The present invention relates to an aqueous solution of hydrogen peroxide stabilizer comprising a specific enabling it to obtain significantly improved compared to the products of prior art properties.

The invention also relates to a method of disinfection or sterilization, implementing the aqueous solution according to the present invention. The invention finally relates to the use of such an aqueous disinfecting solution for disinfecting specifically stabilized packaging.

TECHNICAL BACKGROUND

For disinfecting or sterilizing packaging, a technique for disinfection or sterilization consists in spraying said package with a spray of an aqueous solution of hydrogen peroxide. With this solution, a certain amount of stabilizer (s) is necessary, which leads to the presence in the hydrogen peroxide solution, residues from the decomposition or the presence of stabilizers (in addition to those from the peroxide 'hydrogen).

Stabilizers are essential to the aqueous solution of hydrogen peroxide because they prevent the degradation of hydrogen peroxide (exothermic reaction disproportionation to water and oxygen). This need stabilizing is especially important that the hydrogen peroxide content increases. Thus, for hydrogen peroxide solutions are effective in disinfection or sterilization, the hydrogen peroxide content should be high, and consequently also the content of stabilizer.

However, residues from these stabilizers can clog the nozzle or nozzles and the conduits of the spray apparatus (sputtering).

Of course, it is possible to clean the spray apparatus but it stops the disinfection / sterilization device and the significant additional costs, besides the fact that the sprayer can be irreparably damaged. Only solutions having very low residue levels therefore allow the use of such aqueous solutions of hydrogen peroxide by spraying.

We know at present documents that provide new types of stabilizers, such as in EP 1926502 or WO 2015078830, but none of these solutions can achieve an extremely low level of residues essential to the spray use.

Thus, there is a need for a solution of disinfection / sterilization efficient, stable over time (retention of title of hydrogen peroxide) having a very low content of residues.

SUMMARY OF THE INVENTION

The present invention aims to remedy the aforementioned drawbacks. It proposes for this purpose the use of stabilizers in a very particular chemical family that allow, ideally while completing their primary function (stabilizing hydrogen peroxide) to ensure a particularly low level of residues so the disinfection operations / sterilization of packaging do not cause any risk of damage, even in the very long term, necessary for these operations devices (without requiring further washing / cleaning operations).

In a particularly surprising, the composition of disinfection / sterilization according to the invention ensures the stability of hydrogen peroxide (active ingredient of the composition) at room temperature even in the presence of a low metal contamination. The results of the composition stability of the invention show a very significant improvement in the stability properties, while offering a very low amount of residue that might damage the devices used to dispense (spray, spraying, fogging, spraying, etc .. ) the composition of hydrogen peroxide. Surprisingly, such stability is observed even for contents important hydrogen peroxide, such as those required to ensure disinfection / sterilization effective.

In addition, the composition of disinfection / sterilization according to the invention allows the disinfection of a package for packaging food or feed, cosmetics, pharmaceutical or veterinary products.

Thus, the present invention relates to an aqueous solution of hydrogen peroxide, comprising from 1% to 98%, especially from 3% to 75%, preferably 20 to 98%, preferably 20 to 75%, preferably 20%

65%, preferably 20 to 50% even more preferably from 22% to 38% by weight of the solution of hydrogen peroxide and from 0.01 to 7 mg / kg (milligram per kilogram) of preferably 0.5 to 7 mg / kg, even more preferably 1, 5 to 5 mg / kg by weight of the solution, of a stabilizer, characterized in that the stabilizer is selected from the family of aminopolycarboxylic acids (APCA) or salts thereof, substituted or unsubstituted generic formula:

wherein R and R 'are selected from the following functional groups:

- C 1 -C 3 alkyls, preferably a methyl group,

- carboxylic acids C1-C3.

It is understood that the amount of stabilizers given above refers to a quantity of active material or of the stabilizers, the latter being available, possibly in the trade, as a dilute solution in water.

The present invention is applicable in particular to any implementation of the aqueous solution according to the invention in vaporized form, such as in particular in the application referred to as "aseptic spray" known to those skilled in the art and generally disinfection / sterilization via vaporization of the hydrogen peroxide solution.

In the following, unless otherwise stated, the percentages are given as weight values.

It is understood that the term "stabilizer" refers herein to any component whose function is to ensure the stability in time of the hydrogen peroxide present in the aqueous solution so that it does not decompose or bit and the title of the solution remains substantially the same over time, for example during storage. By way of non-limiting example of such stabilizers used in the prior art there may be mentioned phosphonic acids and their salts, such as amino-tris methylene phosphonic acid, hydroxy ethylene acid

diphosphonic acid, or diethylenetriaminepentaacetic methylphosphonic acid, polyphosphates, pyrophosphates such as sodium acid pyrophosphate, phosphoric acid and its salts, sodium stannate, carboxylic acids, derivatives of ethylenediaminetetraacetic acid.

The "disinfection" of a package within the meaning of the invention can be understood as a partial destruction of microorganisms present on the surface of the package in order to slow down their proliferation, an almost complete destruction of said microorganisms, according to intended application. In the latter case, generally referred to as "sterilization". The aqueous composition of hydrogen peroxide according to the invention is suitable for both uses.

In order to ensure disinfection / sterilization adequate, a minimum content of 20%, preferably 22% hydrogen peroxide relative to the total weight of the composition is required.

Preferably, the solution according to the present invention comprises 20 to 98%, preferably 20 to 75%, preferably from 20% to 65%, preferably from 20 to 50%, more preferably from 22% to 38% peroxide hydrogen relative to the total weight of the composition.

A content of hydrogen peroxide of 22% to 38% relative to the total weight of the composition is particularly suitable for disinfection / sterilization of packaging.

by "residue (s)" means "residue (s) Dry (s)" or "dry evaporation residue" of the solution according to the present invention, the solid recovered after evaporation of the disinfecting composition 10 to 1 C by gravimetric method which will be described later.

Preferably, the residue content of the solution according to the present invention is less than 7 mg / kg (milligram per kilogram of hydrogen peroxide solution), preferably less than 6 mg / kg, preferably less than 5 mg / kg, preferably less than 4 mg / kg, preferably less than 3 mg / kg and more preferably less than 2 mg / kg. These residues may in particular originate from or stabilizers for hydrogen peroxide and / or compounds used in the manufacture of hydrogen peroxide used in the present invention, for example a corrosion inhibitor, an inorganic acid or an additive known to the skilled artisan.

However, the content of stabilizer (s) present (s) originally in the aqueous solution of hydrogen peroxide is decisive to determine the dry residue content present in fine. Thus, the invention aims to reduce or eliminate, the presence of residues from or stabilizers for hydrogen peroxide used in the aqueous solution.

To do this, it is necessary that the stabilizer content is less than 7 mg / kg, preferably less than 6 mg / kg, preferably less than 5 mg / kg, preferably less than 4 mg / kg, preferably less than 3 mg / kg, preferably less than 2.5 mg / kg and more preferably preferably less than 2 mg / kg.

In order to stabilize the hydrogen peroxide in the solution, the stabilizer content is preferably greater than 0.5 mg / kg, preferably greater than 1 mg / kg, and more preferably greater than 1, 5 mg / kg. Advantageously, the stabilizer is from 1 to 2.5 mg / kg by weight of the aqueous solution.

Thus, thanks to the invention it is possible to obtain an amount of dry residue less than 2 mg / kg but it is understood that to obtain such a result, the choice of the hydrogen peroxide solution is essential, otherwise said latter must have a very low dry residue from the manufacture of said peroxide, obviously less than 2 mg / kg.

According to a preferred embodiment of the invention, R or R 'is a methyl group and the other R or R' is a group methanoic acid (formic acid) or its salt, substituted or unsubstituted. In this case, the stabilizer is methylglycinediacetic acid or its salt.

According to another preferred embodiment of the invention, R or R 'is a group ethanoic acid (acetic acid) or its salt, substituted or unsubstituted, and the other R or R' is a group of propionic acid or its salt, substituted or unsubstituted. In this case, the stabilizer is glutamate diacetic acid or its salt.

Other features or embodiments of the invention are presented below:

- advantageously, the aqueous solution according to the invention has a conductivity of 10 to 100 S / cm (micro Siemens per centimeter), preferably from 15 to 50 S / cm, and even more preferably 20 to 40 pS / cm.

- advantageously, the aqueous solution of the invention presents a maximum acidity of 1 mmol / kg (millimoles per kilogram).

- advantageously, the loss of said solution under / stability of the hydrogen peroxide in the solution, measured according to the CEFIC-H2O2-AM-7161 method, is less than or equal to 5%, preferably less than or equal to 3%, and most preferably less than or equal to 2% relative to the initial concentration of hydrogen peroxide.

According to one possibility offered by the invention, the aqueous solution comprises, and preferably consists of:

from 20% to 50% hydrogen peroxide,

From 0.3 to 3 mg / kg, preferably 0.5 to 7 mg / kg by weight of the solution, of a stabilizer as defined above,

optionally, from 1 .10 "4 % to 1 .10 " 2 % by weight of the solution, of additive (s),

the complement to 100% water.

Advantageously, one can prepare a disinfecting composition according to the invention being solely comprised of water, hydrogen peroxide and stabilizer according to the invention. Surprisingly, this simple disinfecting composition is effective to prevent decomposition of hydrogen peroxide when the disinfecting composition is contaminated with metal impurities.

As the disinfecting composition according to the invention inherently has a very low content of dry evaporation residue (from the stabilizer of hydrogen peroxide) can bear a contamination by impurities without the total solids residues crosses the maximum acceptable threshold imposed by the regulations for food packaging (currently set by the "food Chemical Codex").

The present invention also relates to the use of aqueous solution as defined above for disinfection / sterilization of a product.

Preferably, said product to be disinfected is one selected from the group consisting of containers, local, in particular hospital premises, and edible products, in particular fruits or vegetables.

Preferably, said package is selected from the group consisting of food packaging, such as food packaging for human or animal, a package of a cosmetic product, a package of a pharmaceutical product and a packaging of a veterinary product .

Preferably, the disinfection / sterilization of said product is carried out by spraying or spraying said solution onto said product.

The present invention also relates to the use of the aqueous solution as presented above for disinfection / sterilization of a package by spraying the hydrogen peroxide solution described above or for the disinfection by steam said hydrogen peroxide solution.

In the following, the stabilizer selected from the family of aminopolycarboxylic acids (APCA) or salts thereof, substituted or unsubstituted generic formula:

wherein R and R 'are selected from the following functional groups:

- C 1 -C 3 alkyls, preferably a methyl group,

- carboxylic acids C1-C3,

will eventually be referred to as the "stabilizer according to the invention" including the aforementioned acids and their salts.

The invention also relates to a method for disinfection / sterilization of a product as defined above, in particular of a packaging as defined above, characterized in that said product is contacted with the solution aqueous as described above.

Said contacting allows disinfecting / sterilizing said product, preferably said package.

Preferably, said contacting is performed by spraying or spraying said solution onto said product, more preferably by spraying.

Advantageously, the aqueous solution undergoes, prior to being placed in contact with the stabilizer, an operation for purifying said solution, such as for example distillation, one or more passages through ion exchange resins, filtration or by membrane techniques (microfiltration, ultrafiltration, nanofiltration) and / or reverse osmosis, the latter being preferred among membrane techniques.

In the context of the present invention, the passage of the aqueous solution of hydrogen peroxide prior to purification operation may be a combination of operations, that is to say including one or more purification techniques, including those aforementioned known to the skilled person.

The embodiments which will now be described relate in particular both the use of the composition of disinfection / sterilization at disinfection process according to the invention. These modes can be advantageously combined.

EMBODIMENTS DESCRIPTION OF THE INVENTION

The invention is now described in more detail and not limited to the following description.

For making an aqueous solution of hydrogen peroxide according to the invention can be put in the presence of hydrogen peroxide and stabilizer according to the invention by simple mixing. the stabilizer in the solid state may in particular be solubilized in an aqueous solution of hydrogen peroxide. The production of hydrogen peroxide is a well known technique of the art and is not the object of the present invention.

The present invention also relates to a method for producing an aqueous solution of hydrogen peroxide according to the present invention comprising a step a) mixture of:

- 20 to 98%, preferably 20 to 75%, preferably from 20% to 65%, preferably from 20 to 50% even more preferably from 22% to 38%, by weight of the solution of hydrogen peroxide and

- 0.5 to 7 mg / kg by weight of the solution, of a stabilizer as defined above.

Preferably, the mixing step allows solubilization of the stabilizer in the aqueous solution of hydrogen peroxide.

Preferably said method further comprises a step a ') prior to step a) of purifying said aqueous solution comprising hydrogen peroxide.

MEASURES AND METHODS USED PARAMETERS

Where reference is made to a standard method, the implementation of conditions described in this method, unless explicitly mentioned adaptation.

Title of hydrogen peroxide in the disinfecting composition is measured according to the CEFIC-H2O2-AM-7157 method known to those skilled in the art. This method involves titrating the hydrogen peroxide in an aqueous solution of sulfuric acid using a standard volumetric solution potassium permanganate.

The stability of the hydrogen peroxide is measured by the method CEFIC-H2O2-AM-6I 7I. This method consists in determining the percentage loss of hydrogen peroxide by measuring the content of hydrogen peroxide before and after heating at 96 ° C for 16 hours.

The dry residue content of evaporation of the disinfecting composition is measured at 1 10 ° C by the following gravimetric method:

1 to 1 capsule was placed in platinum capacity of about 300-350 ml (milliliter) in a muffle furnace at 900 ° C for one hour. Cooling the capsule in a desiccator and weighed on an analytical balance to the nearest 0.0001 g. This mass is denoted by Y (g).

2 - is weighed to 0.0001 g (gram) near a beaker of about 500 ml and notes its mass. Was added to this beaker approximately 300 g. Is reweighed the beaker to the nearest 0.0001 g. We denote by W1 (in grams) the difference between the mass of the beaker before and after the addition of the sample taken.

3 - is gradually transfers the sample into the evaporating dish made of platinum (immersed in cold water) by means of a peristaltic pump to obtain a feed rate of about 75 grams per hour. Once the transferred specimen and hydrogen peroxide completely decomposed, evaporated to dryness the sample in a water bath. Is repeated 2 and 3 twice operations to obtain a plurality of samples taken between 750 and 1000 g. This provides better accuracy on the determination of the dry residue.

4 - the plate is then placed capsule in an oven at 1 10 ° C for at least 1 hour.

5 - the capsule is cooled in a desiccator for 30 minutes and then weighed to the nearest 0.0001 g. It is noted that Z weight (in g).

6 - We calculate the dry residue content using the formula:

Residue sec to 1 10 ° C (g / kg) = 1000 x (ZY) / (W1 + W2 + W3)

in which

Z (g) represents the mass of the capsule containing the dry residue after evaporation,

Y (g) represents the mass of the empty capsule,

W1, W2 and W3 (g) represent the masses of successive sample taken.

EXAMPLES

The following examples illustrate the invention without limiting it. In particular, they mimic the behavior of aqueous solutions of hydrogen peroxide in implementation of conditions, namely those of an aseptic packaging machine for sterilizing packaging.

In all the examples presented below, it is considered that the amount of hydrogen peroxide in the aqueous solution is 35%. It should be noted that stability is tested here for the pure aqueous solution in the presence of a metal contamination in a low concentration (1 mg / liter of iron). For the latter test, it will be assumed that the maximum threshold value is set to 20% to be in accordance with the invention.

The results of quantities of dry residues include both those from the peroxide (that is to say essentially from its production) as well as those derived from or stabilizers, the latter being the only ones that the present invention intends to eliminate or reduce very significantly, from the aqueous solution (final) of hydrogen peroxide.

It uses the following starting materials:

example 1

The aqueous solution of Example 1 comprising 0.1 mg / kg of methylglycinediacetic acid (or its salt).

example 2

The aqueous solution of Example 2 includes 1, 1 mg / kg of methylglycinediacetic acid (or its salt).

example 3

The aqueous solution of Example 3 comprises 3.3 mg / kg of methylglycinediacetic acid (or its salt).

example 4

The aqueous solution of Example 4 comprises 1, 1 mg / kg of glutamate diacetic acid (or its salt).

Example 5 (comparative)

The aqueous solution of Example 5, is a hydrogen peroxide grade currently commercially (Valsterane ® 35S) available for the disinfection of food packaging by spraying applications, including 4mg / kg of phosphonic acid as stabilizer.

Example 6 (comparative)

The aqueous solution of Example 6 is another grade of hydrogen peroxide currently commercially (Valsterane ® 35SB) available for the disinfection of food packaging by spraying applications, including 16mg / kg of a phosphonic acid as stabilizer.

Example 7 (comparative)

The aqueous solution of Example 7 comprises 1, 1 mg / kg cyclohexanediaminotetraacétique acid (or its salt).

Example 8 (comparative)

The aqueous solution of Example 8 comprises 1, 1 mg / kg diplicolinique acid (or its salt).

Example 9 (comparative)

The aqueous solution of Example 9 includes 1, 1 mg / kg of diethylenetriaminepentaacetic acid (or its salt).

Example 10 (according to the invention, the most preferred range)

The aqueous solution of Example 10 contains 2.3 mg / kg of methylglycinediacetic acid (or its salt).

Example 1 1 (according to the invention, preferred domain)

The aqueous solution of Example 1 1 comprises 4 mg / kg of methylglycinediacetic acid (or its salt).

Example 12 (according to the invention)

The aqueous solution of Example 6 includes 12 mg / kg of methylglycinediacetic acid (or its salt).

The results are shown in the table below:

* expressed in% as loss on H 2 O 2

It is found that only the compositions according to the invention, especially the compositions 2 to 4, exhibit excellent stability over time (with or without infection) and an extremely small amount of dry residue.

CLAIMS

1. aqueous solution of hydrogen peroxide, comprising:

- from 20 to 98% by weight of the solution, hydrogen peroxide, and

- from 0.5 to 7 mg / kg, even more preferably 1, 5 to 5 mg / kg by weight of the solution, of a stabilizer,

characterized in that the stabilizer is selected from the family of aminopolycarboxylic acids (APCA) or salts thereof, substituted or unsubstituted generic formula:

wherein R and R 'are selected from the following functional groups:

- C 1 -C 3 alkyls, preferably a methyl group,

- carboxylic acids C1-C3.

2. Aqueous solution according to claim 1, characterized in that it comprises from 20 to 75%, preferably from 20% to 65%, preferably from 20 to 50%, more preferably from 22% to 38% by weight of the solution of hydrogen peroxide.

3. Aqueous solution according to claim 1 or 2, characterized in that R or R 'is a methyl group and the other R or R' consists of methanoic acid group or its salt, substituted or not, so the stabilizer consists of methylglycinediacetic acid or its salt.

4. Aqueous solution according to claim 1 or 2, characterized in that R or R 'consists of an ethanoic acid group or its salt, substituted or unsubstituted, and the other R or R' consists of a propionic acid group or its salt, substituted or not, so that the stabilizer consists of glutamate diacetic acid or its salt.

5. An aqueous solution according to any one of the preceding claims, characterized in that it has conductivity from 10 to 100 S / cm, preferably from 15 to 50 S / cm, and even more preferably 20 to 40 pS / cm.

6. An aqueous solution according to any one of the preceding claims, characterized in that it presents a maximum acidity of 1 mmol / kg.

7. Aqueous solution according to any one of the preceding claims, characterized in that it has a dry residue content of 1 10 ° C of at most 7 mg / kg, preferably less than 6 mg / kg, preferably less than 5 mg / kg, preferably less than 4 mg / kg, preferably less than 3 mg / kg and more preferably less than 2 mg / kg.

8. Aqueous solution according to any one of the preceding claims, characterized in that the loss of titer of said solution, measured by the method CEFIC-H2O2-AM-7I 6I is less than or equal to 5%, preferably less than or equal to 3%, and most preferably less than or equal to 2% relative to the initial concentration of hydrogen peroxide.

9. An aqueous solution according to any one of the preceding claims, characterized in that the stabilizer is 0.1 to 5 mg / kg, by weight of the solution, preferably from 1 to 2.5 mg / kg by weight of the solution.

10. An aqueous solution according to any one of the preceding claims, comprising:

- from 20% to 50% hydrogen peroxide by weight of the solution, and

- from 0.3 to 3 mg / kg, preferably 0.5 to 7 mg / kg by weight of the solution, of a stabilizer,

- optionally, from 1 .10 "4 % to 1 .10 " 2 % by weight of the solution, of additive (s),

- the balance to 100% water.

January 1. Use of the aqueous solution as defined according to any one of the preceding claims for disinfection / sterilization of a product, in particular a packaging.

12. Use according to the preceding claim, wherein the disinfectant / sterilizing said product is carried out by spraying or spraying said solution onto said product.

13. A method for disinfection / sterilization of a product, in particular a packing, characterized in that said product is contacted with the aqueous solution according to any one of claims 1 to 10.

14. The method of claim 13, wherein the contacting is carried out by spraying or spraying said solution onto said product.