Soap bar having enhanced antibacterial activity

Abstract

A soap bar comprising: (a) 25 to 85% by weight, based on the total weight of the bar, of fatty acid soap; (b) 0.1 to 100 ppm by weight, based on the total weight of the bar, of at least one silver (I) compound having a selected silver ion solubility, wherein at 25? C., a 1 wt % solution of the bar in water has a pH of from 9 to 11.

Claims

1. A soap bar comprising: (a) 25 to 85% by weight, based on the total weight of the bar, of fatty acid soap; (b) 0.1 to 100 ppm by weight, based on the total weight of the bar, of at least one silver (I) compound having a silver ion solubility in water at 25? C. of at least 1?10.sup.?4 mol/L, wherein at 25? C., a 1 wt % solution of the bar in water has a pH in a range of from 9 to 11.

2. The bar according to claim 1 wherein component (b) is one or more silver compounds selected from one group consisting of silver oxide, silver nitrate, silver acetate, silver sulfate, silver benzoate, silver salicylate, silver carbonate, silver citrate and silver phosphate.

3. The bar according to claim 1 wherein the silver (I) compound comprises silver oxide.

4. The bar according to claim 1 wherein the fatty acid soap comprises an alkali metal salt of aliphatic alkane- and/or alkene monocarboxylic acids having 8 to 18 carbon atoms.

5. The bar according to claim 1 wherein component (b) is one or more silver compounds selected from one group consisting of silver oxide, silver sulfate and silver citrate.

6. The bar according to claim 1 wherein component (b) is present in an amount of 1 to 50 ppm by weight, based on the total weight of the bar.

7. The bar according to claim 1 wherein component (b) is present in an amount of 5 to 20 ppm by weight, based on the total weight of the bar.

8. The bar according to claim 1 wherein the fatty acid soap (a) has been neutralized to an excess free alkali level of 0.01 to 0.05 wt %.

9. A method of reducing Gram positive bacteria on human skin, which comprises; (i) lathering a high pH solid soap composition to form an aqueous soap dilution containing the high pH solid soap composition at a level of from 1 to 25% by weight, based on the total weight of the dilution, wherein the high pH solid soap composition comprises: (a) 25 to 85% by weight, based on the total weight of the high pH solid soap composition, of fatty acid soap; and (b) 0.1 to 100 ppm by weight, based on the total weight of the high pH solid soap composition, of at least one silver(I) compound having a silver ion solubility in water at 25? C. of at least 1?10.sup.4 mol/L, wherein a 1% solution of said high pH solid soap composition has a pH of from 9 to 11; (ii) applying the aqueous soap dilution to the skin for a contact time of less than 1 minute; and (iii) rinsing the aqueous soap dilution from the skin; wherein the method provides a log.sub.10 reduction in biocidal activity against Gram positive bacteria.

10. The method according to claim 9 wherein the aqueous soap dilution is applied to the skin for a contact time of not more than 30 seconds.

11. The method of claim 10 wherein the high pH solid soap composition comprises from 1 to 50 ppm by weight of the silver (I) compound.

12. The method according to claim 9 wherein a 1 wt. % solution of the high pH solid soap composition in water has a pH of from 9.5 to 10.8.

13. The method of claim 10, wherein the contact time period is from 10 to 30 seconds.

14. The method according to claim 9, wherein the high pH solid soap composition provides a log.sub.10 reduction in biocidal activity against Staphylococcus aureus ATCC 6538 of at least 2 at a contact time of 10 seconds.

15. The method according to claim 9, wherein the high pH solid soap composition provides a log.sub.10 reduction in biocidal activity against Staphylococcus aureus ATCC 6538 of at least 3 at a contact time of 10 seconds.

16. The method according to claim 9, wherein the silver (I) compound is selected from the group consisting of silver oxide, silver nitrate, silver acetate, silver sulfate, silver benzoate, silver salicylate, silver carbonate, silver citrate and silver phosphate.

17. A soap bar comprising: (a) 25 to 85% by weight, based on the total weight of the bar, of fatty acid soap; (b) 0.1 to 100 ppm by weight, based on the total weight of the bar, of at least one silver (I) compound having a silver ion solubility in water at 25? C. of at least 1?10 mol/L, wherein: a 1 wt % solution of the bar in water at 25? C. has a pH in a range of from 9 to 11; and the silver (I) compound is selected from the group consisting of silver oxide, silver nitrate, silver acetate, silver sulfate, silver carbonate, silver citrate and silver phosphate.

18. The bar according to claim 17, wherein the fatty acid soap comprises an alkali metal salt of aliphatic alkane- and/or alkene monocarboxylic acids having 8 to 18 carbon atoms.

19. The bar according to claim 17, wherein the fatty acid soap (a) has been neutralized to an excess free alkali level of 0.01 to 0.05 wt %.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts, parts, percentages, ratios, and proportions of material, physical properties of material, and conditions of reaction are to be understood as modified by the word about. All parts, percentages, ratios, and proportions of material referred to in this description are by weight unless otherwise indicated.

(2) The term comprising is meant not to be limiting to any subsequently stated elements but rather to encompass non-specified elements of major or minor functional importance. In other words, the listed steps, elements or options need not be exhaustive. Whenever the words including or having are used, these terms are meant to be equivalent to comprising as defined above. Where the compositions of the subject invention are described as including or comprising specific components or materials, narrower embodiments where the compositions can consist essentially of or consist of the recited components or materials are also contemplated.

(3) It should also be noted that in specifying any range of concentration or amount, any particular upper concentration or amount can be associated with any particular lower concentration or amount.

(4) As used herein the term soap bar is used interchangeably with the terms solid soap composition or bar composition.

(5) Throughout the specification and claims, all references to log.sub.10 reduction in biocial activity against Staphylococcus aureus ATCC 6538, are to be understood as being pursuant to the In Vitro Time-Kill Protocol hereinafter described.

(6) Fatty Acid Soaps

(7) The term fatty acid soap or, more simply, soap is used here in its popular sense, i.e., salts of aliphatic alkane- or alkene monocarboxylic fatty acids preferably having 6 to 22 carbon atoms, and more preferably 8 to 18 carbon atoms. Reference to the fatty acid soap is to the fatty acid in neutralized form. Preferably the fatty acid from which the soap is derived is substantially completely neutralized in forming the fatty acid soap, that is say at least 95%, more particularly at least 98%, of the fatty acid groups thereof have been neutralized. In one or more embodiments it is preferred that the fatty acid soap is neutralized to an excess free alkali level of 0.01 to 0.05 wt %.

(8) Fatty acid soap should comprise 25-85% by weight, preferably 40 to 80% by weight, even more preferably 50 to 75% by weight of the bar composition. Typical thereof are alkali metal or alkanol ammonium salts of fatty acids, although other metal salts thereof, e.g., magnesium salts, may also be employed. Sodium, potassium, magnesium, mono-, di- and tri-ethanol ammonium salts of such acids are among the more common soaps suitable for use herein. Commonly, sodium soaps are used in the compositions of this invention, but up to about 25% of the soap may be potassium or magnesium soaps.

(9) As noted above, the fatty acids from which the soap salts are derived may contain unsaturation. The level of unsaturation should be in accordance with commercially acceptable standards. Excessive unsaturation is normally avoided to minimize color and odor issues. Commonly, not more than 40 wt. % of the fatty acids from which the soap salts are formed are unsaturated. In one or more embodiments, from 10 to 40 wt %, more particularly from 20 to 40 wt. %, of the fatty acids from which the soap salts are formed are unsaturated. In other embodiments, the fatty acids from which soap salts are formed are substantially free of unsaturation, i.e., less than 10 wt % of such fatty acids are unsaturated.

(10) Soaps may be made by the classic kettle boiling process or modern continuous soap manufacturing processes wherein natural fats and oils such as tallow or coconut oil or their equivalents are saponified with an alkali metal hydroxide using procedures well known to those skilled in the art. Alternatively, the soaps may be made by neutralizing fatty acids, such as lauric (C12), myristic (C14), palmitic (C16), or stearic (C18) acids with an alkali metal hydroxide or carbonate. Coconut oil employed for the soap may be substituted in whole or in part by other high-lauric oils, that is, oils or fats wherein at least 50% of the total fatty acids are composed of lauric or myristic acids and mixtures thereof. These oils are generally exemplified by the tropical nut oils of the coconut oil class. For instance, they include: palm kernel oil, babassu oil, ouricuri oil, tucum oil, cohune nut oil, murumuru oil, jaboty kernel oil, khakan kernel oil, dika nut oil, and ucuhuba butter. In at least one embodiment, the soap is derived from coconut oil and/or mixtures of tallow and coconut oil, with the sodium salts thereof being of particular interest.

(11) In one or more embodiments it is preferred that the combination of C.sub.16 and C.sub.18 fatty acids accounts for from 50 to 95 wt. % more particularly from 55 to 90 wt. % of the fatty acids from which the soap salts are formed and, preferably, that the combination of C.sub.12, C.sub.16 and C.sub.18 fatty acids accounts for from 85 to 99 wt. %, more particularly from 90 to 99 wt %, of the fatty acids from which the soap salts are formed. Preferably, the total amount of C.sub.8 and C.sub.10 fatty acids is less than 5 wt. %, and preferably is less than 3 wt. % of the fatty acids from which the soap salts are formed.

(12) Silver Compounds

(13) The silver compounds employed as component (b) of the subject bars are one or more water-soluble silver(I) compounds having a silver ion solubility at least 1.0?10.sup.?4 mol/L (in water at 25? C.). Silver ion solubility, as referred to herein, is a value derived from a solubility product (Ksp) in water at 25? C., a well known parameter that is reported in numerous sources. More particularly, silver ion solubility [Ag+], a value given in mol/L may be calculated using the formula:
[Ag+]=(Ksp.Math.x).sup.(1/(x+1)),
wherein Ksp is the solubility product of the compound of interest in water at 25? C., and x represents the number of moles of silver ion per mole of compound. It has been found that silver (I) compounds having a silver ion solubility of at least 1?10.sup.?4 mol/L are suitable for use herein. Silver ion solubility values for a variety of silver compounds are given in Table 1:

(14) TABLE-US-00001 TABLE 1 Silver ion Solubility Values Ksp Silver Ion (mol/L in Solubility [Ag+] water at (mol/L in water at Silver Compound X 25? C.) 25? C.). Silver nitrate 1 51.6 7.2 Silver acetate 1 2.0 ? 10.sup.?3 4.5 ? 10.sup.?2 Silver sulfate 2 1.4 ? 10.sup.?5 3.0 ? 10.sup.?2 Silver benzoate 1 2.5 ? 10.sup.?5 5.0 ? 10.sup.?3 Silver salicylate 1 1.5 ? 10.sup.?5 3.9 ? 10.sup.?3 Silver carbonate 2 8.5 ? 10.sup.?12 2.6 ? 10.sup.?4 Silver citrate 3 2.5 ? 10.sup.?18 1.7 ? 10.sup.?4 Silver oxide 1 2.1 ? 10.sup.?8 1.4 ? 10.sup.?4 Silver phosphate 3 8.9 ? 10.sup.?17 1.3 ? 10.sup.?4 Silver chloride 1 1.8 ? 10.sup.?10 1.3 ? 10.sup.?5 Silver bromide 1 5.3 ? 10.sup.?13 7.3 ? 10.sup.?7 Silver iodide 1 8.3 ? 10.sup.?17 9.1 ? 10.sup.?9 Silver sulfide 2 8.0 ? 10.sup.?51 2.5 ? 10.sup.?17

(15) Among the silver (I) compounds suitable for use herein are silver oxide, silver nitrate, silver acetate, silver sulfate, silver benzoate, silver salicylate, silver carbonate, silver citrate and silver phosphate, with silver oxide, silver sulfate and silver citrate being of particular interest in one or more embodiments. In at least one preferred embodiment the silver (I) compound comprises silver oxide.

(16) In at least one embodiment the silver compound is not silver dihydrogen citrate. In another embodiment the silver compound is not a salt of alginic acid or substantially depolymerized alginic acid. In one preferred embodiment the silver compound is not in the form of nano particles, attached to nano particles or part of intercalated silicates such as, for example, bentonite.

(17) Desirably, the silver (I) compound (b) is present in the subject bars at levels of 0.1-100 ppm by weight, more particularly 1-50 ppm by weight, even more particularly 5-20 ppm by weight, based on the total weight of the bar. Bars containing 5-15 ppm by weight of such silver (I) compound are of particular interest in one or more embodiments.

(18) In a preferred embodiment, the silver-containing compositions of the invention are used in combination with essential oil antimicrobial actives thymol and terpineol. Preferably, each is present in overall silver-containing composition at level of 0.01 to 2% of the composition.

(19) Thymol is preferably present in 0.02 to 0.5%, more preferably up to 0.3% by weight, further more preferably up to 0.2% by weight of the composition. Thymol may be added to the antimicrobial composition in purified form. Alternatively, thyme oil or thyme extract comprising thymol may be added to the antimicrobial composition, while ensuring that thymol is present in the desired concentration in the composition of the present invention. Thyme oil or thyme extract is obtained from the thyme plant. Thyme plant refers to a plant belonging be genus Thymus and includes but is not limited to the following species: Thymus vulgaris, Thymus zygis, Thymus satureoides, Thymus mastichina, Thymus broussonetti, Thymus maroccanus, Thymus pallidus, Thymus algeriensis, Thymus serpyllum, Thymus pulegoide, and Thymus citriodorus.

(20) The structures of thymol and its isomer carvacrol are given below:

(21) ##STR00001##

(22) Terpineol is preferably present at 0.05 to 1%, more preferably up to 0.5% by weight of the composition. The terpineol is preferably selected from alpha-terpineol, beta-terpineol, gamma-terpineol or mixtures thereof. It is particularly preferred that the terpineol is alpha-terpineol. Terpineol may be added to the antimicrobial composition in purified form. Alternatively pine oil comprising terpineol may be added to the antimicrobial composition.

(23) The structure of a terpineol compound is given below:

(24) ##STR00002##

(25) Optional Ingredients

(26) The subject bars typically include one or more skin benefit agents. The term skin benefit agent is defined as a substance which softens or improves the elasticity, appearance, and youthfulness of the skin (stratum corneum) by either increasing its water content, adding, or replacing lipids and other skin nutrients, or both, and keeps it soft by retarding the decrease of its water content. Included among the suitable skin benefit agents are emollients, including, for example, hydrophobic emollients, hydrophilic emollients, or blends thereof.

(27) Useful skin benefit agents include the following: (a) silicone oils and modifications thereof such as linear and cyclic polydimethylsiloxanes; amino, alkyl, alkylaryl, and aryl silicone oils; (b) fats and oils including natural fats and oils such as jojoba, soybean, sunflower, rice bran, avocado, almond, olive, sesame, persic, castor, coconut, and mink oils; cacao fat; beef tallow and lard; hardened oils obtained by hydrogenating the aforementioned oils; and synthetic mono-, di- and triglycerides such as myristic acid glyceride and 2-ethylhexanoic acid glyceride; (c) waxes such as carnauba, spermaceti, beeswax, lanolin, and derivatives thereof; (d) hydrophobic and hydrophilic plant extracts; (e) hydrocarbons such as liquid paraffin, petrolatum, microcrystalline wax, ceresin, squalene, pristan and mineral oil; (f) higher fatty acids such as lauric, myristic, palmitic, stearic, behenic, oleic, linoleic, linolenic, lanolic, isostearic, arachidonic and poly unsaturated fatty acids (PUFA); (g) higher alcohols such as lauryl, cetyl, stearyl, oleyl, behenyl, cholesterol and 2-hexydecanol alcohol; (h) esters such as cetyl octanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol monolaurate, glycerol distearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate; (i) essential oils and extracts thereof such as mentha, jasmine, camphor, white cedar, bitter orange peel, ryu, turpentine, cinnamon, bergamot, citrus unshiu, calamus, pine, lavender, bay, clove, hiba, eucalyptus, lemon, starflower, thyme, peppermint, rose, sage, sesame, ginger, basil, juniper, lemon grass, rosemary, rosewood, avocado, grape, grape seed, myrrh, cucumber, watercress, calendula, elder flower, geranium, linden blossom, amaranth, seaweed, ginko, ginseng, carrot, guarana, tea tree, jojoba, comfrey, oatmeal, cocoa, neroli, vanilla, green tea, penny royal, aloe vera, menthol, cineole, eugenol, citral, citronelle, borneol, linalool, geraniol, evening primrose, camphor, thymol, spirantol, penene, limonene and terpenoid oils; (j) polyhydric alcohols, for example, glycerine, sorbitol, propylene glycol, and the like; and polyols such as the polyethylene glycols, examples of which are: Polyox WSR-205 PEG 14M, Polyox WSR-N-60K PEG 45M, or Polyox WSR-N-750, and PEG 7M; (k) lipids such as cholesterol, ceramides, sucrose esters and pseudo-ceramides as described in European Patent Specification No. 556,957; (l) vitamins, minerals, and skin nutrients such as milk, vitamins A, E, and K; vitamin alkyl esters, including vitamin C alkyl esters; magnesium, calcium, copper, zinc and other metallic components; (m) sunscreens such as octyl methoxyl cinnamate (Parsol MCX) and butyl methoxy benzoylmethane (Parsol 1789); (n) phospholipids; and (o) anti-aging compounds such as alpha-hydroxy acids and beta-hydroxy acids.

(28) Skin benefit agents typically account for up to 45% by weight of the bar, with levels of from 1 to 15% by weight, more particularly from 1 to 8% by weight, being typical of the levels at which those skin benefit agents generally known as emollients are employed in the subject bars. Preferred skin benefit agents include fatty acids, hydrocarbons, polyhydric alcohols, polyols and mixtures thereof, with emollients that include at least one C.sub.12 to C.sub.18 fatty acid, petrolatum, glycerol, sorbitol and/or propylene glycol. Fatty acid emollients, when present, are distinguished from the fatty acid soap component of the subject bars. When present, the total amount of free fatty acid typically does not exceed 5% by weight of the subject bars.

(29) Additional optional ingredients which may be present in the subject bars are, for example: fragrances; sequestering and chelating agents such as tetrasodium ethylenediaminetetraacetate (EDTA), ethane hydroxyl diphosphonate (EHDP), and etidronic acid, aka 1-hydroxyethylidene diphosphonic acid (HEDP); coloring agents; opacifiers and pearlizers such as zinc stearate, magnesium stearate, TiO.sub.2, ethylene glycol monostearate (EGMS), ethylene glycol distearate (EGDS), or Lytron 621 (Styrene/Acrylate copolymer) and the like; pH adjusters; antioxidants, for example, butylated hydroxytoluene (BHT) and the like; preservatives; stabilizers; antimicrobials/preservatives such as, for example, 2-hydroxy-4,2,4 trichlorodiphenylether (Triclosan), dimethyloldimethylhydantoin (Glydant XL1000), parabens, sorbic acid, thymol, and terpineol to name a few (with combinations of thymol and terpineol as described, for example, in U.S. Patent Application Publication No. 2011/0223114 incorporated herein by reference, being of particular interest in one or more embodiments); suds boosters, such as for example, coconut acyl mono- or diethanol amides; ionizing salts, such as, for example, sodium chloride and sodium sulfate, and other ingredients such as are conventionally used in soap bars. The total amount of such additional optional ingredients is typically from 0 to 15% by weight, more particularly from 0.01 to 10% by weight, based on the total weight of the bar.

(30) Bar Manufacture

(31) The bars described in this application can be prepared using manufacturing techniques described in the literature and known in the art for the manufacture of soap bars. Examples of the types of manufacturing processes available are given in the book Soap Technology for the 1990's (Edited by Luis Spitz, American Oil Chemist Society Champaign, Ill. 1990). These broadly include: melt forming, extrusion/stamping, and extrusion, tempering, and cutting. A preferred process is extrusion and stamping because of its capability to economically produce high quality bars.

(32) The soap bars may, for example, be prepared by either starting with or forming the soap in situ. When employing the fatty acid or acids that are the precursors of the soap as starting ingredients, such acid or acids may be heated to temperature sufficient to melt same, typically at least 80? C. and, more particularly from 80? C. to below 100? C., and neutralized with an suitable neutralizing agent or base, for example, sodium hydroxide, commonly added as a caustic solution. The neutralizing agent is preferably added to the melt in an amount sufficient to fully neutralize the soap-forming fatty acid and, in at least one embodiment, is preferably added in an amount greater than that required to substantially completely neutralize such fatty acid, for example an amount of 0.01-0.05 wt % greater than that needed for full neutralization.

(33) Following neutralization, excess water may be evaporated and additional composition components, including silver (I) compound added. Desirably water content is reduced to a level such that, based on the total weight thereof, the resulting bars contains no more that 25% by weight, preferably no more than 20% by weight, more preferably no more than 18% by weight of water, with water contents of from 8 to 15% by weight being typical of many bars. In the course of processing, either as part of neutralization and/or subsequent thereto, the pH may be adjusted, as needed, to provide the high pH desired for the subject bars.

(34) The resulting mixture may be formed into bars by pouring the mixture, while in a molten state into molds or, by amalgamation, milling, plodding and/or stamping procedures as are well known and commonly employed in the art. In a typical process, the mixture is extruded through a multi-screw assembly and the thick liquid that exits therefrom, which typically has a viscosity in the range of 80,000 to 120,000 cPs, is made to fall on rotating chilled rolls. When the viscous material falls on the chilled rolls, flakes of soap are formed. These flakes are then conveyed to a noodler plate for further processing. As the name suggests, the material emerging from this plate is in the form of noodles. The noodles are milled, plodded and given the characteristic shape of soap bars.

(35) The bars may also be made by melt cast processes and variations thereof. In such processes, saponification is commonly carried out in an ethanol-water mixture (or the saponified fatty acid is dissolved in boiling ethanol). Following saponification other components may be added, and the mixture is preferably filtered, poured into molds, and cooled. The cast composition then undergoes a maturation step whereby alcohol and water are reduced by evaporation over time. Maturation may be of the cast composition or of smaller billets, bars or other shapes cut from same. In a variation of such process described in U.S. Pat. Nos. 4,988,453 and 6,730,643, incorporated herein by reference, saponification is carried out in the presence of polyhydric alcohol and water, with the use of volatile oil in the saponification mixture being reduced or eliminated. Melt casting allows for the production of translucent or transparent bars, in contrast to the opaque bars typically produced by milling or other mechanical techniques.

(36) In one or more embodiments, the subject bars have a penetration value of from 0.1 mm to 4 mm, preferably from 1 mm to 3 mm. Penetration value is determined using a penetrometer fitted with a weighted, moveable cone (150 g?0.1 g), the cone being further characterized as having a cone angle: of 32.2?, a height of 16 mm, and base width of 9.3 mm; such an instrument is available from Adair Dutt and Company. The sample to be measured is equilibrated to 25? C. and positioned under the cone such that the cone tip just touches the sample surface; the cone is then is released and allowed to fall freely, and its distance of penetration into the sample in a period of 5 seconds is measured to the nearest 0.1 mm. The test is repeated three times, allowing at least 5 mm distance between each measurement position on the sample. The average of the three repeat tests is the penetration value. A higher value indicates a softer bar.

(37) The soap compositions of this invention are of interest with respect to biocidal activity against Gram positive bacteria, including in particular S. aureus. Other Gram positive bacteria against which the soap compositions are of interest are S. epidermidis, and/or Corynebacteria, in particular, Corynebacteria strains responsible for the hydrolysis of axilla secretions to malodorous compounds. Desirably, the bar provides a log.sub.10 reduction in biocial activity against Staphylococcus aureus ATCC 6538 of at least 2, preferably at least 3 more preferably at least 3.5 at a contact time of 30 seconds, and even more preferably provides a Log.sub.10 Reduction against S aureus ATCC 6538 of at least 1, preferably at least 1.5 more preferably at least 2 at a contact time of 10 seconds.

(38) In use, the bars are diluted with water to form what is typically a 1 to 25 wt % solution thereof in water, and the resulting soap solution applied to the skin for contact times under 1 minute, typically 30 seconds or less (with contact times of 10 to 30 seconds being of interest with respect to contact times of a moderate to relatively long duration, and contact times of 10 seconds or less being of interest with respect to contact times of short to moderate duration), and thereafter is removed from the skin, typically by rinsing with water. Preferably the bars have a lather volume of at least 200 ml following the procedure of Indian Standard 13498:1997, Annex C, incorporated herein by reference.

EXAMPLES

(39) The following non-limiting examples are provided to further illustrate the invention; the invention is not in any way limited thereto. The following protocol was used to evaluate biocidal activity.

(40) In-Vitro Time-Kill Protocol

(41) Soap Solution Preparation

(42) The solid soap bar being evaluated is mixed with water and dissolved at 50? C. to give a 10 wt % solution. After dissolution, the resulting soap bar solution is equilibrated at 46? C. prior to performing the bactericidal assay procedure.

(43) Bacteria

(44) Staphylococcus aureus ATCC 6538, were used in this study to represent Gram positive bacteria. The bacteria was stored at ?80? C. Fresh isolates were cultured twice on Tryptic Soy Agar plates for 24 hours at 37? C. before each experiment.

(45) In-Vitro Time-Kill Assay

(46) Time-kill assays are performed according to the European Standard, EN 1040:2005 entitled Chemical Disinfectants and AntisepticsQuantitative Suspension Test for the Evaluation of Basic Bactericidal Activity of Chemical Disinfectants and AntisepticsTest Method and Requirements (Phase 1), incorporated herein by reference. Following this procedure Growth-phase bacterial cultures at 1.5?10.sup.8 to 5?10.sup.8 colony forming units per ml (cfu/ml) are treated with the 10 wt. % soap bar solutions (prepared as described above) at 46? C.

(47) In forming the test samples, 8 parts by weight of the 10 wt. % soap bar solution is combined with 1 part by weight of the culture and 1 part by weight of water, i.e., the concentration of the soap bar composition in the test samples is 8 wt. %. After 10, 30, and 60 seconds of exposure, samples are neutralized to arrest the antibacterial activity of the soap solutions. The resulting solutions are serially diluted, plated on solid medium, incubated for 24 hours and surviving cells are enumerated. Bactericidal activity is defined as the log reduction in cfu/ml relative to the bacterial concentration at 0 seconds. Cultures not exposed to any soap or silver solutions serve as no-treatment controls.

(48) The log.sub.10 reduction is calculated using the formula:
Log.sub.10 Reduction=log.sub.10 (numbers control)?log.sub.10 (test sample survivors)

Examples 1 to 13 and Comparative Examples A to E

(49) Soap bars were prepared according to formulations as indicated in Table 2 below.

(50) TABLE-US-00002 TABLE 2 Ingredient (wt. %) Soap Bar I Soap Bar II Anhydrous Sodium Soap 68.04 68.04 (85 wt. % tallow soap/15 wt. % coconut soap) Soda Ash 0.5 0.5 C10-18-alpha olefin-sulfonate 1.1 1.1 (90 wt. % in water) Talc 6.0 6.0 Glycerine 6.0 6.0 Sodium Chloride 0.8 0.8 Etidronic Acid 0.1 0.10 Tetrasodium EDTA 0.04 0.04 Silver Compound As indicated in Table 3 0 Water To 100% To 100% pH (as a 1 wt % aqueous 10.7 10.7 solution)

(51) The biocidal activity of the bars so produced was evaluated following the above described protocol. Also evaluated were aqueous solutions of silver compound, formulated to a pH comparable to that of the soap solution (i.e., pH 10.7). Biocidal activity results are reported in Tables 3 to 5. Silver levels reported in Examples 1 to 3 are based on the weight percent of silver compound in the soap bar. Silver levels reported in Comparative Examples A and B are reported as the levels of silver in the test solution prior to the combination of 8 parts by weight thereof with one part by weight of culture and 1 part by weight of water.

(52) TABLE-US-00003 TABLE 3 Biocidal Activity Log.sub.10 Reduction against S. aureus ATCC 6538 (Average ? S.D.) Contact Time Example Composition 10 Seconds 30 Seconds 60 Seconds 1 Soap bar I with 2.0 ? 0.5 4.1 ? 0.4 >4.2 0.01 wt. % Ag.sub.2SO.sub.4* 2 Soap bar I with 1.2 ? 0.5 3.5 ? 0.6 >4.1 0.001 wt. % Ag.sub.2SO.sub.4** 3 Soap bar I with 1.5 ? 0.2 3.1 ? 0.3 >4.2 0.001 wt % Ag.sub.2O*** A 0.001 wt % 0.3 ? 0.3 0.3 ? 0.3 0.4 ? 0.2 (Comp.) Ag.sub.2SO4 B 0.0001 wt. % ?0.1 ? 0.1 0.1 ? 0.2 0.2 ? 0.1 (Comp.) Ag.sub.2O C Soap bar II (no 0.3 ? 0.1 0.7 ? 0.2 1.7 ? 0.3 (Comp.) silver compound) *10 wt. % soap bar solution contained 0.001 wt. % Ag.sub.2SO.sub.4. **10 wt. % soap bar solution contained 0.0001 wt. % Ag.sub.2SO.sub.4. ***10 wt/% soap bar solution contained 0.0001 wt. % Ag.sub.2O.

(53) As demonstrated by the Table 3 data, Comparative Example A failed to provide a significant biocidal effect at contact times of 10, 30 and 60 seconds. Likewise, Comparative Example C failed to provide a significant biocidal effect at contact times of 10 and 30 seconds. In contrast, Examples 1 to 3 demonstrate that the combination of soap and silver compound (Ag.sub.2SO.sub.4 or Ag.sub.2O) provides a synergistic effect with respect to biocidal activity at contact times of 10, 30 and 60 seconds.

(54) The next series of Examples, reported in Table 4, compares the biocidal effects of soap bar solutions to which silver compound is post-added at a constant level (0.001 wt. % of the soap bar solution). Test samples were prepared by combining 8 parts by weight of a given soap bar solution with 1 part by weight of culture and 1 part by weight of water. The reported soap bar contents are based on the soap bar content of the final test samples. The level of silver compound in Comparative Example D is the amount of silver in the solution prior to the combination of 8 parts by weight thereof with 1 part by weight of culture and 1 part by weight of water. Biocidal activity of the test samples is evaluated as described above.

(55) TABLE-US-00004 TABLE 4 Biocidal Activity S. aureus ATCC 6538 Log.sub.10 Reduction (Average ? S.D.) Contact Time Example Composition 10 Seconds 30 Seconds 60 Seconds D (Comp.) 0.001% Ag.sub.2SO.sub.4 0.0 ? 0.1 0.1 ? 0.2 0.3 ? 0.4 Example 4 1 wt % Soap 0.7 ? 0.1 2.7 ? 0.1 >3.9 bar II/0.001% Ag.sub.2SO.sub.4 Example 5 2 wt % Soap 1.3 ? 0.1 3.0 ? 0.2 >4.1 bar II/0.001% Ag.sub.2SO.sub.4 Example 6 3 wt % Soap 1.4 ? 0.2 3.1 ? 0.2 >3.9 bar II/0.001% Ag.sub.2SO.sub.4 Example 7 4 wt % Soap 1.4 ? 0.1 3.4 ? 0.2 >4.1 bar II/0.001% Ag.sub.2SO.sub.4 Example 8 6 wt % Soap 1.8 ? 0.2 3.6 ? 0.1 >4.1 bar II/0.001% Ag.sub.2SO.sub.4 Example 9 8 wt % Soap 1.9 ? 0.1 3.9 ? 0.3 >4.1 bar II/0.001% Ag.sub.2SO.sub.4

(56) As demonstrated by the Table 4 data, a synergistic effect is observed for each of the soap bar levels tested.

(57) Table 5 compares the biocidal activity of soap bar solutions containing different post added-silver compounds. Silver compound was post added at the reported levels to 10 wt. % solutions of soap bar II in water. Test samples (prepared by combining 8 parts by weight of silver compound-containing soap bar solution with 1 part by weight of culture and 1 part by weight of water) were evaluated as described above.

(58) TABLE-US-00005 TABLE 5 Biocidal Activity S. aureus ATCC 6538 Log.sub.10 Reduction (Average ? S.D.) Silver Ion Solubility [Ag+] (mol/L in Contact Time Example water at 25? C.). Composition 10 Seconds 30 Seconds 60 Seconds E 1.3 ? 10.sup.?5 Soap bar II/ 0.3 ? 0.2 1.7 ? 0.2 3.1 ? 0.2 (Comp.) 0.001% AgCl 10 2.6 ? 10.sup.?4 Soap bar II/ 2.6 ? 0.5 3.7 ? 0.1 >3.8 0.001% Ag.sub.2CO.sub.3 11 4.5 ? 10.sup.?2 Soap bar II/ 2.6 ? 0.5 >3.8 >3.8 0.001% Ag Acetate 12 1.7 ? 10.sup.?4 Soap bar II/ 2.3 ? 0.5 >3.8 >3.8 0.001% Ag Citrate 13 7.2 Soap bar II/ 2.5 ? 0.5 >3.8 >3.8 0.001% AgNO.sub.3

(59) Comparative Example E which included soap and silver chloride (a silver compound having a silver ion solubility in water at 25? C. of 1.3?10.sup.?5 mol/L (a value under 1?10.sup.?4 mol/L)) lacked significant biocidal activity at a contact time of 10 seconds. At contact times of 30 and 60 seconds, Comparative Example E had significantly lower biocidal activity than the soap/silver compositions of Examples 10 to 13, which contained silver compounds of higher silver ion solubility.