MXPA00007863A - Disinfectant compositions providing sustained biocidal action - Google Patents

Disinfectant compositions providing sustained biocidal action

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Publication number
MXPA00007863A
MXPA00007863A MXPA/A/2000/007863A MXPA00007863A MXPA00007863A MX PA00007863 A MXPA00007863 A MX PA00007863A MX PA00007863 A MXPA00007863 A MX PA00007863A MX PA00007863 A MXPA00007863 A MX PA00007863A
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MX
Mexico
Prior art keywords
disinfectant composition
composition according
disinfectant
water
film
Prior art date
Application number
MXPA/A/2000/007863A
Other languages
Spanish (es)
Inventor
Samuel P Sawan
Sundar Subramanyam
Alexander Yurkovetskiy
Original Assignee
Surfacine Development Company Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Surfacine Development Company Llc filed Critical Surfacine Development Company Llc
Publication of MXPA00007863A publication Critical patent/MXPA00007863A/en

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Abstract

The present invention relates to a composition that, when applied to a substrate, forms an adherent, transparent, water insoluble polymeric film on the substrate surface that provides sustained antimicrobial disinfecting action for prolonged periods, without the necessity for reapplication. The coating provides surface disinfecting action by a contact-killing mechanism, and does not release its components into contacting solutions at levels that would result in solution disinfection. The polymeric film formed by the composition of the invention can be removed by treatment with dilute alcoholic base.

Description

SANITIZING COMPOSITIONS PROVIDING SUSTAINED BIOCIDE ACTION DESCRIPTION OF THE INVENTION • The present invention relates to a composition 5 that forms a transparent, water-insoluble, adherent polymer film on a substrate surface, and provides sustained antimicrobial disinfectant action upon contact with microorganisms for extended periods, without the need for reapplication. The coating ^ 10 provides only surface disinfecting action that kills contact, and does not release its components into liquids that come in contact at levels that would result in disinfection of the solution. The polymeric film of the invention can be easily removed by -treatment with a diluted alcohol base. The constant threat of bacterial contamination and the associated health repercussions have made antimicrobial solutions an omnipresent part of commercial and residential cleaning and waste management processes. disinfection. Diluted aqueous detergents do not show a detectable reduction in the levels of bacteria on the surfaces responsible for bacterial growth and proliferation in susceptible environments, such as hospital areas and in residential kitchens and bathrooms. For another On the other hand, oxidants such as aqueous hypochlorite and phenolic compositions produce substantial reductions in bacterial levels that are relatively short lived ^ (3 to 6 hours). This frequently results in recontamination due to the rejection of such surfaces, which require frequent reapplication of disinfectant. In addition, relatively high concentrations of the active agent must be incorporated in such formulations to obtain broad spectrum disinfection. These high concentrations often have undesirable side effects such ^ 10 as skin and eye irritation, and in addition to being potentially dangerous when placed in contact with food. There is therefore a need for the development of new disinfectant formulations that can provide sustained broad microbial disinfection. spectrum on surfaces for extended periods without reapplication, even after being put in contact with cleaning solutions and after rejection of the surface.
In addition, it is desirable to achieve disinfecting action using low levels of the antimicrobial agent that will not pose problems toxicity to the user. The mode of action of surface-forming substances that form a film to date has been based on solution, that is, the antimicrobial action is obtained by controlled release through diffusion or disillusionment. of the active agents within solutions that put in aqueous or volatile contact. Numerous examples of this equipment of sanitary substances have been reported. Other typical variants involve the hydrolysis or dissolution of the matrix containing an antimicrobial compound, thereby effecting its release within. the solution. However, high levels of preservatives are also released, within the solutions that they put in contact in long-term applications. In such mechanisms, a bioactive compound is covalently bound either directly to the surface of the substrate or to a polymeric material that forms a surface coating that does not dissolve. The antimicrobial compounds in such coatings exhibit greatly diminished activity, unless assisted by the hydrolytic breakdown of the antimicrobial bond or the coating itself. In any case, relatively high levels of preservative must be released into the solution to produce antimicrobial action. It is an object of the invention to provide an antimicrobial composition which can be applied to a surface to provide an insoluble non-permeable water film which is capable of (i) providing immediate antimicrobial disinfection and antiviral action on the surface, and (ii) providing sustained antimicrobial disinfectant action for prolonged periods after of its application, even after contacting water and aqueous surface cleaners. It is also an object of the invention to provide a disinfectant composition which, when applied to a surface, provides a water insoluble film which can be removed from the surface with the application of a formulation which dissolves the non-aqueous film. Another object of the invention is to provide a disinfectant composition which additionally includes an optical reporter, for example, a fluorophore or an optical brightening agent that allows the detection of the composition on a surface by means of suitable detection devices such as irradiation by a source of visible or ultraviolet light. The invention further provides disinfectant compositions that form insoluble films in water, adherent, transparent which, when applied on a surface, annihilate microorganisms that come in contact with the films, but which do not filter or elute significant amounts of antimicrobial species or components within the liquids that are contact contact levels sufficient to provide disinfection in the solution that is contacted. The antimicrobial composition comprises a combination of an organic biguanide polymer and an antimicrobial metal material. More particularly, the disinfectant compositions of the invention comprise a liquid, gel or foam comprising a solution, dispersion, emulsion or ^ suspension of a polymeric material, which forms a film and a metal biocide in a carrier, which, when applied to a surface, forms a polymeric film insoluble in water on the surface to which the biocide binds unfiltered, forms complex with, associates with or disperses. The polymeric film forming the material preferably comprises a polymer, copolymer or adduct which ^ 10 contains segments that, when the polymer forms a film on a surface, are capable of compromising the microorganisms that come in contact with it. The biocide binds without preferentially filtering to, complex form or associates with or disperses within the film, but is capable preferably transferred directly from the polymeric film to the microorganism that comes into contact due to a higher affinity for the proteins within the • microorganisms. In one aspect, the composition comprises a combination of (i) a polycationic polymeric organic material which is capable of forming a layer, film or matrix and (ii) a broad-spectrum metal biocide which, when applied, is intercalated into the layer, film or matrix and which interacts strong enough with the material organic - so that the biocide does not dissolve within or elute from the matrix into the surrounding environment. The organic material must have two important properties: ^ Must be able to bind reversibly or complex with the biocide, and must be able to enter the biocide within the cell membrane of a microorganism in contact with it. The organic material is preferably able to dissolve within or adhere to the cell membrane surrounding the microorganism. Preferred organic materials are those which can be applied over a '(B 10 surface as water-insoluble films and which bind the biocide in such a way as to allow the biocide to be transferred within the microorganism, but which will not release the biocide within the surrounding environment, for example, in the air or within any liquid in contact with coated surface. The biocide is preferably a low molecular weight metal material that is toxic to microorganisms and which is able to complex with or reversibly bind to the organic matrix material, thereby returning to the matrix organic insoluble in water. The biocide exhibits higher binding affinity for the functional groups in the cellular proteins of the microorganisms. When a microorganism comes into contact with the antimicrobial material, the organic material compromises or breaks at least the outer portion of the the lipid bilayer of the cellular membrane of the microorganism sufficiently to allow the entry of the biocide into the microorganism, wherein the cellular proteins or ^ proteins in the lipid bilayer compete effectively for the biocide due to the constant favorable links. Said of In another form, the metallic material is bonded to or forms a complex with the organic material in which the association between the organic material and the metallic material is strong enough so that the layer or film does not elute antimicrobial amounts of the metal within a solution. 10 who gets in touch. However, the metallic material is preferably bound to these proteins in the microorganism and thus transferred from the matrix to the microorganism. The result is a supply system that kills the contact that selectively transfers the biocide to or within the cell membrane of the microorganism on contact, without elution or dissolution of the biocide within the solution, thereby maintaining the long-term antimicrobial efficiency of the composition. The antimicrobial compositions of the present The invention is therefore molecularly designed to allow the biocide linked to the matrix to retain high antimicrobial activity without elution of any compound within the contacting solutions, carriers or other materials. The antimicrobial activity prevents the sustained cooperative biocidal action of its components.
The selective transfer of a component from inside the matrix directly to the microorganism in contact is achieved by means of a mechanism "without intervention" by compromising and penetrating the cell membrane of the microorganism. The antimicrobial material, therefore, maintains long-term efficiency without releasing eluble toxins into the surrounding environment. The organic materials useful in the present invention comprise materials that are capable of: (1) adhering to and / or forming a layer or coating on a variety of substrates, (2) reversibly binding or complexing with the biocide, and (3) introducing the biocide within the cell membrane of the microorganism in contact. A preferred class of materials are those that have the aforementioned properties, and which are capable of complexing and / or bonding a bactericidal metal material. More preferred is the class of organic materials that have antimicrobial activity. For example, a preferred class of materials, polymeric biguanides, form a layer or coating when applied to a substrate. The layer or coating can dissolve in, or adhere to, and penetrate at least the outer portion of the lipid bilayer of the membrane of a microorganism. For this purpose, surfactants, such as cationic compounds, polycationic compounds, anionic compounds, polyanionic compounds, nonionic compounds, polinoionic compounds, or zwitterionic compounds, are useful, these • compounds include, for example, biguanide polymers, or polymers having side chains containing 5 portions of biguanide or other functional cationic groups, such as benzalkonium groups or quaternary groups (eg, quaternary amine groups). The backbone of the polymer can be any polymer capable of forming a coating on a substrate. It is understood that the term "B 10" "polymer" as used herein includes any organic material comprising three or more repeating units, and includes oligomers, polymers, copolymers, terpolymers, etc. The backbone of the polymer can be a polysilane or polyethylene polymer, for example. The The organic materials that are currently most preferred for use in the invention are the polymeric biguanide compounds. The polymeric organic material can be reacted with an organic compound insoluble in water or "hydrophobic agent" to increase its insolubility in water. In a preferred embodiment, the organic material is a polycationic polymer polymer, which is chemically reacted with a hydrophobic agent to form an adduct. The adduct that includes the hydrophobic agent adheres more strongly to certain substrates than the polycationic polymer alone, and exhibits greater insolubility in water. The hydrophobic agents that can be used in the present invention are ^ F organic compounds which are substantially insoluble in water and which can react with the material polycationic to form an adduct. Suitable hydrophobic agents include, for example, compounds, which may be polymers, containing multifunctional organic groups such as isocyanates, epoxides, carboxylic acids, acid chlorides, acid anhydrides, aldehydes of succimidylethers, ketones, alkylmethane sulfonates, alkyltrifluromethane sulfonates, alkylparatoluen methanesulfonates, alkyl halides and multifunctional organic epoxides. In a currently preferred embodiment, the organic material comprises a polymer adduct of polyethamethylenebigumide, and an epoxide, such as methylene-bis- N, N-diglycidylaniline, bisphenol-A-epichlorohydrin or N, N-diglycidyl-oxaniline. 'The biocidal material can be any antimicrobial material which is capable of binding unfiltered to or form complex with an organic matrix, but which, when placed in contact with the microorganism, preferably transfers the proteins into the microorganisms. For this purpose, the metallic materials which bind to the cellular proteins of the microorganisms and which are toxic to microorganisms are preferred. The metallic material can be a metal, metal oxide, metal salt, metal complex, metal alloy or mixtures of the B. same. Metallic materials that are bactericidal or bacteriostatic and that are either substantially insoluble in water or which can become insoluble in water. By a metallic material which is bacteriostatic or bactericidal is meant a metallic material which is bacteriostatic even microorganism, or which is bactericidal to a microorganism, or which is bactericidal to certain microorganisms and bacteriostatic to other microorganisms. Examples of such metals include, silver, zinc, cadmium, lead, mercury, antimony, gold, aluminum, copper, platinum and palladium, their salts, oxides, complexes and alloys, and mixtures thereof. The metallic material is selected based on the use to which the invention is placed. The preferred metallic materials are the silver compounds. In a currently preferred embodiment, a silver halide, more preferably silver iodide, is used. In another preferred embodiment, silver nitrate is used and is converted to water-insoluble silver halide by subsequent chemical reaction with an alkyl halide. More preferably, silver nitrate is converted to silver iodide by reacting it with sodium or potassium iodide. The invention comprises compositions to form an unfiltered antimicrobial layer or coatings on a surface. In one embodiment, the composition is an aspersible composition comprising a solution, dispersion or solution of the organic material and the biocidal material. Alternatively, the antimicrobial material can be suspended in water or in aqueous solutions containing an organic solvent in the form of an emulsion, microemulsion, latex or colloidal suspension. The composition does not need to be a homogeneous solution. If desired, stabilizing agents such as suspending agents or surfactants áFk 10 can be included. If a more hydrophobic coating or film is desired, the solution, dispersion or suspension may also contain the hydrophobic agent. As a first step, the hydrophobic agent and the organic material can be reacted to form an adduct in which the agent hydrophobic is covalently bonded to the polymeric organic material. To form an unfiltered coating or layer that kills contact on a substrate, the at-disinfectant composition is applied to the substrate, for example by rubbing, painting by brush, dipping or sprinkling, or as a aerosol spray using a suitable propellant, under conditions sufficient to form a layer or film of the polymeric organic material on the substrate. The liquids useful as a liquid carrier for the antimicrobial materials in the present invention include any polar solvent, which includes water, alcohols such as ethanol or propanol, polar aprotic solvents such as N, N-dimethyl formamide (DMF), N, N-dimethyl. • acetamide (DMAC), dimethyl sulfoxide (DMSO), dimethyl sulfide (DMS) or N-methyl-2-pyrrolidone (NMP), and mixtures thereof. The currently preferred liquid carrier comprises a mixture of ethanol and water. In alternative embodiments, the carrier comprises a gel or foam. In the methods of the invention described above, the amounts and / or concentrations of the materials used will depend on the nature and stoichiometry of the materials used, and the desired final product. In the presently preferred embodiments, the concentration of total solids of the solution, dispersion or suspension of the composition of the sprayable liquid is typically in the range from about 0.1 to about 5%, preferably in the range from 0.2 to 1.0% by weight. Typically, an organic material comprising a ratio of a polymer: hydrophobic agent in the range of from about 1: 1 to about 3: 1 (percent in weight) will form matrices which will retain without filtering the metal biocide and will preferably transfer the biocide to the microorganism upon contact, as described herein. The concentration of the metal biocide is typically in the range of about 0.001 to about 20% by weight of polymer or adduct of hydrophobic polymeric agent in the composition of the disinfectant solution. In a preferred embodiment, a composition The disinfectant according to the present invention is applied as an aerosol spray to form a layer or film. antimicrobial on the surface of a substrate. In a presently preferred embodiment, the organic matrix is formed by first reacting polyexamethylene biguanide with an epoxy, such as methylene-bis-N, N-diglycidylaniline, to form an adduct. Solutions have been obtained ^ 10 stable coatings of the resulting adduct in absolute ethanol and in aqueous ethanol. The biocidal material, preferably a silver compound, is then added to the adduct solution to form a stable solution or colloidal dispersion or emulsion. The resulting mixture is dilutes to the desired concentration, then applied to the substrate surface by spraying. Spraying can be carried out, for example, using a spray gun Standard or other conventional spray applicator, or from a pressurized aerosol can using a propellant adequate. Such suitable propellants include nitrogen, carbon dioxide, hydrocarbon or a mixture of hydrocarbons. The spray applied liquid layer can be wiped with a cloth to spread the layer equally over the substrate. Once applied to the substrate, the The coating is allowed to dry at room temperature, thereby forming a polymeric film on the substrate. The resulting film is adherent, optically clear stable to • light and insoluble in aqueous solutions. The coating will not be washed with water, soap or most commercial cleaning agents. The coating can be removed, if desired, by rubbing the coated surface with an alcoholic solution containing a surfactant. Examples of alcoholic solutions that can be used include ethanol, aqueous ethanol or isopropanol. Examples of surfactants that B 10 can be used include, for example, sodium lauryl sulfate or sodium dodecyl sulfate (SDS), sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquiolate, sorbitan trioleate, Tween 20, Tween 40, Tween 60, Tween 80, Tween 85, or sorbitan monooleate. Ethanol solutions containing 0.01 to 5% sodium lauryl sulfate, Tween 20 or sorbitan monooleate are currently most preferred for this purpose. The applied film is typically ten microns or less in thickness, although the thickness of the coating may may be varied by well-known techniques, such as increasing the solids content of the resin. In another preferred embodiment, the disinfectant composition of the present invention may additionally contain an optical reporter that allows detection Visual of the presence of the composition on a substrate surface. The optical report material can be a compound that can be detected spectroscopically and that can be a coloring material, fluorophore, optical brightener, pH indicator or thermochromic. Preferred optical report materials are optical brightening agents such as 2, 2 '- (2,5-thiophenediyl) bis [5-tert-butylbenzoxazole] (Uvitex OB) or sodium salt of 4,4'- bis-2-diethylamino- (2, 5-disulfophenyl-amino) -s-triazinyl-6-amino-stilbene-2,2'-disulfonic acid (Tinopal) marketed by Ciba-10 Geigy Corporation, which can be visualized by a UV detector. The disinfectant compositions of the present invention can be used as a hard surface disinfectant, for example as a disinfectant for hospitals and institutions, disinfectant for kitchen and bathroom, cleaning disinfectant or floor and wall cleaner. The disinfectant compositions can also be used as disinfectants for skin, antiseptics, sanitary substances, bandages and liquid wound dressings. The Disinfectant compositions can be used to treat articles in contact with the skin, such as diapers, wound dressings, surgical masks and gowns, and articles that do not come into contact with the body such as hospital bed rails, folders and carpets. The above and other objects, features and advantages of the present invention will be better understood from the following specification when reading together with ^ F the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS 5 Figure IA is a schematic graphic illustration of the polymer / biocide complex of the present invention, in a solvent, as applied to a surface. Figure IB is a schematic graphic illustration of the polymer / biocide composition of the present invention, as applied to a surface, after evaporation of the solvent, leaving a polymer / biocide film on the surface. Figure 1C is a schematic graphic illustration of the ability to kill by contact of the film that forms a matrix / biocide complex of the present invention upon contact of the film with microorganisms, wherein the polymer chains compromise and break the cell membrane of the microorganism. Figure ID shows the penetration of the cellular membrane and the transfer of the biocide from the protein network in the microorganism, causing the death of the cell. Figure 2A is a graph illustrating the efficiency of immediate disinfection (to the application) and Sustained (after contacting with water) of a film formed of the composition of the invention against S. to ureus and E. Coli. Figure 2B is a graph illustrating the efficiency of immediate disinfection (to application) and sustained (after contacting with water) of a film formed of the composition of the invention against P. aeruginosa. Figures 3A and 3B are graphs illustrating the durability in the present antimicrobial coatings after repeated cycles of opposition to P. aeruginosa, incubation and washing. The disinfectant composition of the present invention was applied to a variety of substrates to obtain a coating or layer having antimicrobial and antiviral disinfecting action. The disinfectant compositions according to the present invention can be applied, for example, wood, metals, paper, synthetic polymers (plastics), natural and synthetic fibers, natural rubbers and. synthetics, clothes, glasses, and ceramics. Examples of substrates of synthetic polymers include elastically deformable polymers which may be thermoset or thermoplastic such as polymers or copolymers of, for example, polypropylene, polyethylene, polyvinyl chloride, polyethylene terephthalate, polyurethane, polyesters, rubbers such as polyisoprene or polybutadiene. , polytetrafluoroethylene, polysulfone and polyether sulfone. The inorganic materials to which the present coatings may be applied include glass fiber materials, ceramics such as alumina or silica, and metals. The present antimicrobial spray may also be applied and formed to a coating on substrates of sintered glass and sintered ceramic. The term "microorganism" as used herein includes bacteria, blue-green algae, fungi, yeasts, mycoplasms, protozoa and algae. The term "biocide" as used herein means a bactericidal or bacteriostatic. The term "bactericidal" as used herein means the destruction of microorganisms. The term "bacteriostatic" as used herein means inhibiting the growth of microorganisms, which may be reversible under certain conditions. As used herein, the terms "non-filterable" and "substantially non-filterable" mean that the bioactive components in the films obtained by application of the disinfecting compositions do not dissolve, elute, filter or otherwise provide species within a liquid environment in contact with the films at levels that would result in the disinfection of the solution, that is, in antimicrobially effective amounts. Preferably, this threshold is below the minimum concentrations of solution of such components to impart disinfection to the solution. Organic materials useful in the present invention comprise materials that are capable of: (1) adhering to and / or forming a layer or coating on a variety of substrates, (2) reversibly binding with or complexing with the bactericide, and (3) penetrating the bactericide within the cell membrane of the microorganism. A preferred class of materials are those that have the above properties, which are capable of being immobilized on a surface and which preferably bind a biocidal metal material in such a way that allows the release of the metal biocide to the microorganism, but not to the environment that is get in touch More preferably it is the class of organic materials that have antimicrobial properties, that is, materials which, when applied as a coating, can dissolve within, adhere to, break or penetrate the lipid bilayer membrane of a microorganism in contact with the covering. In a preferred embodiment, the organic material is a polymer that contains segments which, when the polymer forms a coating on a surface, are capable of compromising the microorganisms that come into contact with the coating. By "compromising" is meant that the coating can bind and temporarily immobilize a microorganism in contact with it. For this purpose, surfactants, such as cationic compounds, polycationic compounds, anionic compounds, polyanionic compounds, nonionic compounds, polyanionic compounds, or zwitterionic compounds can be used. The organic materials that are currently most preferred for use in the invention are the polymeric compounds of • 10 biguanide. When applied to a substrate, these polymers form a coating on the substrate which can compromise and break a microorganism as shown in Figure 1. The polymeric materials useful herein invention include benzalkonium chloride derivatives, a-4- [1-tris (2-hydroxyethyl) ammonium-2-butenyl] poly [1-dimethylammonium-2-butenyl] -α-tris (2-hydroxyethyl) ammonium chloride . The Preferred polymeric compounds include polymeric biguanides and their salts of the general formula: Y, - [- NH-C-NH-C-NH-X-] n-Y2 II II NH + NH + 't? Or their water-soluble salts, wherein X is any aliphatic, cycloaliphatic, aromatic, substituted aliphatic, substituted aromatic, heteroaliphatic, heterocyclic, or heteroaromatic compound, or a mixture of any of these, and Yi and Y2 are any aliphatic compound, cycle ^ aliphatic, aromatic, substituted aliphatic, substituted aromatic, heteroaliphatic, heteroalicylic or heteroaromatic, or a mixture of any of these, wherein m is an integer equal to or greater than 1, and wherein Z is an anion such as Cl OH. The most preferred polymeric compound at present is polyexamethylene biguanide (available from Zeneca Biocides, Inc. Of Wilmington, DE as a 20% aqueous solution under the tradename COSMOCIL-CQ). In one embodiment of the present invention, the organic material comprises an organic material which has been reacted with a hydrophobic agent to form an adduct. The hydrophobic agents that can be used in the The present invention are those that react with the organic material to form the adduct. Suitable hydrophobic agents include, for example, organic compounds containing multifunctional groups such as isocyanates, epoxides, carboxylic acids, acid chlorides, acid anhydrides, succimidylether aldehydes, ketones, alkylmethanesulfones, alkyltriofluoromethanesulfonates, alkylparatuelenmetansulfones, alkyl halides and multifunctional organic epoxides. In a currently preferred embodiment, a polyexamethylene biguanide polymer is made React with an epoxide, such as methylene-bis-N, N-diglycidylaniline. The degree of hydrophobicity of the resulting adduct can be adjusted by agent selection • hydrophobic. The organic material can be polymeric or non-polymeric, however the resulting adduct must be capable of forming a coherent film. The biocidal material can be any antimicrobial material which is capable of binding without filtering or forming a complex with the organic matrix, but which, when placed in contact with the microorganism, is preferably transferred to the microorganism. For this purpose, metallic materials that are toxic to microorganisms are preferred. The metallic material can be a metal, metal oxide, metal salt, metal complex, metal alloy, or mixtures thereof. The preferred ones are metallic materials that are bactericidal or bacteriostatic and that are substantially insoluble in water. For a metallic material that is bacteriostatic or bactericidal that wants • say a metallic material that is bacteriostatic to a microorganism, or that is bactericidal to a microorganism, or that is bactericidal to certain microorganisms and bacteriostatic to other microorganisms. Examples of such metals include, for example, silver, zinc, cadmium, lead, mercury, antimony, gold, aluminum, copper, platinum, and palladium their oxides, salts, complexes and alloys, and mixtures thereof. same. The appropriate metallic material is selected based on the final use of the device. The presently preferred metallic materials are the silver compounds, The useful carriers in the present invention include liquids, gels or foams. The liquids useful as the liquid carrier for the antimicrobial materials in the present invention include any polar liquid, which includes water, alcohols such as ethanol or propanol, polar aprotic solvents such as N, N-dimethyl formamide (DMF), dimethyl sulfoxide ( DMSO) or N-methyl-2-pyrrolidone (NMP), and mixtures thereof. The preferred liquid carrier currently comprises a mixture of ethanol and water. The liquid carrier in the present invention can itself be an 'antimicrobial disinfectant capable of causing immediate disinfection to the application of the formula above. a bacterially contaminated surface, which especially includes denatured alcohol (SD-alcohol) which is comprised of 95% ethyl alcohol denatured with 5% isopropanol, or pure isopropanol. The biocidal material can be introduced into the matrix either contemporaneously with or after application of the organic material to a surface. The amount and / or type of the antimicrobial composition which is used in a particular application will vary depending on various factors, including the type and amount of contamination that is likely to occur, and the size of the antimicrobial surface. The amount of antimicrobial used will be a minimum amount necessary to maintain the sterility of the surface. As stated above, this amount will vary depending on various considerations understood by those of ordinary skill in the art. . In a preferred embodiment, when the disinfectant composition is applied to a substrate, the organic material forms an insoluble, non-filtering film having a ^ 10 unique configuration: some of the organic material protrudes into the surrounding environment, that is, "arm" or "tentacles" of organic material are projected away from the matrix and into the surrounding environment. This phenomenon can be understood by referring to Figure 1, which is a schematic graphic illustration of a preferred embodiment of the present invention in which the organic material is a biguanide polymer that is reacted with a compound ^ Organic P insoluble in water to increase the water insolubility of the polymer, and the biocidal metal material is a salt silver halide preferably silver iodide. Figure IA shows the polymer film having tentacles projecting within ambient conditions, with the silver salt being present within the tanks and on the tentacles. Without wishing to join In any theory, it is believed that when a microorganism is contacted with the coating, the biguanide polymer tentacles dissolve within the lipid bilayer that constitutes the cell membrane of the organism surrounding the microorganism, thereby introducing molecules of 5 silver inside the microorganism or the proteins inside the cell membrane. Silver has a higher binding affinity for certain proteins in the microorganism than for the polymer film, and therefore forms complexes with the cellular proteins and flip transfers into the microorganism, thereby causing the denaturation of the protein within the organism that results in his death. Specifically, it is known to platform complexes with the sulfhydryl and amino groups of cellular proteins. In this embodiment, the silver salt binds to or impregnates within the matrix comprising the film and over the polymer's tentacles such that the silver is substantially unfiltered within the surrounding environment, i.e., substantially no silver it filters from the coating within a liquid in contact with the coating. This is verified by performing the standard Kirby-Bauer zone inhibition test using test substrates containing a disinfectant composition. The absence of an area in such tests indicates that the bioactive components of the composition do not dissolve, elute, filter or provide species in the medium that makes contact at the levels necessary to cause death. Again, not wishing to join any theory, it is believed that the silver salt forms complexes with the functional groups in the polymer, and that the silver complex resists filtration within the liquids of the environment or other materials (for example water , and aqueous solutions that include common cleaning liquids) in contact • with the treated surface. However, when the treated surface is exposed to • 10 cellular proteins, silver forms complexes preferably with proteins. In a presently preferred embodiment, the polymeric material is polyhexamethylene biguanide, (PHMB) and the hydrophobic agent is methyl-bis-N, N-diglycidylaniline (MBDGA). The salt Preferred silver is a silver halide, more preferably, silver iodide or silver nitrate, which are easily converted into a silver halide, of greater • preference silver iodide. In this modality, the antimicrobial material is made by the combination of a solution of polyhexamethylene biguanide, with a solution of the hydrophobic agent, and the mixture is reacted under conditions sufficient to form an adduct of PHMB-MBDGA. The ratio of a PHMB to MBDGA is preferably in the range of about 1: 1 to 3: 1 by weight. The concentration of The resin of the resulting adduct is preferably in the range of about 0.5 to about 20% by weight. The biocidal material, preferably silver iodide, is added to the adduct solution to form the liquid antimicrobial composition. Silver solutions having a concentration of about 0.005 to about 0.5% can be used for this step. Silver iodide is currently the most preferred form of the biocidal metal material. It is added either to the adduct solution as such or is obtained by adding silver nitrate to the adduct solution and converting it to silver iodide by the addition of an alkali metal iodide such as sodium or potassium iodide. Silver iodide forms deposits in the matrix, and joins the tentacles. Silver iodide has sufficient affinity for the PHMB polymer that forms an insoluble complex that will not filter into the solutions of the environment or other materials in contact with the material, even at elevated temperatures. However, when a • microorganism comes in contact with the film, the tentacles break the membrane and lipid layer of the microorganism, thereby introducing the silver iodide into the microorganism. Silver iodide has a higher affinity for certain proteins within the microorganism than for the PHMB-MBDGA matrix, and forms complexes with these proteins, that is, the silver preferably transfers from the coating to the microorganism. Silver accumulates in toxic levels in the microorganism and annihilates it. Deposits of silver iodide within the matrix replenish silver iodide within the matrix by recharging the silver iodide in the tentacles lost to the microorganism, restoring equilibrium by the formation of the complex. (Agí + PHMB [PHMBAgl]).
The present invention provides stable compositions of disinfectants which can be used for • apply adherent antimicrobial coatings or films on a wide range of materials, including those commonly used in membranes, manufacturing of medical devices, hospitals, laboratories, kitchens and bathrooms. The antimicrobial layers or films are capable of providing sustained disinfecting action for extended periods. In a In the preferred embodiment, the liquid composition is a sprayable formula which can be applied directly by spraying • to most surfaces without previous modification of the surface. The surfaces treated with the composition The disinfectant according to the present invention exhibits (i) immediate antimicrobial disinfection activity against highly positive and large negative bacteria and yeasts, and is resistant to fungal growth, and (ii) instantaneous antiviral activity. The treated surfaces annihilate organisms completely at challenging levels of 106 - 108 • CFU / mL within 8 to 20 hours at 30 ° C, depending on the type of organisms. The treated surfaces inactivate viruses such as poliovirus, hepatitis B and rhinovirus. Additionally, the disinfectant composition according to the present invention exhibits actimicrobial disinfection activity for prolonged periods after its application, even after coming into contact with water and aqueous solutions P 10 cleansers such as soaps and shampoos. The antimicrobial composition of the present invention can be applied to a surface to form coatings or layers that annihilate on contact on a variety of substrates. As shown in the Examples, the material forms a non-filterable surface that annihilates contact on surfaces such as ceramic tiles, fiberglass or enamel, against synthetic finishes, chrome trimmings, bathroom curtains, mirrors and other clinical or home areas where microbial contamination is a concern. For example, surfaces in medical offices or hospitals, such as treatment tables or consoles in a typical dental office, have proven to be a major source of bacterial contamination that poses potential risks to the health of patients and staff. The coating or treatment of these surfaces with the antimicrobial materials of the present invention • can reduce or prevent microbial contamination on these substrates. In the home, kitchen and 5-bathroom surfaces, including bathroom fittings, counter-frames, mirrors, and fixtures (eg, shower curtains) can be treated with the present composition to reduce or eliminate microbial contamination. The antimicrobial materials present have been tested against the bacteria most commonly found in water (see Examples below). Treated ceramic tiles withstood repeated attempts to introduce microbial contamination at very high challenging levels, while untreated control tiles developed extensive biofilms. The present composition forms a non-grated, optically clear coating of long duration on the • surface to which it is applied. The coating can not be washed with water, soap or cleaning products more commercially available formulated for use in the kitchen or bathroom. The coating can be removed by rubbing the coated surface with an acidic, alkaline or alcoholic solution, for example, with aqueous ethanol, isopropanol or mixtures thereof. The invention is further illustrated by the following examples, which are not intended to be limiting in any way. EXAMPLES All examples consist of adduct resins obtained by the reaction of polyhexamethylenebiguanide hydrochloride salt (PHMB.HCl) or polyhehemethylenemethyleneguanide free base (PHBM) with bifunctional or multifunctional epoxides. The epoxides used in the present invention include methylene-bis-N, N-diglycidyl aniline (MBDGA) sold as Araldite MY-720 by Ciba Resins; bisphenol A epichlorohydrin (average molecular weights ranging from 400 to 1700) (Aldrich Chemical Company); or N, N-diglycidyl-4-glycidyloxinaline (Aldrich Chemical Company). The PHMB (base) or PHMB relationship. HCl to epoxide is from about 2: 1 to 1: 1 (ratio p: p). Example 1 Preparation of PHBM Solutions Example IA to a stirred solution of 160 ml of PHMB solution. HCl (20% by weight aqueous solution sold as Cosmocil CQ by Zeneca Biocides, Wilmington, DE), a solution containing 20 g of methylene-bis-N, N-diglycidylaniline (MBDGA) (Ciba Resins, Hawthorne, NJ) dissolved in 100 mL of N, N-dimethylformamide (DMF) and 130 mL of ethanol was added dropwise. The reaction mixture was refluxed with stirring for 1 hour during which the initially turbid solution became clear. The solution was allowed to cool to room temperature to give the adduct resin as 20% by weight solids. This solution was diluted appropriately with absolute alcohol. Example IB To a stirred solution of 32.5 mL of PHMB base in ethanol (prepared by viewing the NaOH solution, to PHMB, HCL followed by filtration, drying and redissolution in ethanol) containing 13% by weight of solids, 32.5 g of bisphenol-A epichlorohydrin (average molecular weight = 1075) dissolved in 77 mL of DMF was added rapidly with stirring. The reaction mixture was refluxed with stirring for 1 hour during which the initially turbid solution became clear. The solution was allowed to cool to room temperature to give the adduct resin as 20% by weight solids. . This solution was diluted appropriately with absolute alcohol. Example 1C To a stirred solution of 130 mL of solution PHMB. HCL (20% by weight of aqueous solution sold as Cosmocil CQ by Zeneca Biocides), 70mL of deionized water was added followed by a solution containing 17.3 g of N, N-diglycidyl-4-glycidyloxyaniline (Aldrich Chemical Company) dissolved in 25 ml. mL of N, -dimethylformamide (DMF) and 130 mL of ethanol was added dropwise. The reaction mixture was refluxed with stirring for 2 hours during which time the initially turbid solution became clear. The solution was allowed to cool to room temperature 5 to give the adduct resin as 20% by weight solids. This solution was diluted appropriately with absolute alcohol. Example 2 Preparation of Asperjustable Antimicrobial Compositions. Four different formulations were prepared: f 10 1. Example 2A, Formulation ATT1: contains PHMB. HCL and Agí how the active ingredients; formulated as an antimicrobial coating for polar plastics, cellulosics and metals; applied with solutions based on organic solvent. 15 2. Example 2B, Formulation ATT2: contains PHMB. HCL and Agí as the active ingredients; formulated as an antimicrobial coating for general purposes; • applied with solutions based on aqueous ethanol. 3. Example 2C, Formulation ATT3: contains PHMB copolymer. HCL / epoxy and Agi as the active ingredients; formulated as an antimicrobial coating for general purposes; applied with solutions based on aqueous ethanol. 4. Example 2D, Formulation ATT4: contains copolymer PHMB. HCL / epoxy and Agi as the active ingredients; formulated as an antimicrobial coating for general purposes; applied with aqueous solutions with a • Water content of more than 90%. Example 2A 5 Formulation ATT1 20g of Cosmocil CQ (Zeneca Biocides, Wilmington, DE) 4g of silver iodide (Ag) 2g of potassium iodide (Kl) and 80 ml of N, N-dimethylformamide (DMF) were mixed together in a flask for 15 minutes. The volume of the obtained ^ P 10 solution (pale yellow color) was adjusted with DMF to 100 ml. The resulting solution contains 10% (w / v) solids. Prior to application, the standard solution was diluted 10 times with a 1: 1 (v / v) mixture of DMF and ethanol to a final solids content of 1% (w / v). 15 Example 2B Cosmocil CQ ATT2 formulation 20g, 2.8g of dodecyl sulfate • sodium (SDS), 1.3 g of Agi, 0.4 of Kl and 25 ml of DMF, 20 ml of N-methyl-2-pyrrolidone (NMP) and 20 ml of ethanol were mixed together in a flask for 30 minutes. The volume of the obtained standard solution (yellow brown color) was adjusted with 100 ml ethanol. Before application, the standard solution was diluted with 70% (v / v) aqueous ethanol to a solid content of 0.5% (w / v). Example 2C Formulation ATT3 20g Cosmocil CQ was mixed with 25 ml of solution of • DMF containing 5 g of Araldite 720 epoxy resin as described in Example 1A. The resulting suspension was heated to 95-98 ° C. After 30 minutes of stirring at this temperature, the clarified solution was cooled and filtered. Then 40 ml of the obtained solution, 2.8 g of sodium dodecyl sulfate (SDS), 1.3 g of Ag, 0.4g of Kl, 5 ml of DMF, 20 ml of ethanol and 20 ml of NMP 10 together in a flask for 30 minutes. The volume of the obtained standard solution (yellow brown color) was adjusted with ethanol to 100 ml. Before application, the standard solution was diluted with 70% (v / v) aqueous ethanol to a final solids content of 0.5% (w / v). Example 2D ATT4 formulation 25g of Cosmocil CQ was mixed with 25 ml of a DMF solution containing 5 g of bisphenol A epichlorohydrin epoxy resin, average molecular weight 480 (obtained from Aldrich Chemical Co., Milwaukee, Wl) as described at Example IB The resulting suspension was heated to 95-98 ° C.
After 30 minutes of stirring at this temperature, the clarified solution was cooled and filtered. 40 ml of the obtained solution, 2 g of 25 Ag, and 0.6 g of Kl, 2.5 g of a polyvinyl pyrrolidone (PVP) (average molecular weight 29000, obtained from Aldrich Milwaukee, Wl), 20 ml of ethanol and 20 ml of water were mixed. distilled • together in a flask for 30 minutes. The volume of the obtained standard solution (colorless) was adjusted with water to 5 100 ml. Before application, the standard solution was diluted with deionized water to achieve a final solids content of 0.5% (w / v). Example 2E Formulation Sl and S3 10 A 227 ml of a 12.9% PHMB-MBGDA adduct solution in ethanol was added 12.6 g of sodium lauryl sulfate (Aldrich Chemical Company, Milwaukee, Wl) dissolved in a mixture containing 30ml of water and 30ml of ethanol with stirring. To this was added 2.1g of silver nitrate added in a mixture containing 30 ml of water and 30 ml of ethanol. The resulting solution was diluted with 542 ml of ethanol and 51 ml of N-methyl-2-pyrrolidone with stirring. This solution was combined with a solution containing 3.1g of potassium iodide in a mixture of 30ml of water and 30ml of ethanol. The mixture stirred for 1 hour after which the resulting solution was filtered through a 5 micron filter. The resulting emulsion was diluted as much as was necessary to obtain the disinfectant liquid at the use concentration. EXAMPLE 3 Application of Coating The coatings described in Example 2 were applied by spraying onto the surface of glazed tiles. • ceramic (using a standard 22 oz spray gun) and spreading liquid evenly with a soft tissue. A tile surface of one square foot was treated immediately (64 tiles, each 35mm x 35 mm in size). The alcohol-based formulations were dried for 10 minutes, the aqueous or DMF-based formulations were dried for 30 minutes. • 10 Anmicrobial Activity Test The coated samples were tested for antimicrobial efficiency in the following tests (the results are shown in Table 1): A. Standard bactericidal test grade 15 hospital disinfectant; B. Standard fungicidal test grade hospital disinfectant; # C. Standard virucidal test for hospital disinfectant grade; 20 D. Residual efficiency test for disinfectant; E. Multiple microbial challenge test for sustained residual disinfection - the results are shown below; F. Antimicrobial efficiency of the coating after exposure to common solutions for bath cleaning - the results are shown in Example 8; G. Efficiency of antimicrobial coating in the presence of growth support medium - result (not shown) does not indicate growth in coated tiles; and H. Kirby-Bauer inhibition zone test- the results (not shown) did not show a zone of inhibition, indicating that the coatings are not filterable. A-C Standard tests for bacterial, viral and fungicidal activity The tests were run with S3 formulation by the protocols of the American Society of Analytical Chemists 15 (AOAC). The formulation was applied to glass holders that were submitted to defy bacteria, fungi and viruses • for standard test conditions. The formulation was disinfectant, virucide and fungicide under these test conditions. The efficiency data are summarized in Table 1 (lac) D. Sustained residual disinfection test Tests were made on the residual film obtained from the S3 formulation on glass slide holders and ceramic tiles after evaporation of solvents. The residue was immersed in water at 25 ° C for 24 hours, after which it was tested with Psedomonas aeruginosa, Staphylococcus aureus and Salmonella choleraseius. Tiles and holders containing residues after contact with water were inoculated with 0.3 ml of a suspension of microorganisms in PBS. The incubation of the microorganisms was carried out at room temperature (20 ° C) in a humidity chamber. The plantonic microorganisms were recovered from the surface of the tile, then dilutions were made in series and plate count by standard techniques. The reduction in the microorganism count compared with the control tiles is shown in Table ld. E. Achievement of the ATT coating in the microbial mulch challenge test Non-porous glaze tiles, 35x35 mm in length, treated with the ATT formulations were tested for antimicrobial efficiency in a multiple challenge test with gram negative bacteria Pseudomonas aeruginisa and Escherichia coli; gram-positive bacteria, Staphylococcus a ureus; fungi Aspergill us niger (mold); and Candida albicans (yeast). The tiles were inoculated repetitively with 0. 3 ml suspension of microorganisms in PBS. Among the inoculations the tile samples were washed with running water (250 ml per tile) and air dried. The samples were not sterilized between inoculation cycles. The microorganism incubation was carried out at room temperature (20 ° C) in a humidity chamber. The planktonic microorganisms were recovered from the surface of the tile, then serial dilutions were made in series and plate count by standard techniques. The reduction in the microorganism count compared with the control tiles is reported in Table 2.
• Table 1. ANTIMICROBIAL EFFICIENCY OF THE DISINFECTANT FORMULATION I. Initial efficiency of the Spray of Surfazine disinfectant Table 1a. Germicidal Efficiency of Disinfectant Formulation Recovery Mode Replicas Organ Time of you are / without load with load Antimicrobial cfu / sample Percentage of Attempt Lot 'Test Organism ATCC soil floor to act Control Test Log Reduction 10 Remarks Hospital S3xl6 Aspersion P. aeruginosa 15442 W * 4Ó "10 minutes 0 ~ 99.9999 A sample disinfectant S. aureaus 6538 20 10 10 minutes OR 99.9999 of soil S. 10702 20 10 10 minutes OR 99.9999 tested for choleraesuis positive presence * * The data reprecentan 5 lots Table 1b. Efficacy Virucide Formulation Disinfectant ATCC Mode Time A n th tim tcrobian o Load of ti Reduction Pretention Lot test Virus Type Strain to act Soil Replica of Log10 Observations Activity Slxló Aspirció Poliovinis 1 VR-1000 Bmnhilde 10 minutes Yes 5.5 Complete nac vación Virucide Slxl6 Herpes Simplex Viras VR-733 F (l) 10 minutes Yes 5 Complete inactivation Slxl6 Rhinovitus 37 VR-1147 151-1 10 minutes Yes 4 Complete inactivation S3xl6 Hepatitis A VR-1073 HM-175 10 minutes Yes 3 Complete inactivation • Table 1. ANTIMICROBIAL EFFICIENCY OF THE DISINFECTANT FORMULATION (continued) II. Efficiency of Residual Disinfection Sustained by the Disinfectant Formulation Table 1b. Efficiency of Residual Disinfection Sustained by the Disinfectant Formulation) • Table 2 Antimicrobial Efficiency of Spray Coating in Repetitive Challenge Experiments Involving 10 Cycles.
Example 4 Conduct Test for Biocidal Activity • The ceramic tiles were spray coated with the composition described in Example 2B according to the procedure described in Example 3. The biocidal surface activity was tested according to the following procedure: Cultures of the following microorganisms were prepared: 10 Escherichia coli (ATCC # 8139) Pseudomonas aeruginosa (ATCC # 9021) Salmonella cholerasius (ATCC # 1 0108) Staphylococcus a ureus (ATCC # 6538) Candida albicans (ATCC # 9642) 15 Aspergillus niger ( ATCC # 9027) Culture inocula of these microorganisms were prepared according to known procedures. To test the antimicrobial efficiency of the present coatings, ceramic tiles 20 were treated with the untreated control coatings and tiles, sprayed with 106 cfu / ml (cfu = colony forming units) of each of the above organisms. The tiles were incubated for 20 hours in a humidity chamber at 25 ° C. The number of viable organisms on the surface was determined after cleaning the surface of the tiles and cultivating the organisms collected from the surface by the plate propagation method. The presence of the two fungal samples (Candida and A. niger) was also determined by the turbidity method in 5 PBS cleaning extracts. The control tiles showed 104 to 106 cfu / ml. Treated tiles did not show viable organisms. EXAMPLE 5 EFFICIENCY AFTER EXPOSURE TO WATER Ceramic tiles coated with the composition described in Example 4 were further tested for antimicrobial efficiency after washing. To simulate long-term use, the tiles were washed under running water for 2 hours, (total volume, 1 gal / in2). Challenge tests antihyogo and biocides described in Example 4 were repeated. After incubation for 20 to 72 hours, the control tiles showed 104 to 106 fcfu / ml of bacterial counts and • 105 to 106 cfu / ml of mold beads. The tiles coated with the composition of the invention did not show organisms viable. EXAMPLE 6 Kinetics of the Bactericidal Activity The ceramic tiles were sprayed with the compositions described in Example 2 according to the procedures described in Example 3. Some of the sprayed tiles and unsprayed controls were placed under running water running for 2 hours (total volume, 1 gal / in2) of the following organisms: P. aeruginosa, S. aureus and E. coli The tiles were incubated at room temperature and the number of viable organisms was determined quantifiably by the plate propagation method at different times. The antimicrobial efficiency of pre and post-wash spraying was determined as a function of time. The results, illustrated in Figures 3A and 3B, show that the treated tiles completely removed the microorganisms from the surface within 10 minutes, while the untreated tiles showed no reduction. Example 7 Efficiency after the Repetitive Challenge. The ceramic tiles sprayed with the coating as described in Example 6 and the untreated control tiles were challenged with 10 ° cfu / ml of P. aeruginosa. The tiles were incubated at 30 ° C for 3 hours or for 20 hours in a humidity chamber, after which the presence of viable organisms was determined by the plate propagation method. The tiles were washed with water (250 ml / tile) and the bacterial challenge was repeated. This cycle was repeated to obtain a total of 10 challenges each for incubations of three hours and 20 hours. The results, illustrated in Figures 4A and 4B, show that even after 10 repeated washes and bacterial challenges, • the tiles treated with the present composition were free of microbial contamination. Example 8 Efficiency of the Antimicrobial Coating after Exposure to Cleaning Agents' The ceramic tiles were sprayed with the coating described in Example 2B according to • 10 procedure described in Example 3. The coated tiles (indicated in Table 2 below as "Treatments") and the non-sprayed control tiles were exposed to various cleaning agents for 2 minutes, washed with 100 ml of tap water and They were dried by air. The tiles were then inoculated with 10? cfu / ml of P. aeruginosa and incubated for 20 hours at 30 ° C in a humidity chamber, then tested for the presence of • microbes. The results, shown in Table 2 below, indicate that the cleaning agents did not affect the Antimicrobial coating efficiency. Table 2 Example 9 Alcohol-based disinfectant spray formulation that • incorporates modified biguanide. The preparation of the alcohol-based disinfectant formulation was carried out in three stages. .1. Preparation of poly (hexamethylene) biguanide resin (PHMB) - Epoxy (Ep) 2. Preparation of spray concentrate 3. Preparation of spray disinfectant 10 Step 1: Preparation of PHMB-Ep resin: • The PHMB-Ep resin was prepared as it was described in Example IA. Stage 2: Preparation of Aspersion Concentrate: The spray concentrate was prepared as follows: • The BG-Ep resin was placed in a 4 liter Erlenmeyer flask. Aqueous alcoholic solutions of SDS, Kl and AgN03 and NMP were introduced with stirring. The complete solution was allowed to stir for a period of 2 hours to ensure uniform mixing and was then filtered through a Whatman # 4 filter paper and stored in an appropriate package. Stage 3: Preparation of disinfectant spray: The disinfectant spray was prepared as follows: To a 4-liter Erlenmeyer flask was added 1480. 5 g of ethanol and 393.5 g of water. The solution was allowed to mix for at least 10 minutes before the addition of the spray concentrate. The spray concentrate was added dropwise over a period of 20-25 minutes with vigorous stirring. After the addition was complete, the solution was stirred for 1 hour at the same speed and room temperature. After which the solution was filtered through a Whatman # 4 filter paper and stored appropriately. Example 10 Formulation of the disinfected spray based on the alcohol that incorporates modified biguanide An alternative method for the preparation of the alcohol-based disinfectant formulation was carried out involving two stages without passing through a spray concentrate stage. 1. Preparation of poly (hexamethylene) biguanide resin (PHMB) -Epóxica (Ep). 2. Preparation of disinfectant spray. Step 1: Preparation of PHMB-Ep resin: The PHMB-Ep resin was prepared as described in Example IA. Step 2: Preparation of the spray formulation: The spray formulation was prepared as follows: The BG-Ep resin was placed in a 4 liter Erlenmeyer flask. Aqueous alcohol solutions of NMP, SDS, Kl and AgN03 were added with uniform agitation. The complete solution was left to shake for a period of 2 hours to ensure • uniform mixing and then filtered through a Whatman # 4 filter paper and stored in an appropriate package. Example 11 Disinfecting formulation based on alcohol that involves unmodified biguanide: The preparation of the alcohol-based disinfectant formulation was done in two stages. 1. Preparation of the spray concentrate that involves poly (hexamethylene) biguanide (PHMB) 2. Preparation of the disinfectant spray. 15 Stage 1: Preparation of the spray concentrate: The spray concentrate was prepared as follows: • The Cosmocil CQ was placed in a 4 liter Erlenmeyer flask. Aqueous alcoholic solutions of SDS, Ag, Kl and NMP were introduced into the solution with constant stirring. The entire solution was allowed to stir for a • 2 hour period to ensure uniform mixing and then filtered through Whatman # 4 filter paper and stored in an appropriate package. Stage 2: Preparation of the disinfectant spray: The disinfectant spray was prepared as follows: • To a 4 liter Erlenmeyer flask, the required amounts of ethanol and water were added. The solution was allowed to mix for at least 10 minutes before the administration of a spray concentrate. The spray concentrate was added dropwise over a period of 20-25 minutes, with vigorous stirring. After completing the addition the solution was stirred for 1 hour at the same ^ speed and ambient temperature. The solution was then filtered through a Whatman # 4 filter paper and stored appropriately. Equivalents Those skilled in the art will be able to determine, using no more than routine experimentation, many equivalents of the specific embodiments of the invention described herein. These and other equivalents are intended to be understood by the following claims. •

Claims (39)

  1. CLAIMS 1. A disinfectant composition comprising a • organic polymeric antimicrobial material forming film and a metallic material in a liquid carrier, characterized in that the composition when applied to a surface forms a water-insoluble, adherent, non-permanent film, wherein the metallic material is bonded unfiltered or is associated with the film, wherein the film does not elute antimicrobial materials within contact water ^ P 10 at levels capable of imparting disinfecting action to water, and wherein the film can be removed, if desired, by treatment with an alcoholic solution containing a surfactant.
  2. 2. The disinfectant composition according to claim 1, characterized in that the organic polymeric antimicrobial material is a polymeric biguanide material.
  3. 3. The disinfectant composition according to claim 1, characterized in that the material The metal is substantially insoluble in water.
  4. The disinfectant composition according to claim 3, characterized in that the metallic material is selected from the group consisting of a metal, metal salt, metal complex, metal alloy, and 25 combinations thereof.
  5. 5. The disinfectant composition according to claim 4, characterized in that the metal is silver, flp 6.
  6. The disinfectant composition according to claim 4, characterized in that the metallic material 5 is silver nitrate or silver iodide.
  7. The disinfectant composition according to claim 2, characterized in that the polymeric biguanide material comprises polyhexamethylenebiguanide or derivatives thereof.
  8. 8. The disinfectant composition according to claim 2, characterized in that the polymeric biguanide material comprises an adduct obtained by the reaction of the biguanide material with an insoluble organic compound.
  9. 9. The disinfectant composition according to claim 8, characterized in that the water-insoluble organic compound is selected from the group consisting of epoxy compounds, isocyanate compounds, carboxylic acid compounds, acid chloride compounds, 20 composed of acid anhydride, aldehydes, aldehydes of succimidyl ethers, ketones, alkyl methanesulfonates, alkyltrifluoromethanesulfonate compounds, alkyl paratoluenemethanesulfonate compounds and alkyl halide compounds.
  10. 10. The disinfectant composition in accordance with 25 claim 9, characterized in that the water-insoluble organic compound is an epoxy compound selected from the group consisting of methylene-bis-N, N- • diglycidylaniline, bisphenol-A-epichlorohydrin and N, N-diglycidi 1-4-glycidyloxyaniline .
  11. 11. The disinfectant composition of claim 1, further characterized in that it comprises an optical reporter that allows visual detection of the presence of the film.
  12. 12. The disinfectant composition of Claim 11, characterized in that the optical reporter is selected from the group consisting of a dye and an indicator.
  13. 13. The disinfectant composition of claim 12, characterized in that the indicator 15 comprises a pH indicator.
  14. The disinfectant composition of claim 12, characterized in that the indicator comprises a thermochromic material.
  15. 15. The disinfectant composition of claim 11, characterized in that the optical reporter comprises an optical brightening agent.
  16. 16. The disinfectant composition of claim 11, characterized in that the optical reporter comprises a fluorophore.
  17. 17. The disinfectant composition according to claim 16, characterized in that the optical reporter is selected from the group consisting of 2, 2'- (2,5- • thiophenidyl) bis [5- tert -butylbenzoxazole] or sodium salt of the 4,4'-bis-2-diethylamino-4- (2,5-disulfophenyl-amino) -s-5-triazinyl-6-amino-stilbene-2 acid, 2'-disulfonic.
  18. 18. The disinfectant composition according to claim 1, characterized in that it additionally comprises a surfactant, emulsifier, antioxidant or stabilizer.
  19. 19. The disinfectant composition according to claim 18, characterized in that the surfactant is selected from the group consisting of sodium dodecyl sulfate, sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan triolate, Tween-
  20. 20, Tween 40, Tween 60, Tween 80 or Tween 85. The disinfectant composition according to claim 1, characterized in that the liquid carrier comprises water, an organic solvent, solvent mixture 20 organic or a combination of an aqueous solvent and an organic one.
  21. 21. The disinfectant composition according to claim 1, characterized in that the organic solvent is an antimicrobial disinfectant.
  22. 22. The disinfectant composition according to claim 20, characterized in that the liquid carrier is an alkanol or an aqueous alkanol mixture. FF
  23. 23. The disinfectant composition according to claim 22, characterized in that the alkanol is ethanol or isopropanol.
  24. 24. A method for providing an antimicrobial substrate or layer, the method is characterized in that it comprises: applying the disinfectant composition of the claim 1 to the substrate to form an adherent water insoluble film or layer on the substrate.
  25. 25. The method according to claim 24, characterized in that the disinfectant composition is applied to the substrate by spraying from an applicator of 15 aspersion.
  26. 26. The method according to claim 24, characterized in that the disinfectant composition is applied to the substrate by rubbing, brushing or soaking.
  27. 27. The method according to claim 20, characterized in that the disinfectant composition is applied to the substrate as an aerosol spray using a suitable propellant. •
  28. 28 The method according to claim 27, characterized in that the propellant is nitrogen, carbon dioxide or a hydrocarbon or mixtures of hydrocarbons.
  29. 29. The use of the disinfectant composition according to claim 1, as a disinfecting agent for hard surfaces.
  30. 30. The use of the disinfectant composition according to claim 29, characterized in that the hard surface disinfecting agent is selected from the group consisting of disinfectants for institutions and hospitals, kitchen and bathroom disinfectants, cleaning disinfectants, or floor cleaners. and walls. ^ P 10
  31. 31. The use of the disinfectant composition according to claim 1, characterized in that as a skin disinfectant, antiseptic, sanitary or protective substances.
  32. 32. The use of the disinfectant composition according to claim 1 for treating an article or device for skin contact. .
  33. 33. The use according to claim 32, characterized in that the device for contact with the skin is selected from the group consisting of diapers, wound bandages, rags, and surgical masks and gowns.
  34. 34. The use of the disinfectant composition according to claim 1, for treating articles or devices without contact with the body.
  35. 35. The use according to claim 34, characterized in that the article without contact with the body is selected from the group consisting of rails for hospital bed, folders and carpets. ^ P
  36. 36. The use of the composition according to claim 1, characterized in that it forms a water-insoluble, adherent, non-permanent film, wherein the film does not elute antimicrobial materials in contact with water at levels capable of imparting action disinfectant to water, and where the film can be removed, if desired, by treatment with a solution 10 alcoholic containing a surfactant.
  37. 37. The water-insoluble, adherent, non-permanent film formed by the application of the disinfectant composition according to claim 1 to a surface, characterized in that the film does not elute 15 antimicrobial materials in contact with water at levels capable of imparting disinfecting action to water, and wherein the film can be removed if desired, by treatment with an alcoholic solution containing a surfactant.
  38. 38. The surface coating by the film according to claim 37.
  39. 39. The article of manufacture characterized in that it comprises the surface according to claim 38. 25
MXPA/A/2000/007863A 1998-02-12 2000-08-11 Disinfectant compositions providing sustained biocidal action MXPA00007863A (en)

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