FR2761080A1 - New cleaning, disinfecting and decontaminating composition - Google Patents

Abstract

New cleaning, disinfecting and decontaminating composition (I) which is effective against toxic organophosphates and organosulphates comprises: an organic peracid (II), a cationic quaternary ammonium surfactant (III), and a non-ionic surfactant (IV). Preferably (II) is peracetic, perpropionic, perdecanoic, perdodecanoic, pertetradecanoic, perlauric, perdodecanedioic or phthalimidoperpropionic acid, or sodium or potassium percarbonate or magnesium mono-peroxyphthalate. Preferred cationic surfactant (III) is of formula R1R2R3R4N<+>X<-> (i); R1,R2 and R3 are 1-6C (1-2C preferred) (hydroxy)alkyl groups (R1 and R2 possibly together forming a cyclic group); R4 is an 8-24C (ar)alkyl group (cetyl preferred); and X<-> is an anion such as a halogen or an OH<->, sulphate or carbonate group (F<->, Cl<-> and Br<-> preferred). (IV) Is an ester of a fatty acid and sorbitan, a polyalkoxylated ester with 6-22C alkyl chains, an alkylphenol, a dithiol or a polyethylene glycol. (I) comprises 15-50 wt.% (II), 1.0-2.5 wt.% (III) and 5-50 wt.% (III). (I) Is a buffered aqueous solution with pH 7-11. The ratio (I):solvent is 1:20-1:2. (I) contains an emulsion agent.

Description

The present invention relates to the decontamination, disinfection and cleaning of surfaces soiled by toxic agents, and more particularly to an improved composition containing an organic peracid in combination with a cationic quaternary ammonium surfactant and a nonionic emulsion-generating surfactant, allowing decontamination, disinfection and cleaning of surfaces soiled by toxic substances which may contain organophosphorus or organosulfur compounds, without damaging the surfaces or the environment.

Many toxic substances are used in various fields of industry and agriculture, as well as in military applications. In particular, organophosphorus compounds are widely used in agriculture as insecticides or pesticides for the treatment of cultivated surfaces. Thus, there may be mentioned various compounds such as organophosphates, organoamidophosphates, amidophosphates, phosphonothionates, phosphorothionates or even amidophosphorothionates, the most common examples of which are paraoxon <O, O-diethyl-Op-nitro-phenyl phosphate ) and parathion (O, O-diethyl-Op-nitrophenyl phosphorothioate), used as pesticides. On the other hand, the
VX (O-ethyl-S- (diisopropylaminoethyl-2) -methylphosphorothio- late) is well known as a nerve agent of war. Various toxic organosulfur vesicants are also known, such as mustard (2,2'-dichloro-diethyl sulfide).

All these compounds are particularly dangerous and it is therefore essential to be able to have means available to neutralize them or to decontaminate surfaces which could have been soiled by intentional or accidental use of these organosulfur and organophosphate compounds.

For a long time, sodium hydroxide-based compositions have been used to effect the decontamination of surfaces soiled by the aforementioned toxic agents, for example sodium hydroxide solutions in the presence of an amine such as diethylenetriamine, or calcium hypochlorite. However, these known compositions have the shortcoming of substantially degrading the surfaces treated during cleaning or decontamination operations.

The use of peracids, less aggressive towards treated surfaces and generally biodegradable, has been described in various publications, for disinfection and decontamination. Thus, patent FR-A-2,651,133 describes aliphatic peracids with long carbon chains, for example perdecanoic acid or perdodecanoic acid, used in aqueous solution, preferably in combination with surfactants such as bromide. cetyl trimethyl ammonium or cetyl dimethyl 2-hydroxyethyl ammonium bromide. However, although such compositions have been proposed to destroy paraoxon, they are difficult to use in practice because most of these peracids are unstable and are not commercially available. On the other hand, as described in patent EP-A675.680, the activity of the peracid is dependent on the pH and it decreases sharply when the pH increases and is greater than 7.

Patent FR-A-2,676,368 describes a composition containing magnesium monoperoxyphthalate (MPPM) and a surfactant consisting of a quaternary ammonium salt, which can be used to decontaminate surfaces soiled by organosulfur toxic agents and in particular VX et mustard.
Magnesium monoperoxyphthalate is a commercially available compound of the peracid series, soluble in water and alcohols, and relatively stable in aqueous media. It can be prepared by the action of dilute hydrogen peroxide on phthalic anhydride in the presence of magnesium oxide.

However, it is known that certain surfactants can degrade peracids and cause them to lose their activity, and that compositions containing in combination of peracids and surfactants are unstable and tend to dissociate after a few weeks.

On the other hand, C. Lion et al., Phosphorus Sulfur and
Silicon, IS, 141-145 (1993) have shown that certain oxidants, such as potassium monopersulfate, can specifically destroy mustard and analogous compounds.

It is therefore important to be able to have available compositions exhibiting good stability over time, capable of being stored for several months, and making it possible to decontaminate, disinfect or effectively clean surfaces soiled by various toxic agents.

The present invention relates to a cleaning, disinfecting and decontaminating composition with improved efficiency, which can be used for the cleaning, disinfection and decontamination of surfaces soiled by organophosphate or organosulfur toxic agents of the type described above.

A subject of the invention is also a cleaning, disinfecting and decontaminating composition based on peracids, used alone or as a mixture, exhibiting excellent stability over time.

A subject of the invention is also a composition in the form of a solution or emulsion based on organic peracid, intended for cleaning, disinfection and decontamination, by spraying, washing or soaking, of surfaces soiled by toxic agents. .

Finally, the subject of the invention is a cleaning, disinfecting and decontaminating composition containing at least one peracid associated with at least one cationic surfactant and one nonionic surfactant, and having excellent activity at a pH greater than 7.

The composition according to the present invention comprises an active principle of the peracid type, or one of its salts, in combination with a cationic quaternary ammonium surfactant and a nonionic surfactant.

The organic peracids used in the compositions according to the present invention can be chosen from organic mono- or diperacids comprising one or more linear or branched alkyl groups, an aryl group or a heterocyclic group, condensed or not. They can be used alone or as a mixture.

By way of example, a peracid advantageously used in the compositions of the invention can be chosen from peracetic acid, perpropionic acid, perdecanic acid, perdodecanoic acid, pertetradecanoic acid, acid. perlauric, perdodecanediolque acid, phthalimidoperpropionic acid, sodium or potassium percarbonate, or magnesium monoperoxyphthalate. According to the invention, sodium or potassium percarbonate or magnesium monoperoxyphthalate is preferably used.

The concentration of organic peracid in the composition of the invention may be between 15 k and 50 by weight relative to the total weight of the composition (in solid form), and preferably between 20 W and 35 W by weight. This composition can then be diluted in solution or in suspension at the time of its use, as indicated below.

The peracids used in the present invention are commercially available or can be prepared by known methods. For example, long carbon chain peracids can be prepared according to the method described by
M. Feldhues et al., Tetrahedron, II, p. 4195 (1985). In general, hydrogen peroxide is made to act on the corresponding carboxylic acids, in an acidic medium, preferably in cold concentrated sulfuric acid. For example, one can proceed by dissolving the acid, such as acetic acid or dodecanoic acid, in concentrated sulfuric acid and adding hydrogen peroxide at 30W; the mixture is stirred for 2 to 3 hours, then cooled, extracted with ether, washed with water and dried over magnesium sulphate to obtain the desired peracid after evaporation of the solvent.

As indicated above, the compositions of the invention comprise a cationic surfactant which is preferably of the quaternary ammonium type and can be represented by the general formula
R1 R2 R3 R4 N + X in which R1, R2, and R3, the same or different, each represent an alkyl or hydroxyalkyl group of 1 to 6 carbon atoms, or R1 and R2 combine to form a heterocyclic group, and R4 represents a linear or branched alkyl group or an aralkyl group which may contain from 8 to 24 carbon atoms, and X represents an anion such as a halogen or a hydroxyl, carbonate or sulfate group.

Among the cationic surfactants above, preferably used are those for which R1, R2, and R3 represent a methyl or ethyl group, R4 represents a cetyl group, and X is a halogen chosen from fluorine, chlorine and chlorine. bromine.

As examples of quaternary ammonium surfactants which can be used in the compositions of the invention, mention may be made of cetyl trimethyl ammonium chloride and bromide, cetyl dimethyl benzyl ammonium chloride and bromide, cetyl diaza-1,4 bromide. bicyclo [2,2,2] octyl ammonium and cetyl dimethyl 2-hydroxyethyl ammonium chloride.

The concentration of quaternary ammonium surfactant can be between 0.1% and 25 W by weight relative to the total weight of the composition (in solid form).

The quaternary ammonium surfactant used in the invention has the advantage of exerting by itself a certain bactericidal effect, more particularly on gram-positive bacteria. This effect can be combined with the bactericidal effects of magnesium monoperoxyphthalate which is active in particular on S. aureus and M. tuberculosis at concentrations of the order of 1,000 to 4,000 ppm.

The cleaning and decontaminating compositions in accordance with the present invention also contain a nonionic surfactant, acting as a wetting agent facilitating contact of the composition with the surface to be treated, without adversely affecting the effectiveness of the peracid. Preferred nonionic surfactants are chosen from esters of fatty acids and of sorbitan, polyalkoxylated esters comprising alkyl chains of 6 to 22 carbon atoms, and in particular polyoxyethyl esters (POE). It is also possible to use alkylphenols, mercaptans and polyethylene glycols with a molecular weight greater than 2000.

This nonionic surfactant is used in the compositions of the invention in an amount of 5% to 50 g by weight relative to the total weight of the solid composition.

The compositions according to the invention may also contain an activator or a catalyst, and preferably an organometallic compound, intended to improve the oxidation factor of the composition.

The compositions according to the present invention may also contain hydrogen peroxide, in a proportion of preferably less than 10 W by weight of the total weight of the solid composition.

Finally, the compositions of the invention may contain certain additives, such as phosphonic acids or phosphonates intended to improve the stability of the composition. They can also contain anti-redeposition and sequestering agents such as TPP (sodium tripolyphosphate), certain zeolites and certain silicates.

The precise formulation of the composition of the invention can be adapted according to the intended conditions of use and the desired effects. Thus, by way of example, the compositions more particularly intended for the disinfection of lightly soiled surfaces may contain only a lower concentration of peracid, between 1 and 5 W of the total weight of the undiluted solid composition.

The compositions of the invention are preferably in the form of aqueous solutions with a buffered pH of between 6 and 12. A buffer is advantageously used to stabilize the pH at a value of between 6 and 12, and preferably between 8 and 10. For example, a carbonate or bicarbonate buffer can be used. One of the advantages of the compositions in accordance with the present invention, compared with the known compositions, is that they prove to be effective at a neutral or weakly basic pH, that is to say greater than 7, and even between 8 and 10. This efficiency is confirmed for both disinfection and decontamination. A lower pH, between 6 and 9, can be used for disinfection, while a higher pH, between 8 and 10, is generally preferable for decontamination.

The weight ratio of the solid composition described above to the solvent is generally between 1:20 and 1: 2, and preferably between 1:12 and 1: 4. One can for example advantageously use an aqueous solution containing between 100 and 300 g / l of solid composition according to the invention.

The solvent of the composition is preferably water, or a compound comprising one or more alcohol or ketone functions, or a hydrocarbon such as a limonene or a terpene, where appropriate in combination. Depending on the applications envisaged, it may be advantageous to use the composition in the form of an aqueous emulsion.

It is preferable to keep the composition of the invention in solid form and to prepare the solution at the time of use. The solution can however be stored for several hours without losing its effectiveness.

The compositions according to the present invention can be prepared by the usual methods, by mixing the various components such as peracid, quaternary ammonium surfactants and nonionic surfactants mentioned above, and by adding the various additives.

As indicated above, in practice the use of the compositions of the invention is carried out by putting the solid formulation in solution in water, or an appropriate solvent, with moderate stirring, at a temperature ranging from 200C to 450C, respecting a contact time of 1 to 10 minutes before use.

It is also possible to prepare solutions in accordance with the invention by replacing the peracid, active principle, by a peracid precursor in order to generate the desired peracid in situ. The dissolution is then carried out with hydrogen peroxide under the same conditions as above, by mixing at room temperature or by heating slightly to a temperature of between 20 and 450 ° C., with moderate stirring. The concentrations of organic peracid precursor and of hydrogen peroxide are determined so as to obtain a peracid content in the range of values indicated above. The organic peracid precursor can, for example, be an acid such as acetic acid or dodecanoic acid.

The measurements carried out on several samples of compositions in accordance with the present invention have demonstrated excellent stability over time at room temperature, showing that the compositions can be stored in solid form for several months without losing their effectiveness and their homogeneity.

The effectiveness of the compositions according to the present invention was tested on the usual toxic agents: paraoxon, VX and mustard. The kinetics of destruction of toxic agents are followed in a conventional manner by W spectroscopy at 402 nm for paraoxon (corresponding to the absorption maximum of the p-nitrophenate ion released), and by gas chromatography, and mass spectrometry for detect degradation byproducts, for VX and mustard.

The results of the tests carried out using aqueous solutions showed an overall efficiency of between 96 W and 99.8 W in the heterogeneous phase, after a contact time varying between 5 and 15 minutes, and a delay in preparing the solution before use. varying from 2 to 120 minutes. These results show that the composition according to the invention retains its effectiveness, even when it is dissolved.
Tests were carried out to show the possible effects of the compositions of the invention on the surfaces of various objects to be treated (metal plates, electronic circuits, synthetic resins), by immersing the objects in a bath containing a composition of the invention maintained at a temperature of 250C at a pH close to 10.

These tests have shown that the destruction of the toxic agent is almost instantaneous and that the compositions of the invention do not cause any degradation of the treated surfaces, even after a prolonged contact time of several days.

The compositions according to the present invention can be used, preferably in solution or in emulsion, both for the decontamination, the cleaning and the disinfection of surfaces soiled by organophosphate or organosulfur toxic agents, in outdoor areas, in the open air, or in closed rooms. The treatment can be carried out by application directly to the surfaces to be treated, by pouring and spreading using brush devices of the usual type or by cold or hot spraying, at a temperature of the order of 40 to 50 "C, using lances or ramps of known type In the case of the decontamination or disinfection of objects, the operations can be carried out by soaking, the objects being immersed in a tank containing a composition in accordance with the invention. soaking time can vary from a few minutes to a few hours depending on the nature of the objects and the operating conditions.

The following examples illustrate the invention in more detail without limiting its scope. In these examples, the parts and percentages are given by weight, unless otherwise indicated.

Example 1
A composition is prepared containing the compounds indicated below
sodium percarbonate 30%
Cetyl dimethyl benzyl ammonium chloride 8%
ethoxylated fatty alcohol 15%
polyethylene glycol PEG 6000 5 k
activator (tetracetyl ethylene diamine) 16%
15 W sodium tripolyphosphate
10% Na2CO3 / NaHCO3 buffer
This composition is diluted to 20% in water. The pH of the solution is 9.8.

The effectiveness of the aqueous solution obtained as indicated above for the decontamination is tested by measuring the destruction time of paraoxon by comparison with the magnesium monoperoxyphthalate used in aqueous solution at 1 at pH 6 according to a usual technique. It is then observed that the half-reaction time is reduced by a factor of the order of 4 to 5.

Example 2
The procedure is as in Example 1, by preparing a decontamination composition having the composition indicated below
30 W magnesium monoperoxyphthalate
Cetyl dimethyl benzyl ammonium chloride 10 k
ethoxylated fatty alcohol 15%
polyethylene glycol PEG 6000 5
10 W sodium tripolyphosphate
30% Na2CO3 / NaHCO3 buffer
This composition is diluted to 20% in water. The pH of the solution is 9.7.

The results obtained are equivalent to those of Example 1.

Example 3
The procedure is as in Example 1 to prepare the following composition
sodium percarbonate 20 W
cetyl dimethyl benzyl ammonium chloride 15 W
25% ethoxylated fatty alcohol
activator (tetracetyl ethylene diamine) 10%
15k sodium tripolyphosphate
l-hydroxyethylidene-l, l-diphosphonic acid
tetrasodium salt 1k
Na2CO3 / NaHCO3 buffer 14
This composition is diluted to 25% in water to which has been added 5% lemon terpene. The pH of the solution is 9.2.

Example 4
The procedure is as in Example 1, by preparing a decontamination composition having the composition indicated below
magnesium monoperoxyphthalate 35%
Cetyl dimethyl 2-hydroxyethyl ammonium chloride 15%
20% ethoxylated fatty alcohol
sodium tripolyphosphate 15 Co
15 W Na2CO3 / NaHCO3 buffer
The results obtained, after dilution in water supplemented with 5% of a 50/50 mixture of lemon terpene i pine essences (250 mg of composition per 1000 ml of water) are equivalent to those of Example 1 .

Claims (12)

1. Cleaning, disinfectant and decontaminating composition, effective against organophosphate and organosulfur toxic agents, characterized in that it comprises a) an organic peracid b) a cationic quaternary ammonium surfactant c) a nonionic surfactant. 2. Composition according to claim 1, characterized in that the peracid is chosen from organic mono- or diperacids comprising one or more linear or branched alkyl groups, an aryl group or a heterocyclic group, condensed or not. 3. Composition according to claim 2, characterized in that the peracid is chosen from peracetic acid, perpropionic acid, perdecanoic acid, perdo decanoic acid, pertetradecanoic acid, perlauric acid, 1 ' perdodecanediolque acid, phthalimidoperpropionic acid, sodium or potassium percarbonate, or magnesium monoperoxyphthalate. 4. Composition according to claim 1, characterized in that the cationic quaternary ammonium surfactant is represented by the general formula R1 R2 R3 R4N + X in which R1, R2, and R3, identical or different, each represent an alkyl group or hydroxyalkyl of 1 to 6 carbon atoms, or R1 and R2 combine to form a heterocyclic group, and R4 represents a linear or branched alkyl group or an aralkyl group which may have 8 to 24 carbon atoms, and X represents such an anion than a halogen or a hydroxyl, carbonate or sulfate group. 5. Composition according to claim 4, characterized in that R1, R2 and R3 represent a methyl or ethyl group, R4 represents a cetyl group, and X is a halogen chosen from fluorine, chlorine and bromine. 6. Composition according to any one of claims 4 and 5, characterized in that the cationic surfactant is chosen from cetyl trimethyl ammonium chloride and bromide, cetyl dimethyl benzyl ammonium chloride and bromide, sodium bromide. 1,4-cetyl diaza bicyclo [2,2,2] octyl ammonium and cetyl dimethyl 2-hydroxyethyl ammonium chloride. 7. Composition according to Claim 1, characterized in that the nonionic surfactant is chosen from esters of fatty acids and of sorbitan, polyalkoxylated esters comprising alkyl chains of 6 to 22 carbon atoms, polyoxyethylated esters, alkylphenols, mercaptans and polyethylene glycols with a molecular weight greater than 2000. 8. Composition according to claim 1, characterized in that it contains between 15% and 50% by weight of peracid, between 0.1% and 25% by weight of cationic quaternary ammonium surfactant, and between 5% and 50%. % by weight of nonionic surfactant, relative to the total weight of solid composition. 9. Composition according to any one of the preceding claims, characterized in that it is in the form of a buffered aqueous solution with a pH of between 7 and 11. 10. Composition according to claim 9, characterized in that the weight ratio of the solid composition to the solvent is between 1:20 and 1: 2. 11. Composition according to any one of claims 9 and 10, characterized in that the solvent is chosen from water, a compound comprising one or more alcohol or ketone functions or a hydrocarbon. 12. Composition according to any one of claims 9 to 11, characterized in that it contains an emulsifier.