AU2004241665B2

AU2004241665B2 - Biofilm growth prevention

Info

Publication number: AU2004241665B2
Application number: AU2004241665A
Authority: AU
Inventors: Steven Kritzler
Original assignee: Novapharm Research Australia Pty Ltd
Current assignee: Novapharm Research Australia Pty Ltd
Priority date: 2003-05-21
Filing date: 2004-05-18
Publication date: 2009-10-08
Anticipated expiration: 2024-05-18
Also published as: AU2004241665A1

Description

- 1 BIOFILM GROWTH PREVENTION Technical Field This invention relates to a method of, and composition for, reduction or prevention of biofilm formation on moist or wet surfaces, and more particularly to 5 the reduction of pathogens in, and in the vicinity of, air-conditioning systems. The invention has been developed primarily for use in air-conditioning (including air cooling and air heating) systems, and will be described hereinafter with reference to this field of use. However, it will be appreciated that the invention can be applied in other 10 situations in which it is desired to inhibit biofilm formation or micro-organism colonization of a surface. Background Art Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms 15 part of common general knowledge in the field. Air conditioning systems such as are commonly provided in office, residential, health care and other buildings frequently include components with moist or wet surfaces. A good example is the air conditioner condenser which may comprise a plurality of heat exchange fins, for example of aluminium 20 construction, cooled by heat conductive connection with a recirculating refrigerant. Hot air to be cooled is passed over the fins, and moisture in the air condenses on the fins and drains away. In some cases the heat exchange surfaces of the condenser are cooled by a recirculating thin film of water. The cooling surfaces are typically of a large area, are moist or wet, and 25 provide an ideal environment for the immobilization and growth of micro organisms which are carried by the air and which form biofilms on the surfaces. The micro-organisms include bacteria and fungi which multiply on the surface. Within months the space between adjacent heat exchange surfaces may be totally occluded by biofilm growth.

WO 2004/103071 PCT/AU2004/000650 -2 Biofilm reduces efficacy and poses major health risks. Efficacy is lost because the biofilm has poor heat transfer properties and so the thermal efficiency of the condenser is diminished. Microbial activity can also shorten the service life of a system because acidic bacterial exudates can cause serious corrosion and because the 5 increase in biomass on, and in, the components can lessen air-flow and increase back pressure in the system, requiring maintenance cleaning after a short life in service. The health risk arises because the presence of biofilm in turn provides a haven for the further accumulation and further growth of pathogens such as fungi, bacteria, viruses, allergens, yeasts, and moulds. Conditions for the growth of such organisms 10 are especially favourable during periods of high humidity such as may occur when the system is off, for example at night, but also arise during normal operation. The presence of organisms is highly undesirable because they can cause illness or death in humans and animals, create odours and can damage or destroy a wide variety of materials. 15 Of particular concern in terms of human health and safety are endotoxins and mycotoxins which are breakdown components of fungal and bacterial cell walls and which are known human respiratory allergens. In some individuals they can trigger asthma attacks, and in all cases have been shown to cause immune response. It is currently thought that over a period of exposure this reduces the ability of the immune 20 system to respond to antagonists and leaves the subject more prone to infection by bacteria, viruses, etc. Also of concern are fungal spores, bacterial spores and bacteria. In health care facilities such as hospitals and nursing homes the adverse consequences of release of endotoxins and myotoxins from biomass are exacerbated because many of the patients are in a weakened condition due to their primary health 25 care problem. Micro-organisms that would not be a major threat to a healthy person can be fatal to a patient with a diminished capacity to defend themselves from infection. Increasing attention is also being paid to other environments such as public buildings, -3 since if pathogenic micro-organisms find their way via conditioned air or ventilation shafts, into a building they can be rapidly circulated throughout the building thereby greatly increasing the likelihood of the spread of infection and disease. The prevention of spore germination and microbial survival in air 5 conditioning systems would help reduce the risk of illness and hypersensitivity reactions. To date there has been no effective means of prevention of biomass growth and the only means of addressing the problem has been periodic cleaning, which is labour intensive, costly and inconvenient and which does not 10 adequately deal with health concerns between cleaning operations. Although various coating materials have been proposed, none have been able to resist the moist conditions or remain effective in preventing biofilm formation for a useful period. It is an object of the present invention to overcome or ameliorate at least 15 one of the deficiencies of the prior art, or to provide a useful alternative. Many regions of the world employ heated filtered air in buildings as a means of central heating. It will be understood that such systems contribute to the same hazards as described above for air conditioning and the invention is not limited to any particular kind of filter or airflow system. 20 Description Of The Invention According to a first aspect, the present invention provides a biostatic coating composition suitable for application to metal or masonry surfaces and effectively inhibit biofilm growth for at least 12 months comprising a film forming combination of a biocidal complex A-B in which A of the biocidal complex A-B is 25 a phenolic biocide and B of the biocidal complex A-B is selected from the group consisting of polyvinyl pyrrol idone, polyvinylpyrrolidone polymers, polyvinylpyrrolidone copolymers and mixtures thereof, and wherein B is selected so that the biocidal complex A-B is not water soluble but is dispersed in a water based emulsion by inclusion of a polar solvent or is dispersed in a solvent based 30 vehicle. According to a second aspect, the present invention provides a biostatic coating formed by drying a film or thin layer of a biostatic coating composition, - 3a wherein the biostatic coating composition is suitable for application to metal or masonry surfaces and effective to inhibit biofilm growth for at least 12 months and comprises a film forming combination of a biocidal complex A-B in which A of the biocidal complex A-B is a phenolic biocide and B of the biocidal complex 5 A-B is selected from the group consisting of polyvinylpyrrolidone, polyvinylpyrrolidone polymers, polyvinylpyrrolidone copolymers, and mixtures thereof, and wherein B is selected so that the biocidal complex A-B is not water soluble but is dispersed in a water based emulsion by inclusion of a polar solvent or is dispersed in a solvent based vehicle. 10 According to a third aspect, the present invention provides a method of inhibiting the formation of a biofilm on a surface susceptible to such formation comprising the steps of applying a coating of a composition to the surface and drying the composition or allowing the composition to dry, wherein the composition of the coating comprises a film forming combination of a biocidal 15 complex A-B in which A of the biocidal complex A-B is a phenolic biocide and B of the biocidal complex A-B is selected from the group consisting of polyvinylpyrrolidone, polyvinylpyrrolidone polymers, polyvinylpyrrolidone copolymers, and mixtures thereof, and wherein B is selected so that the biocidal complex A-B is not water soluble but is dispersed in a water based emulsion by 20 inclusion of a polar solvent or is dispersed in a solvent based vehicle. It will be understood by those skilled in the art that the phrase "not water soluble" means not water soluble at the temperatures at which the composition is used. Unless the context clearly requires otherwise, throughout the description 25 and the claims, the words'comprise','comprising', and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of"including, but not limited to".

WO 2004/103071 PCT/AU2004/000650 -4 According to a second aspect the invention provides a biostatic coating composition according to the first aspect wherein the coating composition is selected from acrylic polymer based compositions, methacrylic polymer based compositions, acrylic copolymer based compositions, methacrylic copolymer based compositions, 5 vinyl polymer based compositions, vinyl copolymer based compositions, epoxy resins, epoxy esters, and mixtures thereof. Preferably, the coating composition has bacteriostatic and/or fungistatic properties. The film forming composition may be based on an emulsion or latex, a polymer 10 or copolymer solution, or a polymer or copolymer emulsion. The film forming composition may be a water-based polymer or copolymer emulsion. For preference, the film forming composition is or includes an acrylic polymer, acrylic copolymer, mixtures of acrylic polymers, mixtures of acrylic copolymers or mixtures of acrylic polymers and copolymers. More preferably, the film forming 15 composition is or includes an acrylic - styrene copolymer The film forming composition may be or includes an epoxy or epoxy ester. Highly preferred coating compositions are water-based polymers or copolymer emulsion or latex compositions, and especially those including an epoxy ester. The film forming composition may be or includes a vinyl acetate acrylic 20 copolymer. Preferably, the film forming composition is present in an amount of 30 to 80% w/w of the mixture, more preferably the film forming composition is present in an amount of 40 to 70% w/w of the mixture and even more preferably the film forming - composition is present in an amount of 50 to 60% w/w of the mixture. 25 Preferred biocides for use in the biocidal complex A-B are triclosan; diclosan; dichlorophen; oithophenylphenol; orthobenzylparachlorophenol, cresols, xylols, and substituted diphenyl ethers.

WO 2004/103071 PCT/AU2004/000650 -5 More preferably, biocide A is a halogenated phenolic biocide, in preference a chloro-phenolic biocide and most preferably, biocide A is triclosan. Preferably, biocide A is present in an amount of 0.5 to 5% w/w of the mixture, more preferably in an amount of 1 to 2% w/w of the mixture and even more preferably 5 in an amount of 1.5% w/w of the mixture. Preferably, .the complexing partner B is polyvinylpyrrolidone, or may be, for example, a polyvinylpyrrolidone/vinyl acetate copolymer. Preferably, B is present in an amount of 2 to 10% of the mixture, more preferably B is present in an amount of 3 to 8% of the mixture, and even more preferably B is 10 present in an amount of about 5% of the mixture Preferably, the biostatic composition contains solvent in an amount of 20 to 40% of the mixture, more preferably 25 to 35% of the mixture. One preferred solvent is water. It has been practised to combine a PVP/phenolic complex in a hydrophilic film forming polyvinyl pyrrolidone polymer or copolymer whereby the complex may be 15 loosely bound to impregnated paper or textile wipes for cleaning food preparation surfaces and the like. In the forgoing applications the complex is readily leached from the wipe substrate and can readily contact bacteria on the surface being cleaned/disinfected. The complex does not have any long lasting effect on the surface, and the wipe must be disposed of after approximately a dozen washes. The present 20 applicant was thus surprised to discover that inclusion of the PVP complex in a coating composition applied on, for example, a metal or masonry surface, significantly inhibited biofilm growth on the polymer coated surface, when the coating polymer might have been expected to encapsulate the biocide and protect micro-organisms from contact with the biocide. It was even more surprising that coatings including the complex 25 according to the invention have prevented biomass growth on coated metal for periods exceeding three years in an environment in which such growth was previously a major WO 2004/103071 PCT/AU2004/000650 -6 problem. It is also surprising that such a small concentration of biocide is effective for such a long duration. It will be appreciated that PVP/phenolic complexes are not water soluble and their inclusion in coating compositions is not simple. This has been achieved in the case of 5 water based emulsion coating compositions by dispersing the complex in the aqueous phase together with a water soluble high boiling point polar solvent (eg N-methyl pyrrolidone or a glycol ether). After the coating is applied, and as the water evaporates, the relative proportion of the high BP polar solvent increases and at a critical point dissolves the biocidal complex leaving the biocide homogeneously distributed 10 throughout the film. It will also be understood that while water is a preferred vehicle, dispersion in solvent based coating compositions can be similarly achieved. According to a third aspect, the invention provides a biostatic composition according to the first or second aspects further including a water soluble polar solvent having a higher boiling point than a solvent vehicle of the coating composition. 15 Preferably, the high boiling polar solvent aids dispersion of the complex A-B in a polymer emulsion or latex. Preferably, the water soluble polar solvent is selected from N-methyl pyrrolidone, glycol ethers, and combinations thereof. Coatings according to the invention may be used as protective coatings on components susceptible to biomass growth , such as air conditioning condenser plates, 20 vents and on other surfaces, eg susceptible surfaces in operating theatres, to prevent the formation of biofilm on the surface. The invention may also be applied in decorative coatings such as paints to prevent mould growth on susceptible surfaces. Coatings according to the invention may be applied (without limitation to surfaces of metal, masonry, timber, particle board, and other building and construction materials). Some 25 compositions may desirably be baked onto the surface or dried at elevated temperatures.

WO 2004/103071 PCT/AU2004/000650 -7 According to a third aspect, the invention provides a biostatic coating formed by drying a film or thin layer of a biostatic coating composition according to any one of the preceding aspects. The coating is preferably effective to prevent biofilm growth on its surface for in 5 excess of one year, and even more preferably is effective to prevent biofilm growth on its surface for in excess of three years. The coating may be applied to metal, to concrete or a cementitious surface or to a timber surface. The coating may be applied in the form of a decorative coating. One example is 10 in the form of a paint to prevent mould growth. Such a paint can further include paint ingredients selected from the group consisting of suspension agents, thixotropic agents, flow and viscosity modifiers, preservatives and the like. Other paint ingredients may be advantageously selected from the group consisting of corrosion inhibitors and/or pigments. 15 Thus depending on intended end use, compositions according to the invention may be pigmented and in that case will normally include other paint ingredients such as suspension agents, thixotropic agents, flow and viscosity modifiers, preservatives and the like. The compositions need not be pigmented and may include corrosion inhibitors and other additives known to be useful in film-forming coatings. 20 It will be understood that it is sufficient that the treatment is bacteriostatic or fungistatic. That is to say, it is sufficient that the treating agent stops colonisation on the surface rather than kills organisms on a colonised surface. According to a fourth aspect, the invention provides a method of inhibiting the formation of a biofilm on a surface susceptible to such formation comprising the steps 25 of applying a coating of a composition according to the first or second aspects to the surface and drying the composition or allowing the composition to dry.

WO 2004/103071 PCT/AU2004/000650 -8 In preferred embodiments, the surface is an air conditioning surface, an air conditioning condenser plate, an air conditioning condenser vent, or may be a susceptible surface in an operating theatre. In some embodiments, the composition is baked onto the surface or dried at 5 elevated temperatures. According to a fifth aspect, the invention provides a surface treated in accordance with a composition of the fist or second aspects or according to a method of the fourth aspect. Best Modes for Carryinq Out the Invention 10 Various embodiments of the invention will now be more particularly described by way of example only. Suitable biocides for use in the invention include, but are not limited to complexes of PVP or PVP copolymer with triclosan; diclosan; dichlorophen; orthophenylphenol; orthobenzylparachlorophenol, cresols, xylols, and substituted diphenyl ethers. 15 Examples of formulas: Formulations were prepared as shown in the following examples Example 1 Styrene/Acrylic Copolymer Emulsion(50% solids) 60.0%w/w Water 28.5% w/w N-Methyl Pyrrolidone 5.0% w/w PVP/VA S-630 5.0% w/w Triclosan 1.5% w/w WO 2004/103071 PCT/AU2004/000650 -9 Example 2 Acrylic Copolymer Emulsion(50% solids) 60.0%w/w Water 28.5% w/w N-Methyl Pyrrolidone 5.0% w/w PVPNA S-630 5.0% w/w Triclosan 1.5% w/w Example 3 Vinyl Acetate/Acrylic Copolymer Emulsion 60.0%w/w (50% solids) Water 28.5% w/w N-Methyl Pyrrolidone 5.0% w/w PVP/VA S-630 5.0% w/w Triclosan 1.5% w/w Example 4 Acrylic Copolymer Emulsion 30.0 - 50.0%w/w (50% solids) Epoxy Resin 1001 10.0 - 20.0% w/w Propylene Glycol Methyl Ether Acetate 10.0 - 20.0% w/w PVP/VA S630 5.0%w/w 2-Phenoxy Ethanol 2.0 - 5.0% w/w Nonyl Phenol Ethoxylate Sulphate Ammonium Salt 2 - 3.0% w/w Triclosan 1.5% w/w Water qs to 100% w/w WO 2004/103071 PCT/AU2004/000650 -10 Example 5 Acrylic copolymer 70% w/w (50% active solution in ethanol) PVPNA S630 5.0%w/w Triclosan 1.5% w/w Ethanol 23.5% w/w PVPNA S630 is available from ISP corporation. A cooling coil in the airconditioning system of a large city building situated in Sydney was thoroughly cleaned and then monitored at intervals over a 12 month 5 period. A significant growth of biomass was observable on the cooling coil within a month, and the coil required cleaning at intervals of approximately 3 months. The coil was then again cleaned and sections of the coil were coated with formulations , according to each of examples 1 - 3. The coil was inspected at intervals. No biofilm growth was observable on the coil after 12 months on any of the coated sections.

Claims

1. A biostatic coating composition suitable for application to metal or masonry surfaces and effectively inhibit biofilm growth for at least 12 months 5 comprising a film forming combination of a biocidal complex A-B in which A of the biocidal complex A-B is a phenolic biocide and B of the biocidal complex A-B is selected from the group consisting of polyvinylpyrrolidone, polyvinylpyrrolidone polymers, polyvinylpyrrolidone copolymers and mixtures thereof, and wherein B is selected so that the biocidal complex A-B is not water 10 soluble but is dispersed in a water based emulsion by inclusion of a polar solvent or is dispersed in a solvent based vehicle.

2. A biostatic coating composition according to claim 1 wherein the film forming combination is selected from the group consisting of acrylic polymer based compositions, methacrylic polymer based compositions, acrylic 15 copolymer based compositions, methacrylic copolymer based compositions, vinyl polymer based compositions, vinyl copolymer based compositions, epoxy resins, epoxy esters, and mixtures thereof.

3. A biostatic coating composition according to claim 1 or claim 2 wherein the film forming combination is an emulsion, latex composition, a polymer or 20 copolymer solution, a polymer or copolymer emulsion or a water-based polymer or copolymer emulsion.

4. A biostatic coating composition according to any one of the preceding claims wherein the film forming combination is chosen from an acrylic polymer - 12 or acrylic copolymer, an acrylic - styrene copolymer, an epoxy or epoxy ester or a vinyl acetate acrylic copolymer.

5. A biostatic coating composition according to any one of the preceding claims wherein the film forming combination is present in an amount of 30 to 5 80% w/w of the mixture.

6. A biostatic coating composition according to any one of the preceding claims wherein biocide A is selected from the group consisting of triclosan, diclosan, dichlorophen, orthophenylphenol, orthobenzylparachlorophenol, cresols, xylols, and substituted diphenyl ethers. 10

7. A biostatic coating composition according to any one of the preceding claims wherein biocide A is a halogenated phenolic biocide.

8. A biostatic coating composition according to any one of the preceding claims wherein the biocide A is present in an amount of 0.5 to 5% w/w of the mixture. 15

9. A biostatic coating composition according to any one of the preceding claims wherein B is polyvinylpyrrolidone or a polyvinylpyrrolidone/vinyl acetate copolymer.

10. A biostatic coating composition according to any one of the preceding claims wherein B is present in an amount of 2 to 10% of the mixture. 20

11. A biostatic coating composition according to any one of the preceding claims containing solvent in an amount of 20 to 40% of the mixture. -13

12. A biostatic coating composition according to claim 11 further including a water soluble polar solvent having a higher boiling point than a solvent vehicle of the coating composition; wherein the high boiling polar solvent aids dispersion of the complex A-B in a polymer emulsion or latex. 5

13. A biostatic coating formed by drying a film or thin layer of a biostatic coating composition, wherein the biostatic coating composition is suitable for application to metal or masonry surfaces and effective to inhibit biofilm growth for at least 12 months and comprises a film forming combination of a biocidal complex A-B in which A of the biocidal complex A-B is a phenolic biocide and B 10 of the biocidal complex A-B is selected from the group consisting of polyvinylpyrrolidone, polyvinylpyrrolidone polymers, polyvinylpyrrolidone copolymers, and mixtures thereof, and wherein B is selected so that the biocidal complex A-B is not water soluble but is dispersed in a water based emulsion by inclusion of a polar solvent or is dispersed in a solvent based vehicle. 15

14. A biostatic coating according to claim 13 which is effective to prevent biofilm growth on its surface for in excess of one year.

15. A biostatic coating according to claim 13 or claim 14 when applied to metal, a concrete or a cementitious surface or a timber surface.

16. A biostatic coating according to any one of claims 13 to 15 in the form of 20 a paint further including paint ingredients selected from the group consisting of suspension agents, thixotropic agents, flow and viscosity modifiers, preservatives, corrosion inhibitors, pigments and the like. - 14

17. A method of inhibiting the formation of a biofilm on a surface susceptible to such formation comprising the steps of applying a coating of a composition to the surface and drying the composition or allowing the composition to dry, wherein the composition of the coating comprises a film forming combination of 5 a biocidal complex A-B in which A of the biocidal complex A-B is a phenolic biocide and B of the biocidal complex A-B is selected from the group consisting of polyvinylpyrrolidone, polyvinylpyrrolidone polymers, polyvinylpyrrol idone copolymers, and mixtures thereof, and wherein B is selected so that the biocidal complex A-B is not water soluble but is dispersed in a water based emulsion by 10 inclusion of a polar solvent or is dispersed in a solvent based vehicle.

18. A method according to claim 17 wherein the surface is an air conditioning surface like an air conditioning condenser plate or an air conditioning condenser vent or a susceptible surface in an operating theatre.

19. A metal or masonry surface treated in accordance with a composition of 15 any one of claims 1 to 16 or a method according to claim 17 or claim 18.

20. A biostatic coating composition or a method of inhibiting the formation of a biofilm on a surface susceptible to such formation or a metal or masonry surface, substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying drawings and/or 20 examples.