Aqueous composition containing H2O2, acids and Ag,...

Drug – bio-affecting and body treating compositions – Inorganic active ingredient containing – Peroxide or compositions of or releasing gaseous oxygen or...

Reexamination Certificate

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C424S601000, C424S604000, C424S613000, C424S614000, C424S615000, C424S618000, C424S619000, C514S495000, C514S557000, C514S970000, C422S028000, C422S029000, C422S037000, C426S532000, C210S749000, C210S759000, C210S764000

Reexamination Certificate

active

06277414

ABSTRACT:

This application is a 371 of PCT/FR95/01690, filed on Dec. 18, 1995.
FIELD OF THE INVENTION
The present invention relates to an aqueous disinfecting and cleaning composition based on H
2
O
2
, acids and Ag, as a novel industrial product.
It further relates to the method of preparation and to the use of this composition on the one hand in the field of disinfection and/or hygiene, especially for disinfecting or sterilizing hospital and industrial premises, surfaces of various materials, storage containers, pipelines, harvests, foodstuffs and drinking water, and on the other hand in the field of pollution control, especially for controlling pollution in the mining industries (in particular in the prevention of acid mine drainage and the destruction of cyanides in the soil).
PRIOR ART
In the field of disinfection, several technical solutions are known which utilize H
2
O
2
: some involve an aqueous composition containing H
2
O
2
, a percarboxylic acid (RCO
3
H, where R is a C
1
-C
2
-alkyl group) and the corresponding carboxylic acid (RCO
2
H), and others involve an aqueous composition containing H
2
O
2
and silver in the form of a salt or complex.
Thus EP-A-0 370 850 has disclosed an aqueous composition comprising H
2
O
2
(6-8% by weight, based on the total weight of said composition), CH
3
CO
3
H (0.1 to 1% by weight) and CH
3
CO
2
H (2 to 10% by weight) as a hygiene agent for the disinfection of hemodialysis equipment; this composition can be diluted with water before use.
EP-A-0 193 416 has disclosed an aqueous composition comprising H
2
O
2
(1 to 8% by weight), CH
3
CO
3
H (0.005 to 0.1% by weight) and CH
3
CO
2
H in the amount necessary to attain the equilibrium of the system according to the following equation:
H
2
O
2
+CH
3
CO
2
H←→CH
3
CO
3
H+H
2
O  (1a)
said composition being used for rendering contact lenses aseptic.
In its only Example, EP-B-0 087 343 (see top of column 6) has disclosed an aqueous composition comprising H
2
O
2
(19.9% by weight), CH
3
CO
3
H (2% by weight), CH
3
CO
2
H (6.1% by weight), HNO
3
(8.0% by weight) as a preservative, hydroxyethanediphosphonic acid (0.3% by weight) as a stabilizer and/or corrosion inhibitor, and H
2
O (63.7% by weight), this composition being presented as a disinfecting product which is less corrosive towards metals (especially steel) than Javelle water, on the one hand, and the acid CH
3
CO
3
H, on the other.
FR-A-2 321 302 has disclosed an aqueous composition comprising H
2
O
2
(25-40% by weight), RCO
3
H [and/or RCO
2
H] (0.5-20% by weight), phosphonic acid (0.25-10% by weight) and H
2
O (to make up to 100% by weight) as a microbicidal product, the molar ratio H
2
O
2
/RCO
3
H being greater than or equal to 2/1 and preferably between 3/1 and 50/1. The phosphonic acid component present in the aqueous composition according to FR-A-2 321 302 is a hydroxyalkylpolyphosphonic acid, aminoalkylpolyphosphonic acid or polyaminoalkylenepolyphosphonic acid compound or an Na, K, ammonium or &ohgr;-hydroxyalkylammonium salt, this phosphonic acid component acting principally as a corrosion inhibitor.
It is known that a percarboxylic acid is prepared according to equation (1):
H
2
O
2
+RCO
2
H←→RCO
3
H+H
2
O  (1)
and that, to stabilize concentrated aqueous solutions of RCO
3
H, it is recommended, especially by FR-A-2 309 531, FR-A-2 321 301 and EP-A-0 024 219, to incorporate H
2
O
2
into said compositions. In practice, in the case of an acid compound RCO
3
H in aqueous solution, an aqueous composition is ultimately obtained which comprises a mixture of H
2
O
2
, RCO
3
H and RCO
2
H according to equilibrium equation (1) given above.
U.S. Pat. No. 3,035,698, on the other hand, has disclosed an aqueous composition comprising H
2
O
2
and Ag
+
ions as a disinfecting product. However, when the hydrogen peroxide in an aqueous mixture of H
2
O
2
+Ag
+
is concentrated, there is a considerable risk of explosion. To limit this risk, FR-A-2 597 347 envisages a preparative technique which utilizes a strong mineral acid (especially phosphoric acid, nitric acid, hydrobromic acid, hydrochloric acid, sulfuric acid or boric acid) and a stabilizing organic acid (especially tartaric acid, citric acid, maleic acid, malonic acid, 6-acetamidohexanoic acid, hippuric acid or acetoxybenzoic acid).
More precisely, according to FR-A-2 597 347, the method of preparing an aqueous concentrate containing H
2
O
2
+Ag
+
comprises the following steps:
mixing a strong mineral acid (pH<1.6) with a silver salt or a silver complex at a temperature of 50-60° C., the molar ratio strong mineral acid/silver component being greater than or equal to 1;
cooling the resulting mixture to a temperature of 25-30° C. and adding a stabilizing organic acid, optionally together with gelatin; and
incorporating H
2
O
2
into the resulting mixture.
The technical solutions of the prior art, which involve an aqueous composition comprising a mixture of H
2
O
2
+RCO
3
H+RCO
2
H or a mixture of H
2
O
2
+Ag
+
, are found to have an inadequate disinfecting effect (bactericidal, fungicidal, virucidal, algicidal or parasiticidal effect). The following has been observed in particular:
(&agr;) When aqueous compositions corresponding to said technical solutions of the prior art are sprayed into enclosed spaces containing harmful or undesirable strains, the difference between the decimal logarithm of the concentration of said strains at time T=0 and the decimal logarithm of the concentration of the same strains at time T=2 h is not always greater than or equal to 3 for molds or greater than or equal to 4 for bacteria.
In other words, if [S]
T=0
is the concentration (number of germs per ml) of a given strain at time T=0 and [S]
T=2h
is that of the same strain at time T=2 h after exposure to a sprayed aqueous composition for 2 h, the technical solutions of the prior art produce a result (&Dgr;R) given by the relationship
&Dgr;R=log
10
([S]
T=0
)−log
10
([S]
T=2h
)  (2)
which is such that, very often,
&Dgr;R≦3 for molds, and
&Dgr;R≦4 for bacteria.
(&bgr;) There are strains, especially strains of
Penicillium verrucosus
, which resist the aqueous compositions of the technical solutions of the prior art comprising a mixture of H
2
O
2
+RCO
3
H (especially CH
3
CO
3
H)+RCO
2
H (especially CH
3
CO
2
H) or a mixture of H
2
O
2
+Ag
+
.
As far as pollution control is concerned, it should be pointed out that the mining industry has to deal with two major environmental problems: (i) leaching (solubilization) of the metals contained in the soils, due to acid drainage and common to all types of mine, and (ii) contamination of the soils by the cyanides originating particularly from the technique of gold extraction in gold mines and gold works.
Numerous minerals and metals present in mine soils, such as arsenic, selenium and aluminum, can be solubilized and can end up in the subterranean waters and the environment due to acid drainage. The acid drainage of rocks is the result of natural oxidation of the sulfur-bearing ores following their exposure to air and water. These oxidation reactions are often accelerated by certain microorganisms. The chemical and biological reactions cause a lowering of the pH of the water, which then has the property of mobilizing any heavy metal which may be present in the rock residues. If sufficient water is available, it will act as a vehicle and the resulting drainage may contain the products of the acid generation process, typically appreciable amounts of Al, Ca, Si, Mg, Na, K, Fe, other metals and sulfates. This phenomenon causes a negative impact on the quality of the water infiltrating into the environment. By way of example, as sulfur-bearing ores are present throughout the Canadian Shield and in coal mines, the leaching of metals is a very widespread problem in the Canadian mining industries.
Acid generation is the

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