EP0974642A1 - 1,1,1,2,3,4,4,5,5,5-decafluoropentane-based cleaning and drying compositions - Google Patents

1,1,1,2,3,4,4,5,5,5-decafluoropentane-based cleaning and drying compositions Download PDF

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Publication number
EP0974642A1
EP0974642A1 EP99401419A EP99401419A EP0974642A1 EP 0974642 A1 EP0974642 A1 EP 0974642A1 EP 99401419 A EP99401419 A EP 99401419A EP 99401419 A EP99401419 A EP 99401419A EP 0974642 A1 EP0974642 A1 EP 0974642A1
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EP
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Prior art keywords
cleaning
azeotropic
compositions
mee
decafluoropentane
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Granted
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EP99401419A
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German (de)
French (fr)
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EP0974642B1 (en
Inventor
Pascal Michaud
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Arkema France SA
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Elf Atochem SA
Atofina SA
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Classifications

    • 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
    • C11D7/504—Azeotropic mixtures containing halogenated solvents all solvents being halogenated hydrocarbons
    • C11D7/505—Mixtures of (hydro)fluorocarbons
    • 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
    • C23G5/02803—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 fluorine

Definitions

  • the present invention relates to the field of fluorinated hydrocarbons and to more particularly for subject of new compositions usable for cleaning or dry solid surfaces.
  • 1,1,2-Trichloro-1,2,2-trifluoroethane (known in the trade under the designation F113) has been widely used in the industry for cleaning and degreasing of very diverse solid surfaces (metal parts, glasses, plastics, composites), for which an absence - or at least a content residual as low as possible - in impurities, especially organic, is required.
  • the F 113 was particularly suitable for this use because of its non-aggressive character with regard to the materials used.
  • This product was notably used in the manufacturing of printed circuits, to eliminate residues of substances used to improve the quality of welds (designated by the term weld flux). This disposal operation is designated in the trade by the term "defluxing".
  • F113 to degreasing heavy metal parts and high quality mechanical parts cleaning and with great precision like, for example, gyroscopes and military equipment, aerospace or medical.
  • the F113 is most often combined with other organic solvents (eg methanol), to improve its cleaning capacity.
  • azeotropic mixtures or almost azeotropic By quasi-azeotropic mixture is understood within the meaning of present invention a mixture of generally miscible chemical compounds which, under certain particular conditions of proportions, temperature and pressure, tip at substantially constant temperature while retaining substantially the same composition. When heated to reflux, such a mixture almost azeotropic is in equilibrium with a vapor phase whose composition is substantially the same as that of the liquid phase.
  • Such behavior azeotropic or near azeotropic is desirable to ensure functioning satisfactory of the machines in which the operations of cleaning mentioned above, and in particular to ensure recycling by distillation of the cleaning fluid.
  • F113 is also used in the fields, in particular in optics, for which it is required to have water-free surfaces, i.e. surfaces where water is only present as traces undetectable by the method of measurement (Karl Fisher method).
  • the F113 is for this purpose implemented in drying operations (or dewetting) of said surfaces, in combination with hydrophobic surfactants.
  • compositions based on F113 are now prohibited because F113 is one of the chlorofluorocarbons (CFCs) suspected of attacking or degrade stratospheric ozone.
  • CFCs chlorofluorocarbons
  • F113 can be replaced by 1,1-dichloro-1-fluoroethane (known as F141b), but the use of this substitute is already regulated because, although weak, its destructive effect on of ozone is not zero.
  • F141b 1,1-dichloro-1-fluoroethane
  • Application EP 0512885 describes a composition comprising from 93 to 99% by weight of 1,1,1,3,3-pentafluorobutane and from 1 to 7% of methanol, usable as a substitute for F113.
  • 1,1,1,3,3-pentafluorobutane also known in the trade under the name of F365mfc, is devoid of destructive effect vis-à-vis of ozone.
  • the object of the invention is to propose other compositions capable of to be used as a substitute for F113 or F141b, and without effect destructive to ozone.
  • the present invention therefore has for subject of azeotropic or quasi-azeotropic compositions comprising from 1 to 25% of 1,1,1,2,3,4,4,5,5,5,5-decafluoropentane, preferably from 5 to 20%, and 75 to 99% of 1,1,1,3,3-pentafluorobutane, preferably 80 to 95%. Except otherwise indicated, the percentages used in this text to indicate the content of the compositions according to the invention are percentages by weight.
  • the 1,1,1,2,3,4,4,5,5,5-decafluoropentane is a compound (also known as denomination 43-10 mee) completely devoid of destructive effect with respect to ozone.
  • compositions according to the invention make it possible to obtain very good results for cleaning and degreasing solid surfaces, as well as in drying and dewetting operations.
  • these compositions do not show a flash point under standard determination conditions (ASTM D 3828 standard) and therefore allow you to work in complete safety.
  • compositions according to the invention can be easily prepared by simple mixing of the constituents.
  • the 43-10 mee is commercially available; 365mfc can be prepared by at least one of the following methods: Zh. Org. Khim. 1980, 1401-1408 and 1982, 946 and 1168 ;. Zh. Org. Khim. 1988, 1558. J. Chem. Soc Perk. I, 1980, 2258; J Chem. Soc Perk. Trans, 2. 1983, 1713; J. Chem. Soc. C Perk. Trans, 2.198, 1713: J. Chem. Soc. C 1969, 1739: Chem. Soc. 1949, 2860: Zh. Anal. Khim, 1981 36 (6), 1125; J. Fluorite Chem.
  • a ternary composition according to the invention includes 5 to 20% of 43-10 mee, 75 to 90% of 365 mfc, and 1 to 10% of methanol. More particularly preferred is a ternary composition containing 10 15% from 43-10 mee, 80 to 85% from 365 mfc, and 2 to 8% methanol. In this field, there is an azeotrope with a boiling point of 33.2 ° C at normal atmospheric pressure.
  • the cleaning compositions based on 43-10 mee and 365 mfc according to the invention can, if desired, be protected from chemical attack resulting from their contact with water (hydrolysis), with light metals (constituting the solid surfaces to be cleaned), and / or against radical attacks likely to occur in cleaning processes, adding a usual stabilizer such as, for example, nitroalkanes (in particular nitromethane, nitroethane, nitropropane), acetals (dimethoxymethane) and ethers (1,4-dioxane, 1,3-dioxolane).
  • a usual stabilizer such as, for example, nitroalkanes (in particular nitromethane, nitroethane, nitropropane), acetals (dimethoxymethane) and ethers (1,4-dioxane, 1,3-dioxolane).
  • the proportion of stabilizer can range from 0.01 to 5% per relative to the total weight of the composition.
  • compositions according to the invention can be used in the same applications and be implemented in the same manner as previous compositions based on F113 or F141b. They are therefore suitable particularly for use in cleaning and degreasing surfaces solids, preferably for defluxing printed circuits, as well as for surface drying operations.
  • compositions can also be used as blowing agent polyurethane foams, as an agent for dry cleaning textiles, and as a refrigerant.
  • 100 g are introduced into the distiller of a distillation column (30 trays) of 43-10 mee and 100 g of 365mfc. The mixture is then heated at reflux for one hour to bring the system to balance.
  • This azeotrope used for cleaning solder flux or in degreasing of mechanical parts, gives good results.
  • 200 g are introduced into the distiller of a distillation column (30 trays) of a mixture comprising 9% of 43-10 mee and 91% of 365mfc. The mixture is then heated at reflux for an hour to bring the system to equilibrium.
  • 150g of a mixture containing by weight 9% of 43-10 mee, 90.5% of 365mfc and 0.5% of methylal as stabilizer are introduced into a small ultrasonic cleaning tank. After heating the system at reflux for one hour, an aliquot of the vapor phase is taken. Its analysis, by gas chromatography, shows the presence of methylal, which indicates that the mixture is also stabilized in the vapor phase.
  • 100 g are introduced into the distiller of a distillation column (30 trays) of 43-10 mee, 100 g of 365mfc and 50g of methanol. The mixture is then heated at reflux for one hour to bring the system to balance. When a temperature plateau is observed, a fraction of approximately 20 g is collected. This fraction and the fraction of the bottom remaining in the boiler are analyzed. by gas chromatography.
  • This azeotrope used for cleaning solder flux or in degreasing of mechanical parts, gives good results.
  • Example 2 the above azeotropic composition can be stabilized with 0.5% dimethoxymethane.
  • test circuits conforming to the IPC-B-25 standard described in the manual for test methods of the IPC (Institute for Interconnecting and Packaging Electronic Circuits; Lincolnwood, IL, USA). These circuits are coated with rosin-based solder flux (product marketed by ALPHAMETAL under the name R8F flow) and annealed in an oven at 220 ° C for 30 seconds.
  • rosin-based solder flux product marketed by ALPHAMETAL under the name R8F flow
  • these circuits are cleaned using of the azeotropic composition of Example 3, in a small machine ultrasound for 3 minutes by immersion in the liquid phase and 3 minutes by vapor phase.
  • the cleaning is evaluated according to the standardized procedure IPC 2.3.26 (also described in the manual cited above) using a precision conductivity meter.
  • the value obtained, 2.2 ⁇ g / cm 2 eq.NaCl, is lower than the ionic impurity threshold tolerated by the profession (2.5 ⁇ g / cm 2 eq.NaCl).

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Metallurgy (AREA)
  • Detergent Compositions (AREA)

Abstract

The compound is a satisfactory replacement for 1.1.2-trichloro-1,2,2-trifluoroethane (F 113) which has been widely used for cleaning and degreasing, but is now banned due to its suspected degradative action on the ozone layer. The azeotropic or quasi azeotropic compositions comprise 1 - 25% of 1,1,1,2,3,4,4,5,5,5-decafluoropentane (43-10 mee) and 75 - 99% of 1,1,1,3,3-penta-fluorobutane (F 365 mfc), preferably 80 - 95%. This gives a boiling point of 36.5 degrees C. at atmospheric pressure. An Independent claim is also included for the use of these compositions.

Description

La présente invention concerne le domaine des hydrocarbures fluorés et a plus particulièrement pour objet de nouvelles compositions utilisables pour nettoyer ou sécher des surfaces solides.The present invention relates to the field of fluorinated hydrocarbons and to more particularly for subject of new compositions usable for cleaning or dry solid surfaces.

Le 1,1,2-trichloro-1,2,2-trifluoroéthane (connu dans le métier sous la désignation F113) a été largement utilisé dans l'industrie pour le nettoyage et le dégraissage de surfaces solides très diverses (pièces métalliques, verres, plastiques, composites), pour lesquelles une absence - ou du moins une teneur résiduelle aussi faible que possible- en impuretés, notamment de nature organique, est exigée. Le F 113 convenait particulièrement bien à cet usage en raison de son caractère non agressif à l'égard des matériaux utilisés. Ce produit a été notamment utilisé dans le domaine de la fabrication des circuits imprimés, pour éliminer les résidus des substances utilisées pour améliorer la qualité des soudures (désignées par le terme de flux de soudures). Cette opération d'élimination est désignée dans le métier par le terme de "défluxage".1,1,2-Trichloro-1,2,2-trifluoroethane (known in the trade under the designation F113) has been widely used in the industry for cleaning and degreasing of very diverse solid surfaces (metal parts, glasses, plastics, composites), for which an absence - or at least a content residual as low as possible - in impurities, especially organic, is required. The F 113 was particularly suitable for this use because of its non-aggressive character with regard to the materials used. This product was notably used in the manufacturing of printed circuits, to eliminate residues of substances used to improve the quality of welds (designated by the term weld flux). This disposal operation is designated in the trade by the term "defluxing".

On peut mentionner également les applications du F113 au dégraissage de pièces métalliques lourdes et au nettoyage de pièces mécaniques de haute qualité et de grande précision comme, par exemple, les gyroscopes et le matériel militaire, aérospatial ou médical. Dans ses diverses applications, le F113 est le plus souvent associé à d'autres solvants organiques (par exemple le méthanol), afin d'améliorer sa capacité de nettoyage. On préfère alors utiliser des mélanges azéotropiques ou quasi azéotropiques. On entend par mélange quasi azéotropique au sens de la présente invention un mélange de composés chimiques généralement miscibles qui, dans certaines conditions particulières de proportions, de température et de pression, bout à température sensiblement constante tout en conservant sensiblement la même composition. Lorsqu'il est chauffé à reflux, un tel mélange quasi azéotropique est en équilibre avec une phase vapeur dont la composition est sensiblement la même que celle de la phase liquide. Un tel comportement azéotropique ou quasi azéotropique est désirable pour assurer un fonctionnement satisfaisant des machines dans lesquelles sont réalisées les opérations de nettoyage précitées, et notamment pour assurer le recyclage par distillation du fluide de nettoyage.We can also mention the applications of F113 to degreasing heavy metal parts and high quality mechanical parts cleaning and with great precision like, for example, gyroscopes and military equipment, aerospace or medical. In its various applications, the F113 is most often combined with other organic solvents (eg methanol), to improve its cleaning capacity. It is then preferable to use azeotropic mixtures or almost azeotropic. By quasi-azeotropic mixture is understood within the meaning of present invention a mixture of generally miscible chemical compounds which, under certain particular conditions of proportions, temperature and pressure, tip at substantially constant temperature while retaining substantially the same composition. When heated to reflux, such a mixture almost azeotropic is in equilibrium with a vapor phase whose composition is substantially the same as that of the liquid phase. Such behavior azeotropic or near azeotropic is desirable to ensure functioning satisfactory of the machines in which the operations of cleaning mentioned above, and in particular to ensure recycling by distillation of the cleaning fluid.

Le F113 est également utilisé dans les domaines, notamment en optique, pour lesquels il est exigé de disposer de surfaces exemptes d'eau, c'est-à-dire de surfaces où l'eau n'est présente qu'à l'état de traces indétectables par la méthode de mesure (méthode Karl Fisher). Le F113 est dans ce but mis en oeuvre dans des opérations de séchage (ou démouillage) des dites surfaces, en combinaison avec des agents tensio-actifs hydrophobes.F113 is also used in the fields, in particular in optics, for which it is required to have water-free surfaces, i.e. surfaces where water is only present as traces undetectable by the method of measurement (Karl Fisher method). The F113 is for this purpose implemented in drying operations (or dewetting) of said surfaces, in combination with hydrophobic surfactants.

Cependant, l'emploi de compositions à base de F113 est maintenant interdit car le F113 fait partie des chlorofluorocarbures (CFC) suspectés d'attaquer ou de dégrader l'ozone stratosphérique.However, the use of compositions based on F113 is now prohibited because F113 is one of the chlorofluorocarbons (CFCs) suspected of attacking or degrade stratospheric ozone.

Dans ces diverses applications, le F113 peut être remplacé par le 1,1-dichloro-1-fluoroéthane (connu sous la désignation F141b), mais l'utilisation de ce substitut est déjà réglementée car, bien que faible, son effet destructeur vis-à-vis de l'ozone n'est pas nul.In these various applications, F113 can be replaced by 1,1-dichloro-1-fluoroethane (known as F141b), but the use of this substitute is already regulated because, although weak, its destructive effect on of ozone is not zero.

La demande EP 0512885 décrit une composition comprenant de 93 à 99 % en poids de 1,1,1,3,3-pentafluorobutane et de 1 à 7 % de méthanol, utilisable comme substitut du F113. Le 1,1,1,3,3-pentafluorobutane, également connu dans le métier sous la dénomination de F365mfc, est dépourvu d'effet destructeur vis-à-vis de l'ozone.Application EP 0512885 describes a composition comprising from 93 to 99% by weight of 1,1,1,3,3-pentafluorobutane and from 1 to 7% of methanol, usable as a substitute for F113. 1,1,1,3,3-pentafluorobutane, also known in the trade under the name of F365mfc, is devoid of destructive effect vis-à-vis of ozone.

L'invention a pour but de proposer d'autres compositions susceptibles d'être utilisées comme substitut du F113 ou du F141b, et dépourvues d'effet destructeur vis-à-vis de l'ozone.The object of the invention is to propose other compositions capable of to be used as a substitute for F113 or F141b, and without effect destructive to ozone.

Pour contribuer à résoudre ce problème, la présente invention a donc pour objet des compositions azéotropiques ou quasi azéotropiques comprenant de 1 à 25 % de 1,1,1,2,3,4,4,5,5,5-décafluoropentane, de préférence de 5 à 20 %, et de 75 à 99 % de 1,1,1,3,3-pentafluorobutane, de préférence de 80 à 95 %. Sauf indication contraire, les pourcentages utilisés dans le présent texte pour indiquer la teneur des compositions selon l'invention sont des pourcentages en poids. Le 1,1,1,2,3,4,4,5,5,5-décafluoropentane est un composé (également connu sous la dénomination 43-10 mee) totalement dépourvu d'effet destructeur vis-à-vis de l'ozone.To contribute to solving this problem, the present invention therefore has for subject of azeotropic or quasi-azeotropic compositions comprising from 1 to 25% of 1,1,1,2,3,4,4,5,5,5,5-decafluoropentane, preferably from 5 to 20%, and 75 to 99% of 1,1,1,3,3-pentafluorobutane, preferably 80 to 95%. Except otherwise indicated, the percentages used in this text to indicate the content of the compositions according to the invention are percentages by weight. The 1,1,1,2,3,4,4,5,5,5-decafluoropentane is a compound (also known as denomination 43-10 mee) completely devoid of destructive effect with respect to ozone.

Dans ce domaine, il existe un azéotrope dont la température d'ébullition est de 36,5°C à la pression atmosphérique normale (1,013 bar).In this area, there is an azeotrope whose boiling point is 36.5 ° C at normal atmospheric pressure (1.013 bar).

Les compositions selon l'invention permettent d'obtenir de très bons résultats pour le nettoyage et le dégraissage des surfaces solides, ainsi que dans les opérations de séchage et démouillage des surfaces. De plus, ces compositions ne présentent pas de point éclair dans les conditions standard de détermination (norme ASTM D 3828) et permettent donc de travailler en toute sécurité.The compositions according to the invention make it possible to obtain very good results for cleaning and degreasing solid surfaces, as well as in drying and dewetting operations. In addition, these compositions do not show a flash point under standard determination conditions (ASTM D 3828 standard) and therefore allow you to work in complete safety.

Les compositions selon l'invention peuvent être facilement préparées par simple mélange des constituants. Le 43-10 mee est disponible dans le commerce ; le 365mfc peut être préparé par au moins une des méthodes suivantes :
   Zh. Org. Khim. 1980, 1401-1408 et 1982, 946 et 1168;. Zh. Org. Khim. 1988, 1558. J. Chem. Soc Perk. I, 1980, 2258; J Chem. Soc Perk. Trans, 2. 1983, 1713; J. Chem. Soc. C Perk. Trans, 2. 198, 1713: J. Chem. Soc. C 1969, 1739: Chem. Soc.1949, 2860: Zh. Anal. Khim, 1981 36 (6), 1125; J. Fluorine Chem. 1979, 325; Izv, Akad. Nauk. SSSR. Ser Khim. 1980, 2117 (en russe); Rosz. Chem. 1979 (48), 1697 et J.A.C.S. 67. 1195 (1945), 72, 3577 (1950) et 76, 2343 (1954).The compositions according to the invention can be easily prepared by simple mixing of the constituents. The 43-10 mee is commercially available; 365mfc can be prepared by at least one of the following methods:
Zh. Org. Khim. 1980, 1401-1408 and 1982, 946 and 1168 ;. Zh. Org. Khim. 1988, 1558. J. Chem. Soc Perk. I, 1980, 2258; J Chem. Soc Perk. Trans, 2. 1983, 1713; J. Chem. Soc. C Perk. Trans, 2.198, 1713: J. Chem. Soc. C 1969, 1739: Chem. Soc. 1949, 2860: Zh. Anal. Khim, 1981 36 (6), 1125; J. Fluorite Chem. 1979, 325; Izv, Akad. Nauk. SSSR. Ser Khim. 1980, 2117 (in Russian); Rosz. Chem. 1979 (48), 1697 and JACS 67. 1195 (1945), 72, 3577 (1950) and 76, 2343 (1954).

Selon une variante préférée, une composition ternaire selon l'invention comprend de 5 à 20 % de 43-10 mee, de 75 à 90 % de 365 mfc, et de 1 à 10 % de méthanol. Est plus particulièrement préférée une composition ternaire contenant 10 à 15 % de 43-10 mee, 80 à 85 % de 365 mfc, et 2 à 8 % de méthanol. Dans ce domaine, il existe un azéotrope dont la température d'ébullition est de 33,2°C à la pression atmosphérique normale.According to a preferred variant, a ternary composition according to the invention includes 5 to 20% of 43-10 mee, 75 to 90% of 365 mfc, and 1 to 10% of methanol. More particularly preferred is a ternary composition containing 10 15% from 43-10 mee, 80 to 85% from 365 mfc, and 2 to 8% methanol. In this field, there is an azeotrope with a boiling point of 33.2 ° C at normal atmospheric pressure.

Comme dans les compositions de nettoyage connues à base de F113 ou de F141b, les compositions de nettoyage à base de 43-10 mee et 365 mfc selon l'invention peuvent, si on le désire, être protégées contre les attaques chimiques résultant de leur contact avec l'eau (hydrolyse), avec des métaux légers (constituant les surfaces solides à nettoyer), et/ou contre les attaques radicalaires susceptibles de survenir dans les processus de nettoyage, en y ajoutant un stabilisant usuel tel que, par exemple, les nitroalcanes (notamment nitrométhane, nitroéthane, nitropropane), les acétals (diméthoxyméthane) et les éthers (1,4-dioxane, 1,3-dioxolane). La proportion de stabilisant peut aller de 0,01 à 5 % par rapport au poids total de la composition. Comme stabilisant, on préfère utiliser le diméthoxyméthane dont le point d'ébullition est proche de celui des compositions azéotropiques selon l'invention ; de ce fait, ce stabilisant suit parfaitement le cycle d'évaporation et condensation du solvant, ce qui est particulièrement intéressant dans les applications de nettoyage.As in the known cleaning compositions based on F113 or of F141b, the cleaning compositions based on 43-10 mee and 365 mfc according to the invention can, if desired, be protected from chemical attack resulting from their contact with water (hydrolysis), with light metals (constituting the solid surfaces to be cleaned), and / or against radical attacks likely to occur in cleaning processes, adding a usual stabilizer such as, for example, nitroalkanes (in particular nitromethane, nitroethane, nitropropane), acetals (dimethoxymethane) and ethers (1,4-dioxane, 1,3-dioxolane). The proportion of stabilizer can range from 0.01 to 5% per relative to the total weight of the composition. As stabilizer, it is preferred to use dimethoxymethane whose boiling point is close to that of the compositions azeotropics according to the invention; therefore, this stabilizer follows the cycle perfectly solvent evaporation and condensation, which is particularly interesting in cleaning applications.

Les compositions selon l'invention peuvent être utilisées dans les mêmes applications et être mises en oeuvre selon les mêmes modalités que les compositions antérieures à base de F113 ou de F141b. Elles conviennent donc particulièrement à l'utilisation pour le nettoyage et le dégraissage de surfaces solides, de préférence pour le défluxage des circuits imprimés, ainsi que pour les opérations de séchage des surfaces.The compositions according to the invention can be used in the same applications and be implemented in the same manner as previous compositions based on F113 or F141b. They are therefore suitable particularly for use in cleaning and degreasing surfaces solids, preferably for defluxing printed circuits, as well as for surface drying operations.

En ce qui concerne les modalités de mise en oeuvre, on peut citer notamment la mise en oeuvre dans des dispositifs adaptés au nettoyage et/ou séchage des surfaces, ainsi que par aérosol.With regard to the methods of implementation, we can cite in particular the implementation in devices suitable for cleaning and / or drying of surfaces, as well as by aerosol.

Ces compositions peuvent en outre être utilisées comme agent d'expansion des mousses polyuréthane, comme agent pour le nettoyage à sec des textiles, et comme fluide frigorigène.These compositions can also be used as blowing agent polyurethane foams, as an agent for dry cleaning textiles, and as a refrigerant.

Les exemples suivants illustrent l'invention sans la limiter. The following examples illustrate the invention without limiting it.

EXEMPLE 1 : EXAMPLE 1 : a) Mise en évidence d'un azéotrope 43-10mee/365mfc :a) Demonstration of a 43-10mee / 365mfc azeotrope:

Dans le bouilleur d'une colonne à distiller (30 plateaux), on introduit 100 g de 43-10 mee et 100 g de 365mfc. Le mélange est ensuite chauffé à reflux pendant une heure pour amener le système à l'équilibre.100 g are introduced into the distiller of a distillation column (30 trays) of 43-10 mee and 100 g of 365mfc. The mixture is then heated at reflux for one hour to bring the system to balance.

Lorsque l'on observe un palier de température, on recueille une fraction d'environ 20 g . Cette fraction, ainsi que la fraction de pied restant dans le bouilleur sont analysées par chromatographie en phase gazeuse.When we observe a temperature plateau, we collect a fraction about 20 g. This fraction, as well as the fraction of the bottom remaining in the boiler are analyzed by gas chromatography.

L'examen des résultats consignés dans le tableau ci-dessous indique la présence d'une composition azéotropique.

Figure 00040001
Examination of the results recorded in the table below indicates the presence of an azeotropic composition.
Figure 00040001

Cet azéotrope, employé pour le nettoyage de flux de soudure ou en dégraissage de pièces mécaniques, donne de bons résultats.This azeotrope, used for cleaning solder flux or in degreasing of mechanical parts, gives good results.

b) Vérification de la composition azéotropique :b) Verification of the azeotropic composition:

Dans le bouilleur d'une colonne à distiller (30 plateaux), on introduit 200 g d'un mélange comprenant 9 % de 43-10 mee et 91 % de 365mfc. Le mélange est ensuite chauffé à reflux pendant une heure pour amener le système à l'équilibre.200 g are introduced into the distiller of a distillation column (30 trays) of a mixture comprising 9% of 43-10 mee and 91% of 365mfc. The mixture is then heated at reflux for an hour to bring the system to equilibrium.

On soutire une fraction d'environ 20 g, qui est analysée par chromatographie en phase gazeuse.A fraction of approximately 20 g is withdrawn, which is analyzed by gas chromatography.

L'examen des résultats, consignés dans le tableau suivant, indique la présence d'un azéotrope 43-10 mee/365mfc, puisque la fraction recueillie a la même composition que le mélange initial. Il s'agit d'un azéotrope positif puisque son point d'ébullition est inférieur à celui du 43-10 mee (55°C) et à celui du 365mfc (40 °C).

Figure 00040002
Examination of the results, recorded in the following table, indicates the presence of an azeotrope 43-10 mee / 365mfc, since the fraction collected has the same composition as the initial mixture. It is a positive azeotrope since its boiling point is lower than that of 43-10 mee (55 ° C) and that of 365mfc (40 ° C).
Figure 00040002

EXEMPLE 2 : Composition stabilisée au diméthoxyméthane (méthylal) EXAMPLE 2 Composition stabilized with dimethoxymethane (methylal)

Dans une petite cuve de nettoyage à ultrasons, on introduit 150g d'un mélange contenant en poids 9 % de 43-10 mee, 90,5 % de 365mfc et 0,5 % de méthylal comme stabilisant. Après avoir chauffé le système à reflux pendant une heure, on prélève un aliquote de la phase vapeur. Son analyse, par chromatographie en phase gazeuse, montre la présence de méthylal, ce qui indique que le mélange est également stabilisé dans la phase vapeur.

Figure 00050001
150g of a mixture containing by weight 9% of 43-10 mee, 90.5% of 365mfc and 0.5% of methylal as stabilizer are introduced into a small ultrasonic cleaning tank. After heating the system at reflux for one hour, an aliquot of the vapor phase is taken. Its analysis, by gas chromatography, shows the presence of methylal, which indicates that the mixture is also stabilized in the vapor phase.
Figure 00050001

EXEMPLE 3EXAMPLE 3 a) Mise en évidence d'un azéotrope 43-10 mee/365mfc/méthanol :a) Demonstration of an azeotrope 43-10 mee / 365mfc / methanol:

Dans le bouilleur d'une colonne à distiller (30 plateaux), on introduit 100 g de 43-10 mee, 100 g de 365mfc et 50g de méthanol. Le mélange est ensuite chauffé à reflux pendant une heure pour amener le système à l'équilibre. Lorsque l'on observe un palier de température, on recueille une fraction d'environ 20 g. Cette fraction, ainsi que la fraction de pied restant dans le bouilleur sont analysées par chromatographie en phase gazeuse.100 g are introduced into the distiller of a distillation column (30 trays) of 43-10 mee, 100 g of 365mfc and 50g of methanol. The mixture is then heated at reflux for one hour to bring the system to balance. When a temperature plateau is observed, a fraction of approximately 20 g is collected. This fraction and the fraction of the bottom remaining in the boiler are analyzed. by gas chromatography.

L'examen des résultats consignés dans le tableau ci-dessous indique la présence d'une composition azéotropique.

Figure 00050002
Examination of the results recorded in the table below indicates the presence of an azeotropic composition.
Figure 00050002

b) Vérification de la composition azéotropiqueb) Verification of the azeotropic composition

Dans le bouilleur d'une colonne à distiller adiabatique (30 plateaux), on introduit 200 g d'un mélange comprenant 12 % de 43-10 mee, 83 % de 365mfc et 5 % de méthanol. Le mélange est ensuite chauffé à reflux pendant une heure pour amener le système à l'équilibre.In the boiler of an adiabatic distillation column (30 trays), introduced 200 g of a mixture comprising 12% of 43-10 mee, 83% of 365mfc and 5% methanol. The mixture is then heated at reflux for one hour to bring the system to balance.

On soutire une fraction d'environ 20 g, qui est analysée par chromatographie en phase gazeuse. A fraction of approximately 20 g is withdrawn, which is analyzed by gas chromatography.

Les résultats consignés dans le tableau suivant montrent la présence d'un azéotrope positif puisque son point d'ébullition est inférieur à ceux de ses trois composante.

Figure 00060001
The results recorded in the following table show the presence of a positive azeotrope since its boiling point is lower than those of its three components.
Figure 00060001

Cet azéotrope, employé pour le nettoyage de flux de soudure ou en dégraissage de pièces mécaniques, donne de bons résultats.This azeotrope, used for cleaning solder flux or in degreasing of mechanical parts, gives good results.

Comme dans l'exemple 2, la composition azéotropique ci-dessus peut être stabilisée avec 0,5 % de diméthoxyméthane.As in Example 2, the above azeotropic composition can be stabilized with 0.5% dimethoxymethane.

EXEMPLE 4 : Nettoyage de flux de soudure EXAMPLE 4 : Cleaning of welding flux

L'essai suivant est réalisé sur cinq circuits tests conformes à la norme IPC-B-25 décrite dans le manuel des méthodes de test de l'IPC (Institute for Interconnecting and Packaging Electronic Circuits; Lincolnwood, IL, USA). Ces circuits sont enduits de flux de soudure à base de colophane (produit commercialisé par de la Société ALPHAMETAL sous la dénomination flux R8F) et recuits dans une étuve à 220°C pendant 30 secondes.The following test is carried out on five test circuits conforming to the IPC-B-25 standard. described in the manual for test methods of the IPC (Institute for Interconnecting and Packaging Electronic Circuits; Lincolnwood, IL, USA). These circuits are coated with rosin-based solder flux (product marketed by ALPHAMETAL under the name R8F flow) and annealed in an oven at 220 ° C for 30 seconds.

Pour éliminer la colophane ainsi recuite, ces circuits sont nettoyés à l'aide de la composition azéotropique de l'exemple 3, dans une petite machine à ultrasons pendant 3 minutes par immersion dans la phase liquide et 3 minutes en phase vapeur.To eliminate the rosin thus annealed, these circuits are cleaned using of the azeotropic composition of Example 3, in a small machine ultrasound for 3 minutes by immersion in the liquid phase and 3 minutes by vapor phase.

Le nettoyage est évalué selon la procédure normalisée IPC 2.3.26 (décrite également dans le manuel cité précédemment) à l'aide d'un conductimètre de précision. La valeur obtenue, 2,2µg/cm2 éq.NaCl, est inférieure au seuil d'impuretés ioniques toléré par la profession (2,5 µg/cm2 éq.NaCl).The cleaning is evaluated according to the standardized procedure IPC 2.3.26 (also described in the manual cited above) using a precision conductivity meter. The value obtained, 2.2 µg / cm 2 eq.NaCl, is lower than the ionic impurity threshold tolerated by the profession (2.5 µg / cm 2 eq.NaCl).

Claims (7)

Compositions azéotropiques ou quasi azéotropiques comprenant de 1 à 25 % de 1,1,1,2,3,4,4,5,5,5-décafluoropentane, de préférence de 5 à 20 %, et de 75 à 99 % de 1,1,13,3-pentafluorobutane, de préférence de 80 à 95 %.Azeotropic or quasi-azeotropic compositions comprising from 1 to 25% of 1,1,1,2,3,4,4,5,5,5,5-decafluoropentane, preferably from 5 to 20%, and 75 to 99% of 1,1,13,3-pentafluorobutane, preferably 80 to 95%. Composition selon la revendication 1 sous forme d'azéotrope dont la température d'ébullition est de 36,5°C à la pression atmosphérique normaleComposition according to Claim 1 in the form of an azeotrope, the boiling point is 36.5 ° C at normal atmospheric pressure Compositions selon la revendication 1 comprenant de 5 à 20 % de 43-10 mee, de 75 à 90 % de 365 mfc, et de 1 à 10 % de méthanol.Compositions according to claim 1 comprising from 5 to 20% of 43-10 mee, from 75 to 90% of 365 mfc, and from 1 to 10% of methanol. Compositions selon la revendication 3 comprenant 10 à 15 % de 43-10 mee, 80 à 85 % de 365 mfc, et 2 à 8 % de méthanol.Compositions according to claim 3 comprising 10 to 15% of 43-10 mee, 80 to 85% of 365 mfc, and 2 to 8% of methanol. Composition selon l'une des revevendications 3 ou 4 sous forme d'azéotrope dont la température d'ébullition est de 33,2°C à la pression atmosphérique normale.Composition according to one of claims 3 or 4 in the form azeotrope with a boiling temperature of 33.2 ° C at pressure normal atmospheric. Compositions selon l'une des revendications 1 à 5 comprenant en outre au moins un stabilisant, de préférence le diméthoxyméthane.Compositions according to one of claims 1 to 5 further comprising at least one stabilizer, preferably dimethoxymethane. Utilisation des compositions selon l'une des revendications 1 à 6 pour le nettoyage et le dégraissage des surfaces solides, de préférence pour le défluxage des circuits imprimés, ainsi que pour les opérations de séchage des surfaces.Use of the compositions according to one of claims 1 to 6 for the cleaning and degreasing of solid surfaces, preferably for defluxing printed circuits, as well as for surface drying operations.
EP99401419A 1998-07-24 1999-06-11 1,1,1,2,3,4,4,5,5,5-decafluoropentane and 1,1,1,3,3-pentafluorobutane-based cleaning and drying compositions Expired - Lifetime EP0974642B1 (en)

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