EP1040179B1 - Compositions comprising perfluorobutyl methyl ether and use of said compositions - Google Patents

Compositions comprising perfluorobutyl methyl ether and use of said compositions Download PDF

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Publication number
EP1040179B1
EP1040179B1 EP98965826A EP98965826A EP1040179B1 EP 1040179 B1 EP1040179 B1 EP 1040179B1 EP 98965826 A EP98965826 A EP 98965826A EP 98965826 A EP98965826 A EP 98965826A EP 1040179 B1 EP1040179 B1 EP 1040179B1
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weight
approximately
compositions
methyl ether
boiling point
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EP98965826A
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German (de)
French (fr)
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EP1040179A1 (en
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Pierre Barthelemy
Pierre Dournel
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Solvay SA
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Solvay SA
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G11/00—Selection of substances for use as fixing agents
    • 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
    • C11D7/504—Azeotropic mixtures containing halogenated solvents all solvents being halogenated hydrocarbons
    • C11D7/5063—Halogenated hydrocarbons containing heteroatoms, e.g. fluoro alcohols
    • 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
    • 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
    • C11D7/266—Esters or carbonates
    • 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 perfluorobutyl methyl ether (C 4 F 9 -O-CH 3 ) and the use of these compositions, especially as a cleaning or drying agent for solid surfaces.
  • CFCs Fully halogenated chlorofluorocarbons
  • CFC-113 1,1,2-trichloro-1,2,2-trifluoroethane
  • CFC-113 is widely used as solvents in industry for degreasing and surface cleaning various, particularly for solid parts of complicated shape and difficult to clean.
  • CFC-113 is most often associated with other organic solvents, preferably in the form of azeotropic or pseudoazeotropic compositions having substantially the same composition in the vapor phase and in the liquid phase, so that they can be easily used at reflux.
  • compositions based on CFC-113 are also conventionally used as a desiccant, in order to eliminate the water adsorbed on the surface of solid parts.
  • hydrofluorinated chlorine-free compounds are completely inert with respect to the stratospheric ozone layer and there is an increasing use of these compounds in many applications to the detriment of compounds carrying chlorine atoms. .
  • the patent application WO 96/36689 provides azeotropic compositions of perfluorobutyl methyl ether with one or more organic solvents selected from linear or branched cyclic or acyclic alkanes comprising 6 to 8 carbon atoms, cyclic or acyclic ethers comprising 4 to 6 carbon atoms, ketones comprising 3 carbon atoms, chlorinated alkanes comprising 1.3 or 4 carbon atoms, chlorinated alkenes comprising 2 to 4 carbon atoms, 3 carbon atoms, alcohols comprising 1 to 4 carbon atoms, partially fluorinated alcohols comprising 2 to 3 carbon atoms, 1-bromopropane, acetonitrile, HCFC-225ea, and HCFC-225cb.
  • organic solvents selected from linear or branched cyclic or acyclic alkanes comprising 6 to 8 carbon atoms, cyclic or acyclic ethers comprising 4 to 6 carbon atoms,
  • compositions for cleaning and degreasing metal parts comprising mixtures based on alkoxy-substituted perfluorinated compounds and cosolvents, such as, in particular, the esters; the use of a mixture of perfluorobutyl methyl ether and methyl decanoate is specifically described therein.
  • WO 96/36688 discloses pseudo-azeotropic compositions based on perfluorobutyl ethyl ether and, inter alia, esters containing 4 carbon atoms, which can be used for the formulation of composition for surface coating.
  • EPC discloses the use as a toner fixing agent for a recording medium of a mixture of perfluorobutyl methyl ether and 5% by weight of methyl acetate.
  • compositions optionally forming azeotropes or pseudoazeotropes, which are particularly effective when used as a cleaning agent in solvent cleaning processes.
  • the invention also relates to such compositions having properties particularly suitable for cleaning printed circuit boards.
  • Another object of the invention is to provide such compositions devoid of destructive effect vis-à-vis the ozone layer.
  • the invention also relates to compositions having particularly suitable properties as a toner fixing agent to a recording medium in a printing apparatus or reproduction of documents.
  • the present invention therefore relates to azeotropic or pseudo-azeotropic compositions comprising at least one perfluorobutyl methyl ether of general formula C 4 F 9 -O-CH 3 where C 4 F 9 is a linear or branched perfluorinated chain and at least one ester chosen of, methyl acetate, ethyl formate and methyl formate, said compositions containing about 21 to 52% by weight of methyl acetate or about 22 to 53% by weight of ethyl formate or about 40 to 92% by weight of methyl formate CF 3 - (CF 2 ) 3 -O-CH 3 , the (CF 3 ) 2 CF-CF 2 -O-CH 3 and mixtures thereof are the preferred perfluorobutyl methyl ethers.
  • the term "perfluorobutyl methyl ether" is used to designate a mixture of these 2 compounds, marketed by 3M under the name HFE-7100.
  • thermodynamic state of a fluid is defined by four interdependent variables: pressure (P), temperature (T), composition the liquid phase (X) and the composition of the gas phase (Y).
  • a true azeotrope is a particular 2 or more component system for which, at a given temperature and at a given pressure, the composition of the liquid phase X is exactly equal to the composition of the gas phase Y.
  • a pseudoazeotrope is a two or more component system 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 and pseudo-azeotropic systems can not They can not be separated easily by distillation and therefore their composition remains substantially constant in the solvent cleaning operations, as well as in the recovery operations of solvents used by distillation.
  • a pseudo-azeotropic mixture is understood to mean a mixture of two constituents whose boiling point (at a given pressure) differs from the boiling point of the true azeotrope of 0.5.degree. maximum. Mixtures whose boiling point differs from the boiling point of the true azeotrope of up to 0.2 ° C are preferred. Mixtures whose boiling point differs from the boiling point of the true azeotrope by up to 0.1 ° C are particularly preferred.
  • compositions according to the invention can vary widely, depending on the intended use.
  • compositions according to the invention contain at least 1% by weight of perfluorobutyl methyl ether. They advantageously contain at least 5%. In a particularly preferred manner, they contain at least 10%. They can contain up to 99%. Most often, they contain at most 95%.
  • compositions according to the invention are those which contain perfluorobutyl methyl ether and an ester in proportions in which they form a minimum boiling azeotrope or pseudoazeotrope.
  • compositions of the azeotropic mixtures according to the invention were estimated on the basis of the results of the experimental measurements presented in the examples below.
  • Perfluorobutyl methyl ether and methyl acetate form a binary azeotrope or pseudo-azeotrope when their mixture contains about 21 to 52% by weight of methyl acetate.
  • the binary compositions containing about 28 to 48% by weight of methyl acetate are preferred.
  • the binary composition consisting essentially of about 61% by weight of perfluorobutyl methyl ether and about 39% by weight of methyl acetate constitutes a true azeotrope, whose boiling point is about 52.6 ° C. This composition is very particularly preferred.
  • Perfluorobutyl methyl ether and ethyl formate form a binary azeotrope or pseudoazeotrope when their mixture contains about 22 to 53% by weight of ethyl formate.
  • Binary compositions containing about 26 to 46% by weight of ethyl formate are preferred.
  • the binary composition consisting essentially of about 68% by weight of perfluorobutyl methyl ether and about 32% by weight of ethyl formate constitutes a true azeotrope, whose boiling point is about 50.2 ° C. This composition is very particularly preferred.
  • Perfluorobutyl methyl ether and methyl formate form a binary azeotrope or pseudoazeotrope when their mixture contains about 40 to 92% by weight of methyl formate.
  • Binary compositions containing about 59 to 80% by weight of methyl formate are preferred. Under a pressure of 102.2 kPa, the binary composition consisting essentially of about 36% by weight of perfluorobutyl methyl ether and about 64% by weight of methyl formate constitutes a true azeotrope whose boiling point is about 31.2 ° C. This composition is very particularly preferred.
  • compositions according to the invention may optionally be present in the compositions according to the invention.
  • the compositions according to the invention may thus contain stabilizers, surfactants or any other additives making it possible to improve the performance of the compositions according to the invention during their use.
  • the nature and the quantity of these additives depend on the intended use and are easily defined by those skilled in the art.
  • 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 than 10%.
  • compositions according to the invention have a boiling point suitable for replacing CFC-113-based compositions in existing cleaning apparatus. As regards its impact on the environment, perfluorobutyl methyl ether appears to be particularly interesting since it has a zero ozone destruction potential.
  • the compositions according to the invention are further inert against the different types of surfaces to be treated, whether they are metal, plastic or glass.
  • compositions according to the invention can therefore be used in the same applications and according to the same techniques as the prior compositions based on CFC-113.
  • the compositions according to the invention can be used as a cleaning agent, solvent, degreasing agent, defluxant or desiccant.
  • the invention therefore also relates to the use of the compositions according to the invention as a cleaning agent, as a degreasing agent for solid surfaces, as a cleaning agent for printed circuit boards, contaminated with a stripping flux and residues thereof. as a desiccant to remove adsorbed water on the surface of solid objects.
  • the compositions according to the invention can also be used as a toner fixing agent for a recording medium in a printing or copying apparatus.
  • Perfluorobutyl methyl ether compositions useful as a toner fixing agent are compositions containing a C3-C6 hydrofluorocarbon.
  • C3-C6 hydrofluorocarbon is meant saturated hydrocarbons, aliphatic or alicyclic, consisting solely of carbon, fluorine and hydrogen, comprising from 3 to 6 carbon atoms, at least one fluorine atom and at least one atom hydrogen.
  • C 3 -C 6 hydrofluorocarbons are hydrofluoroalkanes such as 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and 1,1,1,2,2,3,4,6,6,6-decafluoropentane (HFC-43-10mee).
  • 1,1,1,3,3-Pentafluorobutane is particularly suitable.
  • C3-C6 perfluorobutyl methyl ether / ester / hydrofluorocarbon terefinal compositions are used.
  • the invention therefore also relates to the use of the compositions according to the invention as a toner fixing agent to a recording medium in a printing device or reproduction of documents.
  • azeotropic or pseudoazeotropic compositions according to the invention between perfluorobutyl methyl ether and an ester, a glass apparatus consisting of a 50 ml boiler flask surmounted by a reflux condenser was used. . The temperature of the liquid was measured by means of a thermometer immersed in the flask.
  • the determination of the azeotropic composition was carried out by recording the evolution of the boiling point of the mixture as a function of its composition.

Abstract

Perfluorobutyl methyl ether forms azeotropic or pseudoazeotropic compositions with esters. These compositions can be used in particular as solvent for cleaning and defluxing electronic components, for degreasing metals, for removing water adsorbed at the surface of solids and for fixing a toner to a printing substrate.

Description

L'invention concerne des compositions comprenant du perfluorobutyl méthyl éther (C4F9-O-CH3) et l'utilisation de ces compositions, notamment comme agent de nettoyage ou de séchage de surfaces solides.The invention relates to compositions comprising perfluorobutyl methyl ether (C 4 F 9 -O-CH 3 ) and the use of these compositions, especially as a cleaning or drying agent for solid surfaces.

Les hydrocarbures chlorofluorés complètement halogénés (CFC), en particulier 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. Outre leur utilisation en électronique, dans le nettoyage des flux de soudure pour éliminer le flux décapant qui adhère aux circuits imprimés, ils sont également classiquement utilisés pour dégraisser des pièces métalliques ou pour nettoyer des pièces mécaniques de haute qualité et de grande précision. Dans ces diverses applications, le CFC-113 est le plus souvent associé à d'autres solvants organiques, de préférence sous forme de compositions azéotropiques ou pseudo-azéotropiques ayant sensiblement la même composition dans la phase vapeur et dans la phase liquide, de sorte qu'elles peuvent être aisément employées au reflux.Fully halogenated chlorofluorocarbons (CFCs), particularly 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), are widely used as solvents in industry for degreasing and surface cleaning various, particularly for solid parts of complicated shape and difficult to clean. In addition to their use in electronics, in the cleaning of solder flux to eliminate flux flux adhering to printed circuits, they are also conventionally used to degrease metal parts or to clean mechanical parts of high quality and high accuracy. In these various applications, CFC-113 is most often associated with other organic solvents, preferably in the form of azeotropic or pseudoazeotropic compositions having substantially the same composition in the vapor phase and in the liquid phase, so that they can be easily used at reflux.

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, in order to eliminate the water adsorbed on the surface of solid parts.

Toutefois, le CFC-113, de même que d'autres chlorofluoroalcanes complètement halogénés, est aujourd'hui suspecté d'être impliqué dans la destruction de la couche d'ozone stratosphérique.However, CFC-113, along with other fully halogenated chlorofluoroalkanes, is now suspected of being involved in the destruction of the stratospheric ozone layer.

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.As a result, there is currently an urgent need to find new compositions that do not adversely affect the ozone layer.

Les composés hydrofluorés exempts de chlore sont totalement inertes vis-à-vis de la couche d'ozone stratosphérique et l'on constate une utilisation de plus en plus large de ces composés dans de nombreuses applications au détriment des composés porteurs d'atomes de chlore.The hydrofluorinated chlorine-free compounds are completely inert with respect to the stratospheric ozone layer and there is an increasing use of these compounds in many applications to the detriment of compounds carrying chlorine atoms. .

A cette fin, la demande de brevet WO 96/36689 propose des compositions azéotropiques de perfluorobutyl méthyl éther avec un ou plusieurs solvants organiques choisis parmi les alcanes linéaires ou ramifiés cycliques ou acycliques comprenant de 6 à 8 atomes de carbone, les éthers cycliques ou acycliques comprenant de 4 à 6 atomes de carbone, les cétones comprenant 3 atomes de carbone, les alcanes chlorés comprenant 1,3 ou 4 atomes de carbone, les alcènes chlorés comprenant 2 à 3 atomes de carbone, les alcools comprenant 1 à 4 atomes de carbone, les alcools partiellement fluorés comprenant 2 à 3 atomes de carbone, le 1-bromopropane, l'acétonitrile, le HCFC-225ea, et le HCFC-225cb.For this purpose, the patent application WO 96/36689 provides azeotropic compositions of perfluorobutyl methyl ether with one or more organic solvents selected from linear or branched cyclic or acyclic alkanes comprising 6 to 8 carbon atoms, cyclic or acyclic ethers comprising 4 to 6 carbon atoms, ketones comprising 3 carbon atoms, chlorinated alkanes comprising 1.3 or 4 carbon atoms, chlorinated alkenes comprising 2 to 4 carbon atoms, 3 carbon atoms, alcohols comprising 1 to 4 carbon atoms, partially fluorinated alcohols comprising 2 to 3 carbon atoms, 1-bromopropane, acetonitrile, HCFC-225ea, and HCFC-225cb.

Le document WO 96/22356 divulgue des compositions de nettoyage et de dégraissage de pièces métalliques comprenant des mélanges à base de composés perfluoré alkoxy-substitués et de co-solvants, tels que, notamment, les esters ; l'utilisation d'un mélange de perfluorobutyl méthyl éther et de décanoate de méthyle s'y trouve spécifiquement décrite.The document WO 96/22356 discloses compositions for cleaning and degreasing metal parts comprising mixtures based on alkoxy-substituted perfluorinated compounds and cosolvents, such as, in particular, the esters; the use of a mixture of perfluorobutyl methyl ether and methyl decanoate is specifically described therein.

Le document WO 96/36688 décrit des compositions pseudo-azéotropiques à base de perfluorobutyl éthyl éther et, inter alia, d'esters à 4 atomes de carbone, qui peuvent être utilisées pour la formulation de composition pour le recouvrement de surfaces.The document WO 96/36688 discloses pseudo-azeotropic compositions based on perfluorobutyl ethyl ether and, inter alia, esters containing 4 carbon atoms, which can be used for the formulation of composition for surface coating.

Le document WO 98/24003 , art antérieur selon l'art. 54(3) CBE, divulgue l'utilisation comme agent fixateur d'un toner à un support d'enregistrement d'un mélange de perfluorobutyl méthyl éther et de 5 % en poids d'acétate de méthyle.The document WO 98/24003 prior art according to art. 54 (3) EPC discloses the use as a toner fixing agent for a recording medium of a mixture of perfluorobutyl methyl ether and 5% by weight of methyl acetate.

Un des objectifs de la présente invention est de fournir d'autres compositions formant éventuellement 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 de cartes de circuits imprimés. Un autre objectif de l'invention est de fournir de telles compositions dépourvues d'effet destructeur vis-à-vis de la couche d'ozone.It is an object of the present invention to provide other compositions optionally forming azeotropes or pseudoazeotropes, which are particularly effective when used as a cleaning agent in solvent cleaning processes. The invention also relates to such compositions having properties particularly suitable for cleaning printed circuit boards. Another object of the invention is to provide such compositions devoid of destructive effect vis-à-vis the ozone layer.

L'invention a également pour objet des compositions possédant des propriétés particulièrement adaptées comme agent fixateur d'un toner à un support d'enregistrement dans un appareil d'impression ou de reproduction de documents.The invention also relates to compositions having particularly suitable properties as a toner fixing agent to a recording medium in a printing apparatus or reproduction of documents.

La présente invention concerne dès lors des compositions azéotropiques ou pseudo-azéotropiques comprenant au moins un perfluorobutyl méthyl éther de formule générale C4F9-O-CH3 où C4F9 est une chaîne perfluorée linéaire ou ramifiée et au moins un ester choisi parmi, l'acétate de méthyle, le formiate d'éthyle et le formiate de méthyle, lesditescompositions contenant environ 21 à 52% en poids d'acétate de méthyle ou environ 22 à 53% en poids de formiate d'éthyle ou environ 40 à 92% en poids de formiate de méthyle Le CF3-(CF2)3-O-CH3, le (CF3)2CF-CF2-O-CH3 et leurs mélanges sont les perfluorobutyl méthyl éthers préférés. Dans la suite de l'exposé, le terme "perfluorobutyl méthyl éther" est utilisé pour désigner un mélange de ces 2 composés, commercialisé par 3M sous la dénomination HFE-7100.The present invention therefore relates to azeotropic or pseudo-azeotropic compositions comprising at least one perfluorobutyl methyl ether of general formula C 4 F 9 -O-CH 3 where C 4 F 9 is a linear or branched perfluorinated chain and at least one ester chosen of, methyl acetate, ethyl formate and methyl formate, said compositions containing about 21 to 52% by weight of methyl acetate or about 22 to 53% by weight of ethyl formate or about 40 to 92% by weight of methyl formate CF 3 - (CF 2 ) 3 -O-CH 3 , the (CF 3 ) 2 CF-CF 2 -O-CH 3 and mixtures thereof are the preferred perfluorobutyl methyl ethers. In the following description, the term "perfluorobutyl methyl ether" is used to designate a mixture of these 2 compounds, marketed by 3M under the name HFE-7100.

Fondamentalement, l'état thermodynamique d'un fluide est défini par quatre variables interdépendantes : la pression (P), la température (T), la composition 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, la composition de la phase liquide X est exactement égale à la composition de la phase gazeuse 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 substantiellement 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), temperature (T), composition the liquid phase (X) and the composition of the gas phase (Y). A true azeotrope is a particular 2 or more component system for which, at a given temperature and at a given pressure, the composition of the liquid phase X is exactly equal to the composition of the gas phase Y.
A pseudoazeotrope is a two or more component system 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 and pseudo-azeotropic systems can not They can not be separated easily by distillation and therefore their composition remains substantially constant in the solvent cleaning operations, as well as in the recovery operations of solvents used by distillation.

Aux fins de la présente invention, on entend par mélange pseudo-azéotropique, un mélange de deux 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. Les mélanges dont le point d'ébullition diffère du point d'ébullition de l'azéotrope vrai de 0,2 °C au maximum sont préférés. Les mélanges dont le point d'ébullition diffère du point d'ébullition de l'azéotrope vrai de 0,1 °C au maximum sont particulièrement préférés.For the purpose of the present invention, a pseudo-azeotropic mixture is understood to mean a mixture of two constituents whose boiling point (at a given pressure) differs from the boiling point of the true azeotrope of 0.5.degree. maximum. Mixtures whose boiling point differs from the boiling point of the true azeotrope of up to 0.2 ° C are preferred. Mixtures whose boiling point differs from the boiling point of the true azeotrope by up to 0.1 ° C are particularly preferred.

Les teneurs en perfluorobutyl méthyl éther et en ester dans les compositions selon l'invention peuvent varier dans de larges mesures, selon l'utilisation envisagée.The contents of perfluorobutyl methyl ether and ester in the compositions according to the invention can vary widely, depending on the intended use.

Généralement, les compositions selon l'invention contiennent au moins 1 % en poids de perfluorobutyl méthyl éther. Elles en contiennent avantageusement au moins 5 %. De manière particulièrement préférée, elles en contiennent au moins 10 %. Elles peuvent en contenir jusqu'à 99 %. Le plus souvent, elles en contiennent au plus 95 %.Generally, the compositions according to the invention contain at least 1% by weight of perfluorobutyl methyl ether. They advantageously contain at least 5%. In a particularly preferred manner, they contain at least 10%. They can contain up to 99%. Most often, they contain at most 95%.

Des compositions selon l'invention tout particulièrement préférées sont celles qui contiennent le perfluorobutyl méthyl éther et un ester dans des proportions dans lesquelles ils forment un azéotrope ou un pseudo-azéotrope à point d'ébullition minimum.Particularly preferred compositions according to the invention are those which contain perfluorobutyl methyl ether and an ester in proportions in which they form a minimum boiling azeotrope or pseudoazeotrope.

Les compositions des mélanges azéotropiques selon l'invention ont été estimées sur base des résultats des mesures expérimentales présentées dans les exemples ci-après.The compositions of the azeotropic mixtures according to the invention were estimated on the basis of the results of the experimental measurements presented in the examples below.

Le perfluorobutyl méthyl éther et l'acétate de méthyle forment un azéotrope ou un pseudo-azéotrope binaire lorsque leur mélange contient environ de 21 à 52 % en poids d'acétate de méthyle. Les compositions binaires contenant environ de 28 à 48 % en poids d'acétate de méthyle sont préférées. Sous une pression de 102,3 kPa, la composition binaire constituée essentiellement d'environ 61% en poids de perfluorobutyl méthyl éther et d'environ 39 % en poids d'acétate de méthyle constitue un azéotrope vrai, dont le point d'ébullition est d'environ 52,6 °C. Cette composition est tout particulièrement préférée.
Le perfluorobutyl méthyl éther et le formiate d'éthyle forment un azéotrope ou un pseudo-azéotrope binaire lorsque leur mélange contient environ de 22 à 53 % en poids de formiate d'éthyle. Les compositions binaires contenant environ de 26 à 46 % en poids de formiate d'éthyle sont préférées. Sous une pression de 102,6 kPa, la composition binaire constituée essentiellement d'environ 68 % en poids de perfluorobutyl méthyl éther et d'environ 32 % en poids de formiate d'éthyle constitue un azéotrope vrai, dont le point d'ébullition est d'environ 50,2 °C. Cette composition est tout particulièrement préférée.Perfluorobutyl methyl ether and methyl acetate form a binary azeotrope or pseudo-azeotrope when their mixture contains about 21 to 52% by weight of methyl acetate. The binary compositions containing about 28 to 48% by weight of methyl acetate are preferred. Under a pressure of 102.3 kPa, the binary composition consisting essentially of about 61% by weight of perfluorobutyl methyl ether and about 39% by weight of methyl acetate constitutes a true azeotrope, whose boiling point is about 52.6 ° C. This composition is very particularly preferred.
Perfluorobutyl methyl ether and ethyl formate form a binary azeotrope or pseudoazeotrope when their mixture contains about 22 to 53% by weight of ethyl formate. Binary compositions containing about 26 to 46% by weight of ethyl formate are preferred. Under a pressure of 102.6 kPa, the binary composition consisting essentially of about 68% by weight of perfluorobutyl methyl ether and about 32% by weight of ethyl formate constitutes a true azeotrope, whose boiling point is about 50.2 ° C. This composition is very particularly preferred.

Le perfluorobutyl méthyl éther et le formiate de méthyle forment un azéotrope ou un pseudo-azéotrope binaire lorsque leur mélange contient environ de 40 à 92 % en poids de formiate de méthyle. Les compositions binaires contenant environ de 59 à 80 % en poids de formiate de méthyle sont préférées. Sous une pression de 102,2 kPa, la composition binaire constituée essentiellement d'environ 36 % en poids de perfluorobutyl méthyl éther et d'environ 64 % en poids de formiate de méthyle constitue un azéotrope vrai, dont le point d'ébullition est d'environ 31,2 °C. Cette composition est tout particulièrement préférée.Perfluorobutyl methyl ether and methyl formate form a binary azeotrope or pseudoazeotrope when their mixture contains about 40 to 92% by weight of methyl formate. Binary compositions containing about 59 to 80% by weight of methyl formate are preferred. Under a pressure of 102.2 kPa, the binary composition consisting essentially of about 36% by weight of perfluorobutyl methyl ether and about 64% by weight of methyl formate constitutes a true azeotrope whose boiling point is about 31.2 ° C. This composition is very particularly preferred.

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 optionally be present in the compositions according to the invention. The compositions according to the invention may thus contain stabilizers, surfactants or any other additives making it possible to improve the performance of the compositions according to the invention during their use. The nature and the quantity of these additives depend on the intended use and are easily defined by those skilled in the art. In general, 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 than 10%.

Les compositions selon l'invention présentent un point d'ébullition adéquat pour remplacer les compositions à base de CFC-113 dans les appareillages de nettoyage existants. En ce qui concerne son impact sur l'environnement, le perfluorobutyl méthyl éther apparaît particulièrement intéressant, puisqu'il présente un potentiel de destruction de l'ozone nul. 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 have a boiling point suitable for replacing CFC-113-based compositions in existing cleaning apparatus. As regards its impact on the environment, perfluorobutyl methyl ether appears to be particularly interesting since it has a zero ozone destruction potential. The compositions according to the invention are further inert against the different types of surfaces to be treated, whether they are metal, plastic or glass.

Les compositions selon l'invention peuvent dès lors être utilisées dans les mêmes applications et selon les mêmes techniques que les compositions antérieures à base de CFC-113. En particulier, les compositions selon l'invention peuvent être utilisées comme agent de nettoyage, solvant, dégraissant, défluxant ou dessicatif.The compositions according to the invention can therefore be used in the same applications and according to the same techniques as the prior compositions based on CFC-113. In particular, the compositions according to the invention can be used as a cleaning agent, solvent, degreasing agent, defluxant or desiccant.

L'invention concerne dès lors aussi l'utilisation des compositions selon l'invention comme agent de nettoyage, comme agent dégraissant de surfaces solides, comme agent de nettoyage de cartes de circuits imprimés, contaminées par un flux décapant et des résidus de ce flux ou comme agent dessicatif pour éliminer l'eau adsorbée à la surface d'objets solides.
Les compositions selon l'invention, peuvent également être utilisées comme agent fixateur d'un toner à un support d'enregistrement dans un appareil d'impression ou de reproduction de documents.The invention therefore also relates to the use of the compositions according to the invention as a cleaning agent, as a degreasing agent for solid surfaces, as a cleaning agent for printed circuit boards, contaminated with a stripping flux and residues thereof. as a desiccant to remove adsorbed water on the surface of solid objects.
The compositions according to the invention can also be used as a toner fixing agent for a recording medium in a printing or copying apparatus.

Des compositions à base de perfluorobutyl méthyl éther utilisables comme agent fixateur d'un toner sont des compositions contenant un hydrofluorocarbure en C3-C6. Par hydrofluorocarbure en C3-C6, on entend désigner les hydrocarbures saturés, aliphatiques ou alicycliques, constitués uniquement de carbone, de fluor et d'hydrogène, comprenant de 3 à 6 atomes de carbone, au moins un atome de fluor et au moins un atome d'hydrogène. Des exemples typiques d'hydrofluorocarbures en C3-C6 sont des hydrofluoroalcanes tels que le 1,1,1,3,3-pentafluoropropane (HFC-245fa), le 1,1,1,3,3-pentafluorobutane (HFC-365mfc) et le 1,1,1,2,2,3,4,6,6,6-décafluoropentane (HFC-43-10mee). Le 1,1,1,3,3-pentafluorobutane convient particulièrement bien. De préférence, on utilise des compositions ternaires perfluorobutyl méthyl éther/ester/hydrofluorocarbure en C3-C6.Perfluorobutyl methyl ether compositions useful as a toner fixing agent are compositions containing a C3-C6 hydrofluorocarbon. By C3-C6 hydrofluorocarbon is meant saturated hydrocarbons, aliphatic or alicyclic, consisting solely of carbon, fluorine and hydrogen, comprising from 3 to 6 carbon atoms, at least one fluorine atom and at least one atom hydrogen. Typical examples of C 3 -C 6 hydrofluorocarbons are hydrofluoroalkanes such as 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and 1,1,1,2,2,3,4,6,6,6-decafluoropentane (HFC-43-10mee). 1,1,1,3,3-Pentafluorobutane is particularly suitable. Preferably, C3-C6 perfluorobutyl methyl ether / ester / hydrofluorocarbon terefinal compositions are used.

L'invention concerne dès lors aussi l'utilisation des compositions selon l'invention comme agent fixateur d'un toner à un support d'enregistrement dans un appareil d'impression ou de reproduction de documents.The invention therefore also relates to the use of the compositions according to the invention as a toner fixing agent to a recording medium in a printing device or reproduction of documents.

Les exemples ci-après, non limitatifs, illustrent l'invention de manière plus détaillée.The following nonlimiting examples illustrate the invention in more detail.

Exemples 1-3Examples 1-3

Pour mettre en évidence l'existence de compositions azéotropiques ou pseudo-azéotropiques selon l'invention entre le perfluorobutyl méthyl éther et un ester, 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 a été mesurée au moyen d'un thermomètre plongeant dans le flacon.In order to demonstrate the existence of azeotropic or pseudoazeotropic compositions according to the invention between perfluorobutyl methyl ether and an ester, a glass apparatus consisting of a 50 ml boiler flask surmounted by a reflux condenser was used. . The temperature of the liquid was measured by means of a thermometer immersed in the flask.

Une quantité de perfluorobutyl méthyl éther pur déterminée avec précision a été chauffée sous une pression connue jusqu' à ébullition, puis de petites quantités d'ester, pesées avec précision, ont été progressivement introduites dans le flacon au moyen d'une seringue, via une tubulure latérale.An accurately determined amount of perfluorobutyl methyl ether was heated under known pressure to boiling, and then small amounts of ester, accurately weighed, were gradually introduced into the vial by means of a syringe, via a syringe. lateral 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.The determination of the azeotropic composition was carried out by recording the evolution of the boiling point of the mixture as a function of its composition.

Ces mesures ont été réalisées pour des mélanges contenant du perfluorobutyl méthyl éther et des quantités croissantes d'acétate de méthyle (exemple 1), de formiate d'éthyle (exemple 2) et de formiate de méthyle (exemple 3).These measurements were made for mixtures containing perfluorobutyl methyl ether and increasing amounts of methyl acetate (Example 1), ethyl formate (Example 2) and methyl formate (Example 3).

La pression à laquelle les mesures ont été prises est mentionnée. Les résultats obtenus sont présentés dans le tableau I. Tableau 1 Exemple 1 Exemple 2 Exemple 3 Composition perfluorobutyl méthyl éther /acétate de méthyle Composition perfluorobutyl méthyl éther /formiate d'éthyle Composition perfluorobutyl méthyl éther /formiate de méthyle (Pression : 102,3 kPa) (Pression : 102,6 kPa) (Pression : 102,2 kPa) % en poids d'acétate de méthyle T°éb (°C) % en poids de formiate d'éthyle T°éb (°C) % en poids de formiate de méthyle T°éb (°C) 0 60,2 0 60,2 0 60,2 1,86 58,8 1,98 58,2 0,92 57,2 2,78 58 3,40 56,8 4,49 49 3,76 57,6 4,96 55,6 7,08 44,4 4,88 56,8 6,83 54,6 8,95 42 7,29 55,6 9,26 53,4 18,55 35 9,69 54,8 12,16 52,4 22,91 33,8 13,72 53,8 13,95 52 34,50 32,4 16,74 53,4 16,07 51,6 39,66 31,8 19,03 53,3 18,74 51,2 45,22 31,6 21,44 53,1 22,24 50,8 51,69 31,4 24,26 53 26,47 50,4 63,96 31,2 33,96 52,8 31,44 50,2 79,91 31,3 39,11 52,6 40,10 50,4 87,66 31,4 44,32 52,7 49,47 50,6 90,82 31,6 48,58 52,8 54,13 50,8 93,31 31,8 52,68 53,2 67,56 51,2 95,47 32 79,09 52,2 The pressure at which the measurements were taken is mentioned. The results obtained are shown in Table I. Table 1 Example 1 Example 2 Example 3 Perfluorobutyl Methyl Ether / Methyl Acetate Composition Perfluorobutyl methyl ether / ethyl formate composition Perfluorobutyl Methyl Ether / Methyl Formate Composition (Pressure: 102.3 kPa) (Pressure: 102.6 kPa) (Pressure: 102.2 kPa) % by weight of methyl acetate T ° b (° C) % by weight of ethyl formate T ° b (° C) % by weight of methyl formate T ° b (° C) 0 60.2 0 60.2 0 60.2 1.86 58.8 1.98 58.2 0.92 57.2 2.78 58 3.40 56.8 4.49 49 3.76 57.6 4.96 55.6 7.08 44.4 4.88 56.8 6.83 54.6 8.95 42 7.29 55.6 9.26 53.4 18,55 35 9.69 54.8 12.16 52.4 22.91 33.8 13.72 53.8 13.95 52 34.50 32.4 16.74 53.4 16,07 51.6 39.66 31.8 19,03 53.3 18.74 51.2 45,22 31.6 21.44 53.1 22.24 50.8 51.69 31.4 24.26 53 26.47 50.4 63,96 31.2 33.96 52.8 31.44 50.2 79.91 31.3 39,11 52.6 40,10 50.4 87.66 31.4 44.32 52.7 49.47 50.6 90.82 31.6 48.58 52.8 54.13 50.8 93.31 31.8 52.68 53.2 67.56 51.2 95.47 32 79,09 52.2

Claims (9)

  1. Azeotropic or pseudo-azeotropic composition comprising at least one perfluorobutyl methyl ether of formula C4F9-O-CH3, in which C4F9 represents a linear or branched perfluorinated chain, and at least one ester, characterized in that the ester is chosen from methyl acetate, ethyl formate and methyl formate, said composition comprising approximately 21 to 52 % by weight of methyl acetate or approximately 22 to 53 % by weight of ethyl formate or approximately 40 to 92 % by weight of methyl formate.
  2. Composition according to Claim 1, wherein the perfluorobutyl methyl ether is chosen from CF3-(CF2)3-O-CH3, (CF3)2CF-CF2-O-CH3 and their mixtures.
  3. Composition according to Claim 1 or 2, comprising approximately 28 to 48 % by weight of methyl acetate or approximately 26 to 46 % by weight of ethyl formate or approximately 59 to 80 % by weight of methyl formate.
  4. Minimum boiling point azeotropic composition according to Claim 1 or 2, composed of approximately 61 % by weight of perfluorobutyl methyl ether and of approximately 39 % by weight of methyl acetate, the boiling point of which is approximately 52.6°C under a pressure of 102.3 kPa.
  5. Minimum boiling point azeotropic composition according to Claim 1 or 2, composed of approximately 68 % by weight of perfluorobutyl methyl ether and of approximately 32 % by weight of ethyl formate, the boiling point of which is approximately 50.2°C under a pressure of 102.6 kPa.
  6. Minimum boiling point azeotropic composition according to Claim 1 or 2, composed of approximately 36 % by weight of perfluorobutyl methyl ether and of approximately 64 % by weight of methyl formate, the boiling point of which is approximately 31.2°C under a pressure of 102.2 kPa.
  7. Use of the compositions according to any one of Claims 1 to 6 as cleaning agent, as agent for degreasing solid surfaces, as agent for cleaning printed circuit boards contaminated by a soldering flux and residues from this flux, or as drying agent for removing the water adsorbed at the surface of solid objects.
  8. Composition according to any one of Claims 1 to 6, additionally comprising a C3-C6 hydrofluorocarbon.
  9. Use of perfluorobutyl methyl ether, of the compositions comprising it and, in particular, of the compositions according to any one of Claims 1 to 6 and 8 as agent for fixing a toner to a recording substrate in a device for printing or reproducing documents.
EP98965826A 1997-12-15 1998-12-12 Compositions comprising perfluorobutyl methyl ether and use of said compositions Expired - Lifetime EP1040179B1 (en)

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