FR2565125A1 - SELF-EMULSIBLE COMPOSITIONS BASED ON FLUOROCHLOROHYDROCARBONS AND PHOSPHORIC ESTERS - Google Patents

Abstract

The compositions based on fluorochlorohydrocarbons and phosphoric esters are in the form of aqueous emulsions of the "water-in-oil" type. They are appropriate to clean objects made of various materials, by eliminating dust, fingerprints, greases.

Description

SELF-EMULSIBLE COMPOSITIONS BASED ON
PLUOROCHLOROHYDROCARBONS AND PHOSPHORIC ESTERS
The subject of the present invention is compositions based on fluorochlorohydrocarbons and phosphoric esters, the said compositions being 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 the French patent application No. 82.09213. Such compositions can be used for cleaning articles of various natures. They are particularly suitable for the removal 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) - a solvent containing at least 50Z by weight of trichloro -1,1,2 trifluoro - 1,2, 2 ethane, - from 0.05 to 10% of a mixture of phosphoric esters with free phosphoric acid function and with neutralized phosphoric acid function and carboxylic acid, - from 0.05 to 1% of the alkali metal salt or of ammonium of an oxyalkylenated phosphoric or sulfuric acid, - from 1 to 8% of water, the total weight of the constituents, including solvent being 1002.

dans laquelle le symbole Y représente un radical de formule -O-T-(OCmH2a)rOH où r représente un nombre entier compris entre 2 et 30, m représente 2, 3 ou 4, le symbole T représente un radical divalent aliphatique, saturé ou insaturé, aromatique ou aliphatique-aromatique, les radicaux précités pouvant renfermer jusqu'à 40 atomes de carbone, le symbole Z représente un radical Y ou un groupe OH, le symbole T et le symbole r étant en outre tels que le nombre total d'atomes de carbone du radical Y est supérieur à 20.More precisely, in the invention is used - as a phosphoric ester with a free phosphoric acid function, a product of formula

in which the symbol Y represents a radical of formula -OT- (OCmH2a) rOH where r represents an integer between 2 and 30, m represents 2, 3 or 4, the symbol T represents a divalent aliphatic, saturated or unsaturated radical, aromatic or aliphatic-aromatic, 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 being further such that the total number of atoms of carbon of radical Y is greater than 20.

dans laquelle le symbole R représente un radical monovalent aliphatique, saturé ou non saturé renfermant jusqu'à 25 atomes de carbone et les symboles R', qui peuvent être identiques ou différents, représentant un radical aliphatique, éventuellement substitué par un groupement hydroxyle ou un radical acyle, renfermant de 10 à 30 atomes de carbone, ledit radical comportant au moins une double liaison carbonecarbone éthylénique, et n représente un nombre entier compris entre 1 et 9, - à titre d'acide carboxylique, un produit de formule
R' - COOH (III) dans laquelle le symbole R' possède la signification donnée ci-avant dans le cadre de la définition du produit de formule (II). - As phosphoric ester with neutralized phosphoric acid function, an ester of formula (I) of which at least one phosphoric acid function is neutralized by an amine salt of formula

in which the symbol R represents an aliphatic, saturated or unsaturated monovalent radical containing up to 25 carbon atoms and the symbols R ', which may be identical or different, representing an aliphatic radical, optionally substituted by a hydroxyl group or a radical acyl, containing from 10 to 30 carbon atoms, said radical comprising at least one ethylene carbon carbon double bond, and n represents an integer between 1 and 9, - as carboxylic acid, a product of formula
R '- COOH (III) in which the symbol R' has the meaning given above in the context of the definition of the product of formula (II).

formules dans lesquelles le symbole M représente un métal alcalin ou un groupement ammonium, les symboles Y et Z et les symboles m et r possèdent les significations données précédemment dans le cadre de la définition du produit de formule (I), le symbole R" représente un radical alkyle, linéaire ou ramifié, un radical alcényle ou un radical aromatique le dit radical renfermant de 6 à 24 atomes de carbone.- As the alkali metal or ammonium salt of an oxyalkylenated phosphoric or sulfuric acid, a salt chosen from the group consisting of the products of formulas

formulas in which the symbol M represents an alkali metal or an ammonium group, the symbols Y and Z and the symbols m and r have the meanings given above in the context of the definition of the product of formula (I), the symbol R "represents an alkyl radical, linear or branched, an alkenyl radical or an aromatic radical, the so-called radical containing from 6 to 24 carbon atoms.

It should be understood that, in the 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 solvent and water
- the phosphoric ester of formula (I)
- the amine salt of formula (II)
- the alkali metal or ammonium salt of formula (IV) or
(V), the amine salt being used in an amount such that part of the phosphoric acid functions of the ester of formula (I) is neutralized by said amine salt, and to collect all of the reaction medium.

 The compositions defined above constitute another object of the invention.

soit supérieur à 1 et de préférence soit compris entre 1,1 et 3,5, A désignant le poids du mélange d'esters phosphoriques résultant de la réaction de l'ester phosphorique initial avec le sel d'amine, B désignant le poids du sel d'amine, IAI désignant l'indice d'acide dudit mélange d'esters phosphoriques et IA2 désignant l'indice d'acide du sel d'amine.In the implementation of this process 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 the amine salt, IAI designating the acid number of said mixture of phosphoric esters and IA2 designating the acid number of the amine salt.

 It appears from the above indications that, in general and by application of the process defined above, the amount of acid of formula (III) is defined by the ratio of phosphoric aminelester salt of formula (I), the number of group -GOOH being substantially equal to the number of phosphoric acid functions reacting with the amine salt of formula (II).

 The same mine salt / phosphoric ester ratio of formula (I) defines the proportion of the acid phosphoric esters of formula (I) and of the 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. Another acid of formula (III) can also be added to the acid (III) originating from the amine salt. The excess of acid relative to the stoichiometry corresponding to the neutralization of part of the phosphoric ester (I) by the amine salt (III), is preferably at most 10%.

 As has been specified, 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 saturated chlorinated aliphatic hydrocarbons or chlorofluors 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 / oxypro pylene groups. Mention will be made most particularly of the esters in which the oxyalkylene chain or chains containing from 3 to 25 oxyethylene units, that is to say to 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.

 As specific examples of esters of formula I, mention will be made of 2-ethylhexyl phosphates with 20 ethylene oxide units, of nonylphenyl with 6 ethylene oxide units, of nonylphenyl with 9 ethylene oxide units. etylene, 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 in admixture, containing one or two groups phosphoric ester.

 The second constituent of the compositions in accordance with the invention is chosen from phosphoric esters of formula (I) of which at least one phosphoric acid function is neutralized by reaction with the amine salt of formula (II). These 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 (CH2) nNH2 (VI), formulas in which the symbols R, R 'and n have the meaning given above.

 By way of nonlimiting examples of the acids of formula (II), mention will be made in particular of undecylenic, dodecylenic, tetradecylenic, hexadecylenic, oleic, linoleic, linolenic, ricinoleic and acetylricinoleic acids. It is obviously possible to use a mixture of at least two of these acids.

 By way of illustration of the diamines of formula (VI), there may be mentioned in particular caprylaminopropylene amine, laurylaminopropylene amine, myristylaminopropylene amine, palmitylaminopropylene amine, stearylaminopropylene amine, oleylaminopropylene amine. It is of course possible to use a mixture of at least two of these amines.

 By way of illustration of the amine salts of formula (II), mention will be made in particular of oleylaminopropylene amine dioleate, oleylaminopropylene amine diundecylenate, stearylamine nopropylene amine dioleate, palmitylaminopropylene amine dioleate, dilinoleate oleylaminopropylene 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 amine function is designated by a radical corresponding to the trivial name of the acid, it being recognized that this radical is exclusively hydrocarbon. By way of examples, 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.

 By way of illustration of the alkali metal or ammonium salts of formulas IV and V, mention will be made in particular of sodium laurylethersulfates, stearylethersulfates, etc. 'ethylene, the said packaging 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-ethylhexyl enchanments / ethylene oxide units, nonylphenyl / ethylene oxide unit, oleocetyl / ethylene oxide units, number of patterns which can preferably range from 3 to 12.

 In the compositions according to the invention, the amount of water is determined according to the amount of additives used (phosphoric esters, acid, salt, optionally amine salt). 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.

 The 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 440 ° 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 metal, glass, refractory and / or plastic parts in order to rid them, very particularly, 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 more often by immersion of said parts in said compositions. In the latter case, it is useful to agitate the liquid bath. Agitation of the bath is carried out by any means known per se, and preferably by means of ultrasound. the contact time of 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 liquid trichloro-1,1,2-trifluoro-1,2,2-ethane, then preferably by contacting with vapors of 1,1 trichloro, 2-trifluoro-1,2,2-ethane.

 The following example illustrates the invention.

Example 10) Composition
A composition is prepared containing
- 92 g of trifluoro-1,1,2 trichloro-1,2,2 ethane,
- 0.75 g of oleylaminopropylene amine dioleate,
- 1.95 g of dodecyl acid phosphate with 6 ethylene oxide units (mixture of mono and diester in a molar ratio of 1.5 / 1).

 - 0.3 g of aqueous solution containing 0.078 g of oxyethylenated sodium lauryl ether sulfate (3 ethylene oxide units).

 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 Cemulcat ODO by S.F.O.S.

 This composition is prepared at room temperature (230C) 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 Im Pa.s (milli Pascal / second) at this temperature.

20) Implementation
The emulsion prepared according to paragraph 1 is used 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 vapor of trichloro1,1,2 trifluoro-1,2,2 ethane for about iman.

30) Samples and results
3.1. Elimination of fingerprints on copper plate.

After the treatment according to paragraph 2, we no longer observe
with the naked eye no trace of fingerprint. In this state of
satisfactory cleanliness is added to an improvement in power
reflective of the copper plate, which means a
removal of the metal oxide surface layer.

3.2. Elimination of polishing paste on steel parts
stainless.

The paste includes an abrasive and an organic binder (grease
natural). After treatment according to paragraph 2, we
observed by weighing 1/10 mg and observing at magnification
50 that the parts are completely free of
residual traces of polishing paste.

3.3. Elimination of fingerprints on glass plates
microscope, and mineral or resin spectacle lenses
synthetic (polymethacrylic).

After treatment according to paragraph 2, a
impeccable cleanliness: control is carried out in a
observation chamber comprising a light source and a
matt black background: the observation is made at once by
transparency through the glass and by reflection of the
light on the surface: no trace is detected.

3.4. Elimination of fatty traces, dust and fingerprints
digital on a brass clockwork mechanism.

The part is cleaned under the conditions of paragraph 2,
with the exception of the duration of the immersion: 5 min.

There is excellent removal of pollutants and
improvement of the reflective power of brass (observation
visual).

Claims (7)

1.- Composition based on fluorochlorohydrocarbons, phosphoric ester with free phosphoric acid function, phosphoric ester with phosphoric acid function neutralized by an amine and carboxylic acid salt, characterized in that it is in the form an emulsion of the "water in oil" type, said emulsion comprising (by weight) - a solvent containing at least 50% by weight of 1,1,2-trichloro-1,2,2-trifluoro-1,2,2 ethane, - of 0.05 to 10Z of a mixture of phosphoric esters with free phosphoric acid function and with neutralized phosphoric acid function and carboxylic acid, - from 0.05 to 1% of the alkali metal or ammonium salt of a oxyalkylenated phosphoric or sulfuric acid, - from 1 to 8% of water, the total weight of the constituents, including the solvent, being 100%. 2.- Composition according to claim 1, characterized in that the phosphoric ester with free phosphoric acid function is a product of formula

 in which the symbol Y represents a radical of formula -OT- (OCmH2m) rOH H, r OH where r represents an integer between 2 and 30, m represents 2, 3 or 4, the symbol T represents a divalent aliphatic radical, saturated or unsaturated, aromatic or aliphatic-aromatic, 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 being further such as the total number carbon atoms of radical Y is greater than 20. 3.- Compositions according to any one of claims i or 2, characterized in that 11 phosphoric ester with neutralized phosphoric acid function is an ester of formula (I) of which at least one phosphoric acid foacilon is neutralized by an amine salt of formula

 in which the symbol R represents a monovalent aliphatic radical, saturated or unsaturated containing up to 25 carbon atoms and the symbols R ', which may be identical or different, represent an aliphatic radical, optionally substituted by a hydroxyl group or a radical acyl, containing from 10 to 30 carbon atoms, said radical comprising at least one ethylenic carbon carbon double bond, and n represents an integer between 1 and 9. 4.- Composition according to any one of claims 1 to 3, characterized in that the alkali metal or ammonium salt of an oxyalkylenated phosphoric or sulfuric acid is chosen from the group consisting of products of formulas

 formulas in which the symbol M represents an alkali metal or an ammonium group, the symbols Y and Z and the symbols m and r have the meanings given above in the context of the definition of the product of formula (I), the symbol R "represents an alkyl radical, linear or branched, an alkenyl radical or an aromatic radical, the so-called radical containing from 6 to 24 carbon atoms. 5.- A process for preparing the compositions according to any one of claims 1 to 4 characterized in that it consists in mixing with the solvent and with water  - the phosphoric ester of formula (I)  - the amine salt of formula (II)  - the alkali metal or ammonium salt of formula (IV) or  (v), the amine salt being used in an amount such that part of the phosphoric acid functions of the ester of formula (I) is neutralized by said amine salt, and to collect all of the reaction medium. 6.- Method according to claim 5, characterized in that the phosphoric ester (I) and the amine salt (II) 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 the amine salt, IAI denoting the acid number of said mixture of phosphoric esters and IA2 denoting the acid number of the amine salt. 7.- Application of the compositions according to any one of claims 1 to 5 to the cleaning of metal parts, glass, refractory materials and / or plastic materials to rid them, especially, of dust and / or fingerprints digital, and / or grease and / or polishing paste in the case of metal parts.