Antimicrobial phosphonium and sulfonium polyhalide compositions

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Phosphorus containing other than solely as part of an...

Reexamination Certificate

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C514S079000, C514S095000, C514S099000, C514S114000, C514S120000, C514S125000, C514S126000, C514S129000, C514S134000, C514S139000, C514S372000, C514S557000, C514S558000, C514S574000, C514S714000, C424S402000, C424S405000, C424S443000, C424S600000, C424S613000, C424S614000, C424S615000, C424S616000, C424S660000, C424S661000, C424S662000, C424S663000, C424S664000, C424S665000, C424S667000, C424S668000, C424S669000, C424S712000, C424S718000, C424S723000, C422S004000, C422S005000, C422S028000, C422S029000, C422S

Reexamination Certificate

active

06506737

ABSTRACT:

FIELD OF THE INVENTION
The invention relates to antimicrobial compositions containing an oxidizing species. The materials are made by reacting cooperating ingredients at controlled proportions to form an antimicrobial that can have a variety of end uses. The antimicrobial species of the invention is generated in situ and is stable for limited periods, typically less than a few days.
BACKGROUND OF THE INVENTION
Peroxygen sanitizers and halogen sanitizers are known. Peroxygen sanitizers include compounds such as hydrogen peroxide, percarboxylic acids, percarbonates, perborates, etc. These materials are relatively well characterized and understood and are commonly used in a variety of end uses. Halogen sanitizers include compounds such as hypochlorite (HOCl), chlorine dioxide (ClO
2
), perchlorate (HClO
4
), perbromate (HBrO
4
), and others. Halide and quaternary ammonium base sanitizers are also known. These materials are generally not considered oxidizing materials but provide sanitizing properties to materials.
One type of halogen based sanitizers are those that can contain species such as I
3
−1
, IBrCl
−1
, and other similar species. Representative examples of such materials include Rembaum et al., U.S. Pat. No. 3,898,336; Rembaum et al., U.S. Pat. No. 3,778,476; Hollis et al., U.S. Pat. No. 4,960,590; Hollis et al., U.S. Pat. No. 5,093,078 and Dammann, European Patent Application No. 156646. These references describe isolated polymeric quaternary ammonium polyhalides based on synthetic polymeric ionene (known in the industry as polymeric quats), epi-amine, and cationic acrylamide polymer resins (containing 2 or more cationic groups) precipitated with polyhalogens. Similarly, Corby, U.S. Pat. No. 4,822,513; Corby, U.S. Pat. No. 5,047,164; and Corby, U.S. Pat. No. 5,202,047 describe mixed interhalogen salts limited to 4 halogens with a maximum of one iodine or bromine atom per complex.
Asensio, EP 0 799 570 A1 discloses a five component antimicrobial mix containing two quaternary tri-iodides (prepared via conventional molecular halogen addition, not by in-situ reaction). LaZonby, et al., U.S. Pat. No. 5,658,467 describes the use of peracetic acid in combination with a non-oxidizing biocide for industrial process waters.
None of the aforementioned references teach the use of in-situ, labile antimicrobial compositions generated via halide salts and oxidants; especially peroxygen oxidants. All of these examples deal with stable, isolated antimicrobials that would remain in the application environment (e.g., food surface) indefinitely. In-situ, labile antimicrobial compositions utilizing quaternary or protonizable nitro en compounds complexed with polyhalides are described in U.S. Ser. No. 09/277,592 filed on Mar. 26, 1999, now U.S. Pat. No. 6,436,445 and Ser. No. 09/277,626 filed on Mar. 26, 1999 now abandoned.
Other compounds have been described in the art as having antimicrobial efficacy, including some compounds having phosphonium or sulfonium functionality. For example, non-soluble, solid phase disinfectant resins that release halides include Costin, U.S. Pat. No. 4,076,622; Hatch, U.S. Pat. Nos. 4,187,183 and 4,190,529; Lund, U.S. Pat. No. 5,431,908; Messier, U.S. Pat. No. 5,639,452; and Bahr et al., DE 2 059 379.
Similar compounds are described in Nurdin et al., “Biocidal Polymers Active by Contact. III. Aging of Biocidal Polyurethane Coatings in Water,” Journal of Applied Polymer Science, vol. 50 (1993) pp. 671-678; Kanazawa et al., “Polymeric Phosphonium Salts as a Novel Class of Cationic Biocides. III. Immobilization of Phosphonium Salts by Surface Photografting and Antibacterial Activity of the Surface-Treated Polymer Films,” Journal of Applied Polymer Science: Part A: Polymer Chemistry, vol 31, No. 6 (1993) pp. 1467-1472; and Kanazawa et al., “Polymeric Phosphonium Salts as a Novel Class of Cationic Biocides. VI. Antibacterial Activity of Fibers Surface-Treated with Phosphonium Salts Containing Trimethoxysilane Groups,” Journal of Applied Polymer Science, vol. 52 (1994) pp. 641-647.
Non-polymeric phosphonium compounds such as phosphonium sulfates and mono halides are also known as co-antimicrobials used in conjunction with other antimicrobial agents. Examples include LaMarre et al., U.S. Pat. Nos. 4,661,518 and 4,800,235 and Canadian Patent No. CA 1 269 300; Kaplan, U.S. Pat. No. 4,861,511; McCoy et al., U.S. Pat. No. 5,702,684; and McCarthy et al., U.S. Pat. No. 5,922,745.
Phosphorane trihalides are described as antimicrobials in Driscoll et al., U.S. Pat. Nos. 3,374,256 and 3,437,473. These patents disclose phosphonium polyhalides having C═P olefinic structures. A phosphonium biocide currently on the market is represented as [(HOCH
2
O)
4
P]
2
═SO
4
2−
, described for example in Davis et al., U.S. Pat. No. 4,673,509; Talbot et al., U.S. Pat. Nos. 4,775,407 and 5,139,561; Bryan et al., U.S. Pat. No. 5,385,896; Davis et al., U.S. Pat. No. 5,606,105; and Cooper et al., U.S. Pat. No. 5,741,757.
SUMMARY OF THE INVENTION
We have discovered a synergistic effect resulting from the combination of a source of protonizable phosphorous or sulfur, and a halide source, for example, an elemental halogen(s), or metal or ammonium halide salt(s), preferably including an iodide salt. More specifically, we have found that a synergistic oxidizing species is created from this combination. Since reaction is almost immediate, an in-situ aqueous or non-aqueous use solution can be available for use immediately after mixing as an antimicrobial or antiviral composition; or the active composition can be stabilized and post-incorporated into a nonaqueous liquid, gel, aerosol, powder, or solid formulation. It is also possible to produce solid sanitizing substrates containing this oxidizing species that have residual antimicrobial and antiviral effectiveness; such as in air filters or as packaging or plastic or as cutting board additives.
Accordingly, the invention is found in a composition for antimicrobial or antiviral use, the composition being the product of an in-situ reaction of a source of a protonizable phosphorus or sulfur compound, and a halide source.
The invention also resides in an antimicrobial or antiviral composition that includes a combination of a source of a protonizable phosphorus or sulfur compound, and a halide source, with the balance being water.
The invention is also found in a two-part liquid concentrate antimicrobial and antiviral composition. The first part includes about 0.1 to 80 wt-% of a source of a protonizable phosphorus or sulfur compound, with the balance being water. The second part includes about 0.1 to 80 wt-% of a halide source, with the balance being water.
Another embodiment of the invention is found in a method of reducing microbial or viral populations on surfaces, objects and bodies of water. The method includes applying thereto an effective amount of a complex of the formula
wherein R, R

, R

and R
′″
are each independently a straight or branched, saturated or unsaturated, hydrocarbon group of 1 to 24 carbon atoms, in which hydrocarbon is unsubstituted or substituted by carboxyl, or alkylamido, or in which the hydrocarbon chain is uninterrupted or interrupted by a heteroatom; an aryl group, or aralkyl group in which alkyl has 1 to 4 carbon atoms;
V is a non-halogen anion;
u is an integer from 0 to 6;
w is an integer from 1 to 8;
y and y, are each independently integers from 0 to 4; and
z is an integer from 0 to 1.
The invention is also found in a process for preparing a solvent-free liquid, gel, powder, or solid antimicrobial or antiviral complex, the process including steps of applying or generating heat to a mixture of a solid, gel, or powder composition having a source of a protonizable phosphorus or sulfur compound and a halide source. The process further includes cooling the resulting complex to ambient temperature.
DETAILED DESCRIPTION OF THE INVENTION
The invention involves a complex for antimicrobial or antiviral use, including the product of the in-situ, i.e., in place, react

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