WO2004108171A1

WO2004108171A1 - Disinfecting, aqueous and ready-to-use composition of a stabilized complex of peracetic acid, hydrogen peroxide, peroxyacids and acetic acid

Info

Publication number: WO2004108171A1
Application number: PCT/FR2004/001393
Authority: WO
Inventors: Marcel Halberstam
Original assignee: Klaver Trend, S.A.R.L.
Priority date: 2003-06-04
Filing date: 2004-06-04
Publication date: 2004-12-16
Also published as: FR2855759B1; FR2855759A1; EP1638618A1

Abstract

Disinfecting aqueous composition based on a complex of peracetic acid, hydrogen peroxide, peroxyacids and acetic acid, comprising less than 0.15 % in volume of peracetic acid as well as a stabilizer formed by a mixture of non-oxidized essential oils and triacids ; the water in the composition is ultra-pure water of less than 2 microsiemens (Ms) and having a resistivity of more than 108 O/m. The invention finds application in the disinfection particularly of breakable medical devices in neurology or ophthalmology (fiber optics, 3-mirror or quadraspherical glasses) or in contactology (contact lenses).

Description

Disinfecting, aqueous and ready-to-use composition of a stabilized complex of peracetic acid, hydrogen peroxide. peroxyacids and acetic acid

The present invention relates to a stabilized, ready-to-use, disinfectant aqueous composition based on low concentration peracetic acid, peroxyacids, hydrogen peroxide and acetic acid, as well as to a process for its manufacture.

Peracetic acid has the general formula: CH ₃ -CO ₃ H. It is known to be explosive and to have an unpleasant odor. There are already known disinfectant compositions based on peracetic acid, such as those described for example in documents EP-797,387-A, FR-2,823,978-A and FR-2,829,394-A. These compositions of the prior art include peracetic acid (in high concentrations - greater than 1500 ppm), hydrogen peroxide or hydrogen peroxide and acetic acid. Thus, according to document FR-2,823,978-A, a composition of the above kind is known to which benzotriazole is added as a stabilizer but which is also an irritant.

Document FR-2.829.394-A relates to a process for the preparation of an aqueous disinfecting composition comprising mixing an aqueous solution of the above kind with an aqueous solution containing at least two corrosion inhibitors, at least one of which of the two is a phosphate compound to give a composition which is then diluted in water. The final composition is used to disinfect medical devices.

In document EP-797.387-A, reference is made to previous documents relating to compositions of hydrogen peroxide, acetic acid and peracetic acid, in particular for disinfecting hemodialysis equipment: it is mentioned that such a composition is capable of being diluted in water. It is therefore not a ready-to-use stabilized solution because it requires extemporaneous dilution. The high concentrations of active ingredients are the cause of alterations (functions and transparency) of fragile polymers. These disinfectant compositions of the prior art, which are aggressive and irritating, cannot therefore be used on biomaterials and fragile polymers, such as those used in ophthalmology or contactology. More generally, the known compositions based on peracetic acid, hydrogen peroxide and acetic acid do not contain other peroxyacids and are in fact of two types: compositions to be prepared or activated extemporaneously during their use and ready-to-use compositions.

The former are themselves subdivided into two groups. The first group comprises compositions comprising two compounds: the first based on peracetic acid and the second consisting of an activator, the mixture of the two leading to a disinfectant composition for immediate use. The second group comprises compositions based on peracetic acid in the form of a powder: the addition of water gives the disinfectant composition to be used immediately.

The second include ready-to-use compositions based on peracetic acid, with an "open cap" storage period of at least 8 days.

The present invention is to be classified in this last group of stabilized disinfectant products based on peracetic acid.

Some authors have also tried to stabilize this set using aldehydes, formaldehyde or glutaraldehyde: these materials being volatile, there is a risk of the formation of dangerous and toxic vapors for personnel and the environment. It will be recalled that the disinfectant formulas based on peracetic acid are not only unstable over time (more than hydrogen peroxide), but that in addition they give off a very strong odor of vinegar (acetic acid) which can be inconvenient. users, or give off odorless vapors of hydrogen peroxide potentially toxic to the manipulator (risk of irritation or acute or chronic respiratory pathologies for the manipulator if the H ₂ O ₂ vapors are greater than 1 ppm - exposure limit value ). Compared to that of hydrogen peroxide, the vapors of peracetic acid are very volatile and have a flash point of 56 ° C. They can be corrosive and toxic. One of the aims of the present invention is therefore to provide a disinfectant, aqueous and ready-to-use composition based on a complex of peracetic acid, peroxyacids, hydrogen peroxide and acetic acid. which overcomes the drawbacks recalled above. Another object of the invention is to provide such a composition which is stable over time. The more stable the product in liquid form, the less toxic vapors of peroxides will appear.

These aims, as well as others which will appear subsequently, are achieved by an aqueous disinfectant composition based on a complex of peracetic acid, peroxyacids, hydrogen peroxide and acetic acid, which composition is characterized , according to the present invention, in that it comprises less than 0.15% by volume of peracetic acid in the final composition as well as a stabilizing agent which is a mixture of non-oxidized essential oils and triacids and that the water of said composition is ultra-pure water of less than 2 Ms and of resistivity greater than

10 ⁸ Ω / m.

Preferably, the concentration of peracetic acid is between 0.008 and 0.08% by volume.

The triacids are preferably chosen from phosphoric, tartaric and citric acids, 8-hydroxyquinoline and tridodecylamyne.

Advantageously, this composition comprises from 2 to 6% by volume of hydrogen peroxide.

Preferably, this composition comprises from 0.1 to 1% by volume of essential oil.

Advantageously, this composition comprises at most 2% by volume of the stabilizing agent.

According to the present invention, an aqueous disinfectant composition based on a complex of peracetic acid, peroxyacids, acetic acid and hydrogen peroxide is stabilized as will be described below.

There are two types of hydrogen peroxide or hydrogen peroxide of general formula H ₂ 0 ₂ : hydrogen peroxide A, the characteristics of which are summarized in Table I below and peroxide of hydrogen B, the characteristics of which are summarized in table II below.

TABLE I HYDROGEN PEROXIDE TYPE A MANDATORY RESIDUE FILTRATION AT 0.2 μ

TABLE II HYDROGEN PEROXIDE TYPE B Ultra-pure type and WITHOUT FILTRATION AT 0.2 μ

We. uses a mixture of these two types of hydrogen peroxide in an A / B ratio of between Y * and% by volume.

Acetic acid is more than 90% pure acid, as is peracetic acid.

The essential oil present in the final composition has the function of masking the pungent odor generated by the presence of acetic and peracetic acids and of improving the stabilization of the final formulation: of course, such an essential oil must not oxidize with the mixture hydrogen peroxide - acetic acid. As essential oil, mention will be made of lemongrass, those obtained from rose, mint or thyme, for example, as well as mixtures of shovels.

The water used is ultra-pure water less than 2 microsiemens (Ms) and having a resistivity greater than 10 ⁸ Ω / m.

The stabilizing agent is itself a mixture comprising in particular:

- triacids such as for example: phosphoric, tartaric, citric acids, or traces of tridodecylamyne, - trace elements such as for example copper or iron

- essential oils.

This stabilizing agent is also regulator of the pH of the composition: it thus makes it possible to avoid a chain reaction between the hydrogen peroxide and the acetic and peracetic acids. The stability thus obtained ensures that the essential oil remains present in the composition without oxidizing.

One of the functions of the stabilizing agent is to sequester the heavy metals responsible for accelerating the decomposition of peroxides.

The pH of the composition according to the present invention remains between 4 and 6: the best stability is obtained at a pH as close to 5 as possible.

The compositions according to the present invention therefore have as general formulation:

Hydrogen peroxide A 3% - 5% Hydrogen peroxide B 0.005% - 0.001%

Acetic acid <1.5%

Peracetic acid <0.1%

Peroxyacids <0.5%

Stabilizing agent: Essential oils 0.1% - 1%

Triacids 0.000001% - 0.05%

Metallic trace elements <0.003% Water qs 100% As can be noted, this formulation does not include an organic solvent such as alcohols or toxic glycol derivatives. Essential oils are not oxidized.

The triacids are chosen from phosphoric, tartaric and citric acids, 8-hydroxyquinoline and tndodecylamyne. The metallic trace elements are for example copper and iron.

This composition was subjected to various tests, the results of which are collated in Tables III to VIII below:

TABLE III EUROPEAN STANDARD 1040 in 5 minutes NF EN 1040

MINIMUM REDUCTION 5 Log

TABLE IV

AFNOR NF T 72171 SPECTRUM 4 in the PRESENCE OF INTERFERING SUBSTANCES

MINIMUM REDUCTION 5 Log ^'

TABLE V

EUROPEAN STANDARD NF EN 1275

MINIMUM REDUCTION 4 Log

TABLE VI

AFNOR NF T 72180 STANDARD

MINIMUM REDUCTION 4 Log IN 15 minutes

TABLE VII

AFNOR NF T 72180 STANDARD

MINIMUM REDUCTION 4 Log

TABLE VIII

AFNOR NF T 72231 STANDARD

MINIMUM REDUCTION 5 Log

From these tests, it appears that the composition according to the present invention manifests activity on bacteria, spores, viruses, fungi and this in a very short contact time. Likewise, this composition is active against biofilms, films of 10 to 20 micrometers in thickness maximum produced by the microorganisms themselves, and in particular by those Gram negative. The composition according to the present invention is therefore a disinfectant of oxidizing type, comprising neither activator, nor aldehyde, nor formaldehyde, nor glycol derivatives, nor alcohols, nor of stabilizing agents of triazole type, which also have properties irritating. Such a composition meets the requirements of Ministerial Circular No. 38 of March 2001 on the management of prion risk (mad cow disease / Creuzfeld Jakob disease).

In addition, such a composition has a shelf life "open stopper" greater than 2 years: in fact at least 3 years. This has a great advantage, because in ophthalmology, and more particularly in contactology, only small quantities, generally less than 200 ml, are used each time. As can be noted, such a composition does not in fact comprise any product capable of attacking the plastic materials and fragile polymers used in ophthalmology and in contactology

As indicated above, the present invention also relates to a process for preparing such a composition which comprises the following steps ^• (per 1000 I of composition):

1) A solution of H ₂ 0 is prepared from hydrogen peroxide of type A about 4%;

2) A solution of H ₂ O ₂ is prepared from hydrogen peroxide of type B about 5%; 3) a CH ₃ COOH solution is prepared from a pure acetic acid mixed with ultra-pure water of less than 2 ms; 4 °) A very pure oil is added which must not oxidize;

5 °) Is added to the tank of the H ₂ O _{2 solution} from hydrogen peroxide type A, copper and iron in the proportions of the above formulation; 6 °) The amount of 8-hydroxyquinoline is added; 7 °) We check the precipitation of iron and copper; 8 °) 8 liters of hydrogen peroxide are added to the first tank

B; 9 °) The hydrogen peroxide content is checked between 4 and 5% with a pH between 4 and 6.5; 10 °) 10 liters of acetic acid between 15 and 20% are added; 11 °) One checks the rate of peracetic acid which must be lower than 0.15%;

12 °) essential oil is added again in order to reduce the odors and vapors of acetic acid and of H ₂ Q ₂ and to improve the stability; 13 °) It is checked that the vapors of hydrogen peroxide at temperatures lower and higher than 24 ° C are below 1 ppm; 14 °) Ultra pure water is added as defined above; 15 °) An ammonium, without ethylene glycol, about 0.001% to 1% is added in order to make the solution more bactericidal and virucidal, if necessary according to the indications; 16 °) We will check again after 48 hours the peracetic acid level.

This process is carried out at room temperature.

The composition thus obtained has, on the one hand, an acidic pH as indicated above, and, on the other hand, great stability although the concentration of peracetic acid is low since between 80 and 800 ppm. This composition is used to disinfect medical devices and fragile materials such as those used in ophthalmology, ophthalmic surgery, contactology or any specialty which uses biomaterials and fragile polymers whose functionality or transparency may be impaired by disinfection products. and especially Oxidant disinfectants.

Claims

R E V E N D I C A T I O N S

1 - Disinfecting, aqueous and ready-to-use composition, based on a complex of peracetic acid, hydrogen peroxide, peroxyacids and acetic acid, characterized in that it comprises less than 0.15% by volume of pure peracetic acid in the final solution, as well as a stabilizing agent which is a mixture of non-oxidized essential oils and triacids and that the water of said composition is ultra-water pure less than 2 Ms and resistivity greater than 10 ⁸ / m.

2 - Composition according to claim 1, characterized in that it comprises from 0.0080% to 0.08% by volume of pure peracetic acid in the final solution.

3 - Composition according to claim 1, characterized in that it comprises from 2 to 6% by volume of hydrogen peroxide.

4 - Composition according to claim 1, characterized in that it comprises from 0.1 to 1% by volume of essential oil.

5 - Composition according to claim 1, characterized in that it comprises at most 2% by volume of stabilizing agents.

6 - Composition according to claim 1, characterized in that the triacids are chosen from phosphoric, tartaric and citric acids, 8-hydroxyquinoline and tridodecylamyne

7 - Composition according to claim 1, characterized in that it has a bactericidal, virucidal, fungicidal and sporicidal disinfectant activity and makes it possible to have at least partial disinfectant activity on the prion (group II disinfectant / circular No. 138 -2001) because its composition responds to French circular n ° 138 of March 14, 2001 on prion risk management.

8 - Composition according to claim 1, characterized in that it is compatible with biomaterials and fragile polymers (example polymethyl methacrylate) thus allowing disinfection of delicate medical devices such as those for ophthalmology (3 mirror glasses) or contactology (contact lenses)

9 - Composition according to claim 1, characterized in that it makes it possible to guarantee the transparency of fragile optical materials and sensitive to aggressive solvents, after more than 100 disinfections in ophthalmology (3-mirror glasses) and more than 30 disinfections ^ n contactology (contact lenses).

10 - Composition according to claim 1, characterized in that the complex of stabilizing agents is also regulator of the pH of the composition (acid pH between 3 and 6.5).