Classifications

• • 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
  • C23G5/06—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using emulsions
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K13/00—Etching, surface-brightening or pickling compositions
• • 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
  • C11D7/30—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
  • C11D7/36—Organic compounds containing phosphorus

Definitions

• compositions based on fluorochlorohydrocarbons and phosphoric esters are in the form of an emulsion of the water in oil type.
• compositions comprising a fluorochlorohydrocarbon, a phosphoric ester with a free phosphoric acid function, a phosphoric ester with a phosphoric acid function neutralized by an amine salt and an acid have been described in French patent application No. 82.09213.
• Such compositions can be used for cleaning articles of various natures. They are particularly suitable for the elimination by solubilization of water from the surfaces to which they are applied.
• the present invention relates to a new composition based on fluorochlorohydrocarbons, phosphoric ester with free phosphoric acid function, phosphoric ester with phosphoric acid function neutralized by an amine salt and carboxylic acid, this composition being characterized in that '' it is in the form of an emulsion of the "water in oil” type, said emulsion comprising (by weight):
• the invention uses:
• m represents 2, 3 or 4
• the symbol T represents a divalent aliphatic, saturated or unsaturated, aromatic or aliphatic-aromatic radical, the abovementioned radicals being able to contain up to 40 carbon atoms
• the symbol Z represents a radical Y or an OH group
• the symbol T and the symbol r also being such that the total number of carbon atoms of the radical Y is greater than 20.
• a phosphoric ester with neutralized phosphoric acid function an ester of formula ( I) at least one phosphoric acid function of which is neutralized by an amine salt of formula
• compositions in accordance with the invention it is possible to use, for each of the constituents, a single product or a mixture of products meeting the definitions and formulas indicated:
• the invention also relates to a process for preparing the compositions defined above, said process being characterized in that it consists in mixing with the solvent and with water:
• compositions defined above constitute another object of the invention.
• the constituents of the mixture are used in an amount such that the ratio either greater than 1 and preferably between 1, 1 and 3.5, A denoting the weight of the mixture of phosphoric esters resulting from the reaction of the initial phosphoric ester with the amine salt, B denoting the weight of amine salt, I AI denoting the acid number of said mixture of phosphoric esters and I A2 denoting the acid number of the amine salt.
• the amount of acid of formula (III) is defined by the amine salt / phosphoric ester ratio of formula (I) , the number of -COOH group being substantially equal to the number of phosphoric acid functions reacting with the amine salt of formula (II).
• the same amine salt / phosphoric ester ratio of formula (I) defines the proportion of acid phosphoric esters of formula (I) and phosphoric esters of which at least one phosphoric acid function is neutralized. It is naturally possible to use an amount of acid (III) greater than the amount of acid of the amine salt released by the reaction of the phosphoric acid functions with said salt.
• the solvent contains at least 50% by weight of 1,1,2-trichloro-1,2,2-trifluoroethane.
• the complement to 100% can naturally be constituted by the same solvent or by one or more chlorinated or chlorofluorinated saturated aliphatic hydrocarbons containing 1 or 2 carbon atoms, such as for example methylene chloride.
• the phosphoric esters of formula (I), which are preferably used in an amount of 0.04 to 8% relative to the weight of the composition, can be chosen from the various mono and diesters resulting from the reaction of phosphorus compounds with oxyalkylenated linear alcohols. Among these products, mention will be made in particular of esters with oxyethylene, oxypropylene or oxyethylene / oxypropylene groups.
• esters in which the oxyalkylene chain or chains containing from 3 to 25 oxyethylene units that is to say the esters of formula (I) in which m is equal to 2 and r is between 3 and 25, the radical represented by the symbol T in said formula (I) possibly being in particular one of the divalent radicals corresponding to the following radicals: hexyl, octyl, isooctyl, 2-ethylhexyl, decyl, isodecyl, t.dodecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, oleocetyl, nonylphenyl.
• esters of formula I mention will be made of phosphates of 2-ethylhexyl with 20 ethylene oxide units, of nonylphenyl with 6 ethylene oxide units, of nonylphenyl with 9 ethylene oxide units , tridecyl with 6 ethylene oxide units, dodecyl with 6 ethylene oxide units, oleocetyl with 5 ethylene oxide units, the various aforementioned phosphates, which can be used as a mixture, containing one or two phosphoric ester groups.
• the second constituent of compositions in accordance with the invention is chosen from phosphoric esters of formula (I) in which at least one phosphoric acid function is neutralized by reaction with the amine salt of formula (II).
• amine salts which are preferably used in an amount of 0.01 to 2% relative to the weight of the composition in the process defined above can be obtained by reaction of one or more carboxylic acids of formula R ' -COOH (III) with a diamine of formula R.NH (CH 2 ) n NH 2 (VI), formulas in which the symbols R, R 'and n have the meaning given above.
• diamines of formula (VI) there may be mentioned in particular amine caprylaminopropylene, amine laurylaminopropylene, amine myristylaminopropylene, amine palmitylaminopropylene, amine stearylinopropylene, amine oleylaminopropylene. It is of course possible to use a mixture of at least two of these amines.
• the amine salts of formula (II) there may be mentioned in particular the amine oleylaminopropylene dioleate, the amine oleylaminopropylene diundecylate, the amine stearylamopropylene dioleate, the amine palmitylaminopropylene dioleate, the oleylaminopropylene dilinoleate amine. It is naturally possible to use a mixture of at least two of these salts. It should be noted that in the foregoing, the substituent of an amino function is designated by a radical corresponding to the trivial name of the acid, it being recognized that this radical is exclusively hydrocarbon.
• the stearyl radical denotes here the octadecyl radical
• the oleyl radical denotes the octadecenyl radical
• the palmityl radical denotes the hexadecyl radical
• the myristyl radical denotes the tetradecyl radical.
• alkali metal or ammonium salts of formulas IV and V there may be mentioned in particular sodium, potassium laurylethersulfates, stearylethersulfates, ammonium, the term ether advantageously designating a chain of ethylene oxide units, the said chain comprising for example from 2 to 10 units and preferably from 3 to 6 units; Mention will also be made of the alkyl ether - mono and sodium diphosphates, potassium and ammonium, the expression alkyl ether designating in particular the 2-ethyl hexyl sequences / ethylene oxide units, nonylphenyl / ethylene oxide unit, oleoketyl / ethylene oxide units, number of units which can preferably range from 3 to 12.
• the amount of water is determined according to the amount of additives used (phosphoric esters, acid, salt, optionally salt d 'amine). As indicated, the amount of water generally represents from 1 to 8% of the total weight of the composition. From a practical point of view, an amount of water representing 1.5 to 5 times the total amount of additives is advantageously used.
• compositions in accordance with the invention can be prepared by simple mixing with stirring and at room temperature of its constituents, that is to say either the phosphoric esters with free phosphoric acid function and with neutralized acid function, the carboxylic acid and the alkali metal or ammonium salt, ie the phosphoric ester with a free phosphoric acid function, the amine salt and the alkali metal or ammonium salt.
• These emulsions are stable at room temperature, and more generally between 5 and 44 ° C, more specifically between 10 and 40 ° C, the emulsion having, in the high temperature zone, an opalescent appearance without settling of the aqueous phase.
• the emulsions in accordance with the invention are particularly suitable for cleaning parts of metal, glass, refractory materials and / or plastics to rid them, in particular, of dust and / or fingerprints, and / or grease and / or polishing paste in the case of metal parts. As such, they find their application in particular in the chemical, electronic, electrical, mechanical and in particular precision mechanical industries, in watchmaking, jewelry, optics, metrology.
• the actual cleaning process consists in bringing said parts into contact with said compositions of the invention, for example by spraying, by spraying and most often by immersion of said parts in said compositions. In the latter case, it is useful to stir the liquid bath.
• the agitation of the bath is carried out by any means known per se, and preferably by means of ultrasound, the contact time of the soiled parts with the agitated liquid bath generally varies between 0.5 and 5 min.
• the cleaning of the parts is followed by a rapid rinsing with 1,1,2-trichloro-1,2,2-trifluoro-ethane liquid, then preferably with contact with 1,1-trichloro vapors, 2-trifluoro-1,2,2-ethane.
• a composition is prepared containing: - 92 g of trifluoro-1,1,2 trichloro-1,2,2 ethane,
• the phosphate acid number (acidity of the diester and first acidity of the monoester) is 83.
• the amine salt has an acid number of 125. It is marketed under the brand Cémulcat 0D0 by S. F. O.S. This composition is prepared at room temperature (23 ° C) with stirring: it is in the form of an emulsion of the water in oil type, very slightly opalescent at 23 ° C. Its viscosity is lm Pa.s (milli Pascal / second) at this temperature. 2o) Implementation The emulsion prepared according to paragraph 1 is implemented in a tank provided with ultrasonic transducers.
• the parts to be cleaned are immersed in the emulsion (cleaning bath) - duration of the immersion 2 min -, then removed and rinsed for 1 min in trichloro1,1,2 trifluoro-1,2,2 ethane liquid, also agitated by ultrasound and are finally placed in an atmosphere of trichloro-1,1,2 trifluoro-1,2,2 ethane vapors for about 1mm. 3o) Samples and results
• the paste includes an abrasive and an organic binder (natural fat). After treatment according to paragraph 2, it can be seen by weighing 1/10 mg and observing at magnification 50 that the parts are completely free of residual traces of polishing paste.

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

Applications Claiming Priority (2)

Publications (1)

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Citations (3)

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• 1984
  • 1984-05-30 FR FR8408555A patent/FR2565125A1/fr active Pending
• 1985
  • 1985-05-28 AU AU44026/85A patent/AU4402685A/en not_active Abandoned
  • 1985-05-28 WO PCT/FR1985/000134 patent/WO1985005643A1/fr not_active Application Discontinuation
  • 1985-05-28 EP EP85902567A patent/EP0182839A1/fr not_active Withdrawn
  • 1985-05-28 JP JP60502384A patent/JPS61502965A/ja active Pending
  • 1985-05-28 GR GR851308A patent/GR851308B/el unknown
  • 1985-05-29 PT PT80550A patent/PT80550B/pt unknown
  • 1985-05-29 ES ES543599A patent/ES8702162A1/es not_active Expired
  • 1985-06-22 CN CN198585104794A patent/CN85104794A/zh active Pending

Patent Citations (3)

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