CA2402653C - Antiseptic coating for the prevention of disease transmission via biofilms - Google Patents

Abstract

The invention provides an improved means for creating a surface that strongly resists microbial colonization. The invention involves a process that can be instigated in the environment of an applied coating. Non-toxic microbicides and halogen-free flame retardants are added as components of the coating which is manufactured using traditional methods and then applied by traditional methods to the hard or soft surface that is to be protected.

Description

Antiseptic coating for the prevention of disease transmission via biofilms.
Technical field The present invention relates to the formulation of an antiseptic interior coating such as a coating that uses enzymatic action to produce a biologically active compound.
The invention also relates to the generation of a biologically active compound that has a short half-life and does not pollute the surrounding environment with toxic fumes, because it is broken down in the overlying condensation layer to harmless compounds. The invention also relates to the formulation of an antiseptic coating that is safe to touch. The invention further relates to the formulation of an antiseptic coating that will be fire retardant without the release of toxic fumes. The invention furthermore relates to the use of the inventive coating for coating specific surfaces and preventing biofilm formation on these.
Background In all conditions where living animals including humans are crowded the air becomes filled with bacteria and viruses, and humidity is elevated. Bacteria released from humans etc , into the air will attach to surrounding walls, and, particularly in conditions of increased humidity, will begin growth and division at a logarithmic rate.
In order to adhere to surfaces, bacteria produce extracellular polymers which not only serve to attach and protect the bacteria, but also function to trap moisture. The network of extracellular polymers also serves to trap viruses and dirt particles and support growth of fungi.

In very enclosed conditions, such as a space capsule or station, this bacterial growth is very significant. Humans are crowded into a very small unventilated area.
Added to the normal shedding of bacteria are the following problems: reduced immune system efficiency as indicated by a seven-fold increase in shedding of the Epstein-Barr virus and presumed increased bacterial load caused by space-sickness and the generally poor ability to maintain normal hygiene levels.
This is further indicated by the bad smell associated with such vehicles. Astronauts control biofilm build-up by wiping accessible areas with antiseptic cloths, but biofilms will build up in the inaccessible areas, and become so thick and unstable that the film sloughs off and small particles of biofilm float through the capsule and are inhaled by the astronauts causing negative effects on astronaut health.

The same conditions also apply although to a lesser degree in aeroplanes, busses, mobile homes, caravans, cars, and yachts. Especially in aeroplanes flying at high altitude the possibilities for exchanging air with the surroundings are very limited due to the low oxygen tension at high altitude. Most of the air in aeroplanes is re-circulated and thus during long flights, the germ count in the air constantly increases and biofilm may build up, especially in the ventilation systems and on contact surfaces.

In ventilation systems, particularly in public buildings (sick building syndrome), hotels (legionnaires disease), hospitals and aeroplanes, the growth of biofilms is also associated with the transfer of disease. Thick bacterial mats can trap viruses, and as the mats become unstable and break up, particles of biofilm travel through the ventilation systems and are inhaled by others. Ventilation systems are generally not painted, and the current cleaning practise, physical removal of biofilm by abrasion and cleaning compounds when health problems or legislation dictate are generally not sufficient. To many cleaning companies, cleaning of ventilation systems is considered to be extremely hazardous because of the extremely high bacteria and virus load, with extreme clothing and respiration protection afforded to workers.

Ventilation systems are believed to be associated with the spread of disease in:
public buildings (hospitals, hospices, nursing homes, offices, hotels, schools, universities, sports facilities), private homes and transport vehicles (aeroplanes, submarines, ships, trains, busses) and buildings enclosing animals for human use or consumption, such as rabbits, mink, furred animals, poultry, goats, pigs, sheep, cattle, horses etc.
In hospitals and other medical care facilities, biofilms are believed to be a factor responsible for the spread of disease. Bacteria, which may be antibiotic resistant, cover the surfaces of wards, operating theatres etc , as well as being transferred through the ventilation system. Current cleaning practises are insufficient to prevent deaths due to drug resistant bacteria which readily infect patients due to their weakened state.

Biofilms are also readily found on most surfaces exposed to air and moisture.
Considered particularly risky are: public toilets, walls in all health care institutions (hospitals, hospices, nursing homes), walls in all public buildings (hospitals, hospices, nursing homes, offices, hotels, schools, nurseries, universities, sports facilities), surfaces in public transport vehicles (aeroplanes, submarines, ships, trains, busses), enclosures for farm animals also slaughterhouses, dairies, abattoirs, food preparation facilities and private homes. Current remediation practises (cleaning products) do not control the health problems caused by biofilms, and in some cases may result in the generation of resistant bacteria due to incomplete disfection.

Generally in the case of most of the mentioned surfaces government regulations require that the materials used fulfil certain requirement with relation to flame retardancy.

Generally in the art it is known to add enzymes to water based paints to inhibit the growth of microorganisms before the paint is applied to a surface. One group of examples of such compositions are disclosed in WO 00/68324 (Novo Nordisk AS).
However no reference is made to inhibiting the formation of biofilm on a surface coated with such a water based paint.

Enzyme base systems are also known that are capable of inhibiting biofilm formation in coated surfaces permanently in contact with an aqueous environment.
One example is a hexose oxidase based paint disclosed in WO 00/75293 (Danisco).
The disclosure mentions coating of the hull of a marine vessel as a possible use of the paint.
Another example of an enzyme based paint adapted for coating the hull of a marine vessel is disclosed in US 6,150,146 (Nippon Paint). The enzymes used in that particular disclosure are lipase which releases butyric acid from tributyrin, and cholesterol oxidase which releases hydrogen peroxide through oxidation of cholesterol.

However the prior art does not teach that any of these paints are capable of inhibiting biofilm formation, when the surface is not permanently in contact with water such as surfaces in enclosed environments. Furthermore, the prior art does not teach a paint which is simultaneously capable of inhibiting biofilm formation and possesses flame retarding properties.

Summary According to a first aspect the invention relates to a coating composition comprising i. a surface coating material, ii. at least a first enzyme, and iii. at least one flame retarding compound, wherein said first enzyme is capable of directly and/or indirectly inhibiting attachment and/or growth of microorganisms when exposed to moisture after applying said coating composition to a surface and allowing it to form a film.

By combining an enzyme based antimicrobial system with flame retardency, which preferably conforms with fire regulations for public buildings and/or vehicles it is possible not only to inhibit the formation of biofilm but also to retard flames.
Preferably, both the enzyme based system for inhibiting biofilm formation and the flame retardency system are not based on release of toxic fumes. This makes the composition especially adapted for used in an enclosed environment.
Ventilation systems present a particular problem in the present context.
Ventilation shafts are normally non-coated and biofilms therefore form easily on the surfaces of these. Coating the surfaces of ventilation shafts with an antiseptic coating solves or reduces the problem of biofilm formation and the associated spread of infectious diseases and allergens. However, ventilation shafts also present a fire hazard, since fires often spread in buildings, ships and aircrafts through the ventilation systems.
The coating compositions according to the present invention solve both problems by providing a coating, which reduces or eliminates biofilm formation and by making said coating composition flame retardant to reduce the fire hazard.

The at least one flame retardant compound may either be one that is added to the coating composition or the binder may be flame retardant in itself by being essentially non-combustible at elevated temperatures.

5 According to a further aspect the invention relates to a coating composition comprising i. a surface coating material, ii. at least a first enzyme, and iii. at least one antimicrobial compound, wherein said first enzyme is capable of directly and/or indirectly inhibiting attachment and/or growth of microorganisms when exposed to moisture after applying said coating composition to a surface and allowing it to form a film.

The inventive coating composition comprises both a passive system (antimicrobial compound) and an active system (the enzyme system) which are both directed to inhibition of biofilm formation on the coated surfaces. The enzyme based system is "activated" by exposure to elevated moisture levels such as a relative humidity above 50%. Most microorganisms require the presence of a certain amount of moisture to sustain growth; therefore it is only relevant to inhibit attachment and/or growth of the microorganisms when moisture levels increase.

Basically there are two different ways of inhibiting growth and/or attachment of microorganisms via an enzyme based system. Firstly, the enzyme can produce a product, which has antimicrobial activity. Secondly the enzyme may be chosen so that it degrades compounds in the extracellular matrix of the microorganisms such as polysaccharides thereby predominantly inhibiting the attachment of the microorganisms. A further enhancement of action may be obtained by including an enzyme which degrades substrates that the microorganisms metabolise and thus "starve" the microorganisms.

According to a further aspect the invention relates to the use of a composition according to the invention, in particular for coating surfaces.

By using the compositions according to the invention for coating surfaces, biofilm formation can be reduced or even eliminated while the risk that the coated surfaces catch or spread fire is reduced to a minimum due to the flame retardency.

According to a still further aspect the invention relates to a method for controlling growth of microorganisms on coated surfaces comprising applying to a surface a coating composition comprising a surface coating material, at least one enzyme, and a substrate for said enzyme, allowing said coating composition to form a film, whereby said coating composition upon subsequent exposure to moisture levels above 50% releases an antimicrobially effective amount of an antimicrobially active compound as a consequence of a conversion of said substrate through said enzyme.

According to this aspect of the invention, it is possible to control biofilm formation on surfaces which are exposed to air. Known enzyme based antiseptic coating compositions are designed for use on surfaces, which are more or less permanently in contact with water, such as the hull of a ship. In these cases the presence of water ensures that the enzymes are continuously active. On surfaces exposed to air, the problems are very different.

By the method according to the invention, the at least one enzyme contained in the coating composition is automatically activated when moisture raises and produces an antimicrobially effective amount of a compound, which inhibits growth of the microorganism. Biofilm formation on such surfaces is mostly only a problem when the ambient humidity raises above a certain level.
According to a further aspect the invention relates to a method for controlling growth of microorganisms on coated surfaces comprising applying to a surface a coating composition comprising a surface coating material, at least one enzyme, allowing said coating composition to form a film, whereby said coating composition upon subsequent exposure to moisture levels above 50% (RH) inhibits attachment of at least one species of microorganism as a consequence of a the action of said enzyme.

According to this aspect of the invention, it is possible to control biofilm formation on surfaces which are exposed to air. By the method according to the invention, the at least one enzyme contained in the coating composition is automatically activated when moisture raises and produces an antimicrobially effective amount of a compound, which inhibits attachment of the microorganism, e.g. by degrading compounds in the attachment matrix. Biofilrn formation on such surfaces is mostly only a problem when the ambient humidity raises above a certain level.
Definitions The term "antiseptic" as used herein refers to the action of inhibiting bacterial or fungal or mycoplama growth on surfaces to the extent that it inhibits biofilm formation.

The term "biofilm" used herein refers to the growth of bacteria that occurs on surfaces exposed to living organisms especially where there is a high ambient humidity. This bacterial growth if unchecked, results in the production of extracellular polymers which in turn create a water retaining matrix that supports fungi and algae as well as trapping viruses and air-borne particles.

The term "coating" as used herein in a preferred embodiment relates specifically to water-borne silicones, but generally does not exclude polyurethanes, silicones, epoxides, alkyds, latex vinyls, acrylics etc:. either water or solvent based, 1 or 2 component, so long as it conforms to the safety regulations for the purpose for which it is intended.

The term "surface" as used herein relates to any surface that may be covered by a biofilm, specifically, but not limited to: space ship interiors, ventilation systems, medical care facility interiors, public building interiors, pulp mills, sports facility interiors, public transport interiors such as aeroplanes, ambulances, and busses, cars, mobile homes, caravans, private homes, ship interiors, abattoirs, slaughterhouses food preparation facilities, dairies, and animal housing.
The term "moisture" as used herein refers to the moisture level as indicated by the relative humidity (RH).

The term "biocide" as used herein refers to a compound capable of inhibiting the growth of a microorganism and/or inhibiting the attachment of a microorganism to a surface.

The term "enzymes" as used herein refers specifically, but is not limited to amylases and oxidases, and can include oxidoreductases and hydrolytic enzymes as well as other enzymes including but not limited to oxidase, laccase, peroxidase, haloperoxidase, amylase, lipidase, esterase, deaminase, urease, polysaccharide hydrolase.

The term "accelerator" as used herein refers specifically to iodide salts, but may also include metal salts and thiocyanate ion further enhancing the action of enzymes and enzyme products.

The term "substrate" as used herein in connection with enzymes refers preferably to inulin or other fructans, but could include starches or other carbohydrates.
The term "flame retardancy" as used herein refers to compounds which act by removing or replacing oxygen and so to stop combustion, e.g. by release of halogen gas or water vapour. Alternatively the coating may be non-flammable or non-combustible in itself. The flame retardant may either be a compound that is added to the coating composition or it may be the binder, which is in effect non-combustible.
Detailed description Accordingly it is an object of the invention to provide improved methods for controlling the growth of microorganisms, in particular the formation of biofilms in enclosed habitats, ventilation systems etc.. For example, it is desired to create a coating that will inhibit the development of biofilms by controlled release of an environmentally friendly bioactive compound that does not accumulate in the surroundings and cause discomfort.
It is desired to create a coating that contains or generates an antimicrobial compound (e.g. H202) such that when humidity is elevated, the water film on the overlying surface is disinfected without causing build up of toxic fumes (e.g.

breaking down into H2O and 02).
It is desired that the generation of H2O2 should ideally be reasonably constant over a period of 1 or more years depending on the intended use. It is therefore the object of the invention to combine the components of the composition in such a way as to support this. For example, it is an object of this invention to select enzymes whose activity is in some way controlled by the presence of moisture and oxygen in order to control the activity of the enzymes.

It is an object of this invention that the generation of the antiseptic compound (e.g H202) is high enough to control bacterial growth over the working life of the coating.
For example the level of H202 in a surface film preferably is >5mM, depending on the aggressiveness of the environment.

It is a further object of the invention that the coating should also conform to fire regulations for public buildings, but should also be possible to avoid flame control by release of toxic fumes where the coating is required for used in enclosed environments (e.g. by using a water based silicone binder).

It is a further object of the invention that the coating or variations of the coating should be suitable for application on all typical surface materials (e.g. by using a water based silicone binder).

It is an object of the invention that the coating be safe for use in domestic environments, i.e. the antiseptic ingredient for coatings exposed to humans should be non-toxic.

In accordance with these objectives there has been provided in accordance with one embodiment of the present invention a coating composition that includes an example of an enzyme modulated generation of H202 over a 3 year working life, preferably over a 3+ year working life, in a water based silicone system to produce a 5 coating that has non-toxic antiseptic properties as well as non-toxic fire retardant properties.

Binder 10 The coating composition is based on a binder which determines the physical properties and chemical resistance of the cured/dried film. The binder type or possible binder types do not limit the effectiveness of the invention. Thus the binder may be of an oil-based type in an organic solvent or it may be a binder, which is dissolved or dispersed in water to reduce the requirements for VOCs (volatile organic compounds).

The antimicrobial coating in question may be based on any type of binder system, including but not limited to such as epoxy, alkyd, acrylic, vinyl, urethane, latex, modified rubber, silicone, may be paint, lacquer, varnish or spray, and may be applied using methods known to the art such as brush, roller, air-spray and airless spray.

The coatings may be water-borne or solvent-borne, but one particularly preferred embodiment is a water-borne silicone.
Preferably the binder is a binder, which is dissolved or dispersed in water because these binders are more environmentally friendly and because there is a great demand in industry for such binders.

The binder may thus comprise a modified rosin such as rosin maleic acid or gloss oil. Alternatively the binder comprises a shellac, such as French polish.

Further examples of binder include but are not limited to an oxidised rubber, a water-based styrene butadiene latex system, a water based styrene acrylic, a chlorinated polyolefin, a modified water-borne silicone, Among these the mostly preferred binder is the modified water-based silicone binder, this being a naturally flame retardant binder.

Further examples of binder include modified sucrose, water-borne polyvinylidene, chloride based latex terpopolymers, vinyl acetate, polyvinyl alcohol, polivinyl acetals, vinylidene fluoride, polyurethanes, epoxides, water-soluble acrylics.

Preferably the binder and the other constituents of the coating composition do not do not inhibit the activity of the enzyme.

Anti-microbial compounds The coating composition may comprise an additional antimicrobial such as a biocide, although it is preferred that the coating does not contain a biocide.
When the coating composition comprises an antimicrobial compound in addition to the enzyme system this is preferably selected from the group consisting of: oxides of heavy metals, such as zinc oxide; organic compounds such as organic biocides such as citrus oil, chilli oil, herbanero extract, cranberry extract, seaweed extract (e.g. from Gigartina stellata); non-leaching biocides such as 2,4,4-trichloro-hydroxy-diphenyl ether, 5-chloro-2-phenol; polyvalent carbohydrate molecules such as polyvalent glycosylated casein; class V metals such as bismuth; carbamates with diethanolamide as a potentiator.

Other examples of suitable biocides comprise oils selected from the group consisting of vetiver oil, camphor oil, ceder oil, tea-tree oil. Still further examples include naturally occurring anti-bacterial compound selected from the group consisting of honey, natural tree resins, preferably from pine trees or Elemi;
Copal;
Dammar. Furthermore compounds such as sodium fluoride and/or dodecylamine and/or tricolsan and/or chlorhexidine may be added to the coating composition according to the invention to act as antimicrobial compounds.

Still further examples of anti-microbial compounds include: an anti-microbial salt selected from the group consisting of iodide salts and/or metal salts, cupric chloride, cupric sulphate, silver nitrate, colloidal bismuth subcitrate, bismuth citrate, aluminium phosphate, aluminium hydroxide hydrate, gold chloride.

Preferably the antimicrobial compound comprises silver nitrate or a cupric salt, except in the case of acrylate based binders, which interfere negatively with the presence of such metals.

The amount of antimicrobial compound preferably is less than 40 % (w/v), such as less than 35%, more preferably less than 30 %, such as less than 25%, more preferably less than 20%, such as less than 15%, more preferably less than 10%, such as less than 7.5%, more preferably less than 5%, such as less than 4%, less than 3%, less than 2%, less than 1 %, or less than 0.5%.

Flame retardant For this invention the coating also possesses non-toxic flame retarding/fire resistant properties. Flame resistance my be intrinsic to the binder system (silicones) or afforded through addition of macroplegmatic or other flame/fire resistant compounds.
The at least one flame retardant compound is preferably selected from the group comprising: macroplegmatic compounds (for example as described in WO
98/03228); a flame retarding mixture comprising malamine cyanurate, silica, and phosphoric acid (as described in US 5,852,082); a flame retarding mixture comprising sodium carbonate, pyrophosphate, ammonium salts, boric acid, phosphoric acid (as described in US 6,066,198); a halogen-based flame retardant such as organic chlorine compounds, organic bromide compounds such as brominated aromatic bisimide compounds, brominated aromatic epoxy compounds, brominated polycarbonates, brominated benzyl arcylates, brominated polystyrene;
phosphorous based flame retardents such as phosphate salts, phosphate esters, nitrogen containing phosphorous compounds and red phosphorous; inorganic flame retardents such as zinc borate ammonium borate, ammonium sulphamate, ammonium bromide etc;

To further enhance flame-retardancy one or more oxides of antimony; sodium antimonate; aluminium or magnesium hydroxide can be added to the coating composition.

When the coating composition according to the invention is to be used in an enclosed environment the flame retardency system should not be based on the release of toxic fumes. One example of a preferred system for such enclosed environments include a water based silicone binder or a composition comprising a macroplegmatic flame retardant or non-flammable compositions.
Flame retardents typically work by removing or replacing oxygen and so stopping combustion. In halide containing (5-25% by weight) paints, extreme heat breaks down the coating releasing halogen gas which replaces oxygen at the surface and stops combustion. Macroplegmatic coatings contain high amounts of molecular water which is released under conditions of extreme heat, replacing oxygen and stopping combustion. Other coatings, such as a water based silicone binder, require temperatures so far in excess of what could be experienced in a normal fire (e.g., they can withstand the heat from rocket exhausts) that they are, for the purpose intended, non-flammable/non-combustible. Finally, a coating composition may be rendered flame retardant by adding non-combustible filler, such as clay, silicon or glass.

The composition according to the present invention may comprise from 1 to 50%
(w/v) of flame retardant, preferably from 5 to 25%, such as from 5-10%, from 15%, from 15-20%, or from 20-25%. When the flame retardancy is caused by the binder, this may constitute up to 75% (w/v) of the coating composition, such as up to 70 %, for example up to 65%, such as up to 60 %, for example up to 55 %, such as up to 50%, for example up to 45 %, such as up to 40%, for example up to 35%, such as up to 30%, for example up to 25%.
Preferably the compositions conform with fire regulations for public buildings and/or vehicles and/or ships.

Further additives The coating composition may preferably further comprise pigments, fillers additives and solvents as mentioned in the examples (see below).

Apart from these additives, the composition may further comprise fibres such as cellulosic fibres. One purpose of adding fibres may be to increase the physical strength of the paint film. Another purpose may be to act as an "anchor" for the enzymes so that they do not migrate through the paint. A third purpose may be to act as substrates for the enzymes, such as may be the case when using cellulosic fibres for a coating comprising a cellulase. A further purpose of fibres may be to give a wall paint the desired texture.

Preferably the enzyme and/or substrate and/or a biocide is/are bound to said fibres.
One effect of anchoring an enzyme to a fibre may be to (i) improve dispersion of the enzyme in the paint and/or to (ii) prevent migration of the enzyme through the paint (iii) and/or to increase the amount of substrate to increase performance lifetime (e.g., substrate added as filler and fibres), and/or (iv) one may possibly use fibres to control release of an organic biocide.

Malodour Malodour is associated with certain compounds, such as sulphur containing compounds, and short free fatty acids such as butyric acid. These are often generated by micro-organisms growing on the surfaces of walls or by deposition from the air (e.g. in kitchens). Different types of enzymes (peroxidases, lipases, proteinases, oxidoreductases), can be selected to breakdown the different types of compounds and reduce smell.

Hydrogen peroxide In one preferred embodiment, the enzyme action results in the generation of hydrogen peroxide, where the antimicrobial action may the result of H2O2 acting on an enhancer such as thiocyanate, or alone. H2O2 may be generated for example through the action of peroxidases, such as lactoperoxidase &/or of oxidases such alcohol oxidase; amine oxidase; arylalcohol oxidase; aspartate oxidase;
cholesterol oxidase; D-amino acid oxidase; D-glutamate oxidase; ethanolamine oxidase;

glucose oxidase; galactose oxidase; hexose oxidase; L-amino acid oxidase;
lathosterol oxidase; malate oxidase; NADH oxidase; pyranose oxidase;
superoxide dismutase; urate oxidase and so forth.

5 Hydrogen peroxide is produced through the action of an enzyme/enzymes on a substrate. The substrates are not limited to, but can include:
carbohydrate/sugars, cellulose, dextran, hexoses, galactose, glucose, lactose, 2-deoxyglucose, fructose, pyranose, pectin, inulin, starch or mixtures thereof. In one preferred embodiment the enzyme is hexose oxidase acting on glucose.
According to an especially preferred embodiment of the invention hydrogen peroxide is generated in an amount to prevent biofilm formation on the surface of the composition. The advantages of enzyme systems based on hydrogen peroxide are several. Hydrogen peroxide is highly reactive and therefore has a very short half-life in the presence of water, spontaneously degrading into water and oxygen.
Therefore the compound is non-toxic and does not accumulate in the environment.
Furthermore hydrogen peroxide released from the surface coating may assist in fighting unpleasant odours.

A high level of peroxide may also help by killing the bacteria whose activity releases smelly by-products (e.g., ammonia) Preferably the composition and the enzyme system are adapted to produce at least 5mM hydrogen peroxide in an overlying water film.
The enzymes and substrates should be added in an amount to ensure effective prevention of biofilm formation for at least 1 year, preferably at least 2 years, more preferably at least 3 years, such as at least 4 years, for example at least 5 years, such as at least 6 years, for example at least 7 years, such as at least 8 years, for example at least 9 years, such as at least 10 years.

Control of enzyme action There are various ways of controlling the action of the at least one enzyme contained in the coating composition. Examples include having the enzyme activated by changes in ambient humidity and/or ambient temperature and/or ambient pH and/or ambient oxygen levels.

By far the most preferred control system is simply control through increases in moisture level. It is to be understood that at least one enzyme may have an activity sufficient to inhibit biofilm formation, when ambient humidity is above 40%, such as above 45%, for example above 50%, such as above 55%, for example above 60%, such as above 65%, for example above 70%, such as above 75%, for example above 80%, such as above 85%, for example above 90%, such as above 95%.
Surprisingly, it has turned out that the enzymes in the compositions according to the present invention are active and effective even in the absence of a visible water film on the coated surfaces.

Preferably the enzymes are active in the temperature interval between 5-40 C, such as 5-10 C, 10-15 C, 15-20 C, 20-25 C, 25-30 C, 30-35 C, or 35-40 C.

The at least one enzyme may have an optimum in the interval between pH 4 and 11, such as an optimum in the interval of pH 4-5, pH 5-6, pH 6-7, pH 7-8, pH 8-9, pH 9-10, pH 10-11. pH varies from paint to paint, tending to the acidic. The pH
optimum of amylases tends to be acidic to neutral (e.g., 3.5 7.0) but amylases can be active at high pH's e.g., > 8. The pH optimum of oxidases depends on source. Hexose oxidase from marine sources typically has an optimum around 8 and has been shown to demonstrate adequate activity around pH 7, however glucose/glucose oxidase (fungal) generating hydrogen peroxide has been shown to work between pH
5 and 7.

Similarly, the at least one enzyme may have an optimum at 50-100 % oxygen saturation.

Enzyme requirements Preferably the at least one enzyme does not lose substantial activity when repeatedly hydrated and de-hydrated. By absence of substantial loss of activity is meant a loss in activity after which the enzyme is still capable of preventing biofilm formation, such as a loss smaller than 90% compared to the initial activity, preferably a loss smaller than 80 %, more preferably a loss smaller than 75%, such as smaller than 70%, for example smaller than 60%, such as smaller than 50%, for example smaller than 45%, such as smaller than 40%, for example smaller than 35%, such as smaller than 30%, for example smaller than 25%, such as smaller than 20%, for example smaller than 15%, such as smaller than 10%, for example smaller than 5%.

Preferably the at least one enzyme does not lose substantial activity when dried to below 20% moisture content and rehydrated again, preferably below 19%, such as below 18%, for example below 17%, such as below 16%, for example below 15%, such as below 14%, for example below 13%, such as below 12%, for example below 11%, such as below 10%, for example below 9%, such as below 8%, for example below 7%, such as below 6 %, for example below 5%, such as below 4%, for example below 3%, such as below 2%, such as below 1.5%, for example below 1 %. This compares with the typical moisture content of a dried coating which is in the vicinity of 2-7%.

Enzymes The antimicrobial activity may be the result of one or more enzymes, acting independently (e.g., one-step: glucose/hexose oxidase; glucose/glucose oxidase, L
amino acid/L amino acid oxidase, galactose/galactose oxidase, 2-deoxyglucose/glucose oxidase, pyranose/pyranose oxidase and mixtures thereof, or, cocktails of proteases, amylases, lipases, cutinases, cellulases etc..) or step-wise (the substrate for one enzyme is produced by the action of a precursor enzyme acting on substrates selected from polymers and oligomers of substrates for oxidative enzymes such as: Starch, cellulose, dextrose, lactose, peptide, inulin &
mixtures thereof).

The enzymes may act directly, to prevent attachment by bacteria, fungi or algal spores, or act by generating an antimicrobial compound such as hydrogen peroxide.
The enzymes in question may be derived from microbial, plant or animal sources and may be naturally occurring or modified and should be commercially available.
Preferably, the enzymes are available for use for the food and beverage industry.

The enzymes should ideally have at least 80% of optimal activity within typical accommodation temperatures, possibly 10 to 40 C, more ideally between 15 to 30 `C, or more preferably between 20 and 25 C. But not be destroyed after application by brief exposure to temperatures between 1 and 50 'C. The enzymes should have within 80%
of optimal activity with the pH conditions experienced with the coating, such that for alkaline coatings, the optimal activity is between 7 and 12, whereas for more acid coatings, the pH optimum is between 4 and 7.

The enzymes may be added directly, or may be immobilized by spray coating on fillers, substrates, fibres, ceramic particles, glass particles or spheres, pigments or thixotropic agents; or may be immobilized in gels/capsules and may be added as part of a 1-component or multi-component coating.

The enzymes may be the sole source of antimicrobial properties or may work in conjunction with antimicrobial polymers such as polysiloxanes with propyl pendant groups or antimicrobial compounds, such as cranberry extract (US 6,210,681) or other antimicrobial compounds mentioned above.

Enzymes suitable for use according to the present invention include but are not limited to oxidases, and can include oxidoreductases and hydrolytic enzymes, laccases, peroxidases, haloperoxidases, amylases, lipidases, esterases, deaminases, ureases, polysaccharide hydrolases, and nucleases.

Oxidoreductases The oxidoreductase in the context of the present invention may be any oxidoreductase or combination of different oxidoreductases or combination of oxidoreductases with other enzymes. Accordingly, when reference is made to "an oxidoreductase " this will in general be understood to include combinations of one or more oxidoreductases.
It is to be understood that oxidoreductase variants (produced, for example, by recombinant techniques) are included within the meaning of the term "oxidoreductase".

SUBSTITUTE SHEET

The enzyme classification employed in the present specification with claims is in accordance with Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology, Academic Press, Inc., 1992.

Accordingly, the types of oxidoreductases which may appropriately be applied for the present invention include oxidoreductases (EC 1.-.-.-).

Preferred oxidoreductases in the context of the invention are any peroxidase belonging to the classification group EC 1. 11. 1--, any laccase belonging to EC
1.10.3.2, any catechol oxidase belonging to EC 1.10.3.1, any bilirubin oxidase belonging to EC 1.3.3.5 or any monophenol monooxygenase belonging to EC
1.14.99.1 or any oxidases belonging to EC 1.1.3.-.
Laccase and laccase related enzymes Preferred laccase enzymes and/or laccase related enzymes are enzymes of microbial origin. The enzymes may be derived from plants, bacteria or fungi (including filamentous fungi and yeasts).

Peroxidases and Compounds possessing Peroxidase Activity Compounds possessing peroxidase activity may be any peroxidase enzyme comprised by the enzyme classification (EC 1.11.1.7), or any fragment derived therefrom, exhibiting peroxidase activity. In the context of this invention, compounds possessing peroxidase activity comprise peroxidase enzymes and peroxidase active fragments derived from cytochromes, haemoglobin or peroxidase enzymes.

Preferably, the peroxidase employed in the method of the invention is producible by plants (e. g. horseradish or soybean peroxidase) or microorganisms such as fungi or bacteria.

Also haloperoxidases such as chromo-, bromo-and/or iodoperoxidases are suitable for controlling biofilm formation according to the present invention.
Haloperoxidases form a class of enzymes which are able to oxidize halides (Cl-, Br-, I-) in the presence of hydrogen peroxide or a hydrogen peroxide generating system to the corresponding hypohalous acids according to: H202 + X-+ H+-- > H2O 4- HOX, wherein X-is a halide and HOX is a hypohalous acid. If a convenient nucleophilic 5 acceptor is present, a reaction will occur with HOX and a halogenated compound will be formed.

There are three types of haloperoxidases, classified according to their specificity for halide ions: Chloroperoxidases (E. C. 1.11.1.10) which catalyse formation of hypo-10 chlorit from chloride ions, hypo-bromit from bromide ions and hypo-iodit from iodide ions; Bromoperoxidases which catalyse formation of hypo-bromit from bromide ions and hypoiodit from iodide ions; and iodoperoxidases (E. C. 1.11.1.8) which solely catalyze the formation of hypoiodit from iodide ions. However, hypoiodit undergoes spontanous disproportionation to iodine and thus, iodine is usually the observed 15 product of the reaction. These hypo-halit compounds may subsequently react with other compounds forming halogenated compounds.

Haloperoxidases have been isolated from various organisms: mammals, marine animals, plants, algae, a lichen, fungi and bacteria. It is generally accepted that 20 haloperoxidases are the enzymes responsible for the formation of halogenated compounds in nature, although other enzymes may be involved.

Haloperoxidases have been isolated from many different fungi, in particular from the fungus group dematiaceous hyphomycetes, such as Caldariornyces, e. g., C.
fumago, Alternaria, Curvularia, e. g., C. verruculosa and C. inaequalis, Drechslera, Ulocladium and Botrytis (see US Patent No. 4,937,192).

Another particularly preferred enzyme is hexose oxidase (D-hexose: 02-oxidoreductase, EC 1.1.3.5), which catalyses the oxidation of D-glucose or D-galactose to y-D-gluconolactone or y-D-galactolactone and hydrogen peroxide.

Specific examples of combinations of enzyme and substrate include but are not limited to: malate oxidase-malic acid; glucose oxidase-glucose; hexose oxidase-glucose; cholesterol oxidase-cholesterol; arylalcohol oxidase-arylalcohol:
galactose oxidase-galactose; alcohol oxidase-alcohol; lathosterol oxidase-lathosterol;

aspartate oxidase-aspartic acid; L-amino-acid oxidase-L-amino acid; D-arnino-acid oxidase-D-amino acid; amine oxidase-amine; D-glutamate oxidase-glutamine;
ethanolamine oxidase-ethanolamine; NADH oxidase-NADH.; urate oxidase (uricase)-uric acid; superoxide dismutase-superoxide radical; glucose/hexose oxidase; glucose/glucose oxidase; L amino acid/L amino acid oxidase;
galactose/galactose oxidase; lactose/P-galactosidase/hexose oxidase; lactose/ -galactosidase/glucose oxidase; 2-deoxyglucose/glucose oxidase;
pyranose/pyranose oxidase; and mixtures thereof.

The coating composition may comprise at least 0.0001 % (w/v) of enzyme, such as at least 0.001 %, for example at least 0.01 % such as at least 0.05, for example at least 0.1%, such as at least 0.5%, such as at least 1%, for example at least 1.5%, such as at least 2%, for example at least 2.5%, such as at least 3%, for example at least 3.5%, such as at least 4%, for example at least 4.5%, such as at least 5%.
According to a further embodiment of the invention, the coating composition comprises a second enzyme capable of converting a compound into a substrate for the first enzyme. Generally speaking the second enzyme will often be one that is capable of degrading a naturally occurring polymer (polysaccharide, lignin, protein, polyphenol etc.) into its monomer constituents. The second enzyme may be an amylase, which converts starch into a substrate for a hexose oxidase or a cellulase, which converts cellulose into a substrate for a hexose oxidase, or a fructase, which converts a fructan such as inulin into hexoses, or a proteinase which converts protein into amino acids, or a ligninase which converts lignin into monomers.
According to another embodiment, the composition may comprises at least a third enzyme, such as at least a fourth enzyme, such as at least a fifth enzyme. One example of combinations of enzymes, which interact to improve the antiseptic effect of the coating composition is the combination of a proteinase, a lipase and an amylase and/or an oxidase, which together may prevent the microorganisms from attaching to the surfaces by degrading their attachment matrix, or which degrade the substrates the microorganisms can use for metabolism, such as short fatty acids or sulphur containing compounds.

The enzymes and substrates may simply be dissolved or dispersed in the coating composition, but the may also preferably be encapsulated such as being Oencapsulated in mesoporous silicates. By encapsulating the enzymes and substrates you may control the movement of the enzyme (migration) andior may control the activity of the enzyme by controlling access to active sites.

Uses The coating compositions according to the present invention may be used for coating any type of surface which is exposed to micro-organisms. An especially preferred use is for coating surfaces in enclosed habits such as a spacecraft.
The humidity levels in spacecrafts are high because the possibilities for ventilation are very limited. By providing the walls of the spacecrafts with a composition according to the invention, the formation of biofilm can be prevented, the need for wiping walls can be greatly reduced and the general health of the astronauts and cosmonauts can be improved.

Another preferred use is for coating surfaces in ventilation systems. Such surfaces are normally inaccessible for cleaning and great saving are expected by employing the coating compositions according to the invention for such surfaces.
Important is also the flame retardancy features of the compositions according to the present invention, since fires often spread through ventilation systems in buildings and in aeroplanes.

A further preferred use is for coating surfaces in medical and other health care systems such as operating theatres. The hygiene requirements.of such surfaces are very high and fire regulations also require that the coatings be flame retardant. It is of course possible to design the coating compositions to have stronger or weaker "anti-biofilm" action through adjustments of the concentrations of the constituents. In this way coating compositions especially adapted for surfaces in medical and other health care systems such as operating theatres can be made.

Generally the coating compositions according to the present invention are very suitable for coating surfaces in public buildings and in buildings with high hygiene requirements and fire regulations. Such buildings include but are not limited to educational facilities, such as universities and schools, sports facilities, offices, and public sanitation facilities.

Another type of enclosed environment in which the use of the coating compositions according to the present invention is advantageous include vehicles, such as aircrafts, ship interiors, particularly yachts, busses, mobile homes, caravans. In these vehicles the humidity levels are often high due to the presence of a number of passengers/patients/inhabitants and the limited possibilities for ventilation (especially in aircrafts). This produces a high load of microorganisms in the atmosphere and a potential risk for biofilm formation. In addition to this, all of these vehicles possess a high risk for catching fire. The use of the coating compositions according to the present invention at least for the interior surfaces of such vehicles solves both of these problems at the same time with the possibility of doing this without accumulation of toxic fumes.
The advantages of the coating compositions according to the present invention are also evident when used for coating surfaces in private homes, preferably in bathrooms and/or kitchens; as well as when used for coating surfaces in animal housings such as stables, and including slaughterhouses, abattoirs and food preparation facilities.

Test of coated surfaces.

Coated panels are incubated at different atmospheric conditions with different microorganisms. For example, the panels are exposed to wet/dry cycles; carbon dioxide; and light/dark cycles which imitate the "worst-case-scenario"
condition-wise, with an axenic innoculum of bacteria, algae, fungi or mixtures thereof.
Screening tests will identify which formulations inhibit biofilm by examination of the cultures growing on the surface. Long-term tests can be done using accelerated ageing, laboratory testing under controlled conditions and in-situ testing.

Examples Example 1. Non-toxic antimicrobial, flame retarding water-borne silicone for various applications Example 1 a Mix the following 20 parts approx. colloidal silica (e.g., Snowtex TM30 , Nissaq chemical Industries Ltd., with min 30% effective component) 70 parts approx. of the following mixture (approx. 10 parts dodecylbenzenesulphonic acid dissolved in approx. 485 parts water, added to a mixture of approx.
500pts octamethylcyclotetrasiloxane with approx. 5 parts phenyltriethosilane).

Neutralize the mixture with sodium carbonate Add approx. 1 part of a mixture comprising approx. 30 parts dioctyltin dilaurate with approx. 5 parts polyoxyethylene nonyiphenylether;

Add approx. 0.5 parts silatrane D to make a silicone water-based emulsion composition To the mixture add: 0.001-200 mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500 mg of glucose, galactose, or fructose/ml mixture 2. Also add 0.002 to 200 mg of starch which has been spray applied with hexose oxidase with an activity within 0.001 - 100 U (where 1 U produced 1 mmol of H2O2/min at 25 C) Example lb Mix the following:

20 parts approx. colloidal silica (e.g., Snowtex TM30 , Nissaq chemical Industries Ltd., with min 30% effective component) 70 parts approx. of the following mixture (approx. 10 parts dodecylbenzenesulphonic acid dissolved in approx. 485 parts water, added to SUBSTITUTE SHEET

a mixture of approx. 500pts octamethylcyclotetrasiloxane with approx 5 parts phenyltriethosilane) Neutralise the mixture with sodium carbonate Add approx. 1 part of a mixture comprising approx, 30 parts dioctyltin dilaurate with approx. 5 parts polyoxyethylene nonylphenylether.

Add approx. 0.5 parts Silatrane D to make a silicone water-based emulsion 10 composition.

To the mixture add a cocktail of enzymes such as:
Protease (e.g., Esperase ; Alcalase. ; Durazym ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from 15 GIST-Brocades ) at the amount of 0.0001 - 0.5 % by weight of mixture 2.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 2, Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 2.

Amylase (e.g., a and b amylases such as Purafect Ox Am from Genencor@, Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 2..

Example 2. Non-toxic flame retarding antimicrobial coating for application to cardboard for use in shanty towns Fire retarding mixture with a silicone latex rubber binder, such as: a mixture of the following (weight percent) 15-20% phosphoric acid or disodic phosphate or monosodic phosphate or sulphamic acid, 1 - 5% boric acid, 5 .. 10% ammonium sulphate or ammonium chlorate, 1 - 5% sodium carbonate, 0.1 - 5%
pyrophosphate.
Alternatively, for some applications, phosphoric acid can be excluded and replaced by Boric acid.

Mix the following approximate amounts:
44 mis water 21 g phosphoric acid 13 g ammonium sulphate 4 g boric acid 1.4 g sodium carbonate 1 g pyrophosphate Take 75 g of this mixture (mixture 1) and combine with 25 g silicone rubber latex (mixture 2).

To mixture 2 add 0.001 -200 mg/mi of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500mg of glucose, galactose or fructose/ml mixture 2. Also add 0.002 to 200mg of starch which has been spray applied with hexose oxidase with an activity within 0.001 - 100 U (where 1 U
produced 1 mmol of H2O2/min at 25 C).

Example 2b.

Alternatively to mixture 2 add a cocktail of enzymes such as:
Protease (e.g., Esperase ; Alcalase. ; Durazym ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapern from GIST-Brocades ) at the amount of 0.0001 - 0.5% by weight of mixture 2.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Hum icola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 2.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano" , AMANO Pharmaceutical Co. Ltd. Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also Lipomax from GIST-Brocades and Lipolase from Novozymes. Alternatively a mixture of the named type of lipases combined with a cutinase at the amount of 0.0001 - 3% by weight of mixture 2.
Amylase (e.g., a and b amylases such as Purefact Ox Am from Genencor, Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 2.

Example 2c for various applications Mix 75% by weight of mixture 1 with 25% vinyl resin to make a paint additive (mixture 3) For one kilo of paint mix 25 g of mixture 3 with 75 g of the following:
10-50% acrylic resin (e.g., Neocry 1727 (Zeneca resins), Synocryl 874 (Cray Valley), Acryloid B66 (Rohm & Haas)) or, a vinyl resin solution (e.g., UCAR VAGH , UCAR
VYHH , UCAR VMCC (Dow Chemical/Union Carbide), Hostaflex CM150 (Hoechst), Laroflex MP25 (BASF)).
5 - 40% pigments (e.g., Titanium Dioxide (Ti-Pure R902 , DuPont), iron oxides, carbon black, graphite, metallic aluminum, zinc oxide, or other suitable pigments) 5 - 40% fillers (e.g., carbohydrates, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics (including spheres, fibres & powder), calcium carbonate, barium sulphate) 1 - 5% additives (e.g., thixatropic agents, f low control agents) SUBSTITUTE SHEET

0.1 - 90% solvents (e.g., glycol ethers, alcohols, Solvesso 150, toluene, acetates, ketones) To the mixture add 0.001 -200 mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500 mg of glucose, galactose or fructose/ml mixture 1. Also add 0.002 to 200 mg of starch which has been spray applied with hexose oxidase with an activity within 0.001 - 100 U (where 1 U
produced 1 mmol of H2O2/min at 25 C).

Example 2d For one kilo of paint mix 25 g of mixture 1 with 75 g of the following:
10-50% acrylic resin (e.g., Neocryl 727 (Zeneca resins), Synocryl 874 (Cray valley), Acryloid B66 (Rohm & Haas)) or, a vinyl resin solution (e.g., UCAR VAGH, UCAR
VYHH, UCAR VMCC (Dow Chemical/Union Carbide), Hostaflex CM150 (Hoechst), Laroflex MP25 (BASF)).
5 - 40% pigments (e.g., Titanium dioxide (Ti-Pure R902, DuPont), iron oxides, carbon black, graphite, metallic aluminium, zinc oxide or other suitable pigments) 5 - 40% fillers (e.g., carbohydrates, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics (including spheres, fibres & powder), calcium carbonate, barium sulphate) 1 - 5% additives (e.g., thixatropic agents, flow control agents) 0.1 - 90% solvents (e.g., glycol ethers, alcohols, Solvesso 150, toluene, acetates, ketones) To the mixture add a cocktail of enzymes such as:

Protease (e.g., Esperase ; Alcalase. ; Durazym ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapern from GIST-Brocades ) at the amount of 0.0001 - 0.5% by weight of mixture 1.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.
Amylase (e.g., a and b amylases such as Purafect Ox Am from Genencor , Termamyl , Ban(&, Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 1.

Example 3. An antimicrobial heat ablative water-borne silicone for extreme applications (e.g., space) Example 3a Mix the following:
Part1 Approx. 2 g epoxy silane resin Approx. 8 g xylene Approx. 15 g epoxy resin Approx. 4 g silicone intermediate Approx. 1 g organotin Approx. 0.5 g organozinc Part 2 Approx. 66 g silicone modified polyether Approx. 1 g thixotropic agent 5 Approx. 5 g ceramic fibre filer Approx. 16 g clay filler To this mixture add approx. 8 g xylene, approx. 2 g aminosilane, and 2 g amine catalyst Mix parts 1 & 2 together.

To this mixture add 0.001 -200 mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where '1 AGU produces mmol glucose/min at 25 C), alternatively add 0.001 to 500 mg of glucose, galactose or fructose/ml mixture 1. Also add 0.002 to 200 mg of starch which has been spray applied with hexose oxidase with an activity within 0.001 - 100 U (where 1 U
produced 1 mmol of H202/min at 25 C).

Example 3b.
Partl Approx. 2 g epoxy silane resin Approx. 8 g xylene Approx. 15 g epoxy resin Approx. 4 g silicone intermediate Approx. 1 g organotin Approx. 0.5 g organozinc Part 2 Approx. 66 g silicone modified polyether Approx. 1 g thixotropic agent Approx. 5 g ceramic fibre filer Approx. 16 g clay filler To this mixture add approx. 8 g xylene, approx. 2 g aminosilane, and 2 g amine catalyst Mix parts 1 & 2 together.

To the mixture add a cocktail of enzymes such as:

Protease (e.g., Esperase ; Alcalase. ; Durazym ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocades ) at the amount of 0.0001 - 0.5 % by weight of mixture 1.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.

Amylase (e.g., a and b amylases such as Purafect Ox Am from Genencor , Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 1.

Example 4. A flame retardant antimicrobial composition for housing and industrial use Example 4a a thermoplastic vinyl or acrylic for industrial use Mixture 1 10-50% acrylic resin (e.g., Neocryl 727 (Zeneca resins), Synocryl 874 (Cray valley), Acryloid B66 (Rohm & Haas)) or, a vinyl resin solution (e.g., UCAR VAGH, UCAR
VYHH, UCAR VMCC (Dow Chemical/Union Carbide), Hostaflex CM150 (Hoechst), Laroflex MP25 (BASF)).
5 - 40% pigments (e.g., Titanium dioxide (Ti-Pure R902, DuPont), iron oxides, carbon black, graphite, metallic aluminium, zinc oxide or other suitable pigments) 5 - 40% fillers (e.g., particularly silicone, gypsum, lime) 1 - 5% additives (e.g., thixatropic agents, flow control agents,) 0.1 - 90% solvents (e.g., glycol ethers, alcohols, Solvesso 150, toluene, acetates, ketones) To the above add 3 - 10% w/w macroplegmatic compound (Mc 30,000 to 50,000) created by mutiprocessing polystyrene and coppolymers.

To the mixture add 0.001 -200 mg/mI of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500 mg of glucose, galactose or fructose/ml mixture 1. Also add 0.002 to 200 mg of starch which has been spray applied with hexose oxidase with an activity within 0.001 - 100 U
(where 1 U produced 1 mmol of H2O2/min at 25 C).
Example 4b Mixture 1 10-50% acrylic resin (e.g., Neocryl 727 (Zeneca resins), Synocryl 874 (Cray valley), Acryloid B66 (Rohm & Haas)) or, a vinyl resin solution (e.g., UCAR VAGH, UCAR
VYHH, UCAR VMCC (Dow Chemical/Union Carbide), Hostaflex CM150 (Hoechst), Laroflex MP25 (BASF)).

- 40% pigments (e.g., Titanium dioxide (Ti-Pure R902, DuPont), iron oxides, carbon black, graphite, metallic aluminium, zinc oxide or other suitable pigments) 5 - 40% fillers (e.g., particularly silicones, gypsum, lime) 1 - 5% additives (e.g., thixatropic agents, flow control agents,) 0.1 - 90% solvents (e.g., glycol ethers, alcohols, Solvesso 150, toluene, acetates, ketones) To the above add 3 - 10% w/w macroplegmatic compound (Mc 30,000 to 50,000) created by mutiprocessing polystyrene and coppolymers.

To the mixture add a cocktail of enzymes such as:
Protease (e.g., Esperase ; Alcalase. ; Durazym ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocades ) at the amount of 0.0001 - 0.5% by weight of mixture 1.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.
Amylase (e.g., a and b amylases such as Purafect Ox Am from Genencor , Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 1.

Example 5. Composition based on a thermoplastic chlorinated rubber or acrylated rubber resin Example 5a.
Mixture 1 Approx. 10-50 % chlorinated rubber resin solution e.g. Pergut S10 (Bayer), Clortex (Caffarro) or an acrylated rubber resin solution e.g. Pliolite AC4, AC80, AC-L
10 (Goodyear Chemicals) Approx. 5 - 40% Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range Approx. 5 - 40 % Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, silicones, gypsum, lime,zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Approx. 1-5% Additives, typically including: thixatropic agents, flow control agents.
1-5%

Approx. 0.1 - 90% Solvents including xylene, hydrocarbons e.g. Solvesso 150;
toluene, alcohols, acetates, glycol ethers, ketones Optional: antimicrobials in the range 0.1-10%
Approx. 3 - 10% macroplegmatic compounds To the above add 0.001 -200 mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500 mg of glucose, galactose or fructose/ml mixture 1. Also add 0.002 to 200 mg of starch which has been spray applied with hexose oxidase with an activity within 0.001 - 100 U (where 1 U
produced 1 mmol of H2O2/min at 25 C).

Example 5b.

Mixture 1 Approx. 10-50 % chlorinated rubber resin solution e.g. Pergut 310 (Bayer), Clortex 10 (Caffarro) or an acrylated rubber resin solution e.g. Pliolite AC4, AC80, AC-L
10 (Goodyear Chemicals) Approx. 5 - 40% Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range Approx. 5 - 40 % Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, silicones, gypsum, lime,zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Approx. 1-5% Additives, typically including: thixatropic agents, flow control agents.
1-5%

Approx. 0.1 - 90% Solvents including xylene, hydrocarbons e.g. Solvesso 150;
toluene, alcohols, acetates, glycol ethers, ketones Optional: antimicrobials in the range 0.1-10%
Approx. 3 - 10% macroplegmatic compounds To the above add a cocktail of enzymes such as:

Protease (e.g., Esperase ; Alcalase. ; Durazym ; 8/or Savinase(D available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocades) at the amount of 0.0001 - 0.5% by weight of mixture 1.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.
Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.

Amylase (e.g., a and b amylases such as Purafect Ox Am from Genencor , Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 1.

Example 6: Where the coating composition is based on a hydroxy functional acrylic or hydroxy functional polyester resin cured by an isocyanate for various uses Example 6a.
Mixture 1 Approx. 10-60% hydroxy functional acrylic resin solution e.g. Desmophen A160 (Bayer) or a hydroxy functional polyester resin solution e.g. Setal 168 (Akzo Nobel) Approx. 5 - 30% isocyanate curing agent e.g. Desmodur N75 (Bayer) Tolonate HDB75 (Rhodia) Desmodur N3390 Bayer Approx. 5-40% Pigments, preferably one or more of the following: Titanium Dioxide -Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments Approx 5-40% Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, silicone, gypsum, lime,zinc oxide, zinc phosphate, clay, I I

kaolin, silicates, glass, ceramics (including spheres, fibres & powder), or carbohydrates Additives, typically including: thixatropic agents, flow control agents, 1-5%
Approx. 3-10% Fire retardant compounds, particularly macroplegmatic compounds of multiprocessed polystyrene and copolymers Approx. 10-50% Solvents including xylene hydrocarbons e.g. Solvesso 150 ;
toluene, alcohols, acetates, glycol ethers, ketones To the above add 0.001-200 mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU produces 1mmol glucose/min at 25 C); alternatively add 0.001 to 500 mg of glucose, galactose or fructose/ml of mixture 1. Also add 0.002 to 200 mg of starch which has been spray applied with hexose oxidase with an activity within 0.001-100 U
(where 1 U produced 1 mmol of H2O2/min at 25 C).

Example 6b Approx. 10-60% hydroxy functional acrylic resin solution, e.g., Desmophan A160 (Bayer) or a hydroxy functional polyester resin solution e.g. Setal 168 (Akso Nobel) Approx. 5-30% isocyanate curing agent e.g. Desmodur N75 (Bayer) Tolonate HDB75 (Rhodia) Desmodur N3390 (Bayer);

Approx. 5-40% Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminum, or other suitable coloured pigments Approx. 5-40% Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, silicone, gypsum, lime, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics (including spheres, fibres & powder), or carbohydrates SUBSTITUTE PAGE

Additives, typically including: thixatropic agents, flow control agents. 1-5%

Approx. 3-10% Fire retardant compounds, particularly macroplegmatic compounds of multiprocessed polystyrene and copolymers Approx. 10-50% Solvents including xylene, hydrocarbons e.g. Solvesso 150;
toluene, alcohols, acetates, glycol ethers, ketones To the above mixture add a cocktail of enzymes such as:
Protease (e.g., Esperase ; Alcalase. ; Durazym(F ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocades) at the amount of 0.0001 - 0.5% by weight of mixture 1.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.
Amylase (e.g., a and b amylases such as Purafect Ox Amc from Genencor , Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 1.

Example 7 Where the coating is based on an aqueous dispersed polymer for various uses Example 7a I I

Mixture 1 Approx. 5-50% emulsion polymer including a continuous aqueous phase and a dispersed polymer phase, e.g. acrylic latex - Maincote HG54 (Rohm & Haas) or similar;
Polyurethane dispersion - Neorez 960 (Zeneca resins), Styrene acrylic latex -Haloflex 202S (Zeneca resins) Approx. 5-40% Pigments, preferably one or more of the following: Titanium Dioxide -Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminum, or other suitable coloured pigments Approx. 5-40% Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, silicone, gypsum, lime, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Additives, typically including: wetting agents, surfactants, dispersants e.g.
Nopcosperse 44 , polyurethane thickeners, e.g., Acrysol RM8 (Rohm & Haas), cellulosics and modified cellulosic thickeners, acrylic thickeners, matting agents and defoamers in the range 0.1-5.0%

Coalescing solvents, including alcohols, e.g. Texanol (Rohm & Haas), glycols, glycol ethers, ketoximes in the range 1-5%

Optional antimicrobials in the range 0.1-10%

Approx. 3-10% fire retardants - macroplegmatic compounds derived from multiprocessing polystyrene and copolymers.

To the above mixture 1 add 0.001-200 mg/mL of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU
produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500 mg of glucose, galactose or fructose/ml of mixture 1. Also, add 0.002 to 200 mg of starch which has been spray applied with hexose oxidase with an activity within 0.001-100 U
(where 1 U
produced 1 mmol of H2O2/min at 25 C).

SUBSTITUTE PAGE

Example 7b Mixture 1 Approx. 5 - 50% emulsion polymer including a continuous aqueous phase and a dispersed polymer phase, e g. acrylic: latex - Maincote HG54 (Rohm & Haas) or similar; Polyurethane dispersion - Neorez 960, (Zeneca resins), Styrene acrylic latex - Haloflex 202S (Zeneca resins) Approx. 5 - 40% Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments Approx. 5 - 40% Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, silicone, lime, gypsum, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Additives, typically including: wetting agents, surfactants, dispersants e.g.
Nopcosperse 44, polyurethane thickeners, e.g. Acrysol RM8 (Rohm & Haas), cellulosics and modified cellulosic thickeners, acrylic thickeners, matting agents and defoamers in the range 0.1-5.0 %

Coalescing solvents including alcohols, e.g. Texanol (Rohm & Haas), glycols, glycol ethers ketoximes in the range 1-5%

Optional antimicrobials in the range 0.1-10%

Approx. 3 - 10% fire retardants - macroplegmatic compounds derived from multiprocessing polystyrene and copolymers.

To the above mixture 1 add a cocktail of enzymes such as:

Protease (e.g., Esperase ; Alcalase. ; Durazym ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocades) at the amount of 0.0001 - 0.5% by weight of mixture 1.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.
Amylase (e.g., a and b amylases such as Purafect Ox Am from Genencor , Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2 % by weight of mixture 1.

Example 8: Where the coating is based on an aqueous dispersed polymer containing active crosslinking groups for various uses.

Example 8a Mixture 1 Approx 5 - 50% dispersed polymer including a continuous aqueous phase and a dispersed polymer phase, e.g. Epoxy dispersion; Hydroxy functional acrylic dispersion or Hydroxyl functional polyester i Approx 1-40% water soluble or dispersed cross linking agent e.g. Amino resins, polyamides polyamines, cycloaliphatic amines, mannich bases, isocyanates, blocked isocyanates, aziridines or similar Approx. 5-40% Pigments, preferably one or more of the following: Titanium Dioxide -Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments Approx. 5-40% Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, silicone, gypsum, lime, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Approx. 0.1-5.0% additives, typically including: wetting agents, surfactants, dispersants e.g. Nopcosperse 44, polyurethane thickeners, e.g. Acrysol RM8 (Rohm & Haas), cellulosics and modified cellulosic thickeners, acrylic thickeners, matting agents and defoamers Approx. 1-5% Coalescing solvents including alcohols, e.g. Texanol (Rohm &
Haas), glycols, glycol ethers ketoximes Optional antimicrobials in the range 0.1-10%

Approx. 3 - 10% Fire retardants, for example macroplegmatic compounds multiprocessed from polystyrene and copolymers.

To the above mixture 1 add 0.001 -200mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU
produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500mg of glucose, galactose or fructose/ml mixture 1. Also add 0.002 to 200mg of starch which has been spray applied with hexose oxidase with an activity within 0.001 - 100 U
(where 1 U produced 1 mmol of H202/min at 25 C).

Example 8b Mixture 1 Approx 5 - 50% dispersed polymer including a continuous aqueous phase and a dispersed polymer phase, e.g. Epoxy dispersion; Hydroxy functional acrylic dispersion or Hydroxyl functional polyester Approx 1-40% water soluble or dispersed cross linking agent e.g. Amino resins, polyamides polyamines, cycloaliphatic amines, mannich bases, isocyanates, blocked isocyanates, aziridines or similar Approx. 5-40% Pigments, preferably one or more of the following: Titanium Dioxide -Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments Approx. 5-40% Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, silicone, gypsum, lime, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Approx. 0.1-5.0% additives, typically including: wetting agents, surfactants, dispersants e.g. Nopcosperse 44, polyurethane thickeners, e.g. Acrysol RM8 (Rohm & Haas), cellulosics and modified cellulosic thickeners, acrylic thickeners, matting agents and defoamers Approx. 1-5% Coalescing solvents including alcohols, e.g. Texanol (Rohm &
Haas), glycols, glycol ethers ketoximes Optional antimicrobials in the range 0.1-10%

Approx. 3 - 10% Fire retardants, for example macroplegmatic compounds multiprocessed from polystyrene and copolymers.
To the above mixture 1 add a cocktail of enzymes such as:

Protease (e.g., Esperase ; Alcalase. ; Durazym ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocades ) at the amount of 0.0001 - 0.5% by weight of mixture 1.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.
Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.

Amylase (e.g., a and b amylases such as Purafect Ox Am from Genencor , Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 1.

Example 9 Where the coating is based on an aqueous hybrid binder composition for various uses Example 9a.
Mixture 1 Combination of organic and inorganic polymers dispersible in water Approx. 5-40% Pigments, preferably one or more of the following: Titanium Dioxide -Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments Approx. 5-40% Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Approx. 0.1-5.0% additives, typically including: wetting agents, surfactants, dispersants e.g. Nopcosperse 44, polyurethane thickeners, e.g. Acrysol RM8 (Rohm & Haas), cellulosics and modified cellulosic thickeners, acrylic thickeners, matting agents and defoamers Coalescing solvents including alcohols, e.g. Texanol (Rohm & Haas), glycols, glycol ethers, ketoximes in the range 1-5%

Optional antimicrobials in the range 0.1-10%

Approx. 3-10% fire retardant macroplegmatic compounds To the above mixture 1 add 0.001 - 200mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU
produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500mg of glucose, galactose or fructose/ml mixture 1. Also add 0.002 to 200mg of starch which has been spray applied with hexose oxidase with an activity within 0.001- 100 U (where produced lmmol of H202/min at 25 C).

Example 9b Mixture 1 Combination of organic and inorganic polymers dispersible in water Approx. 5-40% pigments preferably one or more of the following: Titanium Dioxide -Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminum, or other suitable coloured pigments Approx. 5-40% Fillers preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Approx. 0.1-5.0% additives, typically including: wetting agents, surfactants, dispersants e.g. Nopcosperse 44 , polyurethane thickeners e.g. Acrysol RM8 (Rohm &
Haas), cellulosics and modified cellulosic thickeners, acrylic thickeners, matting agents and defoamers SUBSTITUTE PAGE

I I

Coalescing solvents including alcohols, e.g. Texanol (Rohm & Haas), glycols, glycol ethers ketoximes in the range 1-5%

Optional antimicrobials in the range 0.1-10%

Approx. 3-10% fire retardant macroplegmatic compounds To the above mixture 1 add a cocktail of enzymes such as:
Protease (e.g., Esperase ; Alcalase. ; Durazym ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocades ) at the amount of 0.0001 - 0.5% by weight of mixture 1.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.
Amylase (e.g., a and b amylases such as Purafect Ox Am from Genencor , Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 1.

Example 10 Where the coating composition is based on combined hybrid resin system for various uses Example 10a Mixture 1 I I ~

Approx. 10-70% epoxy siloxane resin e.g. Silikoftal ED (Tego Chemie) Approx. 5-25% amino functional silicone curing agent e.g. Dynasilan AMEO (3-aminopropyl triethoxysilane, Degussa) Approx. 5-40% Pigments, preferably one or more of the following: Titanium Dioxide -Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminum, or other suitable coloured pigments) Approx. 5-40% Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Approx. 1-5% additives, typically including: thixotropic agents, flow control agents Approx. 0.5-50% Solvents including xylene, hydrocarbons e.g. Solvesso 150 ;
toluene, alcohols, acetates, glycol ethers, ketones Optional antimicrobials in the range 0.1-10%

This formulation is expected to be naturally flame resistant To the above mixture 1 add 0.001-200mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU
produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500mg of glucose, galactose or fructose/ml mixture 1. Also add 0.002 to 200mg of starch which has been spray applied with hexose oxidase with an activity within 0.001- 100 U (where produced 1 mmol of H202/min at 25 C).
Example 1 Ob Mixture 1 Approx. 10-70% epoxy siloxane resin e.g. Silikoftal ED (Tego Chemie) in the range SUBSTITUTE PAGE

Approx. 5-25% amino functional silicone curing agent e.g. Dynasilan AMEO (3-aminopropyl triethoxysilane, Degussa) Approx. 5-40% Pigments, preferably one or more of the following: Titanium Dioxide -Ti-Pure R902 (DuPont), iron oxides, carbon black, graphite, metallic aluminum, or other suitable coloured pigments Approx. 5-40% Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates Approx. 1-5% additives, typically including: thixotropic agents, flow control agents Approx. 0.5-50% Solvents including xylene, hydrocarbons e.g. Solvesso 150 ;
toluene, alcohols, acetates, glycol ethers, ketones Optional antimicrobials in the range 0.1-10%

This formulation is expected to be naturally flame resistant.
To the above mixture 1 add a cocktail of enzymes such as:

Protease (e.g., Esperase ; Alcalase ; Durazyme ; &/or Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocaades) at the amount of 0.0001-0.5% by weight of mixture 1.

Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001-3% by weight of mixture 1.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd. Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named SUBSTITUTE PAGE

type of lipases combined with a cutinase at the amount of 0.0001-3% by weight of mixture 1.

Amylase (e.g., a and b amylases such as Purefact Ox Am from Genencor, Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002-2% by weight of mixture 1.

Example 11 Where the coating composition is based on a combined hybrid resin system for various uses Example 11a Mixture 1 Non aromatic epoxy e.g. Eponex 1510 (Resolution), Epodil 757 (Air Products) in the range 15-45%

Alkyl, aryl or alkoxy polysiloxane e.g. Dow Corning 3074 in the range 15-45%

Organooxysilane e.g. A163 Union Carbide/Dow Chemicals, Dow Corning 26070 , in the range 1-10%.

Cured with an aliphatic amine or adduct thereof, polyamidoamide, cycloaliphatic amine or adduct thereof, Aromatic amine, mannich base, ketimine or amino functional silane e.g. Al 100 Union Carbide/Dow Chemicals, Z6020 Dow Corning, in the range 10-20%

Pigments, preferably one or more of the following: Titanium dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminum, or other suitable coloured pigments in the range 5-40%

Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, silicone, lime, gypsum, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%

SUBSTITUTE PAGE

bU

Additives, typically including: thixatropic agents, flow control agents and organometallic catalysts in the range 1-5%

Solvents including xylene, hydrocarbons e.g. Solvesso 150; toluene, alcohols, acetates, glycol ethers, ketones, in the range 5-40%

Optional antimicrobials in the range 0.1-10%

Macroplegmatic fire retarding compound in the range 3-10%

To the above mixture 1 add 0.001 200mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU
produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500mg of glucose, galactose or fructose/ml mixture 1. Also add 0.002 to 200mg of starch which has been spray applied with hexose oxidase with an activity within 0.001 - 100 U
(where 1 U produced 1 mmol of H2O2/min at 25 C).

Example 11 b Mixture 1 Non aromatic epoxy e.g. Eponex 1510 (Resolution), Epodil 757 (Air Products) in the range 15-45 %
Alkyl, aryl or alkoxy polysiloxane e.g. Dow Corning 3074 in the range 15-45%
Organooxysilane e.g. A163 Union Carbide/Dow Chemical, Dow Corning Z6070, in the range 1-10%.
Cured with an aliphatic amine or adduct thereof, polyamidoamide, Cycloaliphatic amine or adduct thereof, Aromatic amine, mannich base, ketimine or amino functional silane e.g. A1100 Union Carbide/Dow chemical, Z6020 Dow Corning, in the range 10-20%

Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%

Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, silicone, lime, gypsum, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%

Additives, typically including: thixatropic agents, flow control agents and organometallic catalysts in the range 1-5%

Solvents including xylene, hydrocarbons e.g. Solvesso 150; toluene, alcohols, acetates, glycol ethers, ketones, in the range 5-40%
Optional antimicrobials in the range 0.1-10%
Macroplegmatic fire retarding compound in the range 3-10%
To the above mixture 1 add a cocktail of enzymes such as:

Protease (e.g., Esperase ; Alcalase. ; Durazym ; 8Jor Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocades ) at the amount of 0.0001 - 0.5% by weight of mixture 1.
Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.

Amylase (e.g., a and b amylases such as Purafect Ox Am from Genencor , Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 1.
Example 12 Where the coating composition is based on an alkyd resin composition for various uses.

Example 12a Mixture 1 An alkyd or modified alkyd resin e.g. Synolac S31, Unithane 655W (Cray Valley), Uralac 390 (DSM Resins) in the range 10-50%
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%

Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%

Additives, typically including: thixatropic agents, flow control agents, driers (aliphatic carboxylic acid salts of metals such as cobalt, manganese, lead, zirconium, calcium and mixtures thereof) and antioxidants e.g. Methylethylketoxime or similar in the range 1-5%

Solvents including xylene, hydrocarbons e.g. Solvesso 150, white spirit;
toluene, alcohols, acetates, glycol ethers, ketones, in the range 10-60%

Optional antimicrobials in the range 0.1-10%

Macroplegmatic Fire retarding compounds in the range 3 to 10%

To the above mixture 1 add 0.001 -200mg/ml of starch which has been spray applied with amyloglucosidase with an activity of 0.00001 to 10 AGU (where 1 AGU
produces 1 mmol glucose/min at 25 C), alternatively add 0.001 to 500mg of glucose, galactose or fructose/ml mixture 1. Also add 0.002 to 200mg of starch which has been spray applied with hexose oxidase with an activity within 0.001 - 100 U
(where 1 U produced 1 mmol of H202/min at 25 C).

Example 12b Mixture 1 An alkyd or modified alkyd resin e.g. Synolac S31, Unithane 655W (Cray Valley), Uralac 390 (DSM Resins) in the range 10-50%

Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%

Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%

Additives, typically including: thixatropic agents, flow control agents, driers (aliphatic carboxylic acid salts of metals such as cobalt, manganese, lead, zirconium, calcium and mixtures thereof) and antioxidants e.g. Methylethylketoxime or similar in the range 1-5%

Solvents including xylene, hydrocarbons e.g. Solvesso 150, white spirit;
toluene, alcohols, acetates, glycol ethers, ketones, in the range 10-60%
Optional antimicrobials in the range 0.1-10%

Macroplegmatic Fire retarding compounds in the range 3 to 10%
To the above mixture 1 add a cocktail of enzymes such as:

Protease (e.g., Esperase ; Alcalase. ; Durazym ; Wor Savinase available from Novozymes. Alternatively Maxatas ; Maxacal ; Properase or Maxapem from GIST-Brocades ) at the amount of 0.0001 - 0.5% by weight of mixture 1.
Cellulase (e.g., commercially available cellulases from microbial origins, e.g., from the fungus Humicola, strain DSM 1800) at the amount of 0.00001 - 3% by weight of mixture 1.

Lipase (e.g., commercially available derived from bacterial or fungal origins, such as Lipase P "Amano", AMANO Pharmaceutical Co. Ltd., Nagoya, Japan) also AMANO-CES NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, also LIPOMAX from GIST-Brocades and LIPOLASE from Novozymes. Alternatively a mixture of the named type of lipases combines with a cutinase at the amount of 0.0001 - 3% by weight of mixture 1.

Amylase (e.g.., a and b amylases such as Purafect Ox Am from Genencor , Termamyl , Ban , Fungamyl and Duramyl from Novozymes) at the amount of 0.0002 - 2% by weight of mixture 1.
Example 13 Where the coating composition is based on an epoxy resin, crosslinked using an amino functional curing agent comprising:

An epoxy resin obtained from the reaction of 2,2-bis(4-hydroxyphenyl)propane with epichlorhydrin e.g. Epikote 1001, Epikote 1003, Epikote 1004, Epikote 828 (Resolution); Araldite 7071, Araldite GY250(Vantico), DER 671, DER 331 (Dow Chemical) or similar in the range 10- 50%.
An amino curing agent selected from the classes: Amino resins, polyamides polyamines, cycloaliphatic amines, mannich bases, e.g. Versamid 115, Versamid 125, Versamid 140 (Cognis) Crayamid 115, Crayamid 125 (Cray Valley) Ancamine 1784 or similar, in the range 10-50%.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%.

Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.
Additives, typically including: accelerators, e.g. 2,4,6-tris (dimethylamino methyl) 5 phenol e.g. Ancamine K54 (Air Products), thixatropic agents e.g. Modified Bentonites, fumed silicas, modified waxes, in the range 0.1-5%.
Solvents including xylene, butanol, hydrocarbons e.g. Solvesso 150; toluene, alcohols, acetates, glycol ethers, ketones, ketimines. in the range 0.1-90%.
Enzymes or antimicrobials in the range 0.1-10%.
Example 14 Where the coating composition is based on a thermoplastic acrylic or vinyl resin comprising:
An acrylic resin solution e.g. Neocryl 727 (Zeneca resins) Synocryl 874 (Cray Valley) Acryloid B66 (Rohm & Haas) or a vinyl resin solution e.g. UCAR VAGH, UCAR VYHH, UCAR VMCC (Dow Chemical/Union Carbide), Hostaflex CM150 Hoechst, Laroflex MP25 (BASF) in the range 10-50%.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%.
Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.
Additives, typically including: thixatropic agents, flow control agents. 1-5%.
Solvents including xylene, hydrocarbons e.g. Solvesso 150, toluene, alcohols, acetates, glycol ethers, ketones, in the range 0.1-90%.
Enzymes or antimicrobials in the range 0.1-10%.
Example 15 Where the coating composition is based on a thermoplastic chlorinated rubber or acrylated rubber resin comprising:

A chlorinated rubber resin solution e.g. Pergut S10 (Bayer), Clortex 10 (Caffaro) or an acrylated rubber resin solution e.g. Pliolite AC4 , AC80 , AC-L (Goodyear Chemicals) in the range 10-50%.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure R902 , (DuPont), iron oxides, carbon black, graphite, metallic aluminum, or other suitable coloured pigments in the range 5-40%.
Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.
Additives, typically including: thixatropic agents, flow control agents: 1-5%.
Solvents including xylene, hydrocarbons e.g. Solvesso 150 , toluene, alcohols, acetates, glycol ethers, ketones, in the range 0.1-90%.
Enzymes or antimicrobials in the range 0.1-10%.
Example 16 Where the coating composition is based on a hydroxy functional acrylic or hydroxy functional polyester resin cured by an isocyanate, comprising:

A hydroxy functional acrylic resin solution e.g. Desmophen A160 (Bayer) or a hydroxy functional polyester resin solution e.g. Setal 168 (Akzo Nobel) in the range 10-60%.
An isocyanate curing agent e.g. Desmodur N75 (Bayer) Tolonate HDB75 (Rhodia) Desmodur N3390 Bayer in the range 5-30%.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminum, or other suitable coloured pigments) in the range 5-40%.
Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.
Additives, typically including: thixatropic agents, flow control agents 1-5%.
Solvents including xylene, hydrocarbons e.g. Solvesso 150 , toluene, alcohols, acetates, glycol ethers, ketones, in the range 10-50%.
Enzymes or antimicrobials in the range of 0.1-10%.

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Example 17 Where the coating is based on an aqueous dispersed polymer comprising:

An emulsion polymer including a continuous aqueous phase and a dispersed polymer phase, e.g. acrylic latex - Maincote HG54 (Rohm & Haas) or similar;
Polyurethane dispersion - Neorez 960, (Zeneca resins), Styrene acrylic latex -Haloflex 202S (Zeneca resins) in the range 5-50%.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%.
Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.
Additives, typically including: wetting agents, surfactants, dispersants e.g.
Nopcosperse 44, polyurethane thickeners, e.g. Acrysol RM8 (Rohm & Haas), cellulosics and modified cellulosic thickeners, acrylic thickeners, matting agents and defoamers in the range 0.1-5.0 %.
Coalescing solvents including alcohols, e.g. Texanol (Rohm & Haas), glycols, glycol ethers ketoximes in the range 1-5%.
Enzymes or antimicrobials in the range 0.1-10%.
Example 18 Where the coating is based on an aqueous dispersed polymer containing active crosslinking groups comprising:
A dispersed polymer including a continuous aqueous phase and a dispersed polymer phase, e.g. Epoxy dispersion; Hydroxy functional acrylic dispersion or Hydroxyl functional polyester in the range 5-50%.
A water soluble or dispersed cross linking agent e.g. Amino resins, polyamides polyamines, cycloaliphatic amines, mannich bases, isocyanates, blocked isocyanates, aziridines or similar in the range 1-40%.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%.

Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.
Additives, typically including: wetting agents, surfactants, dispersants e.g.
Nopcosperse 44, polyurethane thickeners, e.g. Acrysol RM8 (Rohm & Haas), cellulosics and modified cellulosic thickeners, acrylic thickeners, matting agents and defoamers in the range 0.1-5.0 %.
Coalescing solvents including alcohols, e.g. Texanol (Rohm & Haas), glycols, glycol ethers ketoximes in the range 1-5%.
Enzymes or antimicrobials in the range 0.1-10%.
Example 19 Where the coating is based on an aqueous hybrid binder composition:
Combination of organic and inorganic polymers dispersible in water.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%.
Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.
Additives, typically including: wetting agents, surfactants, dispersants e.g.
Nopcosperse 44, polyurethane thickeners, e.g. Acrysol RM8 (Rohm & Haas), cellulosics and modified cellulosic thickeners, acrylic thickeners, matting agents and defoamers in the range 0.1-5.0 %.
Coalescing solvents including alcohols, e.g. Texanol (Rohm & Haas), glycols, glycol ethers ketoximes in the range 1-5%.
Enzymes or antimicrobials in the range 0.1-10%.
Example 20 Where the coating composition is based on combined hybrid resin system comprising:

An epoxy siloxane resin e.g. Silikoftal ED (Tego Chemie) in the range 10-70%.

P 566 DKO() CA 02402653 2002-09-26 An amino functional silicone curing agent e.g. Dynasilan AMEO (3-amiriopropyl triethoxysilane, Degussa) in the range 5-25%.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%.
Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.
Additives, typically including: thixatropic agents, flow control agents, in the range 1-5%.
Solvents including xylene, hydrocarbons e.g. Solvesso 150; toluene, alcohols, acetates, glycol ethers, ketones, in the range 0.5-50%.
Enzymes or antimicrobials in the range 0.1-10%.
Example 21 Where the coating composition is based on combined hybrid resin system comprising:

Non aromatic epoxy e.g. Eponex 1510 (Resolution), Epodil 757 (Air Products) in the range 15-45 %.
Alkyl, aryl or alkoxy polysiloxane e.g. Dow Corning 3074 in the range 15-45%.
Organooxysilane e.g. A163 Union Carbide/Dow Chemical, Dow Corning Z6070, in the range 1-10%.
Cured with an aliphatic amine or adduct thereof, polyamidoamide, Cycloaliphatic amine or adduct thereof, Aromatic amine, mannich base,, ketimine or amino functional silane e.g. A1100 Union Carbide/Dow chemical, Z6020 Dow Corning, in the range 10-20%.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminium, or other suitable coloured pigments in the range 5-40%.
Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.

Additives, typically including: thixatropic agents, flow control agents and organometal catalysts in the range 1-5%.
Solvents including xylene, hydrocarbons e.g. Solvesso 150 , toluene, alcohols, acetates, glycol ethers, ketones in the range 5-40%.
Enzymes or antimicrobials in the range of 0.1-10%.
Example 22 Where the coating composition is based on an alkyd resin comprising:

An alkyd or modified alkyd resin e.g. Synolac S31 , Unithane 655W (Cray Valley), Uralac 390 (DSM Resins) in the range 10-50%.
Pigments, preferably one or more of the following: Titanium Dioxide - Ti-Pure (DuPont), iron oxides, carbon black, graphite, metallic aluminum, or other suitable coloured pigments in the range 5-40%.
Fillers, preferably one or more of the following: talc, calcium carbonate, barium sulphate, zinc oxide, zinc phosphate, clay, kaolin, silicates, glass, ceramics, (including spheres, fibres & powder) or carbohydrates in the range 5-40%.
Additives, typically including: thixatropic agents, flow control agents, driers (aliphatic carboxylic acid salts of metals such as cobalt, manganese, lead, zirconium, calcium, and mixtures thereof) and antioxidants e.g. Methylethylketoxime or similar in the range 1-5%.
Solvents including xylene, hydrocarbons e.g. Solvesso 150 , white spirit, toluene, alcohols, acetates, glycol ethers, ketones in the range 10-60%.
Enzymes or antimicrobials in the range of 0.1-10%.

SUBSTITUTE PAGE

Claims (74)

1. A coating composition comprising i. a surface coating material, ii. at least a first enzyme, and iii. at least one flame retarding compound, iv. at least one antimicrobial compound wherein the first enzyme is capable of directly or indirectly inhibiting attachment and/or growth of microorganisms after applying the coating composition to a surface and allowing it to form a film.

2. The composition according to claim 1, wherein the surface coating material comprises a binder.

3. The composition according to claim 2, wherein the binder is a modified rosin, maleic acid, or gloss oil.

4. The composition according to claim 2, wherein the binder is a shellac.

5. The composition according to claim 2, wherein the binder is an oxidised rubber.

6. The composition according to claim 2, wherein the binder is a water-based styrene butadiene latex system.

7. The composition according to claim 2, wherein the binder is a water-based styrene acrylic.

8. The composition according to claim 2, wherein the binder is a chlorinated polyolefin.

SUBSTITUTE SHEET

9. The composition according to claim 2, wherein the binder is a modified water-borne silicone.

10. The composition according to claim 2, wherein the binder is at least one compound selected from a group consisting of modified sucrose, water-borne polyvinylidene, chloride based latex terpopolymers, vinyl acetate, polyvinyl alcohol, polyvinyl acetals, vinylidene fluoride, polyurethanes, epoxides, and water soluble acrylics.

11. The composition according to any one of claims 1-10, wherein the surface coating composition and the binder do not significantly inhibit the activity of the enzyme.

12. The composition according to claim 11, wherein the antimicrobial compound is a biocide selected from the group consisting of:
zinc oxide;
citrus oil, chili oil, cranberry extract, and/or seaweed extract;
2,4,4-trichloro-2-hydroxy-diphenyl ether, 5-chloro-2-phenol;
polyvalent glycosylated casein;
bismuth; and carbamates with diethanolamide as a potentiator.

13. The composition according to claim 12 wherein the group further includes vetiver oil, camphor oil, cedar oil, tea-tree oil, and citrus oil, each taken alone or in any combination.

14. The composition according to claim 13 wherein the group further includes honey, natural pine tree resins, natural elemi tree resins, copal, and dammar.

15. The composition according to claim 14 wherein the group further includes sodium fluoride, dodecylamine, triclosan, and chlorhexidine, each taken alone or in any combination.

16. The composition according to claim 15, wherein the group further includes iodide salts, metal salts, cupric chloride, cupric sulphate, silver nitrate, colloidal bismuth subcitrate, bismuth citrate, aluminum phosphate, aluminum hydroxide hydrate, and gold chloride, each taken alone or in any combination.

17. The composition according to claim 16, comprising 0.5% to 30% (w/v) of biocide.

18. The composition according to claim 1 wherein the flame retarding compound is selected from a group consisting of: macroplegmatic compounds; a flame retardant mixture of melamine cyanurate, silica, and phosphoric acid; a flame-retardant mixture of sodium carbonate, pyrophosphate, ammonium salts, boric acid, phosphoric acid; a halogen-based flame retardant, organic bromine compounds, brominated aromatic epoxy compounds, brominated polycarbonates, brominated benzyl acrylates, brominated polystyrene; phosphorous based flame retardants, , phosphate esters, nitrogen containing phosphorous compounds, and red phosphorous; inorganic flame retardants; oxides of antimony; sodium antimonate; aluminum hydroxide; and magnesium hydroxide.

19. The composition according to claim 18 wherein flame retarding compound is non-toxic and/or does not release harmful amounts of toxic fumes.

20. The composition according to claim 18 wherein flame retarding compound is present in an amount of 1% to 50% (w/v).

21. The composition according to claim 18 further comprising up to 75% (w/v) of an essentially non-combustible binder.

22. The composition according to any one of claims 1-21, wherein the enzyme and/or a substrate for the enzyme are encapsulated in a material selected from a group including mesoporous silicates, porous ceramic particles, and porous glass spheres.

23. The composition according to claim 22 further comprising cellulosic fibres.

24. The composition according to claim 23 wherein one or more of the enzyme, enzyme substrate, and antimicrobial compound is bound to the cellulosic fibres.

25. The composition according to any one of claims 1-25, further comprising co-factors for the enzyme.

26. The composition according to claims 25 comprising 0.05%-60% (w/v) of enzyme substrate for the enzyme.

27. The composition according to any one of claims 1-26 wherein hydrogen peroxide is generated in an amount to prevent biofilm formation on the surface of the composition.

28. The composition according to claim 17 being adapted to produce at least 5-10 mmol hydrogen peroxide in an overlying moisture film.

29. The composition according to claim 1 wherein the activity of at least one enzyme is controllable by changes in environmental consideration selected from a group consisting of: ambient humidity, ambient temperature, ambient pH, and ambient oxygen levels, each taken alone or in any combination.

30. The composition according to claim 29 wherein at least one enzyme has an activity sufficient to inhibit biofilm formation when ambient humidity is above 40%.

31. The composition according to claim 29 wherein at least one enzyme has an optimum at in the interval between 5 - 40 °C.

32. The composition according to claim 29 wherein at least one enzyme has an optimum in the interval between pH 4 and 11.

33. The composition according to claim 29 wherein at least one enzyme has an optimum at 50 - 100% oxygen saturation.

34. The composition according to any one of claims 1-33 wherein the at least one enzyme does not lose substantial activity when dried and rehydrated repeated times.

35. The composition according to any one of claims 1-33 wherein the at least one enzyme does not lose substantial activity when dried to below 20%
moisture content and rehydrated again.

36. The composition according to any one of claims 22-35 comprising a combination of first enzyme and substrate selected from the group consisting of mixture combinations including: malate oxidase - malic acid;
glucose oxidase - glucose; hexose oxidase - glucose; cholesterol oxidase - cholesterol; arylalcohol oxidase - arylalcohol: galactose oxidase -galactose; alcohol oxidase - alcohol; lathosterol oxidase - lathosterol;
aspartate oxidase - aspartic acid; L-amino-acid oxidase - L-amino acid;

D-amino-acid oxidase - D-amino acid; amine oxidase - amine; D-glutamate oxidase - glutamine; ethanolamine oxidase - ethanolamine;
NADH oxidase - NADH; urate oxidase (uricase) - uric acid; superoxide dismutase - superoxide radical; glucose - hexose oxidase; glucose -glucose oxidase; L amino acid - L amino acid oxidase; galactose -galactose oxidase; lactose - P-galactosidase - hexose oxidase; lactose -galactosidase - glucose oxidase; 2-deoxyglucose - glucose oxidase; and pyranose - pyranose oxidase; each mixture taken alone or in any combination.

37. The composition according to any one of claims 1-36 comprising 0.0001%-5% (w/v) of enzyme.

38. The composition according to any one of claims 1-37 further comprising a second enzyme capable of converting a compound into a substrate for the first enzyme.

39. The composition according to claim 38 wherein the second enzyme is selected from a group consisting of: an amylase, a fructase, a cellulase, a ligninase, a proteinase, and a nuclease.

40. The composition according to claim 38 wherein the compound is a fructan.

41. The composition according to claim 40 wherein the fructan is inulin.

42. The composition according to any one of claims 1-41 comprising a number of enzymes ranging from two to ten enzymes.

43. The composition according to claim 42 wherein the enzymes are selected from a group consisting of: a protease, a lipase, an amylase, and an oxidase, each taken alone or in any combination.

44. The composition according to any one of claims 1-43 further comprising a colored stain.

45. The composition according to any one of claims 1-44 comprising enzymes, and optionally, substrate enough to ensure biofilm prevention for a period of at least 6 months to 6 years.

46. Use of the composition according to any one of claims 1-45.

47. The use according to claim 46 for coating surfaces in an enclosed habitable space.

48. The use according to claim 46 for coating surfaces in ventilation systems.

49. The use according to claim 46 for coating surfaces in an aeroplane.

50. The use according to claim 46 for coating surfaces in medical facilities.

51. The use according to claim 47 for coating surfaces in educational facilities.

52. The use according to claim 47 for coating surfaces within vehicles selected from a group consisting of: a bus, an ambulance, a mobile home, a caravan, a watercraft, and a spacecraft

53. The use according to claim 47 for coating surfaces in sports facilities.

54. The use according to claim 47 for coating surfaces in public buildings.

55. The use according to claim 47 for coating sanitary surfaces in private homes.

56. The use according to claim 47 for coating surfaces in animal housings.

57. The use according to claim 47 for coating surfaces in pulp mills.

58. The use according to claim 47 for coating surfaces in food preparation facilities.

59. The use according to claim 47 for coating surfaces in slaughterhouses.

60. The use according to claim 47 for coating surfaces in sanitation facilities.

61. A method of controlling growth of microorganisms on coated surfaces comprising:
applying to a surface a coating composition comprising a surface coating material, at least one enzyme, and a substrate for the enzyme;
and allowing the coating composition to dry;
whereby the coating composition upon subsequent exposure to moisture releases an antimicrobially effective amount of hydrogen peroxide as a consequence of a conversion of the substrate through the enzyme.

62. Method of controlling growth of microorganisms on coated surfaces comprising:
applying to a surface a coating composition comprising a surface coating material, at least one enzyme; and allowing the coating composition to form a film;
whereby the coating composition upon subsequent exposure to moisture levels above 50% (RH) inhibits attachment of at least one species of microorganisms as a consequence of the action of the enzyme.

63. The method according to claim 61 or 62 wherein the coating composition is a coating composition according to any one of claims 1 to 45.

64. The method according to claim 61 or 62 wherein the surface is a surface in a spacecraft.

65. The method according to claim 61 or 62 wherein the surface is a surface in a ventilation system.

66. The method according to claim 61 or 62 wherein the surface is a surface in a watercraft.

67. The method according to claim 61 or 62 wherein the surface is a surface in a vehicle selected from a group consisting of: an aeroplane, a bus, an ambulance, a mobile home, and a caravan.

68. The method according to claim 61 or 62 wherein the surface is a surface in a medical facility.

69. The method according to claim 61 or 62, wherein the surface is a surface in a public building.

70. The method according to claim 61 or 62, wherein the surface is a sanitary surface in a private house.

71. The method according to claim 61 or 62 wherein the surface is a surface is a surface in animal housing.

72. The method according to claim 61 or 62 wherein the surface is a surface in a food preparation facility.

73. The method according to claim 61 or 62 wherein the surface is a surface in a sanitation facility.

74. The method according to claim 61 or 62 wherein the surface is a surface in an industrial facility.