Drug – bio-affecting and body treating compositions – Preparations characterized by special physical form – Biocides; animal or insect repellents or attractants
Reexamination Certificate
2001-10-23
2003-12-09
Page, Thurman K. (Department: 1615)
Drug, bio-affecting and body treating compositions
Preparations characterized by special physical form
Biocides; animal or insect repellents or attractants
C424S401000, C424S601000, C424S604000, C424S605000, C424S616000, C424S617000, C424S618000
Reexamination Certificate
active
06660289
ABSTRACT:
FIELD OF THE INVENTION
The present invention concerns, as a novel industrial product, an aqueous composition, in particular in gel form, based on H
2
O
2
, acids and Ag
II
, Ag
III
, V
V
, Nb
V
, Ta
V
, Mo
VI
, W
VI
, Co
III
, In
III
or Tl
III
ions. The invention also relates to a preparation process, in particular when said ions are Ag
2+
, and to the use of this composition in the field of disinfection, hygiene and/or decontamination, on the one hand, and in the field of surface treatment (in particular cleaning, stripping and/or passivation), on the other hand.
PRIOR ART
The closest prior art consists of patent document WO-A-96/18301. Before the publication of this document, aqueous disinfecting compositions, some containing hydrogen peroxide and a carboxylic acid/carboxylic peracid mixture of the type RCO
2
H/RCO
3
H (in which R is essentially CH
3
or CH
3
CH
2
) (see in particular to this end EP-A-0 370 850, EP-A-0 193 416, EP-B-0 087 343, FR-A-2 321 301 and FR-A-2 321 302), and others containing hydrogen peroxide and Ag
+
ions (see in particular to this end U.S. Pat. No. 3,035,698 and GB-A-2 189 394), had already been proposed in the past, said aqueous disinfecting compositions being stabilized in each case with a strong acid (essentially H
3
PO
4
).
These prior aqueous disinfecting compositions, namely (i) those of the type H
2
O
2
+RCO
2
H/RCO
3
H+H
3
PO
4
and (ii) those of the type H
2
O
2
+Ag
+
+H
3
PO
4
, are insufficient as regards their absence of efficacy on several strains of bacteria and molds, and in particular on the strains of
Penicillium verrucosum.
A more recent and markedly more effective technique (in particular with regard to said strains of
Penicillium verrucosum
which were resistant to the two abovementioned types of aqueous disinfecting compositions) was described in the abovementioned WO-A-96/18301, which is incorporated herein by way of reference. According to WO-A-96/18301, the recommended technique uses an aqueous disinfecting, hygiene and decontaminating composition, which comprises, in water:
(A) H
2
O
2
,
(B) an RCO
2
H/RCO
3
H mixture (in which R is CH
3
or CH
3
CH
2
),
(C) a silver component as a source of Ag
+
ions, and
(D) a stabilizer (mainly H
3
PO
4
),
Table IX of WO-A-96/18301 demonstrating the synergy of the aqueous composition containing the components A+B+C+D, compared with the aqueous compositions containing the components A+B+D and A+C+D.
It is found that the aqueous solution of A+B+C+D according to WO-A-96/18301 does not act quickly enough with regard to inhibiting or, better still, destroying microorganisms, such as bacteria, molds, viruses and microscopic algae, in particular by making their wall brittle, especially by degrading their biofilm, by perforating their wall or by preventing them from penetrating into the cells of the body or by protecting said cells against their toxins.
Moreover, the procedures described in GB-A-2 189 394 as regards the preparation of the concentrated aqueous silver solution (i.e. component C above) in the presence of H
3
PO
4
, on the one hand, and that of the resulting stabilized concentrated aqueous solution of silver and of hydrogen peroxide (i.e. the aqueous solution containing A+C+D), on the other hand, do not lead to the production of Ag
2+
ions or to that of Ag
3+
ions.
Specifically, GB-A-2 189 394, which recommends a process comprising:
mixing a strong mineral acid (pH<1.6) with a silver component (a silver salt or a silver complex), at a temperature of 50-60° C., the strong mineral acid/silver component molar ratio being greater than or equal to 1/1;
cooling the resulting mixture to a temperature of 25-30° C. and adding a stabilizing organic acid optionally with gelatin; and
incorporating H
2
O
2
into the resulting mixture,
cites (see page 1, lines 46-50) silver (I) compounds which give Ag
+
ions in strong acid medium, these compounds are silver (I) salts and a silver (I) complex salt, namely AgNaCl
2
, on the one hand, and silver (II) and (III) compounds which are soluble only in basic medium, these compounds are silver (II) and (III) oxides which, in strong acid medium, mainly give metallic silver in fine, on the other hand.
More specifically, the silver (I), (II) and (III) oxides give rise, in acid medium, to the following reactions, in which s denotes a solid product:
Ag
2
O(
s
)+2H
+
+2
e
→2Ag(
s
)+H
2
O (1)
2AgO(
s
)+2H
+
+2
e
→Ag
2
O(
s
)+H
2
O (2)
Ag
2
O
3
(
s
)+2H
+
+2
e
→2AgO(
s
)+H
2
O (3)
Since the direct placing in contact (i.e. without a strong acid stabilizer) of H
2
O
2
and of a silver component is liable to cause an explosion, a process different from that recommended by GB-A-2 189 394 should be used to obtain the Ag
2+
ions that are useful according to the present invention.
For the same reasons, the procedures described in WO-A-96/18301 do not allow the oxidation in acid medium of silver (I) to silver (II) according to the reaction:
Ag
+
→Ag
2+
+e.
It is known that, according to U.S. Pat. Nos. 5,017,295 and 5,078,902, Ag
2+
ions have been presented as being more active as bactericidal agents than Ag
+
ions. Now, it is found that the procedures given in these two documents do not promote the production of Ag
2+
or Ag
2+
+Ag
3+
ions since, with regard to reaction (2) above, the silver (II) oxide gives in acid medium a precipitate of silver (I) oxide. Thus, the reactions outlined in Example 1 of U.S. Pat. No. 5,017,295 and in Examples 1 and 2 of U.S. Pat. No. 5,078,902, namely:
3AgO+2H
3
PO
4
→Ag
3
(PO
4
)
2
+3H
2
O,
AgO+2HNO
3
→Ag(NO
3
)
2
+H
2
O,
and
AgO+2HCl→AgCl
2
+H
2
O,
cannot take place. Furthermore, by reproducing the other method for obtaining Ag
2+
ions indicated in Example 2 of U.S. Pat. No. 5,078,902, which comprises the dissolution of AgO in alkaline medium, followed by the addition of an oxidizing source [i.e. oxone (Na
2
O
2
)] which can give hydrogen peroxide [this addition is carried out in alkaline medium (i.e. under conditions in which H
2
O
2
intervenes as the reducing agent)], the resulting concentration of Ag
2+
ions is very low, such that the redox potential of the aqueous solution containing Ag
+
and Ag
2+
is always less than 650 mV (at 298 K). Thus, according to U.S. Pat. Nos. 5,017,295 and 5,078,902, the beneficial effects as stated for the Ag
2+
ions cannot be manifested.
Finally, U.S. Pat. No. 3,702,298 proposes the use of Ag
3+
ions as a germicidal means. However, the mixture Ag
+
+Ag
2+
+Ag
3+
effectively obtained has a redox potential ranging from 0.15 mV to 0.4 mV, which is markedly lower than that desired according to the present invention which is greater than 1000 mV.
It is also known that molybdenum intervenes in human beings and warm-blooded animals as a coenzyme for the detoxifying enzymes located in the liver, such as xanthine oxidase, aldehyde oxidase and sulfite oxidase. Mo is essential for converting purine bases into uric acid, and it promotes the intestinal absorption of iron and the retention of fluorine in the body.
It is also known from U.S. Pat. No. 4,995,987 that molybdate and tungstate ions have been proposed, as agents for inhibiting the growth of sulfate-reducing bacteria, in combination with antimicrobial agents. Document U.S. Pat. No. 4,995,987 neither describes nor suggests the subject of the present invention.
In the field of treating metal surfaces, in particular to strip and/or passivate them, it is known that the conventional oxidizing means, such as chromic acid, chromates and nitric acid, are considered as being products that are harmful to the environment.
U.S. Pat. No. 4,537,778 moreover discloses an aqueous mouthwash or oral rinse composition which comprises 0.5-5% by weight of H
2
O
2
,
Irurzun Jean-Pierre
Lebeau Bernard
Marechal Françoise
Wilmotte Rémi
Di Nola-Baron Liliana
Digol International LTD
Ostrolenk Faber Gerb & Soffen, LLP
Page Thurman K.
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