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Title:
WIPING ARTICLE
Document Type and Number:
WIPO Patent Application WO/2014/089560
Kind Code:
A1
Abstract:
A wiping article, which includes a substrate, a germicidal liquid, and a titanium oxide moiety.

Inventors:
GEOFFRION CHARLES (US)
GROSSMAN CRAIG (US)
Application Number:
PCT/US2013/073879
Publication Date:
June 12, 2014
Filing Date:
December 09, 2013
Export Citation:
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Assignee:
ALLIED BIOSCIENCE SERVICES INC (US)
International Classes:
A47L17/08
Domestic Patent References:
WO2009057046A22009-05-07
Foreign References:
US7262158B12007-08-28
US5569732A1996-10-29
US20090209665A12009-08-20
US20090118152A12009-05-07
Attorney, Agent or Firm:
REGELMAN, Dale, F. (One South Church AvenueSuite 170, Tucson AZ, US)
Download PDF:
Claims:
We claim:

1. A wiping article, comprising:

a substrate;

a germicidal liquid; and

a titanium oxide moiety.

2. The wiping article of claim 1, wherein"

said substrate comprises a fibrous material;

said fibrous material is impregnated with said germicidal liquid and said photocatalyst particles.

3. The wiping article of claim 2, wherein said germicidal liquid comprises a siloxane.

4. The wiping article of claim 3, wherein said siloxane comprises a quarternary ammonium salt.

5. The wiping article of claim 4, wherein said siloxane comprises the structure:

0

1

Me

wherein Rl and R2 are selected from the group consisting of alkyl, alkenyl, phenyl, and benzyl.

6. The wiping article of claim 1, further comprising an oxidizable pigment.

7. The wiping article of claim 6, wherein said oxidizable pigment comprises Methylene Blue.

8. The wiping article of claim 7, wherein said titanium oxide moiety is formed from a titanium tctraalkoxide and a hydroxyacid.

9. The wiping article of claim 8, wherein said titanium oxide moiety is formed from titanium tetraisopropoxide and tartaric acid.

10. The wiping article of claim 1, wherein said titanium oxide moiety comprises titanium dioxide particles.

11. A method for disinfecting a surface, comprising contacting the surface with a wiping article comprising a substrate impregnated with a germicidal liquid and a titanium oxide moiety so that the germicidal solution and the titanium oxide moiety are expressed therefrom.

12. The method of claim 11, wherein said germicidal solution comprises a siloxane.

13. The method of claim 3, wherein said siloxane comprises a quarternary ammonium salt.

14. The method of claim 13, wherein said siloxane is present at a level between about 0.005 grams and about 0.20 grams per gram of said wiping article.

15. The method of claim 13, wherein said siloxane comprises the structure:

wherein Rl and R2 are selected from the group consisting of alkyl, alkenyl, phenyl, and benzyl.

16. The method of claim 11, further comprising an oxidizable pigment.

17. The method of claim 16, wherein said oxidizable pigment comprises Methylene Blue.

18. The method of claim 11 , wherein said titanium oxide moiety is formed from a titanium tetraalkoxide and a hydroxyacid.

19. The method of claim 19, wherein said titanium oxide moiety is formed from titanium tetraisopropoxide and tartaric acid.

20. The method of claim 11 wherein said titanium oxide moiety comprises titanium dioxide particles.

Description:
WIPING ARTICLE

Field Of The Invention

The present invention relates to flexible wiping articles including sponges, as well as woven or non-woven wipes, and the like. More specifically, the present invention relates to wiping articles which can dispose on a surface a coating having a residual long-term antimicrobial effect.

Background Of The Invention

Wiping articles are commonly used in the cleaning of hard surfaces including but not limited to, glass, dishes, porcelain, lavatory fixtures, kitchen fixtures and appliances, sinks, and the like. These take a variety of forms, including woven and non-woven wipes formed of fibrous (natural or synthetic) materials and hydrophilic sponges.

What is needed is a wiping article that can dispose on a surface a material having a long-term antimicrobial effect.

Detailed Description Of Preferred Embodiments

This invention is described in preferred embodiments in the following description with reference to the Figures, in which like numbers represent the same or similar elements. Reference throughout this specification to "one embodiment," "an embodiment," or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of th e present invention. Thus, appearances of the phrases "in one embodiment," "in an embodiment," and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.

The described features, structures, or characteristics of the invention may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are recited to provide a thorough understanding of embodiments of the invention . One skilled in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well- known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.

[0006] The schematic flow charts included are generally set forth as logical flow chart diagrams. As such, the depicted order and labeled steps are indicative of one embodiment of the presented method. Other steps and methods may be conceived that are equivalent in function, logic, or effect to one or more steps, or portions thereof, of the illustrated method. Addit ionally, the format and symbols employed are provided to explain the logical steps of the method and are understood not to limit the scope of the method.

Although various arrow types and line types may be employed in the flow chart diagrams, they are understood not to limit the scope of the corresponding method. Indeed, some arrows or other connectors may be used to indicate only the logical flow of the method. For instance, an arrow may indicate a waiting or monitoring period of unspecified duration between enumerated steps of the depicted method. Additionally, the order in which a particular method occurs may or may not strictly adhere to the order of the corresponding steps shown .

[0007] In certain embodiments. Applicants' wiping articles comprise sponge

substrates, preferably hydrophilic sponges, woven substrates, and non- woven fibrous substrates. In certain embodiments. Applicants' sponge substrates are formed from foamed rubbers (naturally occurring or synthetically produced ), foamed polymers such as polyurethane, poly propylene, polyethy lene, polyester, polyethers. and of regenerated cellulose. Sponges which are particularly useful in the compositions of the present invention arc those w hich are formed from cellulose and are also interchangeably referred as viscose sponges. These are known to the art and are produced from comminuted and ground wood pulp which are then regenerated to form a porous hydrophil ic article.

[0008] With regard to such sponges, it is to be understood that these may be of a single material and of a single layer, or they may be produced as a composite material. What is to be understood as composite material is that two or more differing materials may be combined to form a sponge where at least one layer is hydrophilic, especial ly a first layer of a hydrophilic material which is glued, sewn, or otherwise connected to a second layer of a differing material. Such differing materials include those which are commonly known, including those formed of woven and/or non-woven fabric materials which arc often intended to prov ide an abrasive surface which are not particularly deleterious to soft surfaces. Also, such composite sponges also include those which include one or two differing hydrophilic sponge materials which may be sewn together. In this sponge construction, sponges of two different materials are sewn together at peripheral edges, and further optionally on at least one face of the sponge is further included a woven textile material .

|0009| With regard to woven and/or non-woven substrates, these include a variety of materials which may be formed into wipes by the knitting or weav ing of fibrous materials, particularly polymeric fibrous materials including, but not limited to, polypropylene, polyethylene, polyester, polyamide, regenerated cellulosic fibers as well as those based on naturally occurring materials such as cellulose fibers particularly those which are based on wood pulp fibers as provided by either chemical and/or mechanical pulp fibers. Such fibers may alternately be formed into a non-woven web by a variety of known art techniques including, inter alia, air laying and wet laying of the naturally occurring (cellulose) and/or synthetic (polymeric) fibers into a web. Further useful are non-woven materials wherein a non- woven mat of such fibrous materials a e produced by providing an intermediate adhesive between the individual fibers, or by cross linking of the fibers themselves.

|00010| Further useful woven and/or non-wov en wipes include those which are produced from cellulosic fibers which may be formed into a web by a variety of known art techniques, including air laying and wet laying of the fibers To such woven and/or non-woven fibers may also be added amounts of abrasive materials, including but not limited to, metal oxides especially titanium dioxide.

[00011] It is to be understood that with regard to the description of the wiping articles, the sponges, woven, and non-woven wipes, described above are provided by way of illustration not by way of limitation, and other materials other than described herein may also enjoy the benefits of the present invention.

[00012| The wiping articles according to the invention, including the hydrophilic sponges, may be prepared by any of a number of conventional techniques including but not l imited to: spraying the Applicants' anti-microbial composition onto or into a wiping article, or dipping or soaking the wiping article into a l iquid carrier containing Applicants' anti-microbial composition, or even supplying the biocidal composition in a process step wherein the wiping articles, particularly sponges, are formed.

[00013] I n certain embodiments. Applicants' wiping article comprises a substrate, a siloxane, and a titanium oxide moiety. In certain embodiments, the titanium oxide moiety comprises a plural ity of titanium dioxide particles.

[00014] In certain embodiments, the titanium oxide moiety is forming using a

(RO) 4 Ti starting material . For example, in certain embodiments Applicants form a liquid composition using titanium tetraisopropoxide 2 to form a coating comprising a linear polymeric structure 3.

2 3

[00015] I n certain embodiments. Applicants' titanium oxide moiety is formed from a titanium tetraalkoxidc and a hydroxyacid. In certain embodiments. Appl icants' titanium oxide moiety is formed from titanium

tctrai so p ro po x i d e and tartaric acid. The following example is presented to further illustrate to persons skilled in the art how to make and use the invention. This example is not intended as a limitation, however, upon the scope of the inv ention. ine (9.0) grams of tartaric acid were dissolved in 0. 120 liters of water in an Erlenmeyer flask to give a 0.5 molar solution. This solution was stirred overnight at room temperature. The following day, the tartaric acid solution was filtered through filter paper (Whatman #1), then subsequently through a 0.2 micron PRFW filter to remov e particulates. 25 mL of filtered 0.5 M tartaric acid (0.01249 moles of tartaric acid ) was poured into a round bottom flask and chil led on ice with stirring. 3.69 grams of titanium (IV) isopropoxide was added slowly first with a 1 mL addition. 1 mL aliquots of titanium (IV) isopropoxide were added until all of it was added to the tartaric acid solution.

Upon addition of the titanium (IV) isopropoxide the ice bath was removed. The solution remained a solution for approximately 10 minutes after which it became a clear gel and became progressively opaque (white). The gel was stirred at RT overnight. The gelatinous material was mixed with water, or isopropanol and water to form a liquid composition used as Applicants' titanium oxide moiety in their wiping article.

The germicidal nature of the titanium tetraisopropoxide / tartaric acid composition was determined. The gelatinous product w r as mixed with water, or alcohol ROH and water, and then cast onto a glass sl ide to form a coating thereon.

Depending on the stoichiometry of the starting materials, in certain embodiments Applicants' coating of this Example comprises a tartaric acid / titanium isopropoxide adduct 5, wherein R is H, alky I, and phenyl . When the molar ratio of TI(OR)4 and tartaric acid is greater that about 3, the adduct product 4 predominates.

When the molar ratio of TI(OR)4 and tartaric acid is about 1 , a polymeric product 5 predominates, wherein (r) is between 2 and about 10. When the molar ratio of TI(OR) 4 and tartaric acid is greater than 1 but less than about 3, a mixture of adduct 4 and polymer 5 is obtained. In the Example, the molar ratio is about 5, and adduct 5 is predominately formed.

5 In other embodiments. Applicants' coating composition comprises a reaction product of one or more hydroxyl acids other than tartaric acid and titanium tetraisopropoxide.. In certain embodiments, these one or more hydroxyl acids include one or more alpha hydroxyl acids including glycol ic acid, lactic acid, citric acid, and/or mandelic acid. In certain embodiments, these one or more hydroxyl acids include one or more beta hydroxy! acids including salicyclic acid and/or beta-hydroxy propionic acid.

[00022] In certain embodiments, Applicants' reaction product formed from one or more hydroxyl acids other than tartaric acid and titanium t e t ra i so p ro po x i d e is embodied in a flexible, planar member to form a composite disinfecting wipe. Applicants' composite disinfecting wipe is capable of cleaning and removing residues from soiled surfaces while simultaneously destroying undesirable microorganisms, e.g. bacteria, mold, v iruses, prions and the like that colonize on common surfaces with which people come into contact, such as doorknobs, countertops, toilet seats, floors, beds, walls, and the l ike.

[00023] Glass slides prepared in accord with the reaction product of tartaric acid and titanium tetraisopropoxide were inoculated with bacteria or virus and sampled at various times w ith a sterile cotton swab. That cotton sw ab was placed into a tube containing a neutral izing broth. Methicil lin resistant Staphylococcus aureus ( "M RSA" ) and MS -2 were utilized. MS-2 is a bacteriophage used as a surrogate for Norovirus, Enterovirus, Polio, and the like. The table below recites log reduction of MRSA-inoculated glass slides coated using various w eight percent solutions of the composition of the Example to form a coating on the glass sl ides prior to M RSA inoculation.

Log Reductions Of MRSA Using Reaction Product Of Tartaric Acid And

Titanium Tetraisopropoxide

[00024] The table below recites data using slides coated using a 10 weight percent of the reaction product of tartaric acid and titanium tetraisopropoxide to form a coating on the glass slides prior to either MRSA or MS-2 inoculation. MS-2 was showed an average of 2.4 log reduction at two hours. MRSA showed greater than a 5.6 log reduction at two hours.

[00025] A test using glass slides coated using a 3 weight percent solution of the coating composition formed using the reaction product of tartaric acid and titanium t e t ra i so p ro po x i d e , and inoculated w ith either M RSA or MS-2. wherein the slides were inoculated in the dark, did not show any log reduction. This result shows that the titanium moieties in the glass slide coating were providing anti-microbial function via a photocatalytic effect.

[00026] The table below recites data regarding the anti-microbial efficacy of

coatings formed on glass slides using various weight percent solutions of the coating composition formed using the reaction product of tartaric acid and titanium tetraisopropoxide after one hour.

[00027] An exemplary, non-limiting, process is one according to the following. A quantity of a titanium oxide moiety is disposed in a liquid carrier, such as for example, water and/or organic solvents such as alcohols, glycols, glycol ethers, and the like. Next, a quantity of one or more quarternary ammonium si lanes is dispersed, or dissolved therein. Next, the wiping article intended to be impregnated is then immersed w ithin the liquid carrier and al lowed to fully entrain the titanium oxide moiety / quarternary ammonium si lane composition. Thereafter, the wiping article is withdrawn, the liquid carrier is then substantially driven off (which may require mild heating, drawing of a vacuum, or merely permitting it to sit in the ambient env ironment ). Depending upon the volatility of the liquid carrier, such may evaporate readily into the air.

[00028] Optionally, the wiping article may be first compressed such as through pinch rollers, wrung, or squeezed in order to dry off as much as possible of the liquid carrier containing the titanium oxide moiety / quarternary ammonium silane composition. The recov ered l iquid carrier containing the titanium oxide moiety / quarternary ammonium silane composition is subsequently reused.

[00029] While the efficacy of the quarternary ammonium silane selected for use may vary, and that a higher or lower dosing of quarternary ammonium silane per unit mass of the wiping article may be requi ed, generally good results have been achieved when at least about 0.005 grams of the quarternary ammonium silane are present per gram of wiping article based on the dry weight of the wiping article, viz., in a substantially dehydrated state. In certain embodiments, from about 0.005 grams to about 0.20 grams of the quarternary ammonium silane are present per gram of wiping article, on a dry weight basis, especially where the wiping article is a cellulose sponge. In certain embodiments, the quarternary ammonium silane is present in amounts of from 0.01 grams to 0.1 grams. In certain embodiments, from 0.02 grams to 0. 1 grams per gram of the wiping article, especially sponges, based on the dry weight of the wiping article. It is to be understood that higher dosing of the quarternary ammonium silane will also be expected to impart a longer duration of the anti-microbial properties of the composition deposited onto a surface using Applicants' anti-microbial w ipe.

[00030] In addition, good results have been achieved when at least about 0.005 grams of the titanium oxide moiety are present per gram of wiping article based on the dry weight of the wiping article, viz., in a substantially dehydrated state. In certain embodiments, from about 0.005 grams to about 0.20 grams of titanium oxide moiety are present per gram of wiping article, on a dry weight basis, especially where the w iping article is a cellulose sponge. In certain embodiments, titanium oxide moiety is present in amounts of from 0.01 grams to 0. 1 grams. In certain embodiments, from 0.02 grams to 0.1 grams per gram of the wiping article, especially sponges, based on the d y weight of the wiping article. It is to be understood that higher dosing of titanium oxide moiety, such as and without limitation Ti()2,will also be expected to impart a longer duration of the anti-microbial properties of the composition deposited onto a surface using Applicants' anti-microbial wipe.

As opposed to prior art wiping articles, Applicants' anti-microbial wipes dispose on a surface a long-lasting anti-microbial composition. By "long- lasting," Applicants' mean up to at least thirty (30) days. When

Applicants' anti-microbial wi e is drawn across a surface, a composition comprising a titanium oxide moiety and an ammonium silane is deposited onto that surface.

Applicants have found that manually wiping a surface comprising an initial bacterial concentration Co with an embodiment of Applicants' wiping article comprising a loading of about 0.01 grams Ti0 2 , in combination with about 0.01 grams of quartemary ammonium silane, per gram of wiping article based upon the d y weight of the wiping article, disposes a chemical composition onto the surface, wherein that surface at about time T1.5, i .e. 1 .5 days post-surface treatment, comprises a bacterial concentration Cj .5 DAYS, wherein C ' 1.5 DAYS comprises about a ninety-seven percent (97%) reduction over the initial bacterial concentration Co.

Applicants have found that manually wiping a surface comprising an initial bacterial concentration Co with an embodiment of Applicants' wiping article comprising a loading of about 0.05 grams Ti0 2 , in combination with about 0.05 grams of quartemary ammonium silane, per gram of wiping article based upon the d y weight of the wiping article, disposes a chemical composition onto the surface, wherein that surface at about time T 7 DAYS, i.e. 7 days post-surface treatment, comprises a bacterial concentration C 7 DAYS, wherein C 7 DAYS comprises about a ninety-seven percent (97%) reduction over the initial bacterial concentration Co.

Applicants have found that manually wiping a surface comprising an initial bacterial concentration Co with an embodiment of Applicants' wiping article comprising a loading of about 0. 10 grams Ti0 2 , in combination w ith about 0. 10 grams of quartemary ammonium silane, per gram of wiping article based upon the dry weight of the wiping article, disposes a chemical composition onto the surface, wherein that surface at about time T15 DAYS, i .e. 15 days post-surface treatment, comprises a bacterial concentration C 15 DAYS, wherein C ! 5 DAYS comprises about a ninety-seven percent (97%) reduction over the initial bacterial concentration Co.

Applicants have found that manually wiping a surface comprising an initial bacterial concentration Co with an embodimen t of Applican ts' wiping article comprising a loading of about 0.20 grams TiCV>, in combination with about 0.20 grams of quarternary ammonium si lane, per gram of wiping article based upon the d y weight of the wi ing article, disposes a chemical composition onto the surface, wherein that surface at about time T 30 DAYS, i.e. 30 days post-surface treatment, comprises a bacterial concentration C30 DAYS, wherein C 30 DAYS comprises about a ninety-seven percent (97%) reduction over the initial bacterial concentration Co.

A variety of kno wn art sponges, wiping articl es, and especially woven or non-woven wi ing wipes may provide the benefit of a long-lasting antimicrobial coating disposed on a surface using Applicants' inventive teachings taught herein.

Wiping articles according to the invention, and especially those according to the preferred embodiment, i.e., sponges, may include one or more further constituents to enhance the overall performance of properties. One class of materials are compatible surfactants which do not deleteriously effect the overall antimicrobial benefit provided by Ti0 2 / quarternary ammonium silane composition introduced into the wiping article. These may include any of the known classes including anionic, nonionic, cationic, and zwitterionic.

Exemplary anionic surface active agents include compounds known to the art as useful as anionic surfactants. These include but are not limited to: alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of one or more of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alky laryl polyether sulfates, monoglyccride sulfates, alkylsulfonatcs, alkylamide sulfonates, alkyl ary 1 su I fonates, olefinsulfonates, paraffin sulfonates, alkyl

sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuecinamatc, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl isethionates, and N-acyl taurates. Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.

Further exemplary anionic surface active agents which may be used include fatty acid salts, including salts of oleic, ricinoleic, palmitic, and stearic acids; copra oils or hydrogenated copra oil acid, and acyl lactylates whose acyl radical contains 8 to 20 carbon atoms.

Other anionic surface active agents not particularly enumerated here may also find use in conjunction with the compounds of the present invention. With regard to nonionic surfactants, these include known art nonionic surfactant compounds. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethy lene oxide or with the

polyhydration product thereof, polyethylene glycol, to form a water soluble nonionic surfactant compound. Further, the length of the polycthenoxy hydrophobic and hydrophilic elements may various.

Exemplary nonionic compounds include the polyoxyethylene ethers of alkyl aromatic hydroxy compounds, e.g., alkylated polyoxyethylene phenols, polyoxyethylene ethers of long chain aliphatic alcohols, the polyoxyethylene ethers of hydrophobic propylene oxide polymers, and the higher alkyl amine oxides.

Where such surfactants are included in the wiping articles of the invention, they may be supplied to the wiping article by any effective means including but not limiting to spraying, dipping, soaking a quantity of one or more surfactants dispersed or dissolved in a suitable carrier liquid which my be made us of water, organic solvents or mixtures thereof or which water is most likely to be used. Where one or more surfactants are intended to be used, and the liquid carrier is water, it is desired then that the one or more surfactants be supplied to the wiping articles prior to the process for introduction of the Ti0 2 / quartemary ammonium silane composition to the wiping articles as taught herein.

[00043] In certain embodiments. Applicants' composition and method utilize Ti0 2 in combination with an organosilane comprising a quartemaiy ammonium moiety. In certain embodiments, that functionalized silane comprises compound 1, wherein Rl and R2 are selected from the group consisting of alky 1, alkenyl, phenyl, and benzyl, and wherein X " is selected from the group consisting of chloride, bromide, and iodide.

1

[00044] In certain embodiments, Applicants' wiping article further comprises an oxidizable pigment. In certain embodiments, the o idizable pigment comprises Methylene Blue. After Ti0 2 particles are deposited upon a surface by contacting that surface with Applicants' wiping article a coating comprising Ti0 2 particles and methylene blue is deposited onto the surface. Portions of the surface coated with the Ti0 2 particles visually display the color of the oxidizable pigment. For example, portions of the substrate coated with Ti0 2 particles / Methylene Blue mixture visually appear blue.

Methylene blue

[00045] In marked contrast, portions of the surface not coated with the Ti0 2

particles do not display the color. A subsequent coating application can be applied to the non-colored portions of the surface for a more uniform deposition of the TiO > particles. Exposure of the Ti0 2 particles to UV light then produces free radicals that oxidize the oxidizable pigment. As a result, a substantially contiguous titanium oxide coating is formed on the substrate, and that coating becomes translucent or white.

[00046] The degradation of Methylene Blue after deposition of a Ti0 2 coating on a surface is effected by d the mechanism of Scheme I.

SCHEME I

1 . Ti02 + photon→ e-CB + h+VB

2. 0 2 (ads) + e-CB ~-> 02·-

3. ( H 2 0 ^→ H+ + OH- )(ads) + h+VB→ H+ + ·ΟΗ

4. 0 2 ·- + H+→ Η0 2 ·

5. 2Η0 2 ·→Η 2 0 2 + 0 2

6. Η 2 0 2 + e-→ ·ΟΗ + ΟΗ-

7. Methylene Blue(ads) + ·ΟΗ→ degradation products

[00047] In step (2 ) of Scheme I, 0 2 (ads) comes from ambient 0 2 present in the system and was adsorbed onto the surface of the Ti0 2 . Methylene Blue has a cationic configuration thus it should be favorably adsorbed to the negative sites of the h-Ti0 2 surface, e.g., Ti-O(-) and subsequently attacked by the very active ·ΟΗ moiety, leading to the destruction of the Methylene Blue molecule. The following Examples are presented to further illustrate to persons skilled in the art the antimicrobial effect resulting from depositing Ti0 2 , and a quarternary si loxane onto a surface.

EXAMPLE I

Two inch square formica coupons were cleaned with soap and water and then isopropyl alcohol. A first group of test coupons was coated using an aqueous mixture comprising 3.6 weight percent organosilane 1 . After about fifteen (15) minutes, each of these first test coupons was then coated using an aqueous 3 weight percent colloidal suspension of Ti0 2 . A second group of test coupons was coated using an aqueous 3 weight percent colloidal suspension of Ti0 2 . A third group of test coupons was coated using an aqueous mixture comprising 3.6 weight percent organosi lane 1. A control group of test coupons was not coated. The coated test coupons were then evaluated using Methici 11 in-resistant Staphylococcus aureus ("M RSA" ) inoculates and in accordance with ASTM E2 149 - 10 Standard Test Method for Determining the

Antimicrobial Activity of Immobilized Antimicrobial Agents Under Dynamic Contact Conditions. Table 1 recites, for each of the four groups of test coupons, an Initial M RSA Level, a 3 Hour MRSA Level, the percent MRSA remaining after three hours, and a LOG KI LL.

TABLE 1

Applicants' Ti02 ORGANOSILANE CONTROL Composition ONLY ONLY

Initial MRSA Level 4.80E+07 1.90E+07 2.60E+07 3.00E+07

3 Hour MRSA Level 2.50E+05 5.00E+05 3.20E+05 2.80E+06 Percent M RSA Remaining 0.52 2.63 1.23 9.33 LOG KILL 2.3 1.9 1.6 1.03 The data of Table 1 show that use of only an organosilane coating on the test coupons resulted in about a 2.4 fold increase in the residual MRS A level after three hours compared to use of both an organosilane coating and a Ti0 2 coating. The data of Table 1 further show that use of only a Ti0 2 coating on the test coupons resulted in about a 5. 1 fold increase in the residual MRS A level after three hours compared to use of both an organosilane coating and a TiO > coating. In summary, the data of Table 1 demonstrate that treating the test coupons with a first coating of organosilane 1 followed by a coating of Ti0 2 was much more effective than coating the test coupons with either the organosilane only, or with Ti0 2 only.

EXAMPLE II

A common route of transmission of cold, flu, diarrhea and other common infections is through contact with surfaces contaminated with infectious microorganisms (pathogens). Contamination occurs by settling of droplets from coughs and sneezes onto surfaces, and by touching of surfaces with hands contaminated with pathogens. The pathogens then contaminate the hands of the next person who touches the same surface, and when they bring their hands to their eyes, nose, or mouth infection can result.

Mass transportation systems create an env ironment in which large numbers of persons on a daily basis share space and interact with surfaces found within system vehicles. A recent study in the United Kingdom demonstrated an increase of respiratory infections (colds and flus) to persons if they had ridden in a bus or streetcar five days prev iously.

Application of disinfectants on surfaces has been shown to reduce absenteeism and il lness in schools. Unfortunately surfaces hav e to be disinfected on a regular basis to be effective. There are no prior art methods that prov ide an effectiv e residual property. In marked contrast to prior art methods. Applicants' method creates a surface residual, and therefore, remains effective at reducing pathogen transfer, ev en if the surface became re-contaminated. Bacterial contamination of public buses with a California-based public transit authority were characterized in this study and lab analysis was used to determine the efficacy of Applicants' method to minimize exposure to microbial contaminates and odors in public spaces.

Fourteen buses were selected and divided into two groups; one an

"experimental" group of seven buses that was treated with the Appl icants' method; and one a "control" group of seven buses that received routine transit system treatment. Prior to any treatment, both groups where tested for heterotrophic bacteria in order to establish a baseline profile of each bus. The four-digit code for each bus was recorded.

Samples were taken at five locations in each of the fourteen busses: entry railing, fare box, driver compartment, interior railing, and seat back.

Samples were taken at the end of the working day after the bus returned to the transit facility but before they were cleaned by night maintenance workers.

Sites were sampled w ith a Spongestick (3M, St. Paul. MN) containing a neutralizing broth to neutralize any disinfectant that may have been on the sampled area. Approximately 1 50 sq cm of the surface was sampled at each selected site in the bus.

All samples were inserted in individual bags that were labeled with a random number code. This procedure was used to prev ent workers in the microbiology lab from knowing which samples belonged to which buses, thus establishing a blind study. Once the lab provided the culture results, the codes were used to assign values to the appropriate buses and locations within those buses.

The numbers of heterotrophic bacteria (HPC) were determined on R2A media ( Difco, Sparks, MD) using the spread plate method. Samples were diluted using physiological saline for assay of di lutions. All dilutions were assayed in duplicate. The agar plates were then incubated at room temperature for fiv e days and the resulting colonies of bacteria counted. [00062] A database was developed and all the col lected data from the survey and the laboratory analytical data were entered in the database. The data was log transformed and a multiple analyses of variance (ANOVA) were conducted on the data to SSCSS relationships between demographics and characteristics of the surfaces and their use.

[00063] Completely randomized designs were used to perform the ANOVA with a rejection region of 5% using the F distribution. Because the distribution of bacteria is not normally distributed ( i.e. a bell shaped distribution curve) it is log transformed before analysis.

[00064] Log transform ation is the conversion of the arithmetic number of bacteria to a loglO (i.e. 100 = 2, 1 ,000 = 3, etc.). The geometric mean (average) is then determined.

[00065] Following this procedure used to establish base-line data, the experimental group of 7 buses was treated with the Applicants' method. At the end of thirty days, the same two bus groups (experimental and control) were tested to assess product effectiveness.

[00066] Total bacterial numbers or heterotrophic bacteria on hard surfaces are used as a general measure of the sanitization of public surfaces and the effectiveness of cleaning and disinfection of surfaces. The number of bacteria per 1 50 sq. cm ranged from 80 to 1 7,200.000 on the surfaces tested. The geometric average number of bacteria in the buses used in thi s study is shown in Table 2.

[00067] Geometric averages are always lower than arithmetic averages as they normalize high and low values. The statistical analysis indicated that there was no statistical difference in the numbers of bacteria in the busses that were selected for treatment and those that were not at the beginning (baseline data) of the study. Table 2

Occurrence of Bacteria in Treated vs. Untreated Buses at Baseline

( Day 0 - before treatment of experimental buses)

*buses selected for treatment before treatment was applied

After 30 days, data reported in Table 3A demonstrate that there was a significant difference (p = 0.005) i.e. a 99.95% probability that there is a di fference in the geometric average number of bacteria in the treated and untreated buses. The number of bacteria in the treated buses was significantly less than that found in the untreated buses 30 days after treatment. On average there were 93% fewer bacteria on the surfaces in the treated buses vs. the untreated buses.

Table 3 A

Bacterial Concentrations in Treated vs. Untreated Buses

After 30 Days

Logio Arithmetic

Parameter

Treated Control Treated Control

Number of ^

25* 35 25* Samples

Geometric ^ ^

4.92 5,888 83,176

Mean

St. Dev. 1 -6 1.58 48.9 38.0

*two buses in the control group had been removed from service

The results of Table 3 A demonstrate a significant difference between the bacterial load in the [bus] interior of the treated and untreated buses. With the exception of the entry railing, the bacterial burden at all treated sites was reduced as compared to the untreated sites. [00070] The concentration of bacteria at specific sites tested in treated and untreated busses is shown in Table 4 below. The greatest difference between treated and untreated buses in bacteria numbers was in the driver ' s compartment where there were fewer than 99.8% bacteria in the treated busses. This difference was highly significant (p = 0.007).

100071 1 It appears that the inordinate wear and tear from passenger contact friction on the entrance railings removed Applicants' coating at those places.

Table 3B recites the experimental data excluding this site (entrance railing) as an outlier.

[00072] After 30 days, with this site excluded, there was a significant difference (p

= 0.001 i.e. a 99.99% probability that there is a difference) (Table 3B) in the geometri c average number of bacteria in the treated and untreated buses. On average there were 97%> fewer bacteria on the surfaces in the treated buses vs. the untreated buses.

Table 3B

Bacterial Concentrations in Treated vs. Untreated Buses after 30 Days

(Entry Railing Excluded)

Logio Arithmetic

Parameter

Treated Control Treated Control

Number of 2g ^

28 20 H

Samples

Geometric 42

2,630 81 ,283

Mean

St. Dev. 1 -48 1.52 30.2 33.1

* two buses in the control group had been removed from service

Table 4

Bacterial Concentrations at Specific Tested Sites in Treated and Untreated Buses

[00073] This Example I I shows that at the beginning of the study there was no statistical difference between levels of bacteria in the buses selected for study. This Example II further shows that the concentration of bacteria was significantly less in the interior of the treated vs. untreated buses after 30 days of use. On average there were 97% fewer bacteria on the interior surfaces of the treated buses in comparison to the same surfaces of the untreated surfaces.

[00074] While the preferred embodiments of the present invention have been illustrated in detail, it should be apparent that modifications and adaptations to those embodiments may occur to one ski lled in the art without departing from the scope of the present invention as set forth herein.