CA2239818A1 - Cleaning and degreasing composition with no flash point - Google Patents

Cleaning and degreasing composition with no flash point Download PDF

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Publication number
CA2239818A1
CA2239818A1 CA002239818A CA2239818A CA2239818A1 CA 2239818 A1 CA2239818 A1 CA 2239818A1 CA 002239818 A CA002239818 A CA 002239818A CA 2239818 A CA2239818 A CA 2239818A CA 2239818 A1 CA2239818 A1 CA 2239818A1
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organic compound
composition
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French (fr)
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Pascal Michaud
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Arkema France SA
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    • 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
    • C23G5/024—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing 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
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/509—Mixtures of hydrocarbons and oxygen-containing solvents
    • C—CHEMISTRY; METALLURGY
    • 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
    • C11D7/5013—Organic solvents containing nitrogen
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals
    • 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
    • C11D7/263—Ethers
    • 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
    • C11D7/264—Aldehydes; Ketones; Acetals or ketals
    • 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
    • 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
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds

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

Abstract

La présente invention a pour objet une composition de nettoyage et de dégraissage sans point d'éclair, constituée par au moins un composé organique (A) choisi dans le groupe constitué par les perfluoro-(N-alkylmorpholines), des hydrofluoroalcanes, les perfluoroalcanes, le s hydrofluoroalcènes, les chloromethanes, les éther-fluorés, au moins un mélange d'alcanes ou de cycloalcanes (B) et au moins un composé organique (C) choisi dans le groupe constitué par les cétones, les étheralcools et dérivés .The subject of the present invention is a cleaning and degreasing composition without flash point, consisting of at least one organic compound (A) chosen from the group consisting of perfluoro- (N-alkylmorpholines), hydrofluoroalkanes, perfluoroalkanes, hydrofluoroalkenes, chloromethanes, ether-fluorines, at least one mixture of alkanes or cycloalkanes (B) and at least one organic compound (C) chosen from the group consisting of ketones, etheralcohols and derivatives.

Description

COMPOSITION DE NETTOYAGE ET DE DEGRAISSAGE
SANS POINT D'ECLAIR
* * * * * * * *
La présente invention concerne une composition de nettoyage et de 5 dégraissage à froid de surfaces solides en milieu non aqueux, ladite composition comprenant au moins un mélange d'alcanes ou de cycloalcanes, au moins un composé organique halogérié, notamment fluoré ou perfluoré et au moins un composé organique comprenant une ou plusieurs fonction oxygénées.
Cette composition est utilisable notamment pour des applications de dégraissage de surfaces solides telles que les pièces métalliques, le ciment, les céramique, le verre, les matières synthétiques ayant été souillées par des huiles ou des graisses d'usinage et/ou de leur protection temporaire.
Cette composition est également utilisable pour le défluxage des 15 circuits imprimés. Cette opération de défluxage consiste à éliminer le flux de soudure.
Jusqu'à présent, on utilisait pour ces diverses opérations des solvants hydrocarbonés et principalement des solvants chlorés tels que- notamment le 1,1,1-trichloroéthane connu dans le métier sous la désignation T 111, des 20 chlorofluoroalcanes tels que le 1,1,2-trichloro-1,2,2-trifluoréthane connu dans le métier sous la désignation F1 13 et des hydrochlorofluoroalcanes (HCFC) tels que le 1,1-dichloro-1-fluoroéthane (141-b).
Cependant, ces composés chlorés, fluorochlorés et hydrochlorofluoro-carbonés sont suspectés être responsables de la diminution de la couche 25 d'ozone stratosphérique qui assure une protection contre certaines radiations.
Suite au Protocole de Montréal qui résulte de récentes discussions internationales sur l'environnement, ces composés chlorés ou fluorochlorés devront à brève échéance être remplacés par des substituts ayant peu ou pas d'effet destructeur vis-à-vis de l'ozone stratosphérique.
On a maintenant trouvé une composition de nettoyage et de dégraissage à froid de surface solide en milieu non-aqueux, caractérisée en ce qu'elle est constituée par au moins un composé organique (A) choisi dans le groupe constitué par les perfluoro-(N-alkylmorpholines), le n-tridécafluorohexane (C6F1 3H), le 2,3-dihydrodécafluoropentane (C5H2F1 o, 35 4310 mee), le 3,3,4-trihydroheptafluorobutane (C4F7H13, 347 mcf), le CLEANING AND DEGREASING COMPOSITION
WITHOUT FLASH POINT
* * * * * * * *
The present invention relates to a composition for cleaning and 5 cold degreasing of solid surfaces in a non-aqueous medium, said composition comprising at least one mixture of alkanes or cycloalkanes, at least one halogenated organic compound, in particular fluorinated or perfluorinated and at least one organic compound comprising one or more functions oxygenated.
This composition can be used in particular for applications of degreasing of solid surfaces such as metal parts, cement, ceramic, glass, synthetic materials having been soiled by oils or greases for machining and / or their temporary protection.
This composition can also be used for defluxing 15 printed circuits. This defluxing operation consists in eliminating the flow of welding.
Until now, solvents have been used for these various operations.
hydrocarbons and mainly chlorinated solvents such as - especially 1,1,1-trichloroethane known in the art under the designation T 111, 20 chlorofluoroalkanes such as 1,1,2-trichloro-1,2,2-trifluoroethane known in the trade under the designation F1 13 and hydrochlorofluoroalkanes (HCFC) such than 1,1-dichloro-1-fluoroethane (141-b).
However, these chlorinated, fluorochlorinated and hydrochlorofluoro-carbonaceous are suspected to be responsible for the shrinking of the layer 25 of stratospheric ozone which provides protection against certain radiations.
Following the Montreal Protocol resulting from recent discussions international on the environment, these chlorinated or fluorochlorinated compounds will soon have to be replaced by substitutes with little or no destructive effect with respect to stratospheric ozone.
We have now found a composition for cleaning and cold degreasing of solid surface in non-aqueous medium, characterized in that it consists of at least one organic compound (A) chosen from the group consisting of perfluoro- (N-alkylmorpholines), n-tridecafluorohexane (C6F1 3H), 2,3-dihydrodecafluoropentane (C5H2F1 o, 35 4310 mee), 3,3,4-trihydroheptafluorobutane (C4F7H13, 347 mcf),

2,2,4,4,4-pentahydropentafluorobutane (C4FsHs, 365 mcf), les perfluoroalcanes, les hydrofluoroalcènes, les chlorométhanes, les éthers fluorés, au moins un mélange d'alcanes ou de cycloalcanes (B), et au moins un composé organique (C) choisi dans le groupe constitué par les cétones, les étheralcools et dérivés et en ce que ladite composition ne présente pas de point d'éclair selon la norme ASTM D3828.
A titre d'illustration de perfluoro-(N-alkyl morpholines) utilisables selon 5 la présente invention, on peut citer les composés de formule:
r~ .
O F N-Rf (I) (R1 flrl \~/

10 dans laquelle Rf et R1f, identiques ou différents représentent un radical aliphatique perfluoré, linéaire ou ramifié, ayant un nombre de carbone allant de1 à 4, n est un nombre allant de O à 8, et le symbole F à l'intérieur du cycle signifie que le cycle saturé est totalement fluoré, c'est-à-dire que tous les atomes de carbone sont liés à des atomes de fluor (ou à R1f).
Parmi les composés de formule (I), on préfère utiliser les perfluoro-N-méthyl, -N-éthyl et -N-isopropyl morpholines et tout particulièrement la perfluoro-(N-méthyl morpholine):
r~ .
0~ ~ N-CF3 A titre d'illustration de perfluoroalcanes utilisables selon l'invention, on peut citer le n-perfluorohexane (C6F1 4)-A titre d'illustration d'hydrofluoroalcènes, on peut citer le n-perfluorobutyléthylène (n-C4FgCH = CH2), le n-perfluorohexyléthylène 25 (n-C6F1 3CH = CH2) A titre d'illustration d'éthers fluorés utilisables selon la présente invention, on peut citer le n-nonafluorobutylméthyl éther (C4HgOCH3).
A titre d'illustration de chlorométhanes utilisables selon la présente invention, on peut citer le chlorure de méthylèen CH2CI2.
A titre d'exemple de mélange d'alcanes utilisables selon la présente invention, on peut citer les coupes pétrolières ayant un nombre de carbone allant de 8 à 12 et de préférence allant de 9 à 11.
Parmi ces coupes pétrolières, on préfère utiliser celles qui ne contiennent quasiment pas de composés aromatiques.
A titre d'illustration de telles coupes pétrolières, on peut citer les solvants isoparaffiniques vendus par la Société TOTAL sous les dénominations ISANE IP 155 et ISANE IP 165, les coupes pétrolières ISOPAR G et ISOPAR E
commercialisée par la Société EXXON Chemical.

Par mélange de cycloalcanes, on désigne présentement un mélange d'hydrocarbures saturés mono-ou polycycliques, éventuellement substitués par un ou plusieurs restes alkyle de formule générale CnH2(n + 1 -a) (II) dans laquelle n est un nombre entier allant de 5 à 26 et a représente le nombre de 5 cycles.
De préférence, on utilisera selon la présente invention des mélanges de cycloalcanes de formule (II) dans laquellè n est compris entre 5 et 12 et, de préférence, compris entre 7 et 10 et a = 1 ou 2 et de préférence a = 1 (composés monocycliques).
A titre d'illustration de tels mélanges de cycloalcanes uitlisables selon la présente inveniton, on peut citer les mélanges d'(alkyl)cycloalcanes obtenus par hydrogénation catalytique de coupes pétrolières constituées de composés aromatiques tel que notamment, les alkylbenzènes et les divinylbenzènes et d'oléfines cycliques.
Les mélanges d'(alkyl)cycloalcanes ainsi obtenus sont essentiellement constitués d'hydrocarbures saturés cycliques pouvant avoir un ou plusieurs restes alkyle ayant de 1 à 4 atomes de carbone.
A titre d'illustration de tels mélanges, on peut citer les diethylcyclohexanes (mélange des isomères 1,2; 1,3 et 1,4, cis et trans) les 20 mélanges contenant deux ou plusieurs des composés ci-après: les métyléthylcyclohexanes, les méthylpropylcyclohexanes, les éthylpropylcyclo-hexanes, les dipropylcyclohexanes, les méthylbutylcyclohexanes, les éthyl-butylcyclohexanes .
Selon la présente invention, on peut également utiliser comme mélange 25 de cycloalcanes des coupes pétrolières dites coupes naphtèniques.
Ces coupes naphténiques sont essentiellement constituées par des composées de formule (II) dans laquelle a=1 et n est généralement compis entre 5 et 12. A titre d'illustration de tels composés, on peut citer les diéthylcyclopentanes, les mono, di, et triethylcyclohexanes, les 30 éthyldimethylcyclohexanes, le cyclooctane.
A titre d'exemple de telles coupes naphtèniques, on peut citer les solvants naphténiques vendus par EXXON CHEMICAL sous la dénomination NAPPAR 10.
A titre d'illustration de cétones utilisables selon la présente invention, 35 on peut citer l'éthylamylcétone, I'éthylbutylcétone, la di-n-propylcétone, le diisobutylcétone, la cyclohexanone, la 2-méthylcyclohexanone, le 2,2,4,4,4-pentahydropentafluorobutane (C4FsHs, 365 mcf), perfluoroalkanes, hydrofluoroalkenes, chloromethanes, ethers fluorinated, at least one mixture of alkanes or cycloalkanes (B), and at least one organic compound (C) chosen from the group consisting of ketones, ether alcohols and derivatives and in that said composition does not have any flash point according to ASTM D3828.
By way of illustration of perfluoro- (N-alkyl morpholines) which can be used according to 5 the present invention include the compounds of formula:
r ~.
OF N-Rf (I) (R1 flrl /

10 in which Rf and R1f, which are identical or different, represent a radical perfluorinated aliphatic, linear or branched, having a carbon number ranging from 1 to 4, n is a number ranging from O to 8, and the symbol F inside the ring means that the saturated cycle is completely fluorinated, i.e. all carbon atoms are linked to fluorine atoms (or to R1f).
Among the compounds of formula (I), it is preferred to use perfluoro-N-methyl, -N-ethyl and -N-isopropyl morpholines and especially the perfluoro- (N-methyl morpholine):
r ~.
0 ~ ~ N-CF3 By way of illustration of perfluoroalkanes which can be used according to the invention, it is may include n-perfluorohexane (C6F1 4) -By way of illustration of hydrofluoroalkenes, mention may be made of n-perfluorobutylethylene (n-C4FgCH = CH2), n-perfluorohexylethylene 25 (n-C6F1 3CH = CH2) By way of illustration of fluorinated ethers which can be used according to the present invention, there may be mentioned n-nonafluorobutylmethyl ether (C4HgOCH3).
By way of illustration of chloromethanes which can be used according to the present invention, there may be mentioned methylene chloride CH2CI2.
By way of example of a mixture of alkanes which can be used according to the present invention, mention may be made of petroleum fractions having a carbon number ranging from 8 to 12 and preferably ranging from 9 to 11.
Among these petroleum cuts, we prefer to use those that do not contain almost no aromatic compounds.
By way of illustration of such petroleum cuts, mention may be made of isoparaffinic solvents sold by TOTAL under the names ISANE IP 155 and ISANE IP 165, the ISOPAR G and ISOPAR E oil cuts marketed by the company EXXON Chemical.

By mixture of cycloalkanes, we currently designate a mixture mono- or polycyclic saturated hydrocarbons, optionally substituted by one or more alkyl radicals of general formula CnH2 (n + 1 -a) (II) in which n is an integer ranging from 5 to 26 and a represents the number of 5 cycles.
Preferably, mixtures of cycloalkanes of formula (II) in which n is between 5 and 12 and, from preferably between 7 and 10 and a = 1 or 2 and preferably a = 1 (monocyclic compounds).
By way of illustration of such mixtures of cycloalkanes which can be used according to the present invention, mention may be made of the mixtures of (alkyl) cycloalkanes obtained by catalytic hydrogenation of petroleum fractions consisting of compounds aromatics such as in particular, alkylbenzenes and divinylbenzenes and cyclic olefins.
The mixtures of (alkyl) cycloalkanes thus obtained are essentially made up of saturated cyclic hydrocarbons which may have one or more alkyl radicals having from 1 to 4 carbon atoms.
By way of illustration of such mixtures, mention may be made of diethylcyclohexanes (mixture of isomers 1,2, 1,3 and 1,4, cis and trans) 20 mixtures containing two or more of the following compounds:
methylethylcyclohexanes, methylpropylcyclohexanes, ethylpropylcyclo-hexanes, dipropylcyclohexanes, methylbutylcyclohexanes, ethyl-butylcyclohexanes.
According to the present invention, it is also possible to use as a mixture 25 of cycloalkanes from petroleum cuts called naphthenic cuts.
These naphthenic cuts are essentially constituted by composed of formula (II) in which a = 1 and n is generally compis between 5 and 12. By way of illustration of such compounds, mention may be made of diethylcyclopentanes, mono, di, and triethylcyclohexanes, 30 ethyldimethylcyclohexanes, cyclooctane.
As an example of such naphthenic cuts, mention may be made of naphthenic solvents sold by EXXON CHEMICAL under the name NAPPAR 10.
By way of illustration of ketones which can be used according to the present invention, 35 Mention may be made of ethylamyl ketone, ethylbutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, 2-methylcyclohexanone,

3-méthylcyclohexanone, le 4-méthylcyclohexanone. A titre d'illustration d'étheralcools et dérivés utilisables selon la présente invention, on peut citer le ' CA 02239818 1998-06-19 méthoxypropanol, le 1-éthoxy-2-propanol, le 1-propoxy-2-propanol, le 1-n-butoxy-2-propanol, le 1-tert-butoxy-2-propanol, le 2-méthoxyéthanol, le 2-éthoxyéthanol, I'acétate de propylèneglyxol méthyléther, I'acétate de propyléneglycol éthyléter, I'acétate d'éthylène glycol méthyléther, le 5 di(propylèneglycol)monométhyléter, le di(propyléneglycol)butyléther.
Selon la présente invention, la composition peut comprendre de 1 % à
40 % en poids, et de préférence de 1 % à 25 % en poids de composé (A), de 60 % à 98 % en poids et, de préférence, de 75 % à 98 % en poids d'un mélange d'alcanes ou de cycloalcanes (B) et de 1 % à 15 % en poids et, de 10 préférence de 1 % à 10 % en poids de composé (C).
La composition selon la présente invention est utilisable dans des applications de dégraissage à froid en milieu non aqueux, de surfaces solides telles que les pièces métalliques, le ciment, le verre, les matières synthétiques ayant été souillées par des huiles ou des graisses utilisées lors des opérations15 d'usinage et/ou de leur protection temporaire.
Tout particulièrement, la composition est utilisable dans des applications dites "non-closes" telles que nettoyage au pinceau, au chiffon ou en pulvérisation.
Dans le cas de nettoyage par pulvérisation, la composition selon 20 I'invention peut être conditionnée en aérosol non inflammable. A cet effet, on peut introduire dans un boitier en aluminium un mélange comprenant de 25 %
à 35 % en poids de la composition selon l'invention et de 75 % à 65 % en poids d'un agent propulseur, après certissage du boîtier.
A titre d'agents propulseurs utilisables dans une telle application, on 25 citera l'azote, le gaz carbonique, I'heptafluoropropane (227 ea), le tetrafluoroéthane (134 a) contenant environ 4 % en volume de diméthyéther.
La composition peut être stabilisée. La présence d'une fonction alcool peut en présence de métaux légers, conduire à des réactions d'évolution d'hydrogène indésirables qui seraient susceptibles de mettre en péril 30 I'installation par explosion.
Parmi les inhibiteurs de telles réactions, on peut utiliser des dérivés nitrés tel que le nitrométhane, le nitroéthane, le nitropropane, le nitrotoluène;
des éthers ou des acétals tels que le diméthoxyméthane, le 1,3-dioxolane, le diméthoxyéthane; des amines telles que la triëthylamine, la dipropylamine, la 35 diméthylamine; des dérivés du phosphore tel que le triisodécylphoshite, le triisooctylphosphite .
La composition peut également contenir un ou plusieurs masquants d 'odeur.

' - CA 02239818 1998-06-19 A titre d'exemple de tels produits, on peut citer la vanilline et ses dérivés, les essences de pin, le limonène et ses dérivés.
Ces composés son utilisés en très faibles quantités, généralement comprises entre O,O1 et O,1 parties en poids pour 100 parties en poids de la 5 composition.
La composition selon l'invention présente l'avantage de ne pas avoir de point d'éclair selon la norme ASTM D3828 et peut être facilement éliminée après l'opération de dégraissage.
Les exemples qui suivent illustrent l'invention.

Les compositions sont réalisées avec les constituants ci-après:
Coupe pétrolière (C9-C1 1 ) ISOPAR G, ci-après désignée par ISO G.
Coupe pétrolière (C8-C9) ISOPAR E, ci-après désignée par ISO E.
La perfluoro-(N-méthylmorpholine) I5 r\
O~ ~N-CF3 ci-après C 5 F 11 NO, le n-tridecafluorohexane (n-C6F1 3H), le n-perfluorohexane (n-C6F1 4), le n-perfluorobutyléthylène (n-C4FgCH = CH2), le chlorure de méthylène (CH2CI2), le n-perfluorohexyléthylène (n-C6F13CH=CH2) I'éthylamylcétone, ci-après EAK, le méthoxypropanol, ci-après MP, le di(propylène glycol)monométhyléther, ci-après DPM, le 2,3-dihydrodécafluoropentane (CsH2F10), le n-nonafluorobutylméthyléther (C4HgOCH3).
Dans le tableau ci-après, les pourcentages des constituants sont 30 exprimés en poids.
Les points d'éclair des compositions sont déterminés selon la norme ASTM D 56.
Toutes ces compositions sont efficaces pour le nettoyage des salissures grasses sur des surfaces nettoyables;
Dans ce tableau: N signifie qu'il n'y a pas de point d'éclair selon la norme ASTM D3828.

CONSTITUANTS DE E X E M P L E S

n C6F13H 10 O
n C6F14 2 C5F1 1 NO 1 5 5 2 5 ~ ' n C4F9CH = CH~ 1 5 5 CH~CI~ 15 2 5 C5H~F1 O 30 C4HgOCH3 Point d'éclair 1~C) 42 N N N N N N N N 11 N N N
T,~RI F~U 1 3-methylcyclohexanone, 4-methylcyclohexanone. For illustration ether alcohols and derivatives which can be used according to the present invention, mention may be made of 'CA 02239818 1998-06-19 methoxypropanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-n-butoxy-2-propanol, 1-tert-butoxy-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol acetate methyl ether, acetate ethylene propylene glycol, ethylene glycol methyl ether acetate, 5 di (propylene glycol) monomethyleter, di (propylene glycol) butyl ether.
According to the present invention, the composition can comprise from 1% to 40% by weight, and preferably from 1% to 25% by weight of compound (A), 60% to 98% by weight and preferably 75% to 98% by weight of a mixture of alkanes or cycloalkanes (B) and from 1% to 15% by weight and, Preferably from 1% to 10% by weight of compound (C).
The composition according to the present invention can be used in cold degreasing applications in non-aqueous medium, solid surfaces such as metal parts, cement, glass, plastics having been soiled with oils or greases used during machining operations and / or their temporary protection.
In particular, the composition can be used in so-called "non-closed" applications such as cleaning with a brush, cloth or as a spray.
In the case of spray cleaning, the composition according to The invention can be packaged in a non-flammable aerosol. To this end, we can introduce into a aluminum case a mixture comprising of 25%
at 35% by weight of the composition according to the invention and from 75% to 65% by weight of a propellant, after casing certification.
As propellants usable in such an application, we 25 will include nitrogen, carbon dioxide, heptafluoropropane (227 ea), tetrafluoroethane (134 a) containing about 4% by volume of dimethyl ether.
The composition can be stabilized. The presence of an alcohol function may in the presence of light metals, lead to evolutionary reactions undesirable hydrogen that could jeopardize 30 installation by explosion.
Among the inhibitors of such reactions, derivatives may be used nitrates such as nitromethane, nitroethane, nitropropane, nitrotoluene;
ethers or acetals such as dimethoxymethane, 1,3-dioxolane, dimethoxyethane; amines such as triethylamine, dipropylamine, Dimethylamine; phosphorus derivatives such as triisodecylphoshite, triisooctylphosphite.
The composition can also contain one or more masking agents smell.

'- CA 02239818 1998-06-19 By way of example of such products, mention may be made of vanillin and its derivatives, pine essences, limonene and its derivatives.
These compounds are used in very small quantities, generally between O, O1 and O, 1 parts by weight per 100 parts by weight of the 5 composition.
The composition according to the invention has the advantage of not having flash point according to ASTM D3828 and can be easily removed after the degreasing operation.
The following examples illustrate the invention.

The compositions are produced with the following constituents:
ISOPAR G petroleum cut (C9-C1 1), hereinafter designated by ISO G.
ISOPAR E petroleum cut (C8-C9), hereinafter designated by ISO E.
Perfluoro- (N-methylmorpholine) I5 r \
O ~ ~ N-CF3 below C 5 F 11 NO, n-tridecafluorohexane (n-C6F1 3H), n-perfluorohexane (n-C6F1 4), n-perfluorobutylethylene (n-C4FgCH = CH2), methylene chloride (CH2Cl2), n-perfluorohexylethylene (n-C6F13CH = CH2) Ethylamyl ketone, hereinafter EAK, methoxypropanol, hereinafter MP, di (propylene glycol) monomethyl ether, hereinafter DPM, 2,3-dihydrodecafluoropentane (CsH2F10), n-nonafluorobutylmethylether (C4HgOCH3).
In the table below, the percentages of the constituents are 30 expressed by weight.
The flash points of the compositions are determined according to the standard ASTM D 56.
All of these compositions are effective for cleaning greasy soiling on cleanable surfaces;
In this table: N means that there is no flash point according to the ASTM D3828 standard.

CONSTITUENTS OF EXAMPLES

n C6F13H 10 O
n C6F14 2 C5F1 1 NO 1 5 5 2 5 ~ ' n C4F9CH = CH ~ 1 5 5 CH ~ CI ~ 15 2 5 C5H ~ F1 O 30 C4HgOCH3 Flash point 1 ~ C) 42 NNNNNNNN 11 NNN
T, ~ RI F ~ U 1

Claims (24)

1. Composition de nettoyage et de dégraissage à froid en milieu non aqueux, caractérisée en ce qu'elle est constituée par au moins un composé
organique (A) choisi dans le groupe constitué par les perfluoro-(N-alkylmorpholines), le n-tridécafluorohexane (n-C6F13H), le 1. Composition for cold cleaning and degreasing in non-medium aqueous, characterized in that it consists of at least one compound organic (A) chosen from the group consisting of perfluoro- (N-alkylmorpholines), n-tridecafluorohexane (n-C6F13H), 2,3-dihydrodéca-fluoropentane (C5H2F10, 4310 mee), le 3,3,4-trihydroheptafluorobutane (C4F7H13, 347 mcf), le 2,2,4,4,4-pentahydropentafluorobutane (C4F5H5, 365 mcf), les perfluoroalcanes, les hydrofluoroalcènes, les chloromethanes, les étherfluorés; au moins un mélange d'alcanes ou de cycloalcanes (B) et au moins un composé organique (C) choisi dans le groupe constitué par les cétones, les étheralcools et dérivés et en ce que ladite composition ne présente pas de point d'éclair selon la norme ASTM D3828.
2. Composition selon la revendication 1, caractérisée en ce que le composé organique (A) est une perfluoro-(N-alkylmorpholine) de formule dans laquelle Rf et R1f, identiques ou différents, représentent un radical aliphatique perfluoré, linéraire ou ramifié ayant un nombre de carbone allant de1 à 4 et n est nombre allant de 0 à 8. 2,3-dihydrodeca-fluoropentane (C5H2F10, 4310 mee), 3,3,4-trihydroheptafluorobutane (C4F7H13, 347 mcf), 2,2,4,4,4-pentahydropentafluorobutane (C4F5H5, 365 mcf), perfluoroalkanes, hydrofluoroalkenes, chloromethanes, etherfluoro; at least one mixture of alkanes or cycloalkanes (B) and at minus an organic compound (C) chosen from the group consisting of ketones, ether alcohols and derivatives and in that said composition does not has no flash point according to ASTM D3828.
2. Composition according to claim 1, characterized in that the organic compound (A) is a perfluoro- (N-alkylmorpholine) of formula in which Rf and R1f, identical or different, represent a radical perfluorinated, linear or branched aliphatic having a carbon number ranging from 1 to 4 and n is a number ranging from 0 to 8. 3. Composition selon la revendication 2, caractérisé en ce que la perfluoro-(N-alkyl-morpholine) est la perfluoro-(N-méthyl-morpholine) de formule 3. Composition according to claim 2, characterized in that the perfluoro- (N-alkyl-morpholine) is perfluoro- (N-methyl-morpholine) of formula 4. Composition selon la revendication 1, caractérisée en ce que le composé (A) est le 2,3-dihydrodécafluoropentane (C5H2F10, 4310 mec). 4. Composition according to claim 1, characterized in that the compound (A) is 2,3-dihydrodecafluoropentane (C5H2F10, 4310 mec). 5. Composition selon la revendication 1, caractérisée en ce que le composé A est le n-tridécafluorohexane (n-C6F13H). 5. Composition according to claim 1, characterized in that the compound A is n-tridecafluorohexane (n-C6F13H). 6. Composition selon la revendicaiton 1, caractérisée en ce que le composé (A) est un perfluoroalcane. 6. Composition according to claim 1, characterized in that the compound (A) is a perfluoroalkane. 7. Composition selon la revendication 6, caractérisée en ce que le perfluoroalcane est le n-perfluorohexane (n-C6F14). 7. Composition according to claim 6, characterized in that the perfluoroalkane is n-perfluorohexane (n-C6F14). 8. Composition selon la revendication 1, caractérisée en ce que le composé (A) est un hydrofluoroalcéne. 8. Composition according to claim 1, characterized in that the compound (A) is a hydrofluoroalkene. 9. Composition selon la revendication 8, caractérisée en ce que l'hydrofluoroalcéne est le n-perfluorobutyléthylène (n-C4F9-CH=CH2). 9. Composition according to claim 8, characterized in that the hydrofluoroalkene is n-perfluorobutylethylene (n-C4F9-CH = CH2). 10. Composition selon la revendication 1, caracérisée en ce que le composé (A) est un chlorométhane. 10. Composition according to claim 1, characterized in that the compound (A) is chloromethane. 11. Composition selon la revendication 10, caractérisée en ce que le chlorométhane est le chlorure de méthylène. 11. Composition according to claim 10, characterized in that the chloromethane is methylene chloride. 12. Composition selon la revendication 1, caractérisée en ce que le composé (A) est un étherfluoré. 12. Composition according to claim 1, characterized in that the compound (A) is an etherfluorinated. 13. Composition selon la revendication 12, caractérisée en ce que l'étherfluoré est le n-nonafluorobutylméthyléther (C4H9OCH3). 13. Composition according to claim 12, characterized in that the fluorinated ether is n-nonafluorobutylmethylether (C4H9OCH3). 14. Composition selon la revendication 1, caractérisée en ce que le mélange d'alcanes (B) est une coupe pétrolière ayant un nombre de carbone allant de 8 à 12 et, de préférence allant de 9 à 11. 14. Composition according to claim 1, characterized in that the mixture of alkanes (B) is an oil cut having a carbon number ranging from 8 to 12 and preferably ranging from 9 to 11. 15. Composition selon la revendication 1, caractérisée en ce que le composé organique (C) est une cétone. 15. Composition according to claim 1, characterized in that the organic compound (C) is a ketone. 16. Composition selon la revendication 15, caractérisée en ce que la cétone est l'éthylamylcétone. 16. Composition according to claim 15, characterized in that the ketone is ethylamyl ketone. 17. Composition selon la revendication 1, caractérisée en ce que le composé (C) est un étheralcool. 17. Composition according to claim 1, characterized in that the compound (C) is an ether alcohol. 18. Composition selon la revendication 17, caractérisée en ce que l'étheralcool est le méthoxypropanol. 18. Composition according to claim 17, characterized in that etheralcohol is methoxypropanol. 19. Composition selon la revendication 17, caractérisée en ce que l'étheralcool est le di(propylène glycol)monométhyléther. 19. Composition according to claim 17, characterized in that etheralcohol is di (propylene glycol) monomethyl ether. 20. Composition selon l'une des revendications 1 à 19, caractérisée en ce qu'elle comprend de 1 % à 40 % en poids de composé organique (A), de 60 % à 98 % en poids d'un mélange d'alcanes ou de cycloalcanes (B) et, de 1 % à 15 % en poids de composé organique (C). 20. Composition according to one of claims 1 to 19, characterized in that it comprises from 1% to 40% by weight of organic compound (A), from 60% to 98% by weight of a mixture of alkanes or cycloalkanes (B) and, from 1% to 15% by weight of organic compound (C). 21. Composition selon la revendication 20, caractérisée en ce qu'elle comprend de 1 % à 25 % en poids de composé organique (A), de 75 % à 98 % en poids d'un mélange d'alcanes ou de cycloalcanes (B) et, de 1 % à 10 % en poids de composé organique (C). 21. Composition according to claim 20, characterized in that it comprises from 1% to 25% by weight of organic compound (A), from 75% to 98% by weight of a mixture of alkanes or cycloalkanes (B) and, from 1% to 10% by weight of organic compound (C). 22. Application d'une composition selon l'une des revendications 1 à
21 au nettoyage à froid en milieu non aqueux de surfaces solides. 22. Application of a composition according to one of claims 1 to 21 for cold cleaning in non-aqueous medium of solid surfaces. 23. Application selon la revendication 22 au dégraissage des pièces métalliques. 23. Application according to claim 22 for degreasing parts metallic. 24. Application selon l'une des revendications 22 et 23 au nettoyage et/ou dégraissage en pulvérisation. 24. Application according to one of claims 22 and 23 to cleaning and / or degreasing by spraying.
CA002239818A 1997-06-20 1998-06-19 Cleaning and degreasing composition with no flash point Abandoned CA2239818A1 (en)

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