EP1046703A1 - Cleaning or drying compositions based on pentafluorobutane, methylene chloride, methanol and decafluoropentane - Google Patents
Cleaning or drying compositions based on pentafluorobutane, methylene chloride, methanol and decafluoropentane Download PDFInfo
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- EP1046703A1 EP1046703A1 EP00400777A EP00400777A EP1046703A1 EP 1046703 A1 EP1046703 A1 EP 1046703A1 EP 00400777 A EP00400777 A EP 00400777A EP 00400777 A EP00400777 A EP 00400777A EP 1046703 A1 EP1046703 A1 EP 1046703A1
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- Prior art keywords
- cleaning
- methanol
- pentafluorobutane
- azeotropic
- decafluoropentane
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- 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
- C11D7/5077—Mixtures of only oxygen-containing solvents
- C11D7/5081—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being alcohols only
Definitions
- the present invention relates to the field of fluorinated hydrocarbons and more particularly for the subject of new compositions which can be used for cleaning or drying solid surfaces.
- 1,1,2-Trichloro-1,2,2-trifluoroethane (known in the trade under the designation F113) has been widely used in industry for cleaning and degreasing very diverse solid surfaces (metal parts, glasses, plastics, composites), for which an absence - or at least a residual content as low as possible - in impurities, especially organic, is required.
- the F 113 was suitable particularly well for this use because of its non-aggressive nature towards used materials.
- This product has been used in particular in the field of manufacturing printed circuits, to remove residues from substances used to improve the quality of the welds (designated by the term weld flux). This operation elimination is designated in the art by the term "defluxing".
- F113 to degreasing parts heavy metal and cleaning of high quality and large mechanical parts precision such as, for example, gyroscopes and military, aerospace or medical.
- the F113 is most often associated with other organic solvents (eg methanol), to improve its cleaning capacity.
- azeotropic or quasi-azeotropic mixtures a mixture of compounds generally miscible chemicals which under certain special conditions of proportions, temperature and pressure, tip at substantially constant temperature while retaining substantially the same composition.
- quasi-azeotropic mixture When heated to reflux, such quasi-azeotropic mixture is in equilibrium with a vapor phase whose composition is substantially the same as that of the liquid phase.
- Such azeotropic behavior or almost azeotropic is desirable to ensure satisfactory operation of machines in which the above-mentioned cleaning operations are carried out, and in particular for recycling the cleaning fluid by distillation.
- F113 is also used in the fields, in particular in optics, for which are required to have water-free surfaces, i.e. surfaces where water is only present in traces undetectable by the measurement method (method Karl Fisher).
- F113 is used in drying operations (or dewetting) of said surfaces, in combination with surfactants hydrophobic.
- compositions based on F113 are now prohibited since the F113 is one of the chlorofluorocarbons (CFCs) suspected of attacking or degrading ozone stratospheric.
- 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 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 substitute for F113.
- 1,1,1,3,3-pentafluorobutane also known in the art as denomination of F365mfc, has no destructive effect with respect to ozone.
- EP 0856578 describes a composition comprising from 10 to 90% in weight of 1,1,1,2,3,4,4,5,5,5,5-decafluoropentane, 10 to 90% of dichloromethane, and 0 10% methanol, also usable as a substitute for F113.
- 1,1,1,2,3,4,4,5,5,5-decafluoropentane known in the trade under the name of 43-10mee is also devoid of destructive effect with respect to ozone.
- the object of the invention is to propose other compositions capable of being used as a substitute for F113 or F141b, and devoid of any destructive effect on it of ozone.
- compositions according to the invention make it possible to obtain very good results for cleaning and degreasing of solid surfaces, as well as in drying and dewetting of surfaces.
- these compositions do not have a point flash under standard determination conditions (ASTM D 3828) and allow therefore to work safely.
- 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.
- cleaning compositions based on 365 mfc, dichloromethane, methanol and 43-10 mee can, if desired, be protected against attack chemicals 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 (especially nitromethane, nitroethane, nitropropane), acetals (dimethoxymethane) or ethers (1,4-dioxane, 1,3-dioxolane).
- a usual stabilizer such as, for example, nitroalkanes (especially nitromethane, nitroethane, nitropropane), acetals (dimethoxymethane) or ethers (1,4-dioxane, 1,3-dioxolane).
- the proportion of stabilizer can range from 0.01 to 5% relative to the total weight of the composition.
- compositions according to the invention other solvents such as alcohols, ketones, ethers, acetals, esters, hydrocarbons, solvents chlorinated, brominated, iodinated, sulfones, or water, in the presence of surfactants (anionics, non-ionic or cationic) fluorinated, silicone or not, in order to obtain properties specific, especially in dry cleaning.
- solvents such as alcohols, ketones, ethers, acetals, esters, hydrocarbons, solvents chlorinated, brominated, iodinated, sulfones, or water
- surfactants anionics, non-ionic or cationic fluorinated, silicone or not
- compositions according to the invention can be used in the same applications and be implemented in the same manner as the compositions based on F113 or F141b. They are therefore particularly suitable for use for cleaning and degreasing solid surfaces, preferably for defluxing of printed circuits, as well as for surface drying operations.
- a surfactant hydrophobic soluble in the composition, in order to further improve the elimination of water from surfaces to be treated, until 100% elimination is achieved.
- the composition generally comprises from 92 to 99.5% of the quaternary azeotropic composition, and 0.05 to 8% surfactant.
- compositions according to the invention can cite in particular the implementation in devices adapted to the cleaning and / or drying of surfaces, as well as by aerosol.
- compositions according to the invention can be packaged with, as propellant, 134a (or 227e of formula CF 3 CHF-CF 3 ), and their mixture with 152a and / or DME (Dimethylether) to offer additional cleaning possibilities, especially at room temperature.
- the compositions according to the invention thus conditioned do not have a flame length, according to standard 609F of the European Aerosol Federation (Brussels, Belgium) (Determination of the ignition distance of a spray or a jet emitted at from an aerosol container).
- compositions can also be used as a blowing agent for polyurethane foams, as a dry cleaning agent for textiles, and as a fluid refrigerant.
- 50 g of 43-10 are introduced into the distiller of a distillation column (30 trays) mee and 100 g of 365mfc, 50 g of methanol and 100 g of dichloromethane. The mixture is then heated at reflux for an hour to bring the system to equilibrium.
- a fraction of approximately 20 g is withdrawn, which is analyzed by chromatography in gas phase.
- the above azeotropic composition can be stabilized with 0.5% of dimethoxymethane.
- test circuits conforming to the IPC-B-25 standard. described in the IPC (Institute for Interconnecting and Packaging Electronic Circuits; Lincolnwood, IL, USA). These circuits are coated with flux rosin-based solder (product marketed by ALPHAMETAL under the name flow R8F) and annealed in an oven at 220 ° C for 30 seconds.
- flux rosin-based solder product marketed by ALPHAMETAL under the name flow R8F
- these circuits are cleaned using the azeotropic composition of Example 1, in a small ultrasonic machine for 3 minutes by immersion in the liquid phase and 3 minutes in the vapor phase.
- the cleaning is evaluated according to the standardized procedure IPC 2.3.26 (described also in the manual cited above) using a precision conductivity meter.
- a 5x3 cm stainless steel grid is soaked in water for a few seconds.
- the water retention capacity of this grid is measured by soaking the grid in absolute ethyl alcohol, then assay by the Karl Fisher method used with this alcoholic solution.
- This grid is then immersed for 30 seconds in the composition of drying thus prepared, by stirring manually. We remove the grid from this composition, and the residual water is assayed using the Karl Fischer method, as described above.
- the amount of water called the elimination rate (expressed as a percentage) residual after drying divided by the water retention capacity of the grid (corrected for the water content of the absolute ethyl alcohol used).
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Abstract
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 more particularly for the subject of new compositions which can be used for cleaning or drying 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 industry for cleaning and degreasing very diverse solid surfaces (metal parts, glasses, plastics, composites), for which an absence - or at least a residual content as low as possible - in impurities, especially organic, is required. The F 113 was suitable particularly well for this use because of its non-aggressive nature towards used materials. This product has been used in particular in the field of manufacturing printed circuits, to remove residues from substances used to improve the quality of the welds (designated by the term weld flux). This operation elimination is designated in the art 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 parts heavy metal and cleaning of high quality and large mechanical parts precision such as, for example, gyroscopes and military, aerospace or medical. In its various applications, the F113 is most often associated with other organic solvents (eg methanol), to improve its cleaning capacity. It is therefore preferable to use azeotropic or quasi-azeotropic mixtures. We hear by quasi-azeotropic mixture within the meaning of the present invention a mixture of compounds generally miscible chemicals which under certain special conditions of proportions, temperature and pressure, tip at substantially constant temperature while retaining substantially the same composition. When heated to reflux, such quasi-azeotropic mixture is in equilibrium with a vapor phase whose composition is substantially the same as that of the liquid phase. Such azeotropic behavior or almost azeotropic is desirable to ensure satisfactory operation of machines in which the above-mentioned cleaning operations are carried out, and in particular for recycling the cleaning fluid by distillation.
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 are required to have water-free surfaces, i.e. surfaces where water is only present in traces undetectable by the measurement method (method Karl Fisher). For this purpose, F113 is used in drying operations (or dewetting) of said surfaces, in combination with surfactants hydrophobic.
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 since the F113 is one of the chlorofluorocarbons (CFCs) suspected of attacking or degrading ozone stratospheric.
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 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 substitute for F113. 1,1,1,3,3-pentafluorobutane, also known in the art as denomination of F365mfc, has no destructive effect with respect to ozone.
La demande EP 0856578 décrit une composition comprenant de 10 à 90 % en poids de 1,1,1,2,3,4,4,5,5,5-décafluoropentane, de 10 à 90 % de dichlorométhane, et de 0 à 10 % de méthanol, également utilisable comme substitut du F113. Le 1,1,1,2,3,4,4,5,5,5-décafluoropentane connu dans le métier sous la dénomination de 43-10mee est aussi dépourvu d'effet destructeur vis-à-vis de l'ozone.EP 0856578 describes a composition comprising from 10 to 90% in weight of 1,1,1,2,3,4,4,5,5,5,5-decafluoropentane, 10 to 90% of dichloromethane, and 0 10% methanol, also usable as a substitute for F113. 1,1,1,2,3,4,4,5,5,5-decafluoropentane known in the trade under the name of 43-10mee is also devoid of destructive effect with respect to 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 being used as a substitute for F113 or F141b, and devoid of any destructive effect on it of ozone.
Pour contribuer à résoudre ce problème, la présente invention a donc pour objet des compositions azéotropiques ou quasi azéotropiques comprenant :
- de 45 à 65 % de 1,1,1,3,3-pentafluorobutane, de préférence de 50 à 60 %,
- de 30 à 50 % de dichlorométhane, de préférence de 35 à 45 %
- de 1 à 10 % de méthanol, de préférence de 2 à 5 % et
- de 0,1 à 2 % de 1,1,1,2,3,4,4,5,5,5-décafluoropentane, de préférence de 0,2 à 1%.
- from 45 to 65% of 1,1,1,3,3-pentafluorobutane, preferably from 50 to 60%,
- from 30 to 50% of dichloromethane, preferably from 35 to 45%
- from 1 to 10% of methanol, preferably from 2 to 5% and
- from 0.1 to 2% of 1,1,1,2,3,4,4,5,5,5-decafluoropentane, preferably from 0.2 to 1%.
Sauf indication contraire, les pourcentages utilisés dans le présent texte pour indiquer la teneur des compositions selon l'invention sont des pourcentages en poids.Unless otherwise indicated, the percentages used in this text for indicate the content of the compositions according to the invention are percentages by weight.
Dans ce domaine, il existe un azéotrope dont la température d'ébullition est de 31,9°C à la pression atmosphérique normale (1,013 bar).In this area, there is an azeotrope with a boiling point of 31.9 ° 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 of solid surfaces, as well as in drying and dewetting of surfaces. In addition, these compositions do not have a point flash under standard determination conditions (ASTM D 3828) and allow therefore to work safely.
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).
Comme dans les compositions de nettoyage connues à base de F113 ou de F141b, les compositions de nettoyage à base de 365 mfc, de dichlorométhane, de méthanol et de 43-10 mee, 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) ou 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 F141b, cleaning compositions based on 365 mfc, dichloromethane, methanol and 43-10 mee, according to the invention, can, if desired, be protected against attack chemicals 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 (especially nitromethane, nitroethane, nitropropane), acetals (dimethoxymethane) or ethers (1,4-dioxane, 1,3-dioxolane). The proportion of stabilizer can range from 0.01 to 5% relative to the total weight of the composition. As stabilizer, it is preferable to use dimethoxymethane whose point of boiling is close to that of the azeotropic compositions according to the invention; thereby, this stabilizer perfectly follows the evaporation and condensation cycle of the solvent, which is particularly interesting in cleaning applications.
On peut mélanger aux compositions selon l'invention d'autres solvants comme les alcools, les cétones, les éthers, les acétals, les esters, les hydrocarbures, les solvants chlorés, bromés, iodés, les sulfones, ou de l'eau, en présence de tensio-actifs (anioniques, non ioniques ou cationiques) fluorés, siliconés ou non, afin d'obtenir des propriétés spécifiques, en particulier en nettoyage à sec.It is possible to mix with the compositions according to the invention other solvents such as alcohols, ketones, ethers, acetals, esters, hydrocarbons, solvents chlorinated, brominated, iodinated, sulfones, or water, in the presence of surfactants (anionics, non-ionic or cationic) fluorinated, silicone or not, in order to obtain properties specific, especially in dry cleaning.
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 the compositions based on F113 or F141b. They are therefore particularly suitable for use for cleaning and degreasing solid surfaces, preferably for defluxing of printed circuits, as well as for surface drying operations.
En ce qui concerne cette dernière utilisation, on préfère ajouter un tensio-actif hydrophobe soluble dans la composition, afin d'améliorer encore l'élimination de l'eau des surfaces à traiter, jusqu'à atteindre une élimination de 100 %.Regarding the latter use, it is preferred to add a surfactant hydrophobic soluble in the composition, in order to further improve the elimination of water from surfaces to be treated, until 100% elimination is achieved.
Parmi les tensio-actifs hydrophobes, les diamides de formule :
Selon cette variante préférée des compostions selon l'invention, la composition comprend généralement de 92 à 99,5 % de la composition azéotropique quaternaire, et de 0,05 à 8 % de tensio-actif.According to this preferred variant of the compositions according to the invention, the composition generally comprises from 92 to 99.5% of the quaternary azeotropic composition, and 0.05 to 8% surfactant.
En ce qui concerne les modalités de mise en oeuvre des compositions selon l'invention, on peut citer notamment la mise en oeuvre dans des dispositifs adaptés au nettoyage et/ou séchage des surfaces, ainsi que par aérosol.As regards the methods of implementation of the compositions according to the invention, one can cite in particular the implementation in devices adapted to the cleaning and / or drying of surfaces, as well as by aerosol.
Concernant la mise en oeuvre par aérosol, les compositions selon l'invention peuvent être conditionnées avec, comme agent propulsant, du 134a (ou du 227e de formule CF3CHF-CF3), et leur mélange avec le 152a et/ou le DME (Diméthyléther) pour offrir des possibilités complémentaires de nettoyage, notamment à température ambiante. Les compositions selon l'invention ainsi conditionnées ne présentent pas de longueur de flamme, selon la norme 609F de la Fédération Européenne des Aérosols (Bruxelles, Belgique) (Détermination de la distance d'ignition d'un spray ou d'un jet émis à partir d'un récipient aérosol).Regarding the use by aerosol, the compositions according to the invention can be packaged with, as propellant, 134a (or 227e of formula CF 3 CHF-CF 3 ), and their mixture with 152a and / or DME (Dimethylether) to offer additional cleaning possibilities, especially at room temperature. The compositions according to the invention thus conditioned do not have a flame length, according to standard 609F of the European Aerosol Federation (Brussels, Belgium) (Determination of the ignition distance of a spray or a jet emitted at from an aerosol container).
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 a blowing agent for polyurethane foams, as a dry cleaning agent for textiles, and as a fluid refrigerant.
L'exemple suivant illustre l'invention sans la limiter.The following example illustrates the invention without limiting it.
Dans le bouilleur d'une colonne à distiller (30 plateaux), on introduit 50 g de 43-10 mee et 100 g de 365mfc, 50 g de méthanol et 100 g de dichlorométhane. Le mélange est ensuite chauffé à reflux pendant une heure pour amener le système à l'équilibre.50 g of 43-10 are introduced into the distiller of a distillation column (30 trays) mee and 100 g of 365mfc, 50 g of methanol and 100 g of dichloromethane. The mixture is then heated at reflux for an hour to bring the system to equilibrium.
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 of about 20g. 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.
Dans le bouilleur d'une colonne à distiller (30 plateaux), on introduit 200 g d'un mélange comprenant 56,2% de 365mfc, 39,8% de CH2Cl2, 3,5 % de MeOH, et 0,5 % de 43-10. Le mélange est ensuite chauffé à reflux pendant une heure pour amener le système à l'équilibre.In the boiler of a distillation column (30 trays), 200 g of a mixture comprising 56.2% of 365mfc, 39.8% of CH2Cl2, 3.5% of MeOH, and 0.5% of 43-10. The mixture is then heated at reflux for one hour to bring the system 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 chromatography in gas phase.
L'examen des résultats, consignés dans le tableau suivant, indique la présence
d'un azéotrope quaternaire 365mfc/CH2Cl2/CH3OH/43-10mee, 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 de chacun des produits purs, soit 40°C pour le
365mfc, 40°C pour le CH2Cl2, 65°C pour le CH3OH, et 55 °C pour le 43-10 mee.
La composition azéotropique ci-dessus peut être stabilisée avec 0,5 % de diméthoxyméthane.The above azeotropic composition can be stabilized with 0.5% of dimethoxymethane.
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 IPC (Institute for Interconnecting and Packaging Electronic Circuits; Lincolnwood, IL, USA). These circuits are coated with flux rosin-based solder (product marketed by ALPHAMETAL under the name flow R8F) 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 1, 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 the azeotropic composition of Example 1, in a small ultrasonic machine for 3 minutes by immersion in the liquid phase and 3 minutes in the 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.The cleaning is evaluated according to the standardized procedure IPC 2.3.26 (described also in the manual cited above) using a precision conductivity meter.
La valeur obtenue, 1,9 µg/cm2 éq.NaCl, est inférieure au seuil d'impuretés ioniques toléré par la profession (2,5 µg/cm2 éq.NaCl).The value obtained, 1.9 µg / cm 2 eq.NaCl, is lower than the ionic impurity threshold tolerated by the profession (2.5 µg / cm 2 eq.NaCl).
On prépare 250 ml d'une composition de séchage comprenant 99,8 % de la composition décrite dans l'exemple 1, à laquelle on ajoute 0,2 % de dioléyl d'oléylamido propylène amide (composé de formule (I), dans laquelle R est un radical alkyle comprenant en moyenne 18 atomes de carbone, et n égale 3).250 ml of a drying composition comprising 99.8% of the composition described in Example 1, to which 0.2% of oleylamido dioleyl is added propylene amide (compound of formula (I), in which R is an alkyl radical comprising on average 18 carbon atoms, and n equals 3).
Une grille inox de dimension 5x3 cm est trempée dans de l'eau, durant quelques secondes.A 5x3 cm stainless steel grid is soaked in water for a few seconds.
La capacité de rétention d'eau de cette grille est mesurée par trempage de la grille dans de l'alcool éthylique absolu, puis dosage par la méthode de Karl Fisher mise en oeuvre avec cette solution alcoolique.The water retention capacity of this grid is measured by soaking the grid in absolute ethyl alcohol, then assay by the Karl Fisher method used with this alcoholic solution.
Cette grille est ensuite immergée pendant 30 secondes dans la composition de séchage ainsi préparée, en l'agitant manuellement. On retire la grille de cette composition, et l'on procéde au dosage de l'eau résiduelle au moyen de la méthode de Karl Fischer, comme décrit ci-dessus.This grid is then immersed for 30 seconds in the composition of drying thus prepared, by stirring manually. We remove the grid from this composition, and the residual water is assayed using the Karl Fischer method, as described above.
On appelle taux d'élimination (exprimé en pourcentage) la quantité d'eau résiduelle après séchage divisée par la capacité de rétention d'eau de la grille (corrigée de la teneur en eau de l'alcool éthylique absolu utilisé).The amount of water called the elimination rate (expressed as a percentage) residual after drying divided by the water retention capacity of the grid (corrected for the water content of the absolute ethyl alcohol used).
On mesure un taux d'élimination de l'eau de 100 %.We measure a water removal rate of 100%.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9905130A FR2792647B1 (en) | 1999-04-22 | 1999-04-22 | CLEANING OR DRYING COMPOSITIONS BASED ON F365 mfc, CH2CL2, CH3OH AND 43-10mee |
| FR9905130 | 1999-04-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1046703A1 true EP1046703A1 (en) | 2000-10-25 |
| EP1046703B1 EP1046703B1 (en) | 2003-10-15 |
Family
ID=9544753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00400777A Expired - Lifetime EP1046703B1 (en) | 1999-04-22 | 2000-03-21 | Cleaning or drying compositions based on pentafluorobutane, methylene chloride, methanol and decafluoropentane |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6291416B1 (en) |
| EP (1) | EP1046703B1 (en) |
| JP (1) | JP2000328095A (en) |
| AU (1) | AU764299B2 (en) |
| CA (1) | CA2305019A1 (en) |
| DE (1) | DE60005881T2 (en) |
| ES (1) | ES2208232T3 (en) |
| FR (1) | FR2792647B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008073408A1 (en) * | 2006-12-12 | 2008-06-19 | E. I. Du Pont De Nemours And Company | Azeotrope-like mixtures comprising heptafluorocyclopentane |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254528C (en) * | 2001-02-14 | 2006-05-03 | 株式会社金子化学 | Solvent composition for washing |
| US6979668B2 (en) * | 2002-12-16 | 2005-12-27 | Generex Pharmaceuticals Incorporated | Cleaning compound for and method of cleaning valves and actuators of metered dose dispensers containing pharmaceutical compositions |
| JP2006521460A (en) * | 2002-12-17 | 2006-09-21 | ハネウェル・インターナショナル・インコーポレーテッド | Compositions and methods for cleaning contaminated articles |
| JP3640661B1 (en) * | 2004-03-09 | 2005-04-20 | 株式会社カネコ化学 | Pentafluorobutane composition |
| FR2874383B1 (en) * | 2004-08-18 | 2006-10-13 | Arkema Sa | COMPOSITION BASED ON 1,1,1,3,3 - PENTAFLUOROBUTANE, USEFUL IN DEPOT APPLICATION, CLEANING, DEGREASING AND DRYING |
| JP3955878B1 (en) | 2006-06-28 | 2007-08-08 | 株式会社カネコ化学 | Pentafluorobutane composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5350534A (en) * | 1992-08-21 | 1994-09-27 | Elf Atochem S.A. | Composition based on 1,1,1,3,3-pentafluorobutane, methylene chloride and methanol, for the cleaning and/or drying of solid surfaces |
| WO1996030487A1 (en) * | 1995-03-31 | 1996-10-03 | Solvay (Societe Anonyme) | Hydrofluorocarbon-containing compositions and method for removing water from a solid surface |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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. |
| FR2694942B1 (en) * | 1992-08-21 | 1994-10-14 | Atochem Elf Sa | Composition based on 1,1,1,3,3-pentafluorobutane and methylene chloride, for cleaning and / or drying solid surfaces. |
| US5759986A (en) * | 1997-03-03 | 1998-06-02 | Merchant; Abid Nazarali | Decafluoropentane compositions |
| FR2757871B1 (en) * | 1996-12-27 | 1999-03-26 | Aerospatiale | WATERPROOFING COMPOSITION COMPRISING A HYDROPHOBIC AGENT AND A SOLVENT, APPLICATION FOR THE REMOVAL OF SURFACE WATER IN PARTICULAR FROM WINDSCREENS OF VEHICLES OR AIRCRAFT |
| FR2766836B1 (en) * | 1997-07-31 | 1999-09-24 | Atochem Elf Sa | QUASI AZEOTROPIC MIXTURE BASED ON 1,1,1,3,3- PENTAFLUOROBUTANE, METHYLENE CHLORIDE AND METHANOL FOR THE TREATMENT OF SOLID SURFACES |
| WO1999035210A1 (en) * | 1998-01-02 | 1999-07-15 | E.I. Du Pont De Nemours And Company | Decafluoropentane compositions |
| US6103684A (en) * | 1998-06-25 | 2000-08-15 | Alliedsignal Inc. | Compositions of 1-bromopropane and an organic solvent |
| FR2781499B1 (en) * | 1998-07-24 | 2000-09-08 | Atochem Elf Sa | CLEANING OR DRYING COMPOSITIONS BASED ON 1,1,1,2,3,4,4,5,5,5 - DECAFLUOROPENTANE |
| US6951835B1 (en) * | 1999-03-22 | 2005-10-04 | E.I. Du Pont De Nemours And Company | Azeotrope-like compositions of 1,1,1,3,3-pentafluorobutane |
-
1999
- 1999-04-22 FR FR9905130A patent/FR2792647B1/en not_active Expired - Fee Related
-
2000
- 2000-03-21 EP EP00400777A patent/EP1046703B1/en not_active Expired - Lifetime
- 2000-03-21 ES ES00400777T patent/ES2208232T3/en not_active Expired - Lifetime
- 2000-03-21 DE DE60005881T patent/DE60005881T2/en not_active Expired - Fee Related
- 2000-03-30 JP JP2000092869A patent/JP2000328095A/en not_active Withdrawn
- 2000-04-10 CA CA002305019A patent/CA2305019A1/en not_active Abandoned
- 2000-04-20 AU AU28944/00A patent/AU764299B2/en not_active Ceased
- 2000-04-21 US US09/556,863 patent/US6291416B1/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5350534A (en) * | 1992-08-21 | 1994-09-27 | Elf Atochem S.A. | Composition based on 1,1,1,3,3-pentafluorobutane, methylene chloride and methanol, for the cleaning and/or drying of solid surfaces |
| WO1996030487A1 (en) * | 1995-03-31 | 1996-10-03 | Solvay (Societe Anonyme) | Hydrofluorocarbon-containing compositions and method for removing water from a solid surface |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008073408A1 (en) * | 2006-12-12 | 2008-06-19 | E. I. Du Pont De Nemours And Company | Azeotrope-like mixtures comprising heptafluorocyclopentane |
| US7540973B2 (en) | 2006-12-12 | 2009-06-02 | E. I. Du Pont De Nemours And Company | Azeotrope-like mixtures comprising heptafluorocyclopentane |
| EP2336288A1 (en) * | 2006-12-12 | 2011-06-22 | E.I. Dupont De Nemours And Company | Azeotrope-like mixtures comprising heptafluorocyclopentane |
| CN101553561B (en) * | 2006-12-12 | 2011-12-21 | 纳幕尔杜邦公司 | Azeotrope-like mixtures comprising heptafluorocyclopentane |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2792647B1 (en) | 2001-06-08 |
| US6291416B1 (en) | 2001-09-18 |
| CA2305019A1 (en) | 2000-10-22 |
| AU2894400A (en) | 2000-10-26 |
| ES2208232T3 (en) | 2004-06-16 |
| JP2000328095A (en) | 2000-11-28 |
| EP1046703B1 (en) | 2003-10-15 |
| FR2792647A1 (en) | 2000-10-27 |
| DE60005881T2 (en) | 2004-08-19 |
| DE60005881D1 (en) | 2003-11-20 |
| AU764299B2 (en) | 2003-08-14 |
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