during the water break test were noticeable on the surface of the coupon.
  • "316" stainless steel coupons were soiled with Trimsol metal working fluid
  • "1010" cold rolled steel coupons were soiled with Hocut 711 metal working fluid. All these soiled coupons were cleaned with the preferred azeotrope-like compositions of the invention and evaluated for cleanliness as described above. All the coupons were judged to be totally clean.

Claims (10)

1. Azeotrop-ähnliche 4-Komponentenzusammensetzungen, enthaltend 1,1,2 - Trichlor - 1,2,2 - trifluorethan und Aceton, dadurch gekennzeichnet, daß sie sowohl Nitromethan als auch ein Hexan enthalten und einen Siedepunkt von 44,0±0,2°C bei 0,10132 MPa (760 mm Hg) haben.
2. Azeotrop-ähnliche Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Hexan n-Hexan ist.
3. Azeotrop-ähnliche Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Hexan 2-Methylpentan ist.
4. Azeotrop-ähnliche Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Hexan 3 - Methylpentan ist.
5. Azeotrop-ähnliche Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Hexan 2,2 - Dimethylbutan ist.
6. Azeotrop-ähnliche Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Hexan 2,3 - Dimethylbutan ist.
7. Azeotrop-ähnliche Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Hexan Isohexan ist.
8. Azeotrop-ähnliche Zusammensetzung, dadurch gekennzeichnet, daß sie von 72,7 bis 87,8 Gew.-% 1,1,2 - Trichlor - 1,2,2 - trifluorethan, von 10,0 bis 16,6 Gew.-% Aceton, von 0,005 bis 1,5 Gew.-% Nitromethan und von 0,2 bis 10,6 Gew.-% eines Hexans enthält.
9. Azeotrop-ähnliche Zusammensetzung, dadurch gekennzeichnet, daß sie von 77,9 bis 87,6 Gew.-% 1,1,2 - Trichlor - 1,2,2 - trifluorethan, von 10,0 bis 14,2 Gew.-% Aceton, von 0,05 bis 0,9 Gew.-% Nitromethan und von 1,0 bis 7,9 Gew.-% eines Hexans enthält.
10. Azeotrop-ähnliche Zusammensetzung, dadurch gekennzeichnet, daß sie von 85,0 bis 86,5 Gew.-% 1,1,2 - Trichlor - 1,2,2 - trifluorethan, von 12,0 bis 13,0 Gew.-% Aceton, von 0,03 bis 0;5 Gew.-% Nitromethan und von 1,0 bis 2,0 Gew.-% n-Hexan enthält.
EP85104402A 1984-04-26 1985-04-12 Azeotropähnliche Zusammensetzungen aus Trichlortrifluoräthan, Aceton, Nitromethan und Hexan Expired - Lifetime EP0160854B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US60421084A 1984-04-26 1984-04-26
US604210 1984-04-26
US685871 1984-12-24
US06/685,871 US4790955A (en) 1984-12-24 1984-12-24 Azeotrope-like compositions of trichlorotrifluoroethane, acetone, nitromethane and hexane

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EP0160854A1 EP0160854A1 (de) 1985-11-13
EP0160854B1 true EP0160854B1 (de) 1990-03-14

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EP (1) EP0160854B1 (de)
KR (1) KR900001828B1 (de)
CA (1) CA1268390A (de)
DE (1) DE3576541D1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4655956A (en) * 1985-10-02 1987-04-07 Allied Corporation Azeotrope-like compositions of trichlorotrifluoroethane, methanol, nitromethane and hexane
EP0217181A3 (de) * 1985-10-02 1988-08-31 AlliedSignal Inc. Azeotropähnliche Zusammensetzungen von Trichlorfluoräthan, Methanol, Nitromethan, Hexan und Azeton
JPH01170697A (ja) * 1987-12-26 1989-07-05 Daikin Ind Ltd 不燃性共沸様溶剤組成物
GB2226570A (en) * 1988-12-27 1990-07-04 Allied Signal Inc Azeotrope-like compositions
MY107434A (en) * 1989-10-26 1995-12-30 Momentive Performance Mat Jp Cleaning compositions.
US5503681A (en) * 1990-03-16 1996-04-02 Kabushiki Kaisha Toshiba Method of cleaning an object
US5593507A (en) * 1990-08-22 1997-01-14 Kabushiki Kaisha Toshiba Cleaning method and cleaning apparatus

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903009A (en) * 1973-11-16 1975-09-02 Du Pont Azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane, ethanol and nitromethane
JPS5634798A (en) * 1979-08-29 1981-04-07 Daikin Ind Ltd Azeotropic mixed solvent composition
JPS5634799A (en) * 1979-08-29 1981-04-07 Daikin Ind Ltd Azeotropic mixed solvent composition
JPS56109298A (en) * 1980-01-31 1981-08-29 Daikin Ind Ltd Azeotropic solvent composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4045366A (en) * 1976-05-13 1977-08-30 Allied Chemical Corporation Azeotrope-like compositions of trichlorotrifluoroethane, nitromethane and acetone
US4279664A (en) * 1980-04-09 1981-07-21 Allied Chemical Corporation Azeotrope-like compositions of trichlorotrifluoroethane, acetone and n-hexane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903009A (en) * 1973-11-16 1975-09-02 Du Pont Azeotrope of 1,1,2-trichloro-1,2,2-trifluoroethane, ethanol and nitromethane
JPS5634798A (en) * 1979-08-29 1981-04-07 Daikin Ind Ltd Azeotropic mixed solvent composition
JPS5634799A (en) * 1979-08-29 1981-04-07 Daikin Ind Ltd Azeotropic mixed solvent composition
JPS56109298A (en) * 1980-01-31 1981-08-29 Daikin Ind Ltd Azeotropic solvent composition

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KR900001828B1 (ko) 1990-03-24
DE3576541D1 (de) 1990-04-19
CA1268390A (en) 1990-05-01
KR850007823A (ko) 1985-12-09
EP0160854A1 (de) 1985-11-13

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