FR2983036A1 - OXIDIZING SYSTEM CONTAINING HYDROGEN PEROXIDE, ACID / PERACID, STABILIZER, AMINO OXIDE AND ESSENTIAL OIL, COMPOSITION COMPRISING SUCH A SYSTEM AND USE IN THE FIELD OF DISINFECTION - Google Patents

Abstract

The present invention relates as a new industrial product, an aqueous system usable in the field of disinfection, said system, which comprises hydrogen peroxide, acids, an amine N-oxide substance and an essential oil component, characterized in that (1) it is homogeneous and consists of a single phase, and (2) said essential oil component is selected from the group consisting of (a) water-soluble essential oils, (b) terpinene 4-ol, and (c) their mixtures. The invention also relates to a process for the preparation of such a system.

Description

BACKGROUND OF THE INVENTION The present invention relates, as a product, to an oxidizing system containing hydrogen peroxide, acid / peracid, stabilizer, amine oxide and essential oil, comprising such a system and use in the field of disinfection. industrial novel, to an aqueous system containing hydrogen peroxide, an acid / peracid structure RCO2H / RCO3H structure, an acid stabilizing agent, an amine N-oxide substance and an essential oil. It also relates to a composition containing said system. It also relates to the use of said system and of said composition, particularly in the field of disinfection, that is to say the field of hygiene and cleaning, as biostatic means or biocides for inhibiting the development of microorganisms likely to be pathogenic or, better, destroy said microorganisms. PRIOR ART In the field of disinfection, that is to say the field of hygiene and cleaning as indicated above, chlorinated disinfectants have been used, but less now. It is known that C10 hypochlorite has (i) adverse effects by exposure to heat, especially in the form NaC1O, and (ii) does not eliminate or destroy the biofilms produced for their protection by microorganisms (including bacteria) . It is known that C102 eliminates biofilms but must be prepared in situ by electrolysis. It is also known that chlorinated products are particularly dangerous because they lead to harmful side reaction products such as chloramines. We tried to replace chlorinated disinfectants. Quaternary ammoniums are unsuitable: after drying, they leave sticky or slippery deposits on the treated surfaces. Aldehydes are unsuitable because of their insolubility in water and their high toxicity. As it is known that hydrogen peroxide (1) is capable of destroying bacteria and their biofilms in an enclosed space at rest (ie "static space") such as a Petri dish, but (2) is practically unable to destroy the bacteria protected by their biofilms in a space under agitation (ie "space or dynamic situation") such as water currents, cooling towers and air conditioning systems, several technical solutions based on H202 have been proposed for disinfect, clean up or clean. The first solutions, which have been envisaged, use an aqueous composition consisting of H 2 O 2 and an acid / peracidic mixture of RCO 2 H / RCO 3 H structure where R is an aliphatic residue, see for this purpose published patent documents EP 0 193 416 B1 and EP 0 370 850 Bl. However, such a composition is not very effective because its biocidal activity is insufficient. It has also been proposed to stabilize H 2 O 2 by means of a strong mineral acid, such as H 3 PO 4, to provide an aqueous composition consisting of a ternary mixture H 2 O 2 + RCO 2 H / RCO 3 H + acid stabilizer, see for this purpose EP 0 087 343 B 1 However, the biocidal activity of this ternary mixture is still insufficient. It is also known that the aqueous composition, which comprises only H2O2 and Ag + ions (provided by an inorganic salt such as AgNO3), (i) at a low concentration of H2O2 (in particular 8% by weight relative to the weight of the composition), has a low biocidal activity, and (ii) at a high concentration of H2O2 (especially 60% by weight), presents risks of explosion. EP 0 797 387 B1 and EP 1 175 149 B9 disclose aqueous compositions comprising four essential components: (A) H2O2, (B) an acid / peracidic mixture of the structure RCO2H / RCO3H, where R is an aliphatic residue, ( C) an acidic stabilizer, and (D) a source of AgI ions (according to EP 0 797 387 B1) or ions of Ag ", Ag", V V Nbv, Tav, movi, wvi, Co "In or -IllI (according to EP 1 175 149 B9). The teaching of EP 0 797 387 B1 and EP 1 175 149 B9 is difficult to reproduce. It is now known that the ions provided by said source must necessarily be complexed to give a stable aqueous composition.

These two documents do not mention the necessary presence of ionic complexes, it must perhaps be supposed that the surfactant not exemplified in Examples 1-6 and 11-12 of EP 1 175 149 B9, which acts as anionic wetting agent or non-ionic, would, if necessary, provide the required ionic complexes. EP 0 876 762 B1 describes a particular disinfecting aqueous composition comprising the following essential ingredients: - hydrogen peroxide, - Ag + ions, - a mineral acid (in particular H3PO4), and - an organic stabilizer for Ag + ions (see paragraph [ 0016]), said organic stabilizer being advantageously a polycarboxylic acid such as citric acid or tartaric acid (which acts here as a complexing agent for silver), the latter composition being effective for the treatment of swimming-pool water, especially with regard to bacteria, but has a weak biocidal action with respect to algae. In addition EP 0 797 387 B1 and EP 1 175 149 B9 have many disadvantages. Thus, the use of silver ions provides after evaporation of silver metal deposits on the treated surfaces, which is not very pleasant especially for a surgical instrument. Moreover, the molybdenum compound, which is the best means recommended by the document EP 1 175 149 B9, can not be used to disinfect, depollute or clean, because said molybdenum, heavy metal, is prohibited in the European Union. WO 2006/018549 A1 discloses a process for preparing an aqueous gel from hydrophilic silica, and an aqueous composition comprising: hydrogen peroxide, a mineral and / or organic acid (especially phosphoric acid + picolinic acid according to Example 2), and - a substance chosen in particular from surfactants, sequestering agents, polyols and mixtures thereof, this gel being capable of being dehydrated to give a powdery preparation of H 2 O 2, the powder giving again a gel with water. Finally, WO 2005/110090 A1 discloses an association of H2O2 with an amine oxide for the maintenance of the skin and the removal of make-up. This document neither describes nor suggests the use of an amine oxide in an aqueous composition containing H 2 O 2, RCO 2 H / RCO 3 H and an acid stabilizer in the field of hygiene for disinfecting and cleaning industrial installations, such as: surfaces, - circuits in which water acts as an energy or thermal fluid, and, - ventilation and ventilation ducts. US 2011/0152158 A1 (for cleaning dishes by hand), US 2010/0104528 A1 (for cleaning contact lenses) and EP 0 973 687 A1 (for cleaning hard surfaces) are also known. ), aqueous compositions containing hydrogen peroxide, an H202 stabilizing agent (in particular of the phosphoric acid or phosphonic acid type) and a surfactant such as an amine N-oxide. It is found that these three publications do not describe or suggest an aqueous composition additionally containing terpinene-4-ol or an essential oil that is water-soluble. Also known from US 2009/0131539 A1 is a pest control composition useful in humans and animals, which contains a primary or secondary alcohol, a ketone, an essential oil and H2O2. This document neither describes nor suggests that the essential oil is water soluble. In addition, this document does not envisage or mention the use of an acid / peracid mixture RCO2H / RCO3H. WO 07/25404 A1 discloses an aqueous disinfecting composition comprising hydrogen peroxide, an essential oil and, as amphoteric surfactant, an amine N-oxide substance. This document neither describes nor suggests that the essential oil is water soluble; moreover, it does not propose the incorporation in said composition of an acid / peracid mixture RCO2H / RCO3H. It is the same in WO 98/20735 A1 which provides a similar composition intended to be nebulized. Publication WO 2010/004161 A2 describes a biocidal aqueous composition comprising: (i) H202, (ii) a mixture RCO2H / RCO3H where R is an aliphatic residue with a linear or branched hydrocarbon chain, and (iii) a catalyst allowing the disproportionation of H202 as a whole (i) + (ii) consisting of H 2 O 2 / RCO 2 H / RCO 3 H, said catalyst being complexed with N, N-diacetic glutamic acid (which has a pKa of 9.4) or one of its salts, said catalyst being (a) a transition metal or alkaline earth metal from a source providing +,,,,, Ag3 mn2 + mn3 + mn4 + y4 + Fe2 + ions Ag +, Ag2 +, Fe3 +, Au +, Au3 +, cu2 +, pd2 +, c02 +, Ni2 +, mo3 +, mo6 +, m2 + Cu +, g or mixtures thereof, or (b) an essential oil, advantageously the essential oil of rosemary (see the enumeration provided in WO 2010/004161 A2 page 4 lines 27-30). According to (a), by dilution, the metal ions are released from their complex with N, N-diacetic glutamic acid and act according to the Fenton reaction: (1) H 2 O 2 + Fe 2 + -> OH + OH + Fe3 + where OH * is the hydroxyl radical, or the so-called generalized Fenton reaction when a metal other than iron is involved: (2) nH2O2 + Min + -> nOH + nOH * + M (In + n) ± 30 where M is the metal considered having a maximum oxidation state m + n and a lower oxidation state m [reaction (2) becoming reaction (1) when M is iron, m = 2 and n = 1], the reaction ( 2) being completed by all Haber-Weiss reactions (3) and (4): ## STR2 ## (4) 02 * + H202 -). OH + OH * + 02 where 02 * - is the superoxide radical. Lane (b) is not exemplified. It is not clear how the essential oil is complexed by N, N-diacetic glutamic acid or its sodium or potassium salt. Moreover, it should rather be thought that the route (b) does not provide at the time of dilution all the oxidative activity of all the ROS (reactive oxygen species, "Reactive Oxygen Species") that are the hydrogen peroxide, the hydroxyl radical, the superoxide radical and the singlet oxygen 102: since the essential oil contains substances that are insoluble in water or immiscible with water, its incorporation into the aqueous mixture of H202 with RCO2H / RCO3H leads to a heterogeneous system which triggers the reaction (5) of disproportionation of hydrogen peroxide: (5) 2H202 -> 2H20 + 102 Aim of the invention It is proposed to provide a new technical solution for to overcome the aforementioned defects in the technology of the use of H202 and essential oils in the field of disinfection for the depollution, disinfection and cleaning of various surfaces, various equipment, installations, moving water circuits in which water acts as an energy or thermal fluid, cooling columns and enclosed spaces, including operating theaters. More specifically, it is desired to use hydrogen peroxide according to a new technology that does not use chlorinated compounds, aldehydes, quaternary ammonium or metal ions that must be complexed and then used extemporaneously as soon as they have been complexed. According to a first aspect of the invention, it is proposed to provide an aqueous system, based on hydrogen peroxide, acids, amine N-oxide and antiseptic essential oil, which is particularly advantageous and which retains substantially until the moment of use all its oxidizing potential. Indeed, it is often found, following the teaching of the prior art, that a significant amount of H 2 O 2 was consumed before the start of the intended use: H 2 O 2 was wasted for the oxidation of certain present substances such as acids, alcohols and / or unsaturated compounds of C = C or C = O type According to a second aspect of the invention, it is proposed to provide a composition containing said aqueous system for combating various germs (bacteria , yeasts, molds, fungi, spores, viruses).

Definitions For convenience, in the following, the term "water-soluble substance" is understood to mean a substance which is soluble in water or which is miscible with water in order to provide only a single homogeneous aqueous phase, on the one hand, and by "field of disinfection "is understood to mean the field of hygiene and the field of cleaning, on the other hand. OBJECT OF THE INVENTION To overcome the aforementioned drawbacks, it is recommended to use an aqueous system which can be used in the field of disinfection, said aqueous system, which comprises hydrogen peroxide, acids, an amine N-oxide substance and a essential oil component, characterized in that (1) it is homogeneous and consists of a single phase, and (2) said essential oil component is selected from the group consisting of (a) water-soluble essential oils, (b) terpinen-4-ol of formula (III): and (c) mixtures thereof.

Advantageously, the aqueous system according to the invention contains, in a single homogeneous aqueous phase: (a) hydrogen peroxide, ([3) an acid / peracidic mixture of structure RCO2H / RCO3H, where R is an aliphatic residue in C 1 -C 8 linear or branched hydrocarbon chain, saturated or unsaturated, said R residue may comprise one or more functional groups -OH, -CO2H, an acid stabilizer, an amine N-oxide substance selected from the group consisting of ) the amine N-oxides of formula (I): wherein R 2 and R 3, which may be identical or different, each represent a C 1 -C 14 aliphatic residue with a linear hydrocarbon-based chain, or branched, saturated or unsaturated, or a C 1 -C 3 hydroxyalkyl group, R 1 represents a C 1 -C 20 aliphatic radical with a linear or branched hydrocarbon chain, saturated or unsaturated, or an alkylamidoalkylene radical of structure (II): I R 4 (CH 2 ) - (II) where R4 is a C5-C18 alkyl group linear or branched hydrocarbon chain; and (b) mixtures thereof, and terpinene-4-ol of formula (III) above, a water-soluble essential oil (g) or a mixture thereof. A composition containing said aqueous system is also recommended, in particular in the form of an aerosol or in the form of a gel. Finally, it is recommended to use said aqueous system in the field of disinfection, in particular for the hygiene, cleaning, and decontamination of floors, surfaces, industrial premises, circuits in which water circulates as water. as thermal or energy fluid, ventilation and ventilation ducts and enclosed spaces, which have been polluted by pathogenic microorganisms or brought into contact with said microorganisms. DETAILED DESCRIPTION OF THE INVENTION Hydrogen peroxide It is recommended that in the aqueous disinfecting system according to the invention the concentration of H 2 O 2 be less than or equal to 8% by weight with respect to the weight of said system. This is a threshold beyond which the transport of the formulation by air, by sea and on the ground (road, rail and river networks) is no longer permitted. At the time of use of the system according to the invention for the disinfection, the dilution of said system and bringing it into contact with a foreign body, destabilize and trigger the reaction (5) of disproportionation of peroxide of hydrogen, which induces the generation of singlet oxygen 102. The mixture RCO2H / RCO3H The mixture RCO2H / RCO3H depends on the equilibrium reaction (6): (6) H202 + RCO2H <=> H2O + RCO3H According to this reaction, it is sufficient to contact an acid RCO2H with H202 to obtain the peracid RCO3H in a first ternary aqueous medium H202 + RCO2H + RCO3H. Similarly, if the peracid RCO3H is brought into contact with water, H202 and RCO2H are formed in a second ternary aqueous medium H202 + RCO2H + RCO3H. When one wants a mixture RCO2H / RCO3H with, in equilibrium, a weight ratio [RCO2H] / [RCO3H] predetermined, one has several solutions. It is thus possible to carry out the reaction (6) starting from H 2 O 2 and RCO 2 H and then to adjust, in particular, by addition, as a function of the final concentrations desired at equilibrium, of H 2 O 2, RCO 2 H and / or H 2 O (here a demineralised water having conductivity less than or equal to 0.5 μS / cm). Alternatively, it is more expedient to use an aqueous mixture containing H 2 O 2 + RCO 2 H + RCO 3 H, already commercially available, for example a mixture according to reaction (6) and containing at equilibrium 47.5. % by weight of H 2 O 2 and 1.75% by weight of RCO 3 H.

As indicated above, R represents a C1-C8 aliphatic radical with linear or branched hydrocarbon chain, saturated or unsaturated, said radical R possibly containing one or more functional groups -OH, -CO2H. Among the groups R which are suitable, mention may in particular be made of methyl, ethyl, propyl, isopropyl, n-butyl, -i-butyl, s-butyl, CH 3 CH =CH 2 -, CH 3 CH = CHCH 2 -, HOCH 2 - groups (the rest R of glycolic acid) and CH3CH (OH) - (ie the residue R of lactic acid). When the group R has a single functionality -OH or -COOH, the corresponding acid (RCO2H) can also act as acid stabilizing agent. When said group R has several functional groups -OH and / or -COOH, the corresponding acid may additionally act as a chelator. The RCO2H / RCO3H couple, preferred according to the invention and especially especially recommended here, is the acetic acid / peracetic acid pair.

The acid stabilizer A strong inorganic acid, such as H 3 PO 4 or H 2 SO 4, may be used according to the prior art. But such an acid is likely to be corrosive. To reduce the risk of corrosion by a strong inorganic acid, it is preferred to use organic acids. Advantageously, the acid stabilizer is here a phosphonic acid substance and / or a pyridinecarboxylic acid substance. According to one particular embodiment, the acidic stabilizer is a polyphosphonic acid capable of comprising one or more functional groups -CO 2 H, -OH and / or amine. This polybasic phosphonic acid may in particular be chosen from the group consisting of: - dimethylaminomethanediphosphonic acid, - amino-tris (methylenephosphonic acid), - 2-phosulfonobutane-1,2,4-tricarboxylic acid - 1-hydroxyethane-1-acid , 1-dipho sphonic (other nomenclature: hydroxyethylene-1,1-diphosponic acid), - N, N'-bis- (3-aminopropyl) -ethylenediamine hexa (methylenephosphonic acid), - diethylenetriamine penta (methylenephosphonic acid), - hexamethylenediamine tetra (methylenephosphonic acid), ethylenediamine tetra (methylenephosphonic acid), 2-hydroxyphosponoacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, bis (hexamethylenetriamine) penta (methylenephosphonic acid), phosphonosuccinic acid, phytic acid, and - their mixtures. Phosphonic polyacids have the advantage of having a double action: as a stabilizer of H2O2, on the one hand, and as anticorrosive agent, on the other hand. Alternatively, a portion of said phosphonic polyacids may be replaced by their sodium or potassium salt. The phosphonic acid stabilizer is more particularly recommended: 2-phosphonobutane-1,2,4-tricarboxylic acid and 1-hydroxyethane-1,1-diphosphonic acid. The pyridinecarboxylic acids which are suitable according to the invention are chosen from the group consisting of 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridine carboxylic acid and 2,6-pyridinedicarboxylic acid, the latter being advantageous in view of its double action as a stabilizing agent for H 2 O 2 and a wetting agent. On the other hand, the other acids, namely 2,3-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid and 2,5-pyridinedicarboxylic acid, must be discarded because, because of their insolubility in water at pH less than 7, their use here would raise serious difficulties.

Finally, it is possible to use as acid stabilizer, as was mentioned above in the context of the RCO2H / RCO3H mixture, a polycarboxylic or hydroxycarboxylic acid, such as, in particular, tartaric acid, malic acid, glycolic acid, lactic acid or citric acid. Amine N-oxide The amine N-oxide substances are used according to the invention as disinfectant active agents, on the one hand, and as amphoteric surfactant, on the other hand. Said amine N-oxides are generally prepared by reacting a tertiary amine with hydrogen peroxide according to reaction (7): (7) R 1 R 2 R 3 N + H 2 O 2 R 1 R 2 R 3 N-> O + H 2 O (I) Since the amine N-oxide of formula (I) can be marketed by its manufacturer in combination with H 2 O 2, account should be taken of the hydrogen peroxide content that can be provided by a commercial amine N-oxide for estimate (i) the total intake of initial H2O2 and (ii) the amount of H2O2 available when the equilibrium of the above-mentioned reaction (6) has been obtained. . Preferably, according to the invention, the amine N-oxide substance of formula (I) is such that: R2 = R3 = C1-C3 lower alkyl, preferably methyl or ethyl, and R1 is preferably a group C1-C18 alkyl, in particular decyl, lauryl, myristyl, palmityl or stearyl.

The essential oil It is known that folk medicine has already proposed the use of essential oils as biocidal or antiseptic means. According to the invention it is recommended to incorporate in the aqueous disinfecting system a water-soluble essential oil. As indicated above, it is necessary to use a water-soluble essential oil so that the aqueous disinfecting system of the invention is constituted, before use, of a single homogeneous phase, any heterogeneous element, in particular the oil droplets. an oil-in-water emulsion or a slight precipitate, being capable of destabilizing said system and of inducing the dismutation of the hydrogen peroxide according to the reaction (5). Terpinene-4-ol has been determined to cause lysis of the cell membrane. See the article by Carlson, CF et al., Antimicrobial Agents and Chemotherapy, 46 (6), 1914-1920, (June 2002) entitled "Mechanism of action of Melaleuca alternifolia (Tea Tree) on Staphylococcus aureus". by time-kill, lysis, leakage and knows tolerance assays and electron microscopy ". In practice, the essential oil useful according to the invention is chosen from: - water-soluble essential oils of rosemary, thyme, peppermint, basil, lemon, lemongrass, geranium, eucalyptus, pine, jasmine and balsam tree, - water-soluble essential oils d a plant of the genus Melaleuca, and - their mixtures.

Essential oils are generally obtained from the leaves of the plant concerned by steam distillation (in English: "steam distillation"). To have a water-soluble extract, it is also necessary to extract and collect an aqueous phase. This aqueous phase contains (i) effectively water soluble products and (ii) non-water soluble products which have been rendered water miscible by "entrainment" of the former. In the trade, water-soluble essential oils are often provided in the form of a composition in combination with a surfactant (in an amount of the order of 5 to 20% by weight relative to the total weight of said composition). This surfactant is mainly a nonionic product of the polyethoxylated fatty alcohol type, for example isotridecanol ethoxylated with 3 to 10 ethylene oxide CH 2 CH 2 O groups (in particular the product corresponding to the CAS registry number No. 562-74-3). Terpinene-4-ol is a terpene alcohol which is (i) soluble in water, and (ii) active as an antiseptic agent. It is present in an interesting quantity in several plants of the genus Melaleuca. This terpin alcohol can be used alone to replace the water-soluble essential oil. More than 200 Melaleuca-endemic species have been recorded in Australia, a few species in Malaysia and 7 endemic species in New Caledonia. Advantageously, an essential oil is recommended which is selected from the water-soluble essential oils of plants of the genus Melaleuca, which contain the above terpinene-4-ol. Suitable for this purpose are the water-soluble essential oils of Melaleuca alternifolia (tea tree), Melaleuca dissitiflora, Melaleuca linariifolia, Melaleuca uncinata, and Melaleuca armillaris, and mixtures thereof, the preferred hydrosoluble essential oil according to the invention being that of Melaleuca alternifolia, which has an international standard ISO 4730-2004 fixing the minimum and maximum quantities required for the main components. Said quantities of said components are reproduced in Table I below. Table I Main components of tea tree essential oil (according to ISO 4730-2004) Component Minimum (%) Maximum (%) Terpinolene 1.5 5 1,8-Cineole trace 15 a-terpinene 5 13 y- terpinene 10 28 p-cymene 0.5 8 terpinene-4-ol 30 48 a-terpineol 1.5 8 Limonene 0.5 1.5 Sabinene trace 3.5 aromadendrene trace 3 8-cadinene trace 3 Globulol trace 1 Viridiflorol trace 1 a-pinene 1 6 Viridiflorene trace 3 For information, Table II gives the main components of the water-soluble essential oil of Melaleuca alternifolia with their minimum and maximum contents. The comparison of Tables I and II shows that the extraction of the aqueous phase leads to losses with respect to terpinen-4-ol, which is soluble in water, on the one hand, and shows that insoluble products in water such as a-pinene are rendered water-miscible, on the other hand.

Table II Main components of the water soluble tea tree essential oil Component Minimum (%) Maximum (%) Terpinen-4-ol 15 Isotridecanol Ethoxylated 5 10 α-Terpinene 5 Terpinolene 1 2.5 1.8- In addition to amine N-oxides, other anionic, cationic, nonionic, amphoteric or zwitterionic surfactants can be used. Some of them can intervene effectively as wetting agents. Among the anionic surfactants that may be used, mention may in particular be made of alkyl sulphates, alkyl ether sulphates, sulphated monoglycerides, alkylarylsulphonates, alkylsulphosuccinates [such as sodium bis (or potassium) bis (2-ethylhexyl) sulphosuccinate or potassium sulphate). ], alkylphosphates [such as laurylphosphates and palmitylphosphates], acyl glutamates, alkylsulfoacetates, alkyl ether carboxylates, alkyl phosphates polyethoxylated esters and sulfonated fatty acids. Among the cationic surfactants that may be used, there may be mentioned in particular quaternary ammonium salts, in particular halides having 4 Cl-C22 hydrocarbon groups [such as, for example, cetyl, myristyl, lauryl, oleyl and the like]. or bicarbonates having a C1-C22 hydrocarbon group. The nonionic surfactants that may be used include, in particular, polyethoxylated and polypropoxylated derivatives of fatty alcohols, alkylphenols, fatty acids, monoesters of fatty acids, amines or aliphatic amides. said derivatives having 3 to 10 CH 2 CH 2 O groups and C 8 -C 20 hydrocarbon portions. Useful amphoteric surfactants include, in particular, sodium dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate and betaines. The system according to the invention The aqueous and disinfecting system of the invention is prepared from water, here demineralized water having a conductivity less than or equal to 0.5 μS / cm, and the aforementioned ingredients, with H202, the RCO2H / RCO3H mixture, the acid stabilizer, the amine N-oxide substance, the water-soluble essential oil or terpinene-4-ol, and, as the case may be, g) the other surfactant (s), different from the substance N-amine oxide, which may be present. Advantageously, the system according to the invention will contain: an H 2 O 2 content of less than or equal to 8% by weight, and preferably a content of between 4 and 7% by weight relative to the weight of said system; a content of RCO2H + RCO3H of between 0.02 and 0.35% by weight relative to the weight of said system; an acid stabilizer content of between 0.02 and 0.30% by weight relative to the weight of said system; an amine N-oxide substance content of between 0.02 and 0.30% by weight relative to the weight of said system; (A) a water-soluble essential oil content of between 0.35 and 0.70% by weight, and more preferably a content of 0.5% by weight, based on the weight of said system (the preferred essential oil being water-soluble essential oil of Melaleuca alternifolia), or (b) a terpinene-4-ol content of between 0.07 and 0.14% by weight relative to the weight of said system; and, if present, a content of surfactants different from the amine N-oxide substance of between 0.002 and 0.030% by weight relative to the weight of said system. For convenience, a distinction has been made among surfactants. On the one hand, there are the amine N-oxide substances which are active as antiseptic agents and wetting agents, and, on the other hand, the surfactants structurally different from the amine N-oxides, which have dispersant properties, wetting and, where appropriate, antiseptics, and which are not essential for the implementation of the invention. Preparation of the System According to the Invention In order to prepare the aqueous and disinfecting system of the invention, a method is preferred which comprises the following steps: (1) using an aqueous commercial mixture , in accordance with the H202 + RCO2H <=> H2O + RCO3H equilibrium-containing reaction H202, RCO2H and RCO3H, and wherein (i) the H202 content is especially 45% to 50% by weight based on the weight of said aqueous commercial mixture and (ii) the content of RCO2H + RCO3H mixture is in particular 1.5 to 2% by weight relative to the weight of said aqueous commercial mixture, (2) combine said commercial mixture of the step (1 °) ) with at least one acidic stabilizer, preferably having anti-corrosion properties, and the amine N-oxide substance, to obtain a stock solution, (3) diluting the stock solution thus obtained in step (2) °) with deionized water, preferably demineralized water With a conductivity of 0.5 μS / cm, then incorporate in the resulting dilution the water-soluble essential oil or terpinene-4-ol, and (4 °) allow to stand the resulting aqueous medium obtained at the end of step (3) until a precipitate is formed (i. e. a slight cloud cloud), then filter to collect the filtrate constituting the system of the invention. Conveniently, in step (1 °) an aqueous commercial mixture is provided in which the weight ratio of peracid RCO3H to acid RCO2H is between 1/4 and 8/1, on the one hand, and the weight ratio 13 / a of the acid and peracid group (RCO 2 H + RCO 3 H) to hydrogen peroxide is between 0.01 / 1 and 0.05 / 1, on the other hand. In step (2 °), the reaction is carried out with a weight ratio y / a of the acid stabilizing component to hydrogen peroxide of between 0.001 / 1 and 0.01 / 1, and a weight ratio 8 / a of the substance N hydrogen peroxide amine oxide between 0.001 / 1 and 0.01 / 1. In step (3 °), it is preferred to use the water-soluble essential oil rather than terpinene-4-ol. For convenience, it is recommended to dilute the stock solution with deionized water before incorporating the water-soluble essential oil. The weight ratio 8 / cc of said essential oil which is hydrosoluble with hydrogen peroxide is here in particular between 0.01 / 1 and 0.1 / 1. At the end of step (3 °), the H2O2 content is generally less than 8% by weight, and advantageously between 4 and 7% by weight. Advantageously according to the invention, the dilution of step (3) is carried out so as to obtain two levels of mother solution in the system: one of 10% by weight and the other of 16% by weight, the aim being to provide two interesting products ready for use. The system obtained in step (3 °) can undergo a slow oxidation, due to the presence of peracid RCO3H: the C = C double bonds of the water-soluble essential oil are epoxidized, which leads to a polymerization providing a precipitation (in the form of a disorder) which can trigger the reaction (5) of disproportionation of hydrogen peroxide. The precipitate, which is in the form of a slight cloud cloud, usually occurs about 4 months after the end of step (3 °). In step (4 °) to overcome this difficulty, about 4 months after production, the resulting medium is filtered (especially on Whatman 1001-125 filter paper) to remove said precipitate and collect the filtrate. This filtrate is a product in transparent formulations, which: - are ready for use, - contain all the active ingredients including most of the water-soluble essential oil which has not been polymerized, and - are stable during long-term storage until use. The system according to the invention, which is the clear (ie transparent) filtrate obtained in step (4 °), can be used as it is or can be used for the preparation of compositions containing it, ready for use and presenting itself. advantageously in the form of a gel or an aerosol. Before use, it is important that said system is housed during its preparation, its storage, its possible transformation into a gel and / or aerosol and its storage in the form of gel and / or aerosol, in packages (here containers, vials, containers, reservoirs or reactors) made of material inert to H 2 O 2 and the other above-mentioned ROS, on the one hand, and acids, on the other hand. Among the suitable inert materials, polytetrafluoroethylene (PTFE) is preferred, on the one hand, and even more preferably, high density polyethylene (HDPE), which has been rendered opaque to light, on the other hand. It is also possible to use glass instruments for short periods of time (generally less than or equal to 6 hours). It is also important that the walls of said packages and instruments are clean, because dirt or impurities, in contact with H2O2, may in particular trigger the disproportionation reaction (5). From a practical point of view and in order to comply with national and international regulations, it is important that the receptacles housing the system according to the invention or the composition containing it be (a) provided with a plug having a valve allowing degassing. and (b) arranged for storage and transport in a cool and well ventilated area. The composition As indicated above, the system according to the invention may be marketed in particular in the form of a gel, in the form of an aerosol or in a form suitable for fumigation.

In order to have a gel, the system obtained at the end of step (4 °) is combined with stirring with a fumed colloidal silica, preferably hydrophilic; for example a silica sold under the name CAB-O-SIL M5. The resulting product is thixotropic: if it becomes liquid again, it is then necessary to stir it to recover the desired gelled form. The gel is particularly suitable for disinfection, decontamination and / or cleaning of surfaces that are not horizontal. It can be applied by spraying (such as foam) onto plastic surfaces (such as PVC, polyacrylate, polymethacrylate, polycarbonate and their copolymers), metal surfaces (such as stainless steel, plastics). aluminum, copper and their alloys), refractory surfaces (such as ceramic and porcelain). After about 20 to 40 minutes of contact, these surfaces are rinsed thoroughly (especially to limit the corrosion of the metal surfaces) with softened water. The aerosol form is prepared according to a method known per se. In particular, such a form can be prepared by (i) injection of an inert carrier gas into a reservoir containing the system obtained at the end of step (4 °) and then (ii) by projection. The aerosol form is particularly suitable for disinfecting or sterilizing enclosed spaces. Examples and Tests Other advantages and characteristics of the invention will be better understood on reading the following examples of embodiments and tests. Of course, all of these elements are not limiting but are provided by way of illustration. EXAMPLE I Preparation of the stock solution (Code no .: "pGS") Starting from an aqueous commercial mixture, according to the above-mentioned reaction (6) and containing H 2 O 2, RCO 2 H and RCO 3 H, in which, in equilibrium, the H2O2 content is 47.5% by weight and that in RCO3H is about 1.75% by weight, based on the weight of said aqueous commercial mixture. PGS is prepared from the following formulation, wherein the two phosphonic polyacids are used as stabilizing and anticorrosive agents, and the N-oxide acts as an active and wetting agent: Ingredients Weight content - aqueous commercial mixture 99.60% - hydroxyethyl-1,1-diphosphonic acid 0.15% - 2-phosphonobutane-1,2,4-tricarboxylic acid 0.05% - dimethyldodecylamine-N-oxide 0.20% 100% Example 2 Obtaining a 10-fold system % in pGS (Code No.: "pG02") A system according to the invention is prepared according to the following formulation from demineralised water (conductivity 0.5 μS / cm), pGS and water-soluble essential oil of rosemary : Ingredients Weight content - demineralised water 0.5 μS / cm) 89.5% - pGS 10.0% - water soluble rosemary essential oil 0.5% 100% About 4 months after production, a slight precipitate forms that is filtered on Whatman 1001-125 paper. The filtrate is collected which is stable to storage in the dark. EXAMPLE 3 Obtaining a 16% system in pGS (Code no .: "pGR3) A system according to the invention having the following formulation is prepared as in Example 2: Ingredients Weight content - demineralized water 0.5 μS / cm) 83.5% - pGS 16.0% - water-soluble rosemary essential oil 0.5% 100% About 4 months after production, the precipitate formed is filtered off as in Example 2. Example 4 gel from pGO2 (Code no .: "pG04") A gel was prepared from pGO2 and a colloidal, fumed and hydrophilic silica (CAB-O-SIL® M5) having a mean particle size of 5-20 nm To avoid as much as possible the incorporation of air into the gel, the silica is homogenized pGO2 is transferred to a container provided with a stirring device, and stirred at room temperature at an angular speed. 750 rpm The silica is slowly added (over 20 minutes) to pGO2 with stirring, then stirring is continued for 2 hours. This results in the resulting gel in a high density polyethylene (HDPE) tank provided at its upper end with spray nozzles and a degassing valve. If after resting, the gel gives a liquid, just shake the liquid to restore the gel. The formulation is as follows: Ingredients Weight content - pGO2 96.5% - CAB-O-SIL® M5 3.5% 100% The gel thus obtained adheres for at least 30 minutes to vertical surfaces made of PVC, galvanized steel , stainless steel, copper, aluminum and ceramic. After 30 minutes of contact, rinse thoroughly with softened water. Example 5 Obtaining a gel from pGR3 (Code no .: "pGR5") The procedure is as in Example 4 with the difference that pGR3 is used, a system containing 16% by weight of pGS, instead of pGO2 which employs a 10 weight percent pGS, the formulation being as follows: Ingredients Weight content - pGR3 96.5% - CAB-O-SIL® M5 3.5% 100% As pGO4, gel pGR5 thus obtained adheres for at least 30 minutes to vertical surfaces made of PVC, galvanized steel, stainless steel, copper, aluminum and ceramic. After 30 minutes of contact, rinse thoroughly with softened water.

Examples 6 to 9 Proceeding as indicated successively to Examples 2 to 5, starting from a content of 0.5% by weight of water-soluble essential oil of Melaleuca alternifolia instead of a content of 0.5% by weight of hydrosoluble rosemary essential oil, the following products are respectively obtained: Example 6 (Code No.: "pGO6"), Example 7 (Code No.: "pGR7") Example 8, Gel (Code No.: "pGO8"), and Example 9, gel (Code no .: "pGR9"). Test I The product of Example 2 (pGO2), at various concentrations made by dilution with water, was studied with respect to several strains according to various standards. The results obtained are shown in Table III below. They highlight the antibacterial, antilevide, antifungal, anti-spore and antiviral properties of this product. Table III Activities of pGO2 with respect to bacteria, yeasts, molds, spores and viruses Strain Concentration Duration A Log Standard (% ) (minutes) Bacteria 10 5> 5 EN 1276 Pseudomonas aeruginosa Staphylococcus aureus 20 5> 5 EN 1276 Echerichia coli 20 5> 5 EN 1276 Enterococcus hirea 20 5> 5 EN 1276 Salmonella typhi 10 10> 5 EN 1276 Yeast, mold and fungus Aspergillus piger 40 15> 4 EN 1650 Candida albicans 20 15> 4 EN 1650 Tricophyton mentagrophytes 40 10> 4 EN 1650 Spores Bacillus subtilis 80 30> 3 NF T 72 301 Bacillus cereus 80 30> 3 NF T 72 301 Clostridium sporogenes 80 30> 3 NF T 72 301 Virus Enterovirus polio 60 30> 5 NF T 72 180 Orthopox virus 60 30> 5 NF T 72 180 Human adenovirus 60 30> 5 NF T 72 180 Test 2 The product of Example 2 (pGO2) was also tested as an aerosol in a room initially at 25 ° C, having has a relative humidity of 70% and contains tulip onions contaminated with a fungus, Fusarium oxysporum in a population of 14 spores / ml. An ultrasonic aerosol generator ULTRAMIST providing droplets of 1 .mu.m in diameter marketed by the so-called Air Control B.V. was used. The aerosol of pGO2 was dispersed for 40 minutes, giving a relative humidity of 99.9%. 750 l of water are collected on the skin of the tulip onions. It is determined that there is a fungus population of 1 spore / ml. Test 3 The product of Example 3 (pGR3) was tested as an aerosol against several strains according to two distinct standards. The aerosolization of pGR3 was made using a Clim'O Medic device marketed by the company Metatecta NV, supplying droplets of 5 and 10 de in diameter by two jets in a 58 m3 room having (a) initially a temperature of 20.8 ° C and a relative humidity of 60%, and (b) at the end of the test a temperature of 19.4 ° C and a relative humidity of 99.9%. The dispersion time was 45 minutes to administer a pGR3 dose of 18 g / m3 in the room. After dispersion, an additional contact time of 120 minutes was provided.

With respect to the H1N1 virus, the standard EN 14 476 was followed, pGR3 being contacted at the dose of 60% by weight obtained by dilution with deionized water 0.5 μS / cm) for a period of 60 minutes. The results obtained are shown in Table IV below. Table IV Activities of pGR3 vis-à-vis bacteria, yeasts, spores and viruses Dosage strain Duration A Log Standard (minutes) Bacteria Pseudomonas aeruginosa 18 g / m3 45 + 120> 7 NF T 72 281 Staphylococcus aureus 18 g / m3 45 + 120> 7 NF T 72 281 Streptococcus faecium 18 g / m3 45 + 120> 7 NF T 72 281 Yeast 18 g / m3 45 + 120> 6 NF T 72 281 Candida albicans Spores 18 g / m3 45 + 120> 8 NF T 72 281 Bacillus subtilis Virus 60% 60> 4 EN 14476 H1N1 Finally, the trials carried out with the products pGO6, pGR7, pGO8 and pGR9 gave very good results.

Claims (13)

REVENDICATIONS1. Aqueous system for use in the field of disinfection, said aqueous system, which comprises hydrogen peroxide, acids, an amine N-oxide substance and an essential oil component, characterized in that: (1) it is homogeneous and consists of a single phase, and (2) said essential oil component is selected from the group consisting of (a) water-soluble essential oils, (b) terpinene-4-ol of formula (III): CH3 CH3 and (c) their mixtures. 2. System according to claim 1, characterized in that it contains in a single homogeneous aqueous phase: (a) hydrogen peroxide, ([3) an acid / peracidic mixture of RCO2H / RCO3H structure, where R is a C1-C8 aliphatic residue with linear or branched hydrocarbon chain, saturated or unsaturated, said R residue may comprise one or more functional groups -OH, -CO2H, an acid stabilizer, an amine N-oxide substance selected from the group consisting of by (a) the amine N-oxides of formula (I): wherein R 2 and R 3, which are identical or different, each represent a C 1 -C 14 aliphatic radical with a linear or branched hydrocarbon chain, saturated or unsaturated; , or a C1-C3 hydroxyalkyl group, - R1 represents a C1-C20 aliphatic radical with a linear or branched hydrocarbon chain, saturated or unsaturated, or an alkylamidoalkylene radical of structure (II): I R4 (CH2) - (II) Where R4 is a C5-C18 alkyl chain linear or branched hydrocarbon; and (b) mixtures thereof, and (g) terpinene-4-ol, a water-soluble essential oil or a mixture thereof. 3. System according to claim 2, characterized in that said acidic stabilizer is a polyphosphonic acid capable of having one or more functional groups -CO2H, -OH and / or amine. 4. System according to claim 3, characterized in that said polyphosphonic acid is selected from the group consisting of: - dimethylaminomethanediphosphonic acid, 25 - amino-tris (methylenephosphonic acid), - 2-phosphonobutane-1, 2,4-acid arboxylic tri-1-hydroxy-1,1-diphosphonic acid, N, N'-bis- (3-aminopropyl) -ethylenediamine hexa (methylenephosphonic) acid, diethylenetriamine penta (methylenephosphonic acid), 27 (I) -acidic acid hexamethylenediamine tetra (methylenephosphonic), - ethylenediamine tetra (methylenephosphonic acid), - 2-hydroxyphosponoacetic acid, - 1-hydroxyethylidene-1,1-diphosphonic acid, - bis (hexamethylenetriamine) penta (methylenephosphonic acid), - phosphonosuccinic acid, - acid phytic, and - their mixtures. The system of claim 2 characterized in that said acidic stabilizer is a pyridinecarboxylic acid selected from the group consisting of 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridine carboxylic acid and 2,6-pyridinedicarboxylic acid. 6. System according to claim 2, characterized in that said amine N-oxide substance of formula (I) is such that: R 2 = R 3 = lower alkyl C 1 -C 3, preferably methyl or ethyl, and R 1 is preferably a C 10 -C 18 alkyl group, in particular decyl, lauryl, myristyl, palmityl or stearyl. 7. System according to claim 1 or 2, characterized in that the essential oil is selected from the group consisting of: water-soluble essential oils of rosemary, thyme, peppermint, basil, lemon, lemongrass, geranium, eucalyptus, pine, jasmine and balsamier, the water-soluble essential oils of a plant of the genus Melaleuca, and their mixtures. 8. System according to claim 7, characterized in that said essential oil is selected from the water-soluble essential oils of Melaleuca alternifolia, Melaleuca dissitiflora, Melaleuca linariifolia, Melaleuca uncinata, and Melaleuca armillaris, and mixtures thereof, the water-soluble essential oil of Melaleuca alternifolia being the preferred water-soluble essential oil. 9. System according to claim 1 or 2, characterized in that it comprises: - a content of H202 less than or equal to 8% by weight, and preferably a content of between 4 and 7% by weight relative to the weight of said system; - a content of RCO2H + RCO3H between 0.02 and 0.35% by weight relative to the weight of said system; an acid stabilizer content of between 0.02 and 0.30% by weight relative to the weight of said system; an amine N-oxide substance content of between 0.02 and 0.30% by weight relative to the weight of said system; (a) a water-soluble essential oil content of between 0.35 and 0.70% by weight, and more preferably a content of 0.5% by weight, based on the weight of said system (the preferred essential oil being water-soluble essential oil of Melaleuca alternifolia), or (b) a terpinene-4-ol content of between 0.07 and 0.14% by weight relative to the weight of said system; and, if present, a content of surfactants different from the amine N-oxide substance of between 0.002 and 0.030% by weight relative to the weight of said system. 10. Composition usable in the field of disinfection, characterized in that it comprises a system according to any one of claims 1 to 9. 11. Composition according to claim 10, characterized in that it is in the form of a gel or an aerosol. 12. Use of a system according to any one of claims 1 to 9 in the field of disinfection of floors, surfaces, industrial premises, circuits in which water circulates as a thermal fluid or which have been polluted by pathogenic microorganisms or brought into contact with said microorganisms. 13. Process for preparing a system according to any one of claims 1 to 9, characterized in that it comprises the following steps consisting of: (1 °) using an aqueous commercial mixture, in accordance with the reaction H202 + RCO2H <0> H2O + RCO3Hcontaining the equilibrium H202, RCO2H and RCO3H, and wherein (i) the content of H202 is in particular 45% to 50% by weight relative to the weight of said aqueous commercial mixture and (ii) the content mixed RCO2H + RCO3H is especially 1.5 to 2% by weight relative to the weight of said aqueous commercial mixture, (2) combine said commercial mixture of step (1 °) with - at least one acid stabilizer, having preferably anticorrosive properties, and - the substance N-amine oxide, to obtain a stock solution, (3 °) dilute the mother solution thus obtained in step (2 °) with demineralized water, preferably demineralised water with a conductivity of 0.5μS / cm and then incorporate into the resulting dilution of the water-soluble essential oil or terpinene-4-ol, and (4 °) allowing the resulting aqueous medium to stand at the end of step (3 °) until a precipitate forms , then filter to collect the filtrate.