EP0618288B1 - Compositions comprising pentafluorobutane and use thereof - Google Patents

Compositions comprising pentafluorobutane and use thereof Download PDF

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Publication number
EP0618288B1
EP0618288B1 EP94200718A EP94200718A EP0618288B1 EP 0618288 B1 EP0618288 B1 EP 0618288B1 EP 94200718 A EP94200718 A EP 94200718A EP 94200718 A EP94200718 A EP 94200718A EP 0618288 B1 EP0618288 B1 EP 0618288B1
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EP
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Prior art keywords
pentafluorobutane
compositions according
compositions
weight
ethanol
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EP94200718A
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German (de)
French (fr)
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EP0618288A1 (en
Inventor
Pascal Pennetreau
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Solvay SA
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Solvay 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
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • 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
    • C11D7/5004—Organic solvents
    • C11D7/5018—Halogenated 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
    • C11D7/5077—Mixtures of only oxygen-containing solvents
    • C11D7/5081—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being alcohols only
    • 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
    • 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
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen

Definitions

  • the invention relates to compositions comprising pentafluorobutane. and the use of these compositions, in particular as a cleaning agent and / or for drying solid surfaces.
  • CFCs Fully halogenated chlorofluorinated hydrocarbons
  • CFC-113 1,1,2-trichloro-1,2,2-trifluoroethane
  • These solvents can be used in different ways manners, mainly cold or hot.
  • compositions based on CFC-113 are also conventionally used as a desiccant, to remove water adsorbed on the surface of parts solid.
  • CFC-113 as well as other chlorofluoroalkanes completely halogenated, is today suspected of causing problems environment, on the one hand in the context of the destruction of the ozone layer stratospheric and secondly as part of the warming of the atmosphere (greenhouse effect).
  • patent application EP-A-431458 proposes a cleaning composition containing an aliphatic hydrofluorocarbon of formula C n FmH 2n + 2-m in which 4 ⁇ n ⁇ 6 and 6 ⁇ m ⁇ 12 and optionally an organic solvent selected from hydrocarbons, alcohols, esters and ketones.
  • One of the objects of the present invention is to provide other compositions forming azeotropes or pseudo-azeotropes, which are particularly effective when they are used as a cleaning agent in solvent cleaning processes.
  • a subject of the invention is also such compositions having properties particularly suitable for cleaning printed circuit boards.
  • Another object of the invention is to provide such compositions devoid of effect destructive to the ozone layer, compositions therefore usable in completely chlorofluoroalkane solvent replacement halogenated.
  • the present invention therefore relates to compositions containing 1,1,1,3,3-pentafluorobutane and ethanol in proportions for which they form an azeotrope or a pseudo-azeotrope, said azeotrope or pseudo-azeotrope consisting of 0.25 to 7.5 g of ethanol per 100 g of 1,1,1,3,3-pentafluorobutane.
  • compositions according to the invention can vary within wide limits, depending on the intended use.
  • compositions according to the invention contain at least 75% by weight of 1,1,1,3,3-pentafluorobutane. They contain advantageously at least 85% by weight. Particularly preferred, they contain at least 90% thereof. They preferably contain not more than 99.7% by weight.
  • 1,1,1,3,3-pentafluorobutane The boiling point of pressure 1,1,1,3,3-pentafluorobutane atmospheric is around 40 ° C (39.9 ° C at 995 mbar). Regarding his impact on the environment, 1,1,1,3,3-pentafluorobutane appears particularly interesting, since due to the absence of chlorine in its molecular structure, it has zero ozone destruction potential.
  • compositions according to the invention can thus contain stabilizers, agents surfactants or any other additives to improve the performances of the compositions according to the invention during their use.
  • the nature and quantity of these additives are depending on the intended use and are easily defined by the skilled person.
  • the amount of additives present in the compositions according to the invention does not exceed about 20% of the weight of the composition, most often not more 10%.
  • 1,1,1,3,3-pentafluorobutane and ethanol have the particularity to form binary azeotropic mixtures.
  • the compositions according to the invention contain the 1,1,1,3,3-pentafluorobutane and ethanol in proportions in which they form an azeotrope or a pseudo-azeotrope.
  • thermodynamic state of a fluid is defined by four interdependent variables: pressure (P), the temperature (T), the composition of the liquid phase (X) and the composition of the gas phase (Y).
  • a true azeotrope is a particular system with 2 or more components for which, at a given temperature and at a given pressure, X is exactly equal to Y.
  • a pseudo-azeotrope is a system with 2 or more components for which, at a given temperature and at a given pressure, X is substantially equal to Y. In practice, this means that the constituents of such azeotropic systems and pseudo-azeotropics cannot be separated easily by distillation and therefore their composition remains constant in solvent cleaning operations, as well as in recovery operations for used solvents by distillation.
  • azeotrope is meant or pseudo-azeotrope, a mixture of two or more constituents whose boiling point (at a given pressure) differs from boiling point of true azeotrope of no more than 0.5 ° C, or still whose vapor pressure (at a given temperature) differs from that of the true azeotrope by up to 10 mbar.
  • 1,1,1,3,3-pentafluorobutane and ethanol form a azeotrope or a binary pseudo-azeotrope when their mixture contains 0.25 to 7.5 g of ethanol per 100 g of 1,1,1,3,3-pentafluorobutane.
  • they form an azeotrope or a pseudo-azeotrope when their mixture contains 0.5 to 7 g ethanol per 100 g of 1,1,1,3,3-pentafluorobutane.
  • the binary composition consisting essentially about 98.4% by weight of 1,1,1,3,3-pentafluorobutane and about 1.6% by weight of ethanol constitutes a true azeotrope, with a boiling point of approximately 39.2 ° C. This composition is very particularly preferred.
  • compositions according to the invention are also inert to against the different types of surfaces to be treated, that these are made of metal, plastic or glass.
  • compositions according to the invention are therefore suitable for any solid object cleaning operation, either simply by immersion of the objects to be cleaned in such a composition, either by washing objects with a cloth, sponge or similar flexible absorbent material impregnated with said composition.
  • compositions according to the invention for this application are those in which ethanol is present in a controlled amount to form a azeotrope or pseudo-azeotrope with 1,1,1,3,3-pentafluorobutane. These compositions indeed have the property of not not separate into their constituents by evaporation or by distillation.
  • the invention therefore also relates to the use of compositions according to the invention, as a cleaning agent, solvent, degreaser, defluxing or desiccant.
  • the invention relates in particular to the use of the compositions according to the invention as a degreasing agent for surfaces solid.
  • the invention relates in particular to the use of the compositions according to the invention as a solvent for degreasing steam surfaces.
  • degreasing steam consists of exposure, at temperature ambient, of the surface to be cleaned, with the vapor of the solvent carried to a boil. By condensing on the surface, the vapor of the solvent removes grease and all other contaminations, by dissolution.
  • the steam degreasing operation conventionally consists of first by immersing the part to be cleaned in one or several baths containing the liquid solvent at temperature boiling, possibly combined with treatment with ultrasound, which removes most of the dirt, and finally by exposing the part to the vapor of the solvent which, by condensing on the surface thereof, achieves a final rinse.
  • this last step can be preceded by spraying the part with liquid solvent.
  • the compositions comprising an azeotrope or pseudo-azeotrope between the 1,1,1,3,3-pentafluorobutane and ethanol are particularly well suited to serve as a solvent in these cleaning processes.
  • the invention also relates to the use of the compositions according to the invention as a card cleaning agent printed circuits contaminated by a flux flux and its residues, i.e. to remove from the surface of these cards the flux flux used in the component welding step and residues of this flow.
  • Parts cleaning electronics, including defluxing printed circuit boards is a particularly important cleaning operation from an industrial and increasingly delicate point of view due to the current evolution towards maps of more and more complex printed circuits dense in electronic components.
  • the processes soldering of electronic components on boards works depositing on them, a film of a flow stripper, followed by the passage of the card thus covered in a molten solder.
  • the flux cleans the conductive metal parts and promotes adhesion of the solder.
  • compositions according to the invention indeed have a high solvent power for the flow and its residues without altering the material constituting the support of the card or the electronic components placed on it.
  • the compositions according to the invention have viscosity and tension characteristics particularly superficial, particularly well suited to this application.
  • compositions according to the invention can also be used in any other process to replace the compositions based on CFC-113. They are particularly suitable good as a desiccant, i.e. to remove water adsorbed on the surface of solid objects requiring a surface perfectly clean, such as printed circuit boards, silicon, optical glasses, timepieces and all others precision parts.
  • azeotropic compositions or pseudo-azeotropics between 1,1,1,3,3-pentafluorobutane and ethanol we used a glass apparatus consisting of a 50 ml boiling flask topped with a condenser at reflux. The temperature of the liquid is measured using a thermometer immersed in the bottle.
  • the determination of the azeotropic composition was made by a statement of the temperature evolution of boiling of the mixture according to its composition.
  • the composition for which a boiling point has been observed minimum is the azeotropic composition (at a pressure of 995 mbar).
  • the table below shows the boiling temperatures obtained for different compositions of 1,1,1,3,3-pentafluorobutane (PFBA) and ethanol (EtOH). It is observed that the best estimate of the composition for which the boiling point is minimum (39.2 ° C) is about 98.4% by weight of 1,1,1,3,3-pentafluorobutane and 1 , 6% by weight of ethanol. The boiling point is 39.4 ° C ⁇ 0.2 ° C for a composition containing approximately from 93.5 to 99.5% by weight of 1,1,1,3,3-pentafluorobutane under a pressure of 995 mbar.
  • PFBA 1,1,1,3,3-pentafluorobutane
  • EtOH ethanol

Abstract

The invention relates to compositions comprising 1,1,1,3,3-pentafluorobutane and ethanol. These compositions can be used in particular as solvents for cleaning electronic components and for degreasing metals.

Description

L'invention concerne des compositions comprenant du pentafluorobutane et l'utilisation de ces compositions, notamment comme agent de nettoyage et/ou de séchage de surfaces solides.The invention relates to compositions comprising pentafluorobutane. and the use of these compositions, in particular as a cleaning agent and / or for drying solid surfaces.

Les hydrocarbures chlorofluorés complètement halogénés (CFC), tels que le 1,1,2-trichloro-1,2,2-trifluoroéthane (CFC-113), sont largement utilisés comme solvants dans l'industrie pour le dégraissage et le nettoyage de surfaces diverses, particulièrement pour des pièces solides de forme compliquée et difficiles à nettoyer. Ces solvants peuvent être mis en oeuvre de différentes manières, principalement à froid ou à chaud.Fully halogenated chlorofluorinated hydrocarbons (CFCs), such as 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), are widely used as solvents in industry for degreasing and cleaning surfaces various, particularly for solid parts of complicated shape and difficult to clean. These solvents can be used in different ways manners, mainly cold or hot.

Des compositions à base de CFC-113 sont aussi classiquement utilisées comme agent dessicatif, afin d'éliminer l'eau adsorbée à la surface de pièces solides.Compositions based on CFC-113 are also conventionally used as a desiccant, to remove water adsorbed on the surface of parts solid.

Toutefois, le CFC-113, de même que d'autres chlorofluoroalcanes complètement halogénés, est aujourd'hui suspecté de provoquer des problèmes d'environnement, d'une part dans le cadre de la destruction de la couche d'ozone stratosphérique et d'autre part, dans le cadre du réchauffement de l'atmosphère (effet de serre).However, CFC-113, as well as other chlorofluoroalkanes completely halogenated, is today suspected of causing problems environment, on the one hand in the context of the destruction of the ozone layer stratospheric and secondly as part of the warming of the atmosphere (greenhouse effect).

En conséquence, il y a actuellement un besoin urgent de trouver de nouvelles compositions, n'ayant pas d'influence néfaste sur la couche d'ozone. A cette fin, la demande de brevet EP-A-431458 (DAIKIN) propose une composition de nettoyage contenant un hydrofluorocarbone aliphatique de formule CnFmH2n+2-m dans laquelle 4≤n≤6 et 6≤m≤12 et éventuellement un solvant organique sélectionné parmi les hydrocarbures, les alcools, les esters et les cétones.Consequently, there is currently an urgent need to find new compositions, having no harmful influence on the ozone layer. To this end, patent application EP-A-431458 (DAIKIN) proposes a cleaning composition containing an aliphatic hydrofluorocarbon of formula C n FmH 2n + 2-m in which 4≤n≤6 and 6≤m≤12 and optionally an organic solvent selected from hydrocarbons, alcohols, esters and ketones.

Encore a cette fin, un certain nombre de compositions azéotropiques à base d'hydrofluoroalcanes ont été récemment proposées. En particulier, la demande de brevet EP-A-0512885 (ELF ATOCHEM) propose une composition azéotropique comprenant en poids 93 à 99 % de 1,1,1,3,3-pentafluorobutane (HFA-365mfc) et de 7 à 1 % de méthanol. Again for this purpose, a number of azeotropic compositions based hydrofluoroalkanes have recently been proposed. In particular, the demand EP-A-0512885 (ELF ATOCHEM) proposes a composition azeotropic comprising by weight 93 to 99% of 1,1,1,3,3-pentafluorobutane (HFA-365mfc) and 7 to 1% methanol.

Un des objets de la présente invention est de fournir d'autres compositions formant des azéotropes ou des pseudo-azéotropes, qui soient particulièrement performantes lorsqu'elles sont utilisées comme agent de nettoyage dans des procédés de nettoyage par solvant. L'invention a encore pour objet de telles compositions possédant des propriétés particulièrement adaptées au nettoyage des cartes de circuits imprimés. Un autre objet de l'invention est de fournir de telles compositions dépourvues d'effet destructeur vis-à-vis de la couche d'ozone, compositions dès lors utilisables en remplacement des solvants à base de chlorofluoroalcanes complètement halogénés.One of the objects of the present invention is to provide other compositions forming azeotropes or pseudo-azeotropes, which are particularly effective when they are used as a cleaning agent in solvent cleaning processes. A subject of the invention is also such compositions having properties particularly suitable for cleaning printed circuit boards. Another object of the invention is to provide such compositions devoid of effect destructive to the ozone layer, compositions therefore usable in completely chlorofluoroalkane solvent replacement halogenated.

La présente invention concerne dès lors des compositions contenant du 1,1,1,3,3-pentafluorobutane et de l'éthanol dans des proportions pour lesquelles ils forment un azéotrope ou un pseudo-azéotrope, ledit azéotrope ou pseudo-azéotrope étant constitué de 0,25 à 7,5g d'éthanol pour 100g de 1,1,1,3,3-pentafluorobutane.The present invention therefore relates to compositions containing 1,1,1,3,3-pentafluorobutane and ethanol in proportions for which they form an azeotrope or a pseudo-azeotrope, said azeotrope or pseudo-azeotrope consisting of 0.25 to 7.5 g of ethanol per 100 g of 1,1,1,3,3-pentafluorobutane.

Les teneurs en 1,1,1,3,3-pentafluorobutane et en éthanol dans les compositions selon l'invention peuvent varier dans de larges mesures, selon l'utilisation envisagée.The 1,1,1,3,3-pentafluorobutane and ethanol contents in the compositions according to the invention can vary within wide limits, depending on the intended use.

Généralement, les compositions selon l'invention contiennent au moins 75 % en poids de 1,1,1,3,3-pentafluorobutane. Elles en contiennent avantageusement au moins 85 % en poids. De manière particulièrement préférée, elles en contiennent au moins 90 %. Elles en contiennent de préférence au plus 99,7 % en poids.Generally, the compositions according to the invention contain at least 75% by weight of 1,1,1,3,3-pentafluorobutane. They contain advantageously at least 85% by weight. Particularly preferred, they contain at least 90% thereof. They preferably contain not more than 99.7% by weight.

Le point d'ébullition du 1,1,1,3,3-pentafluorobutane à pression atmosphérique est d'environ 40 °C (39,9 °C à 995 mbar). En ce qui concerne son impact sur l'environnement, le 1,1,1,3,3-pentafluorobutane apparaít particulièrement intéressant, puisqu'en raison de l'absence de chlore dans sa structure moléculaire, il présente un potentiel de destruction de l'ozone nul.The boiling point of pressure 1,1,1,3,3-pentafluorobutane atmospheric is around 40 ° C (39.9 ° C at 995 mbar). Regarding his impact on the environment, 1,1,1,3,3-pentafluorobutane appears particularly interesting, since due to the absence of chlorine in its molecular structure, it has zero ozone destruction potential.

Divers additifs peuvent éventuellement être présents dans les compositions selon l'invention. Les compositions selon l'invention peuvent ainsi contenir des stabilisants, des agents tensioactifs ou tous autres additifs permettant d'améliorer les performances des compositions selon l'invention lors de leur utilisation. La nature et la quantité de ces additifs sont fonction de l'utilisation envisagée et sont aisément définies par l'homme du métier. En règle générale, la quantité d'additifs présente dans les compositions selon l'invention ne dépasse pas environ 20 % du poids de la composition, le plus souvent pas plus de 10 %.Various additives may possibly be present in the compositions according to the invention. The compositions according to the invention can thus contain stabilizers, agents surfactants or any other additives to improve the performances of the compositions according to the invention during their use. The nature and quantity of these additives are depending on the intended use and are easily defined by the skilled person. As a rule, the amount of additives present in the compositions according to the invention does not exceed about 20% of the weight of the composition, most often not more 10%.

Dans les compositions selon l'invention, le 1,1,1,3,3-pentafluorobutane et l'éthanol présentent la particularité de former des mélanges azéotropiques binaires. Les compositions selon l'invention contiennent le 1,1,1,3,3-pentafluorobutane et l'éthanol dans des proportions dans lesquelles ils forment un azéotrope ou un pseudo-azéotrope.In the compositions according to the invention, 1,1,1,3,3-pentafluorobutane and ethanol have the particularity to form binary azeotropic mixtures. The compositions according to the invention contain the 1,1,1,3,3-pentafluorobutane and ethanol in proportions in which they form an azeotrope or a pseudo-azeotrope.

Fondamentalement, l'état thermodynamique d'un fluide est défini par quatre variables interdépendantes : la pression (P), la température (T), la composition de la phase liquide (X) et la composition de la phase gazeuse (Y). Un azéotrope vrai est un système particulier à 2 ou plusieurs composants pour lequel, à une température donnée et à une pression donnée, X est exactement égal à Y. Un pseudo-azéotrope est un système à 2 ou plusieurs composants pour lequel, à une température donnée et à une pression donnée, X est substantiellement égal à Y. En pratique, cela signifie que les constituants de tels systèmes azéotropiques et pseudo-azéotropiques ne peuvent pas être séparés facilement par distillation et dès lors leur composition reste constante dans les opérations de nettoyage par solvant, ainsi que dans les opérations de récupération de solvants usagés par distillation.Basically, the thermodynamic state of a fluid is defined by four interdependent variables: pressure (P), the temperature (T), the composition of the liquid phase (X) and the composition of the gas phase (Y). A true azeotrope is a particular system with 2 or more components for which, at a given temperature and at a given pressure, X is exactly equal to Y. A pseudo-azeotrope is a system with 2 or more components for which, at a given temperature and at a given pressure, X is substantially equal to Y. In practice, this means that the constituents of such azeotropic systems and pseudo-azeotropics cannot be separated easily by distillation and therefore their composition remains constant in solvent cleaning operations, as well as in recovery operations for used solvents by distillation.

Aux fins de la présente invention, on entend, par azéotrope ou pseudo-azéotrope, un mélange de deux ou plusieurs constituants dont le point d'ébullition (à une pression donnée) diffère du point d'ébullition de l'azéotrope vrai de 0,5 °C au maximum, ou encore dont la tension de vapeur (à une température donnée) diffère de celle de l'azéotrope vrai de 10 mbar au maximum.For the purposes of the present invention, by azeotrope is meant or pseudo-azeotrope, a mixture of two or more constituents whose boiling point (at a given pressure) differs from boiling point of true azeotrope of no more than 0.5 ° C, or still whose vapor pressure (at a given temperature) differs from that of the true azeotrope by up to 10 mbar.

Le 1,1,1,3,3-pentafluorobutane et l'éthanol forment un azéotrope ou un pseudo-azéotrope binaire lorsque leur mélange contient de 0,25 à 7,5 g d'éthanol pour 100 g de 1,1,1,3,3-pentafluorobutane. En particulier, ils forment un azéotrope ou un pseudo-azéotrope lorsque leur mélange contient de 0,5 à 7 g d'éthanol pour 100 g de 1,1,1,3,3-pentafluorobutane. Sous une pression de 995 mbar, la composition binaire constituée essentiellement d'environ 98,4 % en poids de 1,1,1,3,3-pentafluorobutane et d'environ 1,6 % en poids d'éthanol constitue un azéotrope vrai, dont le point d'ébullition est d'environ 39,2 °C. Cette composition est tout particulièrement préférée.1,1,1,3,3-pentafluorobutane and ethanol form a azeotrope or a binary pseudo-azeotrope when their mixture contains 0.25 to 7.5 g of ethanol per 100 g of 1,1,1,3,3-pentafluorobutane. In particular, they form an azeotrope or a pseudo-azeotrope when their mixture contains 0.5 to 7 g ethanol per 100 g of 1,1,1,3,3-pentafluorobutane. Under a pressure of 995 mbar, the binary composition consisting essentially about 98.4% by weight of 1,1,1,3,3-pentafluorobutane and about 1.6% by weight of ethanol constitutes a true azeotrope, with a boiling point of approximately 39.2 ° C. This composition is very particularly preferred.

Les compositions selon l'invention sont en outre inertes à l'encontre des différents types de surfaces à traiter, que celles-ci soient en métal, en plastique ou en verre.The compositions according to the invention are also inert to against the different types of surfaces to be treated, that these are made of metal, plastic or glass.

Les compositions selon l'invention conviennent dès lors pour toute opération de nettoyage d'objets solides, soit simplement par immersion des objets à nettoyer dans une telle composition, soit par lavage des objets avec un chiffon, une éponge ou un matériau absorbant souple analogue, imprégné de ladite composition.The compositions according to the invention are therefore suitable for any solid object cleaning operation, either simply by immersion of the objects to be cleaned in such a composition, either by washing objects with a cloth, sponge or similar flexible absorbent material impregnated with said composition.

Elles trouvent également une application dans les techniques de nettoyage ou de dégraissage mettant en oeuvre une évaporation ou une distillation.They also find application in techniques cleaning or degreasing using evaporation or a distillation.

Des compositions conformes à l'invention pour cette application sont celles dans lesquelles l'éthanol est présent en une quantité réglée pour former un azéotrope ou pseudo-azéotrope avec le 1,1,1,3,3-pentafluorobutane. Ces compositions possèdent en effet la propriété de ne pas se séparer en leurs constituants par évaporation ou par distillation.Compositions according to the invention for this application are those in which ethanol is present in a controlled amount to form a azeotrope or pseudo-azeotrope with 1,1,1,3,3-pentafluorobutane. These compositions indeed have the property of not not separate into their constituents by evaporation or by distillation.

L'invention concerne dès lors également l'utilisation des compositions selon l'invention, comme agent de nettoyage, solvant, dégraissant, défluxant ou dessicant.The invention therefore also relates to the use of compositions according to the invention, as a cleaning agent, solvent, degreaser, defluxing or desiccant.

L'invention concerne notamment l'utilisation des compositions selon l'invention comme agent dégraissant de surfaces solides.The invention relates in particular to the use of the compositions according to the invention as a degreasing agent for surfaces solid.

L'invention concerne en particulier l'utilisation des compositions selon l'invention comme solvant pour le dégraissage de surfaces à la vapeur. Dans sa forme la plus simple, le dégraissage à la vapeur consiste en l'exposition, à température ambiante, de la surface à nettoyer, à la vapeur du solvant porté à ébullition. En se condensant sur la surface, la vapeur du solvant élimine les graisses et toutes autres contaminations, par dissolution.The invention relates in particular to the use of the compositions according to the invention as a solvent for degreasing steam surfaces. In its simplest form, degreasing steam consists of exposure, at temperature ambient, of the surface to be cleaned, with the vapor of the solvent carried to a boil. By condensing on the surface, the vapor of the solvent removes grease and all other contaminations, by dissolution.

Pour les salissures plus difficiles à éliminer, nécessitant un traitement à température élevée afin d'améliorer le pouvoir nettoyant du solvant, ou pour les grandes installations de nettoyage dans lesquelles le nettoyage de pièces métalliques ou d'assemblages doit être réalisé efficacement et rapidement, l'opération de dégraissage à la vapeur consiste, classiquement, d'abord en l'immersion de la pièce à nettoyer dans un ou plusieurs bains contenant le solvant liquide à la température d'ébullition, éventuellement conjuguée à un traitement par des ultrasons, ce qui élimine la majeure partie des salissures, et finalement en l'exposition de la pièce à la vapeur du solvant qui, en se condensant à la surface de celle-ci, réalise un rinçage final. Eventuellement, cette dernière étape peut être précédée d'une aspersion de la pièce par du solvant liquide. Les compositions comprenant un azéotrope ou pseudo-azéotrope entre le 1,1,1,3,3-pentafluorobutane et l'éthanol sont particulièrement bien adaptées à servir de solvant dans ces procédés de nettoyage.For dirt that is more difficult to remove, requiring high temperature treatment to improve potency solvent cleaner, or for large installations of cleaning in which the cleaning of metal parts or assemblies must be carried out efficiently and quickly, the steam degreasing operation conventionally consists of first by immersing the part to be cleaned in one or several baths containing the liquid solvent at temperature boiling, possibly combined with treatment with ultrasound, which removes most of the dirt, and finally by exposing the part to the vapor of the solvent which, by condensing on the surface thereof, achieves a final rinse. Optionally, this last step can be preceded by spraying the part with liquid solvent. The compositions comprising an azeotrope or pseudo-azeotrope between the 1,1,1,3,3-pentafluorobutane and ethanol are particularly well suited to serve as a solvent in these cleaning processes.

L'invention concerne également l'utilisation des compositions selon l'invention comme agent de nettoyage de cartes de circuits imprimés contaminées par un flux décapant et ses résidus, c'est-à-dire pour éliminer de la surface de ces cartes le flux décapant utilisé dans l'étape de soudure des composants électroniques et des résidus de ce flux. Le nettoyage de pièces électroniques, notamment le défluxage des cartes de circuits imprimés constitue une opération de nettoyage particulièrement importante d'un point de vue industriel et de plus en plus délicate à réaliser en raison de l'évolution actuelle vers des cartes de circuits imprimés de plus en plus complexes et de plus en plus denses en composants électroniques. Classiquement, les procédés de soudure des composants électroniques sur les cartes mettent en oeuvre le dépôt sur celles-ci, d'une pellicule d'un flux décapant, suivi du passage de la carte ainsi recouverte dans une brasure fondue. Le flux nettoie les parties métalliques conductrices et favorise l'adhérence de la brasure. Des flux de brasage classiques sont constitués de collophane, utilisée seule ou avec certains activants. Le brasage réalisé à température élevée provoque une dégradation au moins partielle du flux. Celui-ci et ses résidus sont éliminés de la surface des cartes de circuits imprimés de manière particulièrement efficace et sélective avec les compositions selon l'invention, même lorsque ces flux sont fortement activés. Les compositions selon l'invention possèdent en effet un pouvoir solvant élevé pour le flux et ses résidus sans cependant altérer le matériau constituant le support de la carte ni les composants électroniques disposés sur celle-ci. En outre, les compositions selon l'invention présentent des caractéristiques de viscosité et de tension superficielle notamment, particulièrement bien adaptées à cette application.The invention also relates to the use of the compositions according to the invention as a card cleaning agent printed circuits contaminated by a flux flux and its residues, i.e. to remove from the surface of these cards the flux flux used in the component welding step and residues of this flow. Parts cleaning electronics, including defluxing printed circuit boards is a particularly important cleaning operation from an industrial and increasingly delicate point of view due to the current evolution towards maps of more and more complex printed circuits dense in electronic components. Conventionally, the processes soldering of electronic components on boards works depositing on them, a film of a flow stripper, followed by the passage of the card thus covered in a molten solder. The flux cleans the conductive metal parts and promotes adhesion of the solder. Flows of conventional soldering consist of rosin, used alone or with certain activators. Brazing performed at temperature high causes at least partial degradation of the flow. This and its residues are removed from the surface of the cards. particularly efficient and selective printed circuits with the compositions according to the invention, even when these streams are highly activated. The compositions according to the invention indeed have a high solvent power for the flow and its residues without altering the material constituting the support of the card or the electronic components placed on it. In addition, the compositions according to the invention have viscosity and tension characteristics particularly superficial, particularly well suited to this application.

Les compositions selon l'invention peuvent également être utilisées dans tout autre procédé en remplacement des compositions à base de CFC-113. Elles conviennent particulièrement bien comme agent dessicatif, c'est-à-dire pour éliminer l'eau adsorbée à la surface d'objets solides nécessitant une surface parfaitement propre, tels que circuits imprimés, plaques au silicium, verres d'optique, pièces d'horlogerie et toutes autres pièces de précision.The compositions according to the invention can also be used in any other process to replace the compositions based on CFC-113. They are particularly suitable good as a desiccant, i.e. to remove water adsorbed on the surface of solid objects requiring a surface perfectly clean, such as printed circuit boards, silicon, optical glasses, timepieces and all others precision parts.

L'exemple ci-après, non limitatif, illustre l'invention de manière plus détaillée.The following example, which is not limitative, illustrates the invention of in more detail.

ExempleExample

Pour mettre en évidence l'existence de compositions azéotropiques ou pseudo-azéotropiques entre le 1,1,1,3,3-pentafluorobutane et l'éthanol, on a utilisé un appareillage en verre constitué d'un flacon bouilleur de 50 ml surmonté d'un condenseur à reflux. La température du liquide est mesurée au moyen d'un thermomètre plongeant dans le flacon.To highlight the existence of azeotropic compositions or pseudo-azeotropics between 1,1,1,3,3-pentafluorobutane and ethanol, we used a glass apparatus consisting of a 50 ml boiling flask topped with a condenser at reflux. The temperature of the liquid is measured using a thermometer immersed in the bottle.

59,43 g de 1,1,1,3,3-pentafluorobutane pur ont été chauffés sous une pression de 995 mbar jusqu'à ébullition, puis de petites quantités d'éthanol, pesées avec précision, ont été progressivement introduites dans le flacon au moyen d'une seringue, via une tubulure latérale.59.43 g of pure 1,1,1,3,3-pentafluorobutane were heated under a pressure of 995 mbar until boiling, then small quantities of ethanol, weighed with precision, were gradually introduced into the vial by means of a syringe, via side tubing.

La détermination de la composition azéotropique a été réalisée par un relevé de l'évolution de la température d'ébullition du mélange en fonction de sa composition. La composition pour laquelle a été observé un point d'ébullition minimum est la composition azéotropique (à une pression de 995 mbar).The determination of the azeotropic composition was made by a statement of the temperature evolution of boiling of the mixture according to its composition. The composition for which a boiling point has been observed minimum is the azeotropic composition (at a pressure of 995 mbar).

Le tableau ci-après rassemble les températures d'ébullition obtenues pour différentes compositions de 1,1,1,3,3-pentafluorobutane (PFBA) et d'éthanol (EtOH). On y observe que la meilleure estimation de la composition pour laquelle le point d'ébullition est minimum (39,2 °C) est d'environ 98,4 % en poids de 1,1,1,3,3-pentafluorobutane et 1,6 % en poids d'éthanol. Le point d'ébullition est de 39,4 °C ± 0,2 °C pour une composition contenant environ de 93,5 à 99,5 % en poids de 1,1,1,3,3-pentafluorobutane sous une pression de 995 mbar. PFBA, g EtOH ajouté,g (qté cumulée) Teneur en EtOH Point d'ébul., °C % poids % moles 59,43 0 0,0 0,0 39,9 0,487 0,8 3,6 39,4 0,974 1,6 7,0 39,2 1,461 2,4 10,2 39,3 1,948 3,2 13,2 39,35 2,435 3,9 15,9 39,4 2,922 4,7 18,5 39,45 3,409 5,4 21,0 39,5 3,896 6,2 23,3 39,6 4,383 6,9 25,4 39,7 4,87 7,6 27,5 39,8 6,77 10,2 34,5 40,0 8,93 13,1 41,0 40,4 12,41 17,3 49,1 41,0 The table below shows the boiling temperatures obtained for different compositions of 1,1,1,3,3-pentafluorobutane (PFBA) and ethanol (EtOH). It is observed that the best estimate of the composition for which the boiling point is minimum (39.2 ° C) is about 98.4% by weight of 1,1,1,3,3-pentafluorobutane and 1 , 6% by weight of ethanol. The boiling point is 39.4 ° C ± 0.2 ° C for a composition containing approximately from 93.5 to 99.5% by weight of 1,1,1,3,3-pentafluorobutane under a pressure of 995 mbar. PFBA, g EtOH added, g (cumulative qty) EtOH content Boiling point, ° C % weight % moles 59.43 0 0.0 0.0 39.9 0.487 0.8 3.6 39.4 0.974 1.6 7.0 39.2 1,461 2.4 10.2 39.3 1,948 3.2 13.2 39,35 2,435 3.9 15.9 39.4 2,922 4.7 18.5 39.45 3,409 5.4 21.0 39.5 3,896 6.2 23.3 39.6 4,383 6.9 25.4 39.7 4.87 7.6 27.5 39.8 6.77 10.2 34.5 40.0 8.93 13.1 41.0 40.4 12.41 17.3 49.1 41.0

Claims (10)

  1. Compositions characterized in that they contain 1,1,1,3,3-pentafluorobutane and ethanol in proportions for which they form a binary azeotrope or pseudoazeotrope, said azeotrope or pseudoazeotrpe consisting of from 0.25 to 7.5 g of ethanol per 100 g of 1,1,1,3,3-pentafluorobutane.
  2. Compositions according to claim 1, characterized in that they contain from 0,5 to 7 g of ethanol per 100 g of 1,1,1,3,3-pentafluorobutane.
  3. Compositions according to claim 1 or 2, comprising at least 75% by weight of 1,1,1,3,3-pentafluorobutane.
  4. Compositions according to anyone of claims 1 to 3 comprising optionally an additive in a quantity of not more than 20% by weight of the composition.
  5. Composition according to claim 3 or 4, characterized in that they contain from about 93,5 to 99,5% by weight of 1,1,1,3,3-pentafluorobutane and from about 6,5 to 0,5% by weight of ethanol.
  6. Composition according to any one of claims 3 to 5, characterized in that it consists essentially of approximately 98.4% by weight of 1,1,1,3,3-pentafluorobutane and approximately 1.6% by weight of ethanol, the boiling point of which is approximately 39.2°C at a pressure of 995 mbar.
  7. Use of the compositions according to any one of claims 1 to 6 as cleaning agents.
  8. Use of the compositions according to any one of claims 1 to 6 as degreasing agents for solid surfaces.
  9. Use of the compositions according to any one of claims 1 to 6 as cleaning agents for printed circuit boards contaminated by a pickling flux and residues from this flux.
  10. Use of the compositions according to any one of claims 1 to 6 as desiccating agents for removing the water adsorbed at the surface of solid objects.
EP94200718A 1993-03-31 1994-03-21 Compositions comprising pentafluorobutane and use thereof Expired - Lifetime EP0618288B1 (en)

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KR100328574B1 (en) 2002-07-08
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CA2119686A1 (en) 1994-10-01
CA2119686C (en) 2006-08-01
ATE214090T1 (en) 2002-03-15
DE69430020D1 (en) 2002-04-11
US5445757A (en) 1995-08-29
DE69430020T2 (en) 2002-11-07
ES2173903T3 (en) 2002-11-01
BE1006894A3 (en) 1995-01-17

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