Aqueous Alcoholic Microbicidal Compositions Comprising Copper Ions

Abstract

Compositions which impart a microbicidal benefit to treated surfaces which compositions comprise (or in certain preferred embodiments may consist essentially of, or may consist of): a copper source material which releases copper ions into the treatment composition, preferably a source of Cu(I) and/or Cu(II) ions; preferably at least from about 20% wt. of at least one alcohol, which is preferably a lower alkyl monohydric alcohol) and water, optionally one or more further surfactants, further optionally one or more constituents which impart one or more advantageous technical or aesthetic benefits to the compositions, including one or more detersive surfactants;, and water, wherein the composition has a pH of at least 4, preferably at least 5, wherein the surface treatment compositions, exhibit a microbicidal or germicidal or antimicrobial effect on treated inanimate surfaces or when used to treat an airspace, e.g. ambient air,. characterized in exhibiting a microbicidal benefit when tested against one or more challenge microorganisms, according to one or more of the following standardized test protocols: ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agents against Viruses in Suspension, or ASTM E1053 Standard Test Method to Assess Virucidal Activity of Chemicals Intended for Disinfection of Inanimate, Nonporous Environmental Surfaces, or European Standard Surface Test, EN13697, or AOAC Germicidal Spray Products as Disinfectant Test Method, AOAC Index, 17.sup.th Ed. (2000, preferably against poliovirus type 1 (Sabin) (“PV1”)

Claims

1. A liquid, inanimate surface treatment composition which imparts a microbicidal benefit to treated surfaces which composition comprises: a copper source material which releases copper ions into the treatment composition, preferably a source of Cu(I) and/or Cu(II) ions; at least one lower alkyl aliphatic monohydric alcohol; water; optionally, one or more further constituents which impart one or more advantageous technical or aesthetic benefits to the compositions, including one or more detersive surfactants; wherein the composition excludes quaternary ammonium surfactant compounds, wherein the composition has a pH of at least 5, wherein the surface treatment compositions are characterized in exhibiting a microbicidal benefit when tested against one or more challenge microorganisms according to one or more of the following standardized test protocols: ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agents against Viruses in Suspension, or ASTM E1053 Standard Test Method to Assess Virucidal Activity of Chemicals Intended for Disinfection of Inanimate, Nonporous Environmental Surfaces, or European Standard Surface Test, EN1369, or AOAC Germicidal Spray Products as Disinfectant Test Method, AOAC Index, 17.sup.th Ed. (2000) preferably against poliovirus type 1 (Sabin) (“PV1”).

2. A liquid, inanimate surface treatment composition which imparts a microbicidal benefit to such treated surfaces which compositions comprises: a copper source material which releases copper ions into the treatment composition; in excess of 0% wt., and up to but excluding 20% wt. of at least one lower alkyl aliphatic monohydric alcohol; water; optionally, one or more further constituents which impart one or more advantageous technical or aesthetic benefits to the compositions, including one or more detersive surfactants; wherein the composition excludes quaternary ammonium surfactant compounds, wherein the composition has a pH of at least 5, wherein the surface treatment compositions are characterized in exhibiting a microbicidal benefit when tested against one or more challenge microorganisms according to one or more of the following standardized test protocols: ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agents against Viruses in Suspension, or ASTM E1053 Standard Test Method to Assess Virucidal Activity of Chemicals Intended for Disinfection of Inanimate, Nonporous Environmental Surfaces, or European Standard Surface Test, EN1369, or AOAC Germicidal Spray Products as Disinfectant Test Method, AOAC Index, 17.sup.th Ed. (2000) against one or more challenge microorganisms, especially preferably against poliovirus type 1 (Sabin) (“PV1”).

3. A liquid, inanimate surface treatment composition which imparts a microbicidal benefit to such treated surfaces which compositions comprises: a copper source material which releases copper ions into the treatment composition, preferably a source of Cu(I) and/or Cu(II) ions; at least one lower alkyl aliphatic monohydric alcohol; at least one further detersive surfactant, other than a quaternary ammonium surfactant compound which provides a microbicidal benefit; water; optionally, one or more further constituents which impart one or more advantageous technical or aesthetic benefits to the compositions, including one or more detersive surfactants; wherein the composition excludes quaternary ammonium surfactant compounds, wherein the composition has a pH of at least 5, wherein the surface treatment compositions are characterized in exhibiting a microbicidal benefit when tested according to one or more of the following standardized test protocols: ASTM E1052 - 96(2002) Standard Test Method for Efficacy of Antimicrobial Agents against Viruses in Suspension, or ASTM E1053-11 Standard Test Method to Assess Virucidal Activity of Chemicals Intended for Disinfection of Inanimate, Nonporous Environmental Surfaces, or European Standard Surface Test, EN1369, or AOAC Germicidal Spray Products as Disinfectant Test Method, AOAC Index, 17.sup.th Ed. (2000) against one or more challenge microorganisms, especially preferably against Poliovirus type 1 (Sabin) (“PV1”).

4. A liquid, inanimate surface treatment composition which imparts a microbicidal benefit to such treated surfaces which compositions comprises (or in certain preferred embodiments may consist essentially of, or may consist of): a copper source material which releases copper ions into the treatment composition, preferably a source of Cu(I) and/or Cu(II) ions; at least one lower alkyl aliphatic monohydric alcohol; at least one further detersive surfactant, other than a quaternary ammonium surfactant compound which provides a microbicidal benefit, which further detersive surfactant is preferably at least one nonionic surfactant; water; optionally, one or more further constituents which impart one or more advantageous technical or aesthetic benefits to the compositions, including one or more detersive surfactants; wherein the composition excludes quaternary ammonium surfactant compounds, wherein the composition has a pH of at least 5, wherein the surface treatment compositions are characterized in exhibiting a microbicidal benefit when tested according to one or more of the following standardized test protocols: ASTM E1052 Standard Test Method for Efficacy of Antimicrobial Agents against Viruses in Suspension, or ASTM E1053 Standard Test Method to Assess Virucidal Activity of Chemicals Intended for Disinfection of Inanimate, Nonporous Environmental Surfaces, or European Standard Surface Test, EN1369, or AOAC Germicidal Spray Products as Disinfectant Test Method, AOAC Index, 17′.sup.11 Ed. (2000) against one or more challenge microorganisms, especially preferably against Poliovirus type 1 (Sabin) (“PV1”).

5. A composition according to claim 1, wherein the composition exhibits a pH of at least at least 6.

6. A composition according to claim 1, wherein ethanol is the predominant alcohol present in the lower alkyl aliphatic monohydric alcohol constituent.

7. A composition according to claim 6 wherein ethanol is the sole alcohol present in the lower aliphatic monohydric alcohol constituent.

8. A microbicidal control system of constituents which comprises: water, one or more one or more C.sub.i-C.sub.4 aliphatic alcohols in an amount of up to, but less than 20% wt., and especially preferably wherein ethanol is the predominant or sole C.sub.1-C.sub.4 aliphatic alcohols present, and, where necessary, a buffer or pH adjusting agent to impart an alkaline pH, preferably an alkaline pH of 7.5 or greater, and optionally one or more further constituents which may or may not provide a further microbicidal benefit, and further wherein the composition excludes quaternary ammonium surfactant compounds,

9. A microbial control system according to claim 8, wherein the microbial control system further includes at least one further detersive surfactant, other than a quaternary ammonium surfactant compound which provides a microbicidal benefit, which further detersive surfactant is preferably at least one nonionic surfactant.

10. A method of controlling the incidence of undesired microorganisms on an inanimate surface, the method comprising the step of: contacting the inanimate surface which is in need of treatment or upon which the presence of one or more undesirable microorganisms are suspected or are known to be present, with an effective amount of a liquid, inanimate surface treatment composition according to claim 1, to provide a microbicidal benefit to the contacted surface.

11. A method of controlling the incidence of undesired microorganisms in air, or in a headspace such as the ambient air within a closed volume such as a room or the interior of a vehicle, the method comprising the step of: delivering and dispersing within an airspace an effective amount of a liquid, inanimate surface treatment composition according to claim 1 to provide a microbicidal benefit to the treated air, preferably to provide a microbicidal benefit to the treated air.

12. A composition according to claim 5, wherein the composition exhibits a pH of at least at least 7.

13. A composition according to claim 2, wherein the composition exhibits a pH of at least at least 6.

14. A composition according to claim 13, wherein the composition exhibits a pH of at least at least 7.

15. A composition according to claim 3, wherein the composition exhibits a pH of at least at least 6.

16. A composition according to claim 15, wherein the composition exhibits a pH of at least at least 7.

17. A composition according to claim 4, wherein the composition exhibits a pH of at least at least 6.

18. A composition according to claim 17, wherein the composition exhibits a pH at least at least 7.

Description

EXAMPLES

[0168] A number of treatment compositions as well as a number of comparative compositions were produced and are described on the following Tables. In these identified compositions, the constituents were used “as supplied” from their respective suppliers and may constitute less than 100% wt. “actives”, or may have been supplied as constituting 100% wt. “active” of the named compound, as indicated below. Treatment compositions which are considered to fall within the scope of the present invention are identified by a digit prepended with the letter “E” which indicates this to be an “example” composition, while compositions provided only for the purposes of comparison are identified by a digit prepended with the letter “C”, which indicates this to be a comparative composition and falling outside of the scope of the present invention. In certain of the treatment compositions, one or more constituents, e.g, a pH adjusting agent, or deionized water was added in “quantum sufficient” “q.s.” in order to provide a desired pH or to provide a sufficient mass in order to provide 100% wt. of each composition. The example compositions disclosed hereinafter include certain presently preferred embodiments of the invention. The comparative compositions are presented on Table C, while treatment compositions of the invention are identified on one or more of the further tables, e.g, Table 1.

[0169] The compositions disclosed on the following tables were produced by simple mixing, under stirring, of the identified constituents, generally in accordance with the following protocol. To a suitably sized laboratory beaker outfitted with a mechanical stirrer or a magnetic stirrer, was first supplied a major proportion of the deionized water. All of the constituents, as well as the laboratory beaker were at room temperature (approx. 20° C.) and as the beaker was open, mixing was at normal atmospheric pressure. Thereafter under stirring conditions (approx. 300 rpm) was added the source of copper ions, and mixing continued until this material was dissolved. Stirring continued for a further 15-30 minutes to ensure a homogenous mixture, to which was next added the alcohol constituent. Subsequently were added any remaining constituents including any further quantity of pH adjusting constituents (if present) in order to establish the desired pH of the surface treatment composition. Constituents identified as being added “q.s.” were added in order to adjust the pH of the formed composition or to bring the weight of the formed composition to 100% wt. Stirring continued for a further 1-15 minutes to ensure the formation of a homogenous mixture, after which the surface treatment composition was withdrawn from the beaker and used or tested.

[0170] These compositions as identified below were formed using the constituents identified on the following Table A which identifies the specific constituents used.

TABLE-US-00001 TABLE A Constituents CuSO4•5H2O CuSO.sub.4•5H.sub.2O, technical grade (100% wt. actives) CuCl2•2H2O CuCl.sub.2•2H.sub.2O, technical grade (100% wt. actives) Cu(OAcO)2•H2O Cu(OAcO).sub.2•H.sub.2O, technical grade (100% wt. actives) Cu D-gluconate Cu D-gluconate, technical grade (100% wt. actives) Cu(I)Cl•H2O Cu(I)Cl•H.sub.2O, technical grade (100% wt. actives) ethanol (100%) ethanol, technical grade,(100% wt. active) ethanol (95%) ethanol, technical grade, (95% wt. active) isopropanol isopropanol, technical grade, (100% wt. active) isobutanol isobutanol, technical grade (100% wt. active) n-propanol n-propanol, technical grade,100% wt. actives propylene glycol n- propylene glycol n-propyl ether (100% wt. propyl ether active) supplied as Dowanol PnP (ex. DOW Chem. Co.) phenol propane glycol phenol propane glycol ether (100% wt. ether active) supplied as Dowanol PPH (ex. DOW Chem. Co.) BTC-65 (50%) C.sub.12-C.sub.16 alkyl dimethyl benzyl ammonium chloride provided in an aqueous alcoholic carrier (50% wt. actives) (ex. Stepan) Onyxide 3300 (33%) quaternary ammonium complex with saccharinate counterion, (33% wt. actives, balance ethanol) (ex. Stepan Co.) Neodol 91-6 nonionic surfactant, C.sub.9-C.sub.11 linear primary alcohol ethoxylate, avg. 6 mols. ethoxylation, 100% wt. actives (ex. Shell Chemical) Steol C5370 anionic surfactant, sodium laureth sulfate, 3 mols EO (70% wt. actives) (ex. Stepan Co.) Glucopon 425N alkylpolyglycoside (50% wt. actives) (ex. Cognis) Plurafac SL62 nonionic surfactant, linear alcohol ethoxylate (100% wt.active) (ex. BASF) Tween 20 sorbitan based surfactant Silwet Hydrostable 212 silylated/organic surfactant blend (used as supplied) (ex. Momentive Performance Materials, Inc.). triethanolamine triethanolamine, technical grade (100% wt. active) (ex. Dow Chemical Company) ethanolamine ethanolamine, technical grade (100% wt. active) (ex. Huntsman) Citrasol 502 (50%) aqueous citric acid solution (50% wt. active) (ex. ADM) Citrosol 502(50%)/6 aqueous solution of citric acid (50% wt. active) (ex. ADM) further diluted 1:5 in deionized water NH4(OH) (29.86%) aqueous solution of ammonium hydroxide (29.86% wt. active) NaOH (50%) aqueous solution of sodium hydroxide, 50% wt. active NaOH (10%) aqueous solution of sodium hydroxide (10% wt. active) citric acid (1.56%) aqueous solution of anhydrous laboratory grade citric acid (1.56% wt. active) ammonium acetate anhydrous solid, reagent grade (ex. JT Baker) (100% wt. actives) Monacor BE borate ester blend, used as supplied comprising MEA-borate ester and MIPA- borate ester (ex. Croda, tradename Crodacor BE) IL2976 corrosion inhibitor comprising mixed acid esters, a proprietary composition believed to be borate esters, used ‘as supplied’ Trilon BX aqueous solution of tetrasodium ethylene diamine tetraacetic acid 38.9% wt. actives) (ex. BASF) di H.sub.2O deionized water, (100% wt. active)

[0171] Further, wherein a specific composition was evaluated for microbicidal efficacy against a challenge microorganism according to one or more of the test protocols identified above, the results of these tests are reported as well. Wherein multiple challenge microorganisms were evaluated in any one test, multiple results are reported.

[0172] In the following tables, the tested microorganisms and their identity as reported on the tables are as indentified on Table B:

TABLE-US-00002 TABLE B Microorganisms Identifier Type/Challenge microorganism “PV1” Virus/Poliovirus type 1 (Sabin), ex. supplied by U.S. Centers for Disease Control and Prevention (CDC) “HAV” Virus/Hepatitis A virus, strain MH-175 ex. Dr. Mark Sobsey, University of North Carolina, Chapel Hill, NC “HAdV” Virus/Human adenovirus type 5, supplied as ATCC VR-5 “FCV” Virus/Feline calicivirus strain F-9, supplied as ATCC VR-782 “IV-A” Virus/Influenza A virus, A/California/04/2009 (H1N1), supplied as Biodefence and Emerging Infections Research Resources Repository (BEI Resource) NR-13658 “HSV” Virus/Herpes simplex type 1, supplied as ATCC VR-1493 “HRV” Virus/Human rhinovirus type 14 strain 1059, supplied as ATCC VR-284 “Rota” Virus/Rotavirus Wa strain, supplied as ATCC VR-2018 “M. bovis” or “Mb” Bacteria/Mycobacterium bovis-BCG, supplied by Organon Teknika, Durham, NC to ATS Labs (used as a surrogate for testing efficacy against Tuberculosis) “S. aureus” or “Sa” Bacteria/Staphylococcus aureus, supplied as ATCC 6538 “E. coli” or “Ec” Bacteria/Escherichia coli, supplied as ATCC 10536 “P. aeruginosa” or “Pa” Bacteria/Pseudomonas aeruginosa (“P. aeruginosa”) (supplied as ATCC 15442); “E. hirae”, or “Eh” Bacteria/Enterococcus hirae, supplied as ATCC 10541 “T. ment” Fungus/Trichophyton metagropytes, supplied as ATCC 9533

[0173] The use of feline calicivirus strain was for its well known function as a ‘surrogate virus’ in place of Norovirus.

[0174] In the following tables, Table C describes various “comparative” examples, (which may be identified by the prepended letter “C”) while subsequent Table 1 describes various examples of inventive compositions according to the invention, (which may also be identified by the prepended letter “E”) as well as the observed physical properties and the results of microbidical testing according to one or more of the following standardized test protocols:

[0175] A) ASTM E1052-96(2002) Standard Test Method for Efficacy of Antimicrobial Agents against Viruses in Suspension, (for a 5 minute contact time, unless specified otherwise) identified on Table 1 as “ASTM E 1052 (log10 reduction)”;

[0176] B) ASTM E 1053-11 Standard Test Method to Assess Virucidal Activity of Chemicals Intended for Disinfection of Inanimate, Nonporous Environmental Surfaces, (for a 10 minute contact time, unless specified otherwise) identified on Table 1 as “ASTM 1053 (log10 reduction)”,

[0177] C) European Standard Surface Test, EN13697, identified on Table 1 as “EN 13697 (log10 reduction)”,

[0178] D) AOAC Germicidal Spray Products as Disinfectant Test Method, AOAC Index, 17th Ed. (2000), identified on Table 1 as “AOAC Germicidal Spray”. In this test, a result of “0/60” or “1/60” is equivalent to a result of “pass” according to that test's protocols. Results of “2” excess thereof for “/60” tested plates/samples are considered as being equivalent to a “fail” according to that test's protocols.

[0179] E) The European Standard Surface Test, EN13697 protocol was used for testing antifungal efficacy against Trichophytort mentagrophytes (supplied as ATCC 9533) the results reported on Tables C and 1 are the log10 reduction of the fungus.

[0180] It is noted that each tested composition was not necessarily tested according to all of the foregoing protocols as, test results of microbicidal efficacy against Poliovirus type 1 Sabin supports the presumption of efficacy against easier to control or eradicate microorganisms.

[0181] In the following tables the amount of the copper ions present are also indicated in parts per million (ppm) and this number is based on the empirical calculation of the available metal ions present in the indicated composition and 100% disassociation of the copper ion from the copper ion source is presumed for this empirical calculation.

[0182] In the following tables the appearance of the test compositions both of Table I and C are indicated; all of the liquid compositions were transparent unless indicated otherwise, e.g. “slight haze” and many were bluish in tint of a lesser or greater substantivity.

[0183] All of the compositions of both Table 1 and C were liquids which were readily pourable and pumpable and had a “water-thin” viscosity.

TABLE-US-00003 TABLE C (Comparative Examples0 C1 C2 C3 C4 C5 C6 CuSO.sub.4•5H.sub.2O — 0.10 0.10 0.1 0.1 0.1 ethanol (100%) 35 — 35 — — — ethanol (95%) — — — — — — BTC-65 (50%) — — — — — — Onyxide 3300 (33%) — — — — — — Neodol 91-6 0.18 — — — — — Plurafac SL62 — — — — — — triethanolamine 0.02 0.30 — — — 0.31 Citrasol 502 (50%) — — 0.055 0.04 — — NH4(OH) (29.86%) — — — — — 0.12 di H.sub.2O 64.88 99.56 64.80 99.86 99.90 99.49 pH 9.08 8.08 3.08 3.08 5.08 9.22 copper ion content (ppm) — 254 254 254 254 254 appearance colorless medium blue colorless colorless colorless colorless ASTM E 1052 (log10 reduction) PV1 ≦ 1.17 PV1 ≦ 1.50 PV1 ≦ 2.44 PV1 < 1.83 PV1 < 1.67 PV1 < 1.67 IV-A< 1.33 FCV < 1.83 IV-A < 0.33 HSV < 2.17 HAdV < 1.73 ASTM 1053 (log10 reduction) — — — — — — AOAC Germicidal Spray — Sa = 60/60 — — — — (fail) Pa = 23/60 (fail) EN 13697 (log10 reduction) Sa > 6.55 Sa < 1.97 — — — — Ec > 5.50 Ec = 0.44 Pa > 4.52 Pa = 0.78 Eh > 6.68 T.ment (log10 reduction) — 0.06 — — — — C7 C8 C9 C10 C11 C12 C13 CuSO.sub.4•5H.sub.2O 0.1 — — — — — — ethanol (100%) — 35 35 35 35 50 50 ethanol (95%) — — — — — — — BTC-65 (50%) — — — — — — — Onyxide 3300 (33%) — — — — — — — Neodol 91-6 — — — — — 0.1 — Plurafac SL62 — — — — — — — triethanolamine 0.31 — 0.002 0.08 — 0.014 0.015 Citrasol 502 (50%) — 0.30 0.02 0.016 0.016 — — NH4(OH) (29.86%) 0.08 — — — — — — NaOH (10%) 0.39 — — — 0.01 — — di H.sub.2O 99.1 64.7 64.98 64.9 64.8 49.88 49.98 pH 10.95 3.07 5.01 9.01 11.15 8.87 8.98 copper ion content (ppm) 254 — — — — — — appearance colorless colorless colorless colorless colorless colorless colorless ASTM E 1052 (log10 reduction) PV1 < 1.42 PV1 ≦ 1.77 PV1 < 1.67 PV1 ≦ 2.10 PV < 1.67 PV1 ≦ 2.00 PV1 ≦ 1.5 FCV > 3.33 FCV < 2.33 FCV > 3.83 ASTM 1053 (log10 reduction) — — — — — — — AOAC Germicidal Spray — — — — — — — EN 13697 (log10 reduction) — — — — — — — T.ment (log10 reduction) — — — — — — — C14 C15 C16 C17 C18 C19 C20 CuSO.sub.4•5H.sub.2O — — — — 0.1 — — ethanol (100%) 20.0 — — 10 10 10 10 ethanol (95%) — — — — — — — isobutanol — 35.0 — — — — — isopropanol — — 35 — — — — n-propanol — — — — — — — BTC-65 (50%) — — — — — — — Onyxide 3300 (33%) — — — — — — — Neodol 91-6 — — — — — — — Plurafac SL62 — — — — — — — triethanolamine 0.003 0.003 0.003 — — — — Citrasol 502 (50%) — — — 0.085 0.04 0.0025 0.02 NH4(OH) (29.86%) — — — — — 0.0035 — NaOH (10%) — — — — — — — di H.sub.2O 80.0 65.0 65.0 89.9 89.9 89.99 89.98 pH 8.81 8.93 8.47 3.07 3.03 5.07 9.22 copper ion content (ppm) — — — — 256 — — appearance colorless light blue, colorless colorless colorless colorless colorless two phases ASTM E 1052 (log10 reduction) PV1 < 0.73 PV1 < 0.83 PV1 < 0.56 PV1 < 0.73 PV1 < 0.46 PV1 < 0.73 PV1 < 0.90 ASTM 1053 (log10 reduction) — — — — — — AOAC Germicidal Spray — — — — — — — EN 13697 (log10 reduction) Sa < 1.02 — — — — — — EC < 1.20 Pa = 0.00 Eh < 1.36 T.ment (log10 reduction) <0.22 — — — — — — C21 C22 C23 C24 C25 C26 C27 CuSO.sub.4•5H.sub.2O — — — — 0.099 — 0.099 ethanol (100%) 10 12 — 17.5 — — — ethanol (95%) — — — — — — — isobutanol — 12 — 17.5 — — — isopropanol — — — — — — — n-propanol — 12 35 — — — — propylene glycol n-propyl — — — — 50.0 50 — ether phenol propane glycol ether — — — — — — 50 BTC-65 (50%) — — — — — — — Onyxide 3300 (33%) — — — — — — — Neodol 91-6 — — — — — — — Plurafac SL62 — — — — — — — triethanolamine 0.15 0.003 0.003 — 0.40 0.003 0.40 Citrasol 502 (50%) — — — — — — — NH4(OH) (29.86%) — — — — — — — NaOH (10%) 0.035 — — — — — — di H.sub.2O 89.98 64.0 65.0 65.0 49.5 50 49.5 pH 11.04 8.21 8.63 8.36 7.95 8.26 8.02 copper ion content (ppm) — — — — 254 — 254 appearance colorless colorless colorless colorless light blue colorless light blue, two phase ASTM E 1052 (log10 reduction) PV1 < 0.56 PV1 < 0.50 PV1 < 0.50 PV1 = 1.17 PV1 < 0.17 PV1 < 0.17 PV1 < 0.17 ASTM 1053 (log10 reduction) — — — — — — — AOAC Germicidal Spray — — — — — — — EN 13697 (log10 reduction) — — — — — — — T.ment (log10 reduction) — — — — — — — C28 C29 C30 CuSO.sub.4•5H.sub.2O — — 0.1 ethanol (100%) — 45 — ethanol (95%) — — — BTC-65 (50%) 0.2 0.2 — Onyxide 3300 (33%) — — — Neodol 91-6 0.1 0.1 0.1 triethanolamine 0.022 0.04 0.39 di H.sub.2O 99.67 54.66 99.4 pH 9 9.09 8.08 copper ion content (ppm) 0 0 254 appearance colorless colorless light blue ASTM E 1052 (log10 reduction) PV1 =< 3.00 PV1 < 2.67 PV1 =< 2.5 IV-A > 5.00 PV1 < 217 IV-A > 6.00 HSV > 6.00 PV1 < 1.53 IV-A > 5.17 HAdV < 2.0 HSV > 6.00 HSV > 7.5 HAdV > 4.5 HSV > 7.0 HRV =< 3.83 HAdV < 1.0 ASTM 1053 (log10 reduction) — — — AOAC Germicidal Spray — — Sa = 57/60 Pa = 27/60 EN 13697 (log10 reduction) Sa = 4.31 — Sa < 1.17 EC > 5.50 Ec = 2.12 Pa > 4.52 Pa = 2.84 Eh = 5.48 Eh < 1.3 T.ment (log10 reduction) — — — C31 C32 C33 C34 C35 CuSO.sub.4•5H.sub.2O 0.1 — 0.1 — 0.1 ethanol (100%) 5 5 10 10 50 ethanol (95%) — — — — — BTC-65 (50%) 0.2 0.2 0.2 0.2 0.2 Onyxide 3300 (33%) — — — — — Neodol 91-6 0.1 0.1 0.1 0.1 0.1 Plurafac SL62 — — — — — triethanolamine 0.31 — 0.31 — — citric acid (1.56%) — — — — — di H.sub.2O 94.3 94.7 89.3 89.70 49.60 pH 8.04 8.44 7.97 8.35 4.74 copper ion content (ppm) 254 0 254 0 — appearance medium blue colorless light blue colorless — ASTM E 1052 (log10 reduction) PV1 =< 0.23 PV1 < 0.23 PV1 < 0.9 PV1 < 0.23 — IV-A > 5.00 HSV > 6.00 ASTM 1053 (log10 reduction) — — — — HRV = 1.50 AOAC Germicidal Spray Sa = 0/30 — — — — Pa = 0/30 EN 13697 (log10 reduction) Sa = 3.48 Sa > 6.40 — — — Ec > 6.58 Ec > 6.58 Pa > 5.16 Pa > 5.16 Eh = 3.43 Eh > 6.74 T.ment (log10 reduction) — — — — — C36 C37 C38 C39 CuSO.sub.4•5H.sub.2O — — — — ethanol (100%) 50 35 35 — ethanol (95%) — — — — BTC-65 (50%) 0.2 0.2 — 0.2 Onyxide 3300 (33%) — — — — Neodol 91-6 0.1 0.1 — — triethanolamine — 0.016 0.025 — di H.sub.2O 0.012 64.68 64.97 99.8 pH 49.68 8.89 9.23 8.58 copper ion content (ppm) 8.64 0 0 0 appearance 0 clear clear clear ASTM E 1052 (log10 reduction) colorless PV1 =< 2.17 PV1 =< 1.83 PV1 =< 1.83 FCV > 6.00 IV-A > 5.00 HSV > 6.00 HAdv < 1.5 ASTM 1053 (log10 reduction) PV1 < 1.25 — — — HAdv > 4.50 HRV > 6.00 FCV > 4.33 FCV > 6.00 AOAC Germicidal Spray — — — Sa = 1/60 PA = 1/60 EN 13697 (log10 reduction) — Sa > 6.35, Sa = 4.60, Sa = 4.47, Ec > 5.35, Ec = 4.19, Ec = 4.28, Pa > 3.85 Pa > 4.52 Pa => 4.52 Eh > 6.68 Eh = 3.83 T.ment (log10 reduction) Sa > 6.12 — 4.84 2.73 Ec > 5.66 Pa > 3.80 Eh > 6.50 — >5.74 — — —

TABLE-US-00004 TABLE 1 (Examples) E1 E2 E3 E4 E5 E6 E7 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.1 0.1 0.1 0.1 0.1 ethanol (100%) 35 35 50 50 35 35 35 ethanol (95%) — — — — — — — BTC-65 (50%) — — — — — — — Onyxide 3300 — — — — — — — (33%) Neodol 91-6 0.10 — 0.10 — — — — triethanolamine 0.41 0.41 0.34 0.45 0.23 0.97 0.20 Citrasol 502 — — — — 0.11 — 0.02 (50%) NH4(OH) — — — — — 0.10 0.10 (29.86%) NaOH (10%) — — — — — — 0.37 di H.sub.2O 64.39 64.49 49.46 49.45 64.6 63.8 64.2 pH 8.09 8.10 8.01 8.11 5.10 8.95 10.98 copper ion 254 254 254 254 254 254 254 content (ppm) appearance light blue light blue light blue light blue colorless colorless colorless ASTM E 1052 PV1 < 2.23 PV1 + 2.50 PV1 < 3.48 PV1 ≦ 3.00 PV1 < 1.5 PV1 < 2.27 PV1 < 3.67 (log10 PV1 ≦ 4.09 reduction) ASTM 1053 — — — — — — — (log10 reduction) AOAC Sa = 0/60 — Sa = 0/60 — — — — Germicidal Pa = 0/60 Pa = 0/60 Spray EN 13697 Sa > 6.23 — Sa > 6.23 — — — — (log10 Ec > 5.50 Ec > 5.50 reduction) Pa > 3.38 Pa > 3.38 Eh > 6.36 Eh > 6.36 T.ment (log10 — — >5.74 — — — — reduction) E8 E9 E10 E11 E12 E13 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.1 0.1 0.1 0.1 ethanol (100%) 50 50 20 — — 10 ethanol (95%) — — — — — — isopropanol — — — 35 — — isobutanol — — — — 35 — BTC-65 (50%) — — — — — — Onyxide 3300 — — — — — — (33%) Neodol 91-6 0.1 — — — — — triethanolamine 0.34 0.45 0.45 0.45 0.40 — Citrasol 502 — — — — — — (50%) NH4(OH) 0.1 0.1 — — — — (29.86%) NaOH (10%) — — — — — — di H.sub.2O 49.4 49.3 79.4 64.4 64.5 89.9 pH 10 10 8.12 8.0 8.08 5.01 copper ion 254 254 254 254 254 254 content (ppm) appearance light blue light blue colorless colorless light blue, two colorless phases ASTM E 1052 PV1 > 3.73 PV1 > 3.73 PV < 2.10 PV < 0.23 PV1 < 1.33 PV1 < 0.73 (log10 reduction) ASTM 1053 PV1 > 4.50 — — — — — (log10 reduction) AOAC Sa = 0/60 — — — — — Germicidal (pass) Spray Pa = 0/60 (pass) EN 13697 — — — — — — (log10 reduction) T.ment (log10 — — — — — — reduction) E14 E15 E16 E17 E18 E19 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.099 0.1 0.099 0.099 ethanol (100%) 10 10 12.0 — 17.5 35.0 ethanol (95%) — — — — — — isopropanol — — 12.0 — — — n-propanol — — 12.0 35.0 — — isobutanol — — — — 17.5 — propylene — — — — — 25.0 glycol n-propyl ether BTC-65 (50%) — — — — — — Onyxide 3300 — — — — — — (33%) Neodol 91-6 — — — — — — triethanolamine 0.30 0.30 0.40 0.50 0.40 0.40 Citrasol 502 — — — — — — (50%) NH4(OH) 0.14 0.12 — — — — (29.86%) NaOH (10%) — 0.35 — — — — di H.sub.2O 89.5 89.1 63.5 64.4 64.5 39.5 pH 9.07 10.97 7.89 8.03 7.90 7.89 copper ion 254 254 254 254 254 254 content (ppm) appearance colorless colorless light blue colorless light blue light blue ASTM E 1052 PV1 ≦ 2.10 PV1 < 0.73 PV1 < 0.67 PV1 < 1.33 PV1 < 1.33 PV1 < 0.50 (log10 FCV < 1.00 reduction) ASTM 1053 — — — — — — (log10 reduction) AOAC — — — — — — Germicidal Spray EN 13697 — — — — — — (log10 reduction) T.ment (log10 — — — — — — reduction) E20 E21 E22 E23 E24 E25 E26 E27 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.199 0.1 0.1 0.1 0.1 0.1 ethanol (100%) 25 45 45 75 35 35 50 50 ethanol (95%) — — — — — — — — BTC-65 (50%) 0.2 0.2 — 0.2 0.2 0.2 0.2 0.2 Onyxide 3300 — — 0.30 — — — — — (33%) Neodol 91-6 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 triethanolamine 0.42 0.19 0.3 0.302 0.443 — — 0.37 ethanolamine — — — — — — — — NH4OH — 0.1 0.09 — — — — — (29.8%) NaOH (10%) — — — — — — — — Citrosol — — — — — — — — 502(50%) ammonium — — — — — 2.0 2.0 — acetate Monacor BE — 0.1 0.1 — — — — — Trilon BX — — — — — — — — di H.sub.2O 74.18 54.21 53.907 24.298 64.157 62.6 47.6 49.22 pH 8.09 9.5 8.85 8.23 8.06 6.82 7.08 8.06 copper ion 254 254 506 254 254 254 254 254 content (ppm) appearance colorless light blue light blue light blue light blue light blue light blue light blue ASTM E 1052 PV1 > 3.67 PV1 > 5.27 PV1 > PV1 > 5.67 PV1 > 4.87 — — PV1 > 5.89 (log10 PV1 > 5.88 5.67 FCV > 6.00 HAdV > 5.00 reduction) HAV > 6.00 HRV > 6.00 FCV > 6.00 HAV > 6.00 FCV > 6.00 ASTM 1053 — 1 minute: — — — PV1 > 4.38 PV1 > PV1 > 3.50 (log10 PV1 > 4.50 HRV > 2.75 3.50 PV1 > 4.50 reduction) 5 minutes: Rota > 2.5 PV1 > 4.50 AOAC — Sa = 0/60 — — — — — Sa = 0/30 Germicidal Pa = 0/60 Pa = 0/30 Spray Test Mb = 0/30 (hard surface test) and ≦5.32 (suspension test) EN 13697 — — — — — — — Sa > 6.29, (log10 Ec > 5.90, reduction) Pa > 4.23, Eh > 5.67 T.ment (log10 — — — — — — — >5.74 reduction) E28 E29 E30 E31 E32 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.1 0.1 0.1 ethanol (100%) 40 40 40 40 40 ethanol (95%) — — — — — BTC-65 (50%) — — — — — Onyxide 3300 0.303 0.303 0.303 0.303 0.303 (33%) Neodol 91-6 0.1 0.1 0.1 0.1 0.1 triethanolamine 0.13 0.13 0.13 0.13 0.13 ethanolamine 0.05 0.05 0.05 0.05 0.05 NH4OH 0.12 0.12 0.12 0.12 0.12 (29.8%) NaOH (10%) — — — — — Citrosol — — — — — 502(50%) ammonium — — — — — acetate Monacor BE — — 0.20 — — Trilon BX — — — — — IL2976 0.060 0.20 — 1.22 0.11 di H.sub.2O 58.6 59.0 59.0 58.0 59.1 pH 9.10 9.10 9.59 9.50 9.10 copper ion 254 254 254 254 254 content (ppm) appearance light blue light blue light blue light blue light blue ASTM E 1052 PV1 =< 3.44 PV1 =< 3.54 PV1 =< 5.10 PV1 =< 3.10 PV1 =< 2.44 (log10 reduction) ASTM 1053 — — — — — (log10 reduction) AOAC — — — — — Germicidal Spray Test EN 13697 — — — — — (log10 reduction) T.ment (log10 — — — — — reduction) E33 E34 E35 E36 E37 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.1 0.1 0.1 ethanol (100%) 50 50 50 50 50 ethanol (95%) — — — — — BTC-65 (50%) 0.2 0.2 0.2 0.2 0.2 Onyxide 3300 — — — — — (33%) Neodol 91-6 0.1 — 0.1 0.1 0.1 triethanolamine 0.48 0.37 0.41 — 0.48 ethanolamine — — — — — NH4OH — — — — — (29.8%) NaOH (50%) — — 0.054 0.03 — Citrosol — — q.s. — — 502(50%) sodium citrate — — — 0.1 — ammonium — — — — — acetate Monacor BE — — — — 0.06 di H.sub.2O 49.12 49.32 49.45 49.57 49.06 pH 8.06 8.10 8.24 8.45 8.52 copper ion 254 254 254 254 254 content (ppm) appearance light blue light blue cloudy colorless — ASTM E 1052 PV1 > 5.00 PV1 = 0.73 PV1 =< 5.00 PV1 > 5.67 — (log10 reduction) ASTM 1053 PV1 > 3.50 — — — — (log10 PV1 > 4.50 reduction) AOAC — — — — — Germicidal Spray Test EN 13697 — — — — — (log10 reduction) E38 E39 E40 E41 E42 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.1 0.1 0.1 ethanol (100%) — 45 45 25 45 ethanol (95%) 50 — — — — isopropanol — — — 20 — BTC-65 (50%) 0.1 — — 0.2 0.2 Onyxide 3300 — 0.3 0.3 — — (33%) Neodol 91-6 0.1 0.1 0.1 0.1 0.1 Steol CS370 — — — — 0.143 triethanolamine 0.31 0.48 0.18 0.4 0.43 ethanolamine — — — — — NH4OH — — 0.11 — — (29.8%) NaOH (10%) — — — — — Citrosol — — — — — 502(50%) Citrosol — — — — — 502(50%)/6 ammonium — — — — — acetate Monacor BE — — — — — Trilon BX — — — — — di H.sub.2O 49.39 54.02 54.21 54.2 54.027 pH 8.1 8.2 9.17 8.03 8.08 copper ion 254 254 254 254 254 content (ppm) appearance light blue light blue light blue light blue dark blue, slight haze ASTM E 1052 — PV1 > 5.27 PV1 > 4.50 PV1 = 4.83 PV1 > 6.00 (log10 HRV > 4.83 reduction) HSV > 6.00 ASTM 1053 — — PV1 > 4.50 (at — — (log10 1 min), reduction) PV1 > 4.50 (at 5 min) AOAC — — Sa = 0/60 — — Germicidal Pa = 0/60 Spray Test EN 13697 — — — — — (log10 reduction) E43 E44 E45 E46 E47 E48 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.1 0.1 0.1 0.1 ethanol (100%) 45 — 45 45 45 45 ethanol (95%) — — — — — — isopropanol — — — — — — n-propanol — 45 — — — — BTC-65 (50%) 0.2 0.2 0.2 — — 0.2 Onyxide 3300 — — — — — — (33%) BTC-2125M — — — 0.2 — — BTC-1010 — — — — 0.2 — Neodol 91-6 0.1 0.1 — 0.1 0.1 — Steol CS370 — — 0.143 — — — Glucopon 425N — — — — — 0.2 triethanolamine 0.41 0.4 0.41 0.42 0.46 0.42 ethanolamine — — — — — — NH4OH — — — — — — (29.8%) NaOH (10%) — — — — — — Citrosol — — — — — — 502(50%) ammonium — — — — — — acetate Monacor BE — — — — — — Trilon BX — — — — — — di H.sub.2O 54.19 54.2 54.14 54.18 54.14 54.08 pH 8.09 8.09 8.11 8.12 8.12 8.13 copper ion 254 254 254 254 254 254 content (ppm) appearance light blue — dark blue, light blue light blue dark blue slight haze ASTM E 1052 PV1 > 6.33 PV1 < 3.00 PV1 > 6.00 PV1 > 6.00 PV1 > 6.00 PV1 > 6.00 (log10 HRV > 6.00 reduction) ASTM 1053 — — — — — — (log10 reduction) AOAC Sa = 0/30 — — — — — Germicidal Pa = 0/30 Spray Test EN 13697 — — — — — — (log10 reduction) E49 E50 E51 E52 E53 E54 E55 E56 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 ethanol (100%) 45 45 40 38 45 38 38 38 ethanol (95%) — — — — — — — — isopropanol — — — — — — — — n-propanol — — — — — — — — BTC-65 (50%) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Onyxide 3300 — — — — — — — — (33%) BTC-2125M — — — — — — — — Neodol 91-6 — — 0.1 0.1 0.1 0.1 0.1 0.1 Steol CS370 — — — — — — — — Ammonyx LO 0.33 — — — — — — — Plurafac SL62 — 0.1 — — — — — — triethanolamine 0.48 0.43 0.42 0.015 0.0102 0.42 0.08 — ethanolamine — — — — — — — — NH4OH — — — — — — 0.11 0.11 (29.8%) NaOH (10%) — — — — — — — — Citrosol — — — 0.08 0.066 — — — 502(50%) ammonium — — — — — — — — acetate Monacor BE — — — — — — — — Trilon BX — — — — — — — — di H.sub.2O 53.88 54.17 59.18 61.58 54.4 61.18 61.41 61.49 pH 8.18 8.14 8.10 5.0 5.04 8.08 9.20 9.38 copper ion 254 254 254 254 254 254 254 254 content (ppm) appearance dark blue light blue light blue light blue light blue light blue light blue — ASTM E 1052 PV1 > 6.00 PV1 > 6.00 PV1 > PV1 > 5.62 PV1 => 4.73 PV1 = 4.54 PV1 > — (log10 5.69 PV1 > 4.73 HRV > 6.00 5.65 reduction) HRV > HAV => 6.00 HAV > 6.00 HAdV > 4.50 6.00 FCV => 3.33 FCV > 6.00 ASTM 1053 — — — — PV1 => 3 — — — (log10 (5 min, reduction) aluminum Can, complete inactivation) PV1 = 3.5 (5 min, glass jar pressured, completed inactivation) AOAC — — — — — — Sa = 0/30 — Germicidal Pa = 0/30 Spray Test EN 13697 — — — Sa > 6.27 — — — — (log10 Ec > 6.25 reduction) Pa > 4.97 Eh > 6.56 E57 E58 E59 E60 E61 E62 CuSO.sub.4•5H.sub.2O 0.1 0.1 0.1 0.1 0.1 0.1 ethanol (100%) 35 35 35 30 25 20 ethanol (95%) — — — — — — BTC-65 (50%) 0.2 0.2 0.2 0.2 — — Onyxide 3300 — — — — 0.30 0.30 (33%) Neodol 91-6 — 0.1 0.1 0.1 0.1 0.1 triethanolamine 0.41 0.4 0.1 0.45 0.1 0.28 ethanolamine — — 0.1 — — — NH4OH — — 0.17 0.21 0.10 0.18 (29.8%) NaOH (10%) — — 0.25 — — — Citrosol — — — — — — 502(50%) ammonium — — — — — — acetate Monacor BE — — — — 0.06 — di H.sub.2O 64.29 64.2 63.98 68.94 74.2 79.0 pH 8.1 8.1 11.03 9.51 9.21 9.16 copper ion 254 254 254 254 254 254 content (ppm) appearance light blue light blue light blue light blue light blue light blue ASTM E 1052 PV1 < 3.33 PV1 ≦ 3.17 PV1 > 5.88 PV1 > 5.17, PV1 ≦ 3.23 PV1 < 3.00 (log10 FCV > 6.0 HAV ≦ 2.00, FCV > 6.00 reduction) HAdV > 4.50, HSV-1 > 6.0 ASTM 1053 — — — — — — (log10 reduction) AOAC — — — — — — Germicidal Spray Test EN 13697 — Sa > 6.12 — Sa > 6.62 — — (log10 Ec > 5.66 Ec > 6.63 reduction) Pa > 3.80 Pa > 6.69 Eh > 6.50 Eh > 6.74 E63 E64 E65 E66 CuSO.sub.4•5H.sub.2O 0.099 0.099 0.05 0.025 ethanol (100%) 45 45 45 45 ethanol (95%) — — — — BTC-65 (50%) — — — — Onyxide 3300 0.151 0.076 0.303 0.303 (33%) Neodol 91-6 0.1 0.1 0.1 0.1 triethanolamine 0.35 0.28 0.2 0.1 ethanolamine — — — — NH4OH 0.09 0.09 0.13 0.08 (29.8%) NaOH (10%) — — — — Citrosol — — — — 502(50%) ammonium — — — — acetate Monacor BE — — 0.06 0.06 di H.sub.2O 54.21 54.35 54.15 54.33 pH 8.97 9.05 9.84 10.06 copper ion 254 254 127 64 content (ppm) appearance light blue light blue light blue light blue ASTM E 1052 PV1 > 5.67 PV1 > 5.67 PV1 > 5.67 PV1 > 5.67 (log10 reduction) ASTM 1053 — — — — (log10 reduction) AOAC — — — — Germicidal Spray Test EN 13697 — — — — (log10 reduction) E67 E68 E69 E70 CuSO.sub.4•5H.sub.2O — — — — CuCl.sub.2•2H.sub.2O 0.1 — — — Cu(OAcO).sub.2• — 0.1 — — H.sub.2O Cu D-gluconate — — 0.1 — Cu(I)Cl•H.sub.2O — — — 0.1 ethanol (100%) 45 45 45 45 ethanol (95%) — — — — BTC-65 (50%) 0.2 0.2 0.2 — Onyxide 3300 — — — 0.3 (33%) Neodol 91-6 0.1 0.1 0.1 0.1 triethanolamine 0.6 0.45 0.45 0.45 ethanolamine — — — — NH4OH — — — — (29.8%) NaOH (10%) — — — — Citrosol — — — — 502(50%) di H.sub.2O 54.0 54.15 54.35 54.05 pH 8.1 8.03 8.03 8.14 copper ion 372 318 140 641 content (ppm) appearance light blue light blue — light blue, slight haze ASTM E 1052 PV1 > 6.00 PV1 > 6.00 PV1 ≦ 5.50 PV! > 6.00 (log10 FCV => 6.00 reduction) ASTM 1053 — — — — (log10 reduction) EN 13697 — — — — (log10 reduction)

[0184] As can be seen from the foregoing results the compositions of the invention exhibited excellent microbicidal efficacy as demonstrated by the various test results, even wherein reduced levels of ethanol was present as a constituent.

[0185] Although this invention has been shown and described with respect to the detailed embodiments thereof, it will be understood by those of ordinary skill in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed in the above detailed description, but that the invention will include all embodiments falling within the scope of the appended claims.