WO2013061082A1

WO2013061082A1 - Anti-microbial composition

Info

Publication number: WO2013061082A1
Application number: PCT/GB2012/052674
Authority: WO
Inventors: Rachel HIRST; Rhiannon Sian HURD; Christopher Plummer; Timothy Jon MILLS; Stephanie BURKE
Original assignee: Byotrol Plc
Priority date: 2011-10-28
Filing date: 2012-10-26
Publication date: 2013-05-02
Also published as: AR088569A1; GB201118673D0; GB2497389A; TW201323603A; GB201219315D0; GB2497389A8

Abstract

The present invention provides an antimicrobial composition comprising: (i) an antimicrobial component comprising a quaternary ammonium component (I) consisting of (a) a component consisting essentially of a single compound of formula (A) wherein R¹ and R² are each independently a straight chain, unsubstituted and uninterrupted Ce-12 alkyl group and X" is chloride, bromide, fluoride, iodide sulphonate, carbonate or bicarbonate and (b) a component consisting essentially of at least one benzalkonium compound having the formula (B) wherein m is from 8 to 18, and X" is chloride, bromide, fluoride, iodide, saccharinate or sulphonate, wherein the ratio by weight of (a) to (b) is from 10:1 to 1:10; and (II) an additional antimicrobial component that does not comprise a quaternary ammonium compound; (ii) at least one siloxane selected from those having the formula (H₃C)[SiO(CH₃)₂]nSi(CH₃)₃, and (H₃C)[SiO(CH₃)H]nSi(CH₃)₃wherein n is an integer of from 1 to 10; (iii) a polar solvent; (iv) at least one surfactant; wherein in terms of parts per million (ppm) the amount of component (iv) is no more than 20 times the amount of component (i); and wherein component (I) is the only component of the composition that comprises a quaternary ammonium compound.

Description

ANTI-MICROBIAL COMPOSITION

This invention relates to anti-microbial compositions. Micro-organisms are known to present health hazards due to infection or contamination. They can also cause spoilage of items such as clothing and unpleasant odours. When micro-organisms are present on the surface of a substrate they can replicate rapidly to form colonies. Many anti-microbial agents that can destroy microorganisms which are present in a wide range of environments such as medical, industrial, commercial, domestic and marine environments are known. Many of the known anti-microbial agents have previously been included in compositions for use in various applications and environments. The known anti-microbial agents and compositions that contain these anti-microbial agents destroy micro-organisms by a number of different mechanisms.

For example, many anti-microbial agents are poisonous to micro-organisms and, therefore, destroy micro-organisms with which they are contacted. Examples of this type of anti- microbial agent include hypochlorites (bleaches), phenol and compounds thereof, arsenene and salts of copper, tin and arsenic. However, some of these agents can be highly toxic to humans and animals as well as to micro-organisms. Consequently these anti-microbial agents are dangerous to handle, and specialist handling, treatment and equipment are therefore required in order to handle them safely. The manufacture and disposal of compositions comprising this type of anti-microbial agent can, therefore, be problematic. There can also be problems associated with the use of compositions containing this type of anti-microbial agent, particularly in consumer materials where it is difficult to ensure that they are used for designated purposes. Herein, unless the context indicates otherwise, "toxicity" is intended to refer to toxicity to complex organisms such as mammals. References to "toxic" are to be construed accordingly.

Once the anti-microbial agents enter the environment they can affect the health of life forms that they were not intended to affect. Furthermore, the anti-microbial agents are often highly stable and can cause environmental problems for long periods of time. Other anti-microbial agents currently in use include antibiotic type compounds. Antibiotics disrupt the biochemistry within microorganisms. Although antibiotics are effective, it is currently believed that they may selectively permit the development of resistant strains of the species that they are used against.

Another method of microbial control is the use of oxidising agents in materials, such as household bleach, which can be based on hypochlorite or peroxides such as hydrogen peroxide. These materials are effective in a wet environment for sterilization and cleansing but stop working shortly after drying.

The listing or discussion of an apparently prior-published document in this specification should not necessarily be taken as an acknowledgement that the document is part of the state of the art or is common general knowledge.

There is a need to provide compositions for a variety of applications and uses, such as cleaning applications that have anti-microbial properties and that address one or more of the problems set out above. However, it is not a straight forward matter to do this. There are regulations such as the Biocidal Products Directive (Directive 98/8/EC) which regulates the use of anti-microbial agents both in terms of the nature and the amount of a given antimicrobial agent that may be used. Additionally, the potential reactivity of an anti-microbial agent once in a composition is important as some anti-microbial agents are rendered inactive by chemical reaction. Even where an anti-microbial agent is not deactivated by chemical reaction it may have its activity suppressed by other components of the composition.

The present inventors have surprisingly found that the foregoing deficiencies can be overcome by certain combinations of components. It has also been found that compositions containing these combinations of components can have some surprising and unexpected properties.

The compositions of the invention are particularly suitable for use on hard surfaces. Some compositions of the invention are suitable for cleaning a hard surface and also provide a residual anti-microbial effect.

The compositions of the invention can be used for a range of applications and are particularly suitable for use on hard surfaces. The compositions of the invention may be used on hard surfaces indoors such as those found in a domestic setting, an office or a public building such as a hospital or out of doors.

The compositions of the invention can also be used on the human or animal body, particularly on skin or hair. The compositions of the invention may, for example, be used as hand sanitizers.

As used herein, by the term cleaning we mean the removal of soils, such as dirt, soap scum and limescale.

The present invention provides an anti-microbial composition comprising:

(i) an antimicrobial component comprising a quaternary ammonium component (I) consisting of

(a) a component consisting essentially of a single compound of formula (A)

wherein R and R² are each independently a straight chain, unsubstituted and uninterrupted Ce-12 alkyl group and X^" is chloride, bromide, fluoride, iodide, sulphonate, carbonate or bicarbonate and

(b) a component consisting essentially of at least one benzalkonium compound having the formula (B)

wherein m is from 8 to 18, and X^" is chloride, bromide, fluoride, iodide, saccharinate or sulphonate,

wherein the ratio by weight of (a) to (b) is from 10:1 to 1:10; and (II) an additional antimicrobial component that does not comprise a quaternary ammonium compound;

(ii) at least one siloxane selected from those having the formula (H₃C)[SiO(CH3)2]nSi(CH₃)3, and (H₃C)[SiO(CH3)H]_nSi(CH₃)3 wherein n is an integer of from 1 to 10;

(Hi) a polar solvent; (iv) at least one surfactant; wherein in terms of parts per million (ppm) the amount of component (iv) is no more than 20 times the amount of component (i) (that is a ratio of no more than 20:1); and

wherein component (I) is the only component of the composition that comprises a quaternary ammonium compound.

While it is envisaged that compositions of the invention can contain additional ingredients as described below and other ingredients that are standard in the art, the compositions of the invention may consist of or consist essentially of the components listed in the paragraph above.

For the avoidance of doubt, in this specification when we use the term "comprising" or "comprises" we mean that the composition or formulation or component being described must contain the listed ingredient(s) but may optionally contain additional ingredients. When we use the term "consisting essentially of or "consists essentially of we mean that the composition or formulation or component being described must contain the listed ingredient(s) and may also contain small (for example up to 5% by weight, or up to 1% or 0.1% by weight) of other ingredients provided that any additional ingredients do not affect the essential properties of the composition, formulation or component. When we use the term "consisting of we mean that the composition or formulation or component being described must contain the listed ingredient(s) only.

By "substantially free" we mean that the composition or formulation or component being described contains less than 3% by weight, preferably less than 1%, more preferably 0.1% or less by weight or 0.01% or less of the stated ingredient. For example, the compositions of the invention that are substantially free of alcohol contain less than 3% by weight of alcohol, preferably less than 1% by weight of alcohol, more preferably 0.1% or less alcohol.

The pH of the compositions of the invention can vary within wide limits. Typically, the pH of a composition of the invention will be similar to that of known compositions which are intended to be used for the same purpose or a similar purpose to a given composition of the invention. For example, a composition that is intended to come into contact with the skin or the hair, such as a hand sanitizer, hand wash formulation or a shampoo formulation or other personal care or first aid formulations as listed above will typically have a pH which will not irritate the skin, for example from about pH 5 to about pH 8, such as from about pH 5.5 to about pH 7.5. On the other hand, formulations for use for purposes such as kitchen or bathroom cleaning may have either a low pH, such as a pH of 3 or below, for example about 2, or a high pH such as a pH of 10 or above, for example 11.

The compositions of the invention comprise any suitable surfactant or combination of surfactants, for example at least one non-ionic, cationic and/or amphoteric surfactant. In a particular aspect of the invention, the composition comprises at least one non-ionic surfactant. Compositions of the invention comprising a non-ionic surfactant may optionally comprise an amphoteric surfactant. The selection of the optional surfactants will depend on the nature of and the intended purpose of the composition. Suitable surfactants for use in formulations intended for different purposes will be within the knowledge of the person of ordinary skill in the art.

In one aspect, the compositions of the invention comprise at least one non-ionic surfactant. For example, the compositions may comprise a surfactant component that consists essentially of at least one non-ionic surfactant or consists of at least one non-ionic surfactant. If the surfactant component consists of at least one non-ionic surfactant it will not contain other types of surfactants, for example it will be free of amphoteric surfactants, anionic surfactants and cationic surfactants. Examples of non-ionic surfactants that can be used are listed below.

Some compositions of the invention comprise an amphoteric surfactant. Amphoteric surfactants can be used alone or in combination with a non-ionic surfactant. If a combination of an amphoteric surfactant and a non-ionic surfactant is used the weight ratio of the two types of surfactant can vary within wide limits, for example from 1 % of amphoteric surfactant to 99% of non-ionic surfactant to 99% of amphoteric surfactant to 1% of non-ionic surfactant, based on the total weight of the optional surfactant component (v). Preferably the amphoteric surfactant and the non-ionic surfactant are used in approximately equal amounts by weight. In one aspect of the invention, the compositions comprise up to about 5% by weight (based on the total weight of the composition) amphoteric surfactant, although higher levels of amphoteric surfactant can be used in some compositions. As an example, the present invention provides compositions having a pH of from about 5 to about 8, more preferably from about 5.5 to about 7.5 and comprising an amphoteric surfactant and a non-ionic surfactant, wherein the amphoteric surfactant is present in an amount of up to about 5% by weight (based on the total weight of the composition). In such compositions, the total amount of surfactant is not particularly limited and the total amount of surfactant may be an amount that is typical in the art for the particular type of composition in question. Examples of preferred compositions comprising an amphoteric surfactant and a non-ionic surfactant have a total surfactant content of about 10% by weight, wherein no more that 5% by weight (based on the total weight of the formulation) is amphoteric surfactant.

Suitable cationic surfactants include but are not limited to pH-dependent primary, secondary or tertiary amines, e.g. fatty amines, linear diamines and polyethoxyated tallow amine, cetyl pyridinium chlorides.

Suitable non-ionic surfactants include but are not limited to ethylene oxide/propylene oxide block polymers, polyethoxylated sorbitan esters, fatty esters of sorbitan, ethoxylated fatty esters (containing from 1 to 25 units of ethylene oxide), polyethoxylated C₈-C₂2 alcohols, (containing from 1 to 25 units of ethylene oxide) such as C_9-11 alcohol ethoxylates, polyethyoxylated C₆-C₂₂ alkylphenols (containing from 5 to 25 units of ethylene oxide), alkylpolyglycosides (APG). Examples include but are not limited to nonyl phenol ethoxylate (9EO), Nonyl phenol ethoxylate (2EO), octyl phenol ethoxylate (10EO), C₁₂/C₁₄ synthetic ethoxylate (8EO), stearyl alcohol ethoxylate (7EO), cetostearyl alcohol ethoxylate (20EO), coconut fatty amine ethoxylate (10EO), sorbitan monolaurate ethoxylate, 80%PO/20%EO, coconut diethanolamide (shampoo foam booster), sorbitan monolaurate, sorbitan monolaurate 4EO, di-isopropyl adipate, alkyl poly glucosides, such as C_6-2o, preferably C₈.io alkyl glucosides, eg Surfac APG (D-Glucopyranose oligomers C₈-io alkyl glucosides, CAS 161074-97-1, available from Seppic, UK), and cetostearyl stearate. Other suitable non-ionic surfactants include alcohol ethoxylates such as those sold under the name Neodol, for example Neodol 25-7 (C12/15 alcohol 7 ethoxylate (EO), CAS 68131-39-5), Surfac LM90/85 (C12/15 alcohol 9 ethoxylate (EO), CAS 68131-39-5), Surfac 65/95 (C9/11 alcohol 6.5 ethoxylate (EO), CAS 68439-45-2), Tomadol PF9 (C9/11 alcohol 6.0 ethoxylate (EO), CAS 68439-46-3), Surfac T80 Veg (Polysorbate 80, Polyoxyethylene sorbate mono oleate, CAS 9005-65-6), Tween 60 (Polysorbate 60, Polyoxyethylene sorbate mono stearate, CAS 9005- 67-8), Tween 40 (Polysorbate 40, Polyoxyethylene sorbate mono palmitate, CAS 9005-66-7), Surfac T-20 (Polysorbate 20, Polyoxyethylene sorbate mono laurate, CAS 9005-64-5), Surfac PGHC (Hydrogenated Castor oil 40EO, CAS 61788-85-0), Ninol 49-CE (Coconut diethanolamide, CAS 68603-42-9). Preferred non-ionic surfactants include alkyl amine oxides, alcohol ethoxylates (Neodols), such as C_9-1i alcohol ethoxylates, and alkyl polyglucosides (APG). An example of an alkyl amine oxide a suitable is Macat Ultra CDO (available from Mason Chemical Company), a 30% solution of coco (C₁₂) amidopropyl dimethyl amine oxide in water.

Suitable amphoteric surfactants include but are not limited to C₆-C₂o alkylamphoacetates or amphodiacetates (such as cocoamphoacetates), C ₀-C₁₈ alkyldimethyl betaines, C₁₀-C₁₈ alkyl amidopropyldimethyl betaines. Examples include but are not limited to coconut amphoteric surfactant cocoamidopropyl betaine (CAPB) (Surfac B4, CAS 61789-40-9), coco imidazoline betaine, oleo amido propyl betaine, and tall oil imidazoline. A particularly preferred amphoteric surfactant is cocoamidopropyl betaine. An example of a Betaine which is suitable for use in the present invention is Macat^® Ultra (available from Mason Chemical Company). Macat^® Ultra CG comprises 30% coco (C₁₂) amidopropyl dimethyl glycine (betaine) in water.

Other suitable surfactants include those that exhibit non-ionic or cationic type properties at pHs below about 8, for example between about pH 5 and about pH 7 or 8. It will be appreciated that the behaviour of such surfactants depends on factors such as their pKa and which surfactants are suitable for use in a given formulation will depend on the pH of the formulations. Examples of surfactants which exhibit properties that can vary with pH and that can be used in the invention include but are not limited to amine oxides such as those having an average carbon chain length of from 8 to 20, eg 12 or 14 such as C ₀-C ₈ alkyldimethyl amine oxides and C₈-C₂2 alkoxyethyldihydroxyethylamine oxides, for example dimethyl laurylamine oxide (eg Surfac AO30 from Surfachem and manufactured by Stepan as Ammonyx LO), alkyl ether carboxylates and alkyl ether phosphates, such as those having an average chain length of from 8 to 12, eg 12 or 14 (eg Laureth 11 carboxylic acid, sold by Univar as Akypo RLM 100 and Laureth 4 phosphate, sold by Surfachem and manufactured by Schill and Seilacher as Silaphos MDE 124). These surfactants can be used in combination with other surfactants such as non-ionic surfactants.

Preferred combinations of surfactants include, but are not limited to, CAPB and a non-ionic surfactant, such as APG, an amine oxide and a non-ionic surfactant, such as APG.

In one aspect of the invention, the compositions of the invention may be free of alcohol alkoxylate. For example, compositions of the invention that contain a compound of formula (C) as defined herein such as those containing N,N-bis(3-aminopropyl)-dodecylamine may be free of alcohol alkoxylate. The compositions of the invention may alternatively or additionally be free of alkyl polyglucoside. For example, compositions of the invention that contain a compound of formula (C) as defined herein such as those containing N,N-bis(3-aminopropyl)- dodecylamine may be free of alkyl polyglucoside (APG).

In one aspect, the compositions of the invention are free of anionic surfactants.

Without wishing to be bound by theory, it has been found that the surfactant component can have several effects on the properties of the compositions of the invention. The presence of a surfactant can improve the cleaning ability of the composition, that is improve the removal of soils and dirt. For example, has been found that the use of a combination of an alcohol alkoxylate in combination with an amine oxide can in some situations improve cleaning performance. Additionally, the inclusion of surfactants can improve the stability of the compositions of the invention.

The present inventors have surprisingly found that by using the combinations described herein stable compositions that provide residual antimicrobial performance and have a desirable cleaning ability can be obtained. The presence of a surfactant can reduce the residual anti-microbial performance of a composition. The present inventors have surprisingly found that by controlling the relative amounts of the antimicrobial component (i) and the surfactant component (iv) a stable composition that provides a residual antimicrobial benefit and has a desirable cleaning ability can be obtained.

In the compositions of the invention, in terms of parts per million (ppm) the amount of component (iv) is no more than 20 times the amount of component (i) for example from 0.1 times to 20 times the amount of component (i), or from 0.5 times to 15 times the amount of component (i), or from equal amounts of components (i) and (iv) to 4 or 10 times more of component (iv) than component (i), such as 5 times more of component (iv) than component (i). In other words, ratio of component (iv) to component (i) is no more than 20:1, for example from 0.1:1 to 20:1 , or from 0.3:1 or 0.5:1 to 15:1 or from 1:1 or 4:1 to 10:1 , such as from about 0.5:1 to about 4:1 or about 5:1.

In one aspect, the compositions of the invention are free of glycol ethers, for example they are free of propylene glycol n-butyl ether and/or free of a binary solvent combination of a glycol with a linear primary alcohol. For example, compositions of the invention that contain a compound of formula (C) such as those containing N,N-bis(3-aminopropyl)-dodecylamine may be free of propylene glycol n-butyl ether and/or free of a binary solvent combination of a glycol ether with a linear primary alcohol.

It will be appreciated that the compositions of the invention can comprise other ingredients commonly used in the art. The nature of any other ingredients used will depend on the nature and intended purpose of the composition. For example, the additional ingredients used in a bath/shower product are likely to be different to those used in a toilet care product, which will be different again from those used in a dishwashing or laundry product. The person of ordinary skill in the art will know which additional ingredients are suitable for use in compositions for different applications. Additional ingredients that may be used in the compositions of the invention include but are not limited to water, antioxidants, thickeners, corrosion inhibitors, foam makers and breakers, abrasives, chelating agents such as tetrasodium EDTA, sodium chloride, acids such as citric acid, colorants, fragrances, emollients and hair and/or skin rejuvenating and/or protecting agents. For personal care products emollients such as glycerol may be used for their moisturising properties and/or to improve the skin feel of a product, which may enhance consumer acceptance. It will be appreciated that the amount of surfactant (iv) in the compositions of the invention will depend on factors such as the intended purpose of the composition. Typically, the compositions of the invention comprise from 0.001 to 1 % by weight of surfactant (iv), preferably from 0.1 to 0.75 % by weight, for example from 0.2 to 0.5 %. By the term "anti-microbial" we mean a compound or composition that kills and/or inhibits the growth of microbes (micro-organisms). The term "microbiocidal" is used to refer to compounds or compositions that kill microbes. The compositions used in the invention are anti-microbial and/or microbiocidal. A micro-organism or microbe is an organism that is microscopic (too small to be seen by the human eye). Examples of micro-organisms include bacteria, fungi, yeasts, moulds, mycobacteria, algae spores, archaea and protists. Micro-organisms are generally single- celled, or unicellular organisms. However, as used herein, the term "micro-organisms" also include viruses. The compositions of the invention comprise at least one anti-microbial agent selected from anti-bacterial, anti-fungal, anti-algal, anti-sporal, anti-viral, anti-yeastal and anti-moldal agents and mixtures thereof. More preferably, the compositions of the invention comprise at least one anti-bacterial, anti-viral, anti-fungal and/or anti-moldal agent.

As used herein, the terms anti-bacterial, anti-fungal, anti-algal, anti-viral, anti-yeastal and anti-moldal agents are intended to refer to agents that inhibit the growth of the respective microorganisms but do not necessarily kill the microorganisms and agents that kill the respective microorganisms. Thus, for example, within the term anti-bacterial we include agents that inhibit the growth of bacteria but may not necessarily kill bacteria and bactericidal agents which do kill bacteria.

As the skilled person will appreciate, the word ending "cidal" as used in for example "bactericidal" and "fungicidal" is used to describe agents which kill the microorganism to which it refers. Thus in these examples, bactericidal refers to an agent that kills bacteria and fungicidal refers to an agent that kills fungus. Examples of bactericides include myobactericides and tuberculocides. Preferably, the compositions of the invention comprise at least one agent selected from bactericidal, fungicidal, algicidal, sporicidal, virucidal, yeasticidal and moldicidal agents and mixtures thereof. More preferably, the compositions of the invention comprise at least one bactericidal, virucidal, fungicidal and/or moldicidal agent.

The compositions of the invention are effective against a wide range of organisms, including Gram negative and Gram positive bacteria, funguses, yeasts, viruses and some spore formers. Compositions containing a compound of formula (C) as defined herein can be particularly effective against fungi.

The quaternary ammonium component (I) consists of (a) a component consisting essentially of a single compound of formula (A)

wherein R¹ and R² are each independently a straight chain, unsubstituted and uninterrupted Cs-12 alkyl group and X^" is halide anions such as chloride, bromide, fluoride, iodide or sulphonate, saccharinate, carbonate or bicarbonate; and

wherein m is from 8 to 18, and X^" is halide anions such as chloride, bromide, fluoride, iodide or sulphonate, saccharinate, carbonate or bicarbonate;

wherein the ratio by weight of (a) to (b) is from 10:1 to 1 :10.

In the compounds of formula (A) each group R¹ and R² is independently a straight chain, unsubstituted, uninterrupted Cs.^ alkyl group, for example an alkyl group containing 8, 9, 10, 11 or 12 carbon atoms. In one aspect the groups R¹ and R² contain the same number of carbon atoms but this is not essential and compounds in which R¹ and R² contain different numbers of carbon atoms can be used.

The anion of the compound of formula (A) may be the same or different to the anion of the compound of formula (B). In one aspect, the anion for each compound is chloride. The compounds of formula (B) are generally called benzalkonium compounds. The benzalkonium compound is provided and/or used as a mixture of C₈-18 alkyl groups, particularly a mixture of straight chain, unsusbtituted and uninterrupted alkyl groups n-C₈H₁₇ to n-Ci₈H37, mainly n-C₁₂H₂5 (dodecyl), n-C ₄H₂9 (tetradecyl), and n-C₁₆H₃₃ (hexadecyl). Preferably m is 8, 10, 12, 14 and/or 16. Most preferably m is from 12 to 16, for example 12, 14 and/or 16.

Examples of quaternary ammonium compounds of formula (A) include di-n-decyldimethyl ammonium chloride, Octyl Decyl Dimethyl Ammonium Chloride and Dioctyl Dimethyl Ammonium Chloride.

Examples of commercially available compounds of formula (A) include Acticide DDQ 50, Bardac 2250, 2280 and Maquat 4480E, from Mason Chemical Company, USA.

Examples of quaternary ammonium compounds of formula (B) include benzethonium chloride, benzyldimethyl-n-tetradecyl-ammonium chloride, benzyldimethyl-n-dodecyl- ammonium chloride, benzyl-C₁₂-C₁₆-alkyl-dimethyl-ammonium chloride, or benzyl-cocoalkyl- dimethyl-ammonium chloride, Ν,Ν-benzyldimethyloctylammonium chloride, N,N- benzyldimethyldecylammonium chloride, N-dodecyl-N-benzyl-N,N-dimethylammonium chloride, N-tetradecyl-N-benzyl-N,N-dimethylammonium chloride, N-hexadecyl-N,N-dimethyl- N-benzylammonium chloride, Ν,Ν-dimethyl N-benzyl N-octadecyl ammonium chloride and mixtures thereof. Commercially available benzalkonium chloride often contains a mixture of compounds with different alkyl chain lengths. Examples of commercially available benzalkonium chlorides that may be used in the present invention are shown in the following Table. It will be appreciated that other commercially available benzalkonium compounds may alternatively or additionally be used.

It will be appreciated that a single CAS number often refers to more than one blend or mixture. A CAS classification for a commercial preparation typically covers blends comprising specified compounds in amounts within defined ranges. The compositions having the CAS numbers quoted above are only examples of compositions having a given CAS number that may be used in the present invention.

An example of component (I) is a mixture consisting of (a) octyl decyl dimethyl ammonium chloride or didecyl dimethyl ammonium chloride or dioctyl dimethyl ammonium chloride, and (b) alkyl (C₁₄, 50%; Ci₂, 40%, C₁₆, 10%) dimethyl benzyl ammonium chloride wherein the weight ratio of (a) to (b) is from 1 : 10 to 10: 1 In component (I) the ratio of the compound of formula (A) to the compound of formula (B) is from 10:1 to 1:10 by weight, preferably from 1 :5 to 5:1, for example from about 0.4:1 to about 4: 1 , about 1:1, about 2: 1 or about 3:2 by weight. The antimicrobial component (i) comprises an additional anti-microbial component (II) that does not comprise a quaternary ammonium compound. Any suitable additional antimicrobial agent(s) may be used, such as those described in the EPA (United States Environmental Protection Agency) Listing and Annex I of the EC Biocides Directive. Preferably, the additional antimicrobial agent(s) are water soluble at room temperature and pressure.

Examples of antimicrobial agents that may be used in component (II) include polymeric biguanidines (e.g. polyhexamethylene biguanidine (PHMB)), and non-polymeric biguanides, silver, octenidine HCI, amphoteric compounds, iodophores, phenolic compounds, amine antimicrobial agents and nitrogen based heterocyclic compounds.

In one aspect of the invention the anti-microbial composition does not comprise any isothiazalones and/or any nitrobromopropanes such as bronopol. In other words, in this aspect, component (II) does not comprise these ingredients.

In one aspect component (II) includes at least one polymeric biguanidine, such as polyhexamethylene biguanidine (PHMB). PHMB is commercially available from Arch Biocides as Vantocil.

In one aspect, the additional antimicrobial agent is not an inorganic material such as silver.

In one aspect, if component (II) comprises a polymeric biguanidine such as PHMB the composition of the invention does not comprise a nitrobromopropane, for example the composition does not comprise bronopol.

If component (II) comprises a nitrobromopropane such as bronopol the composition of the invention may optionally be free of a polymeric biguanidine such as PHMB.

Other antimicrobial agents that may be used as component (II) include, but are not limited, to alkyl betaines, alkyl amine oxides, amine anti-microbial agents, arginine-based cationic surfactants, anionic amino acid based surfactants and mixtures thereof, for example a mixture of alkyl betaine(s) and alkyl amine oxides.

An example of amine anti-microbial agents that may be used in the compositions of the invention is a compound of formula (C)

(CH₂)₃- NH₂

R - N

(CH₂)₃- NH₂

where R is an unsubstituted C₈ to C ₈ alkyl group. Preferably R is from 10 to 14, for example 12. A preferred compound of formula (C) is

This compound is dodecyl dipropylene triamine or N,N-bis(3-aminopropyl)-dodecylamine and has CAS no. 2372-82-9 and is commercially available from Lonzabac as Lonzabac 12, it is also known as Triameen YD12 (available from Akzo Nobel).

In one aspect, the compositions of the invention do not comprise PH B or they may be free of polymeric biguanides or they may be free of biguanidines or free of biguanidines (eg free of polymeric and non-polymeric biguanides).

In one particular aspect, compositions of the invention that comprise a compound of formula (C), for example N,N-bis(3-aminopropyl)-dodecylamine do not comprise PHMB or are free of polymeric biguanidines or free of biguanidines (e.g. free of polymeric and non-polymer biguanidines). However, compositions that comprise a compound of formula (C), for example N,N-bis(3-aminopropyl)-dodecylamine and a biguanidine, such as a polymeric or non-polymer biguanidines, for example PHMB are also envisaged. An example of component (i) is a quaternary ammonium component (I) as described above and at least one polymeric biguanide such as PHMB, which may be the only additional antimicrobial component (II) or the component (II) may contain a further anti-microbial ingredient.

An example of component (i) is a quaternary ammonium component (I) as described above and at least one compound of formula (C), such as N,N-bis(3-aminopropyl)-dodecylamine.

In one aspect, component (i) does not comprise isothiazole. In this aspect, the compositions of the invention are free of isothiazole.

The amount of component (i) in the compositions of in the present invention will vary depending on a number of factors, such as the intended use of composition and the particular compound(s) used as component (i).

The siloxanes used in the present invention are selected from those having formulae (H₃C)[SiO(CH3)2]nSi(CH₃)3, and (H₃C)[SiO(CH₃)H]_nSi(CH3)_3> and mixtures thereof, where n is an integer, of from 1 to 10, more preferably from 1 to 6 and most preferably from 1 to 4, for example n may be 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, especially 1 , 2, 3 or 4. These materials are often referred to as (poly)dimethylsiloxanes (CAS # 9016-00-6) and (poly)methylhydrosiloxanes respectively. These materials are typically liquid at ambient temperature and pressure (e.g. about 20°C at atmospheric pressure). Commercially available siloxanes that may be used in the present invention include those available from Xiameter under the trade names PMX 200 and PMX-1184.

These siloxanes typically have a molecular weight of from about 200 to about 950 g/mol, preferably from about 220 to about 905 (such as from about 222 to about 902 or about 236 to about 762), more preferably from about 220 to about 610 (e.g. from about 222 to about 606 or about 236 to about 522).

Examples of preferred (poly)dimethylsiloxanes are hexamethyldisiloxane (CAS # 107-46-0), octamethyltrisiloxane (CAS # 107-51-7), decamethyltetrasiloxane (CAS # 141-62-8), dodecamethylpentasiloxane (CAS # 141-63-9). These (poly)dimethylsiloxanes correspond to the compounds of formula (H₃C)[SiO(CH₃)2]nSi(CH₃)₃, wherein n = 1, 2, 3 and 4 respectively.

The siloxanes typically have a viscosity of from 0.1 to 5 centistokes, preferably from 0.8 to 4 centistokes at 20°C. Preferred siloxanes have a viscosity of from 0.65 to 3 centistokes at 20°C, e.g. 0.65, 1 , 1.5, 2, 3, 4 or 5 centistokes.

The siloxane component (ii) is generally also strongly hydrophobic. By this we include the meaning that it is repelled from a mass of water and by itself is substantially insoluble in water. By the term "substantially insoluble in water", we mean that the material typically has a solubility of less than 2g/100g water at 20°C and atmospheric pressure, such as less than 1g/100g water, preferably, less than 0.5g/100g water, for example less than 0.1g/100g water, e.g. less than 0.01g/100g water.

The materials described above as suitable for use as component (ii) may be used alone or in combination. In particular, mixtures of siloxanes and/or polysiloxanes of different molecular weight may be used. Many commercially available siloxanes/polysiloxanes are provided as mixtures and these can be used without the need to separate the components of the mixture. Details of commercially available siloxanes which are suitable for use in the compositions of the invention are set out, for example, at http://www.clearcoproducts.com/standard pure silicones.html.

For example a mixture of two, three, four, five or more siloxanes may be used. If a combination of siloxanes is used the materials may be used in equal or differing amounts. For example each siloxane may be used in equimolar amounts or the amount by weight of each siloxane may be the same. Other suitable ratios (in terms of molar amounts or by weight of the total amount of siloxanes) when a mixture of two siloxanes are used range from 0.1 :99.9 to 99.9:0.1, preferably from 1:99 to 99:1, more preferably from 95:5 to 5:95, for example from 10:90 to 90:10 or from 25:75 to 75:25. For example, if a combination of hexamethyldisiloxane and octamethyltrisiloxane is used any ratio described above may be used. One particular combination comprises hexamethyldisiloxane: octamethyltrisiloxane in a ratio of 95:5.

A mixture of two or more siloxanes or polysiloxanes can be used. The use of the combination of hexamethyldisiloxane and octamethyltrisiloxane is preferred as is the use of a shorter chain siloxane such as one or both of these materials together with one or more of polysiloxanes of higher molecular weight described above.

The anti-microbial compositions used in the invention comprise a polar solvent, component (iii). Suitable polar solvents include, but are not limited to, water, alcohols, glycol ethers and mixtures thereof.

Suitable alcohols include, but are not limited to, straight or branched chain d to C₅ alcohols, such as methanol, ethanol, n-propanol, iso-propanol, mixtures of propanol isomers, n- butanol, sec-butanol, tert-butanol, iso-butanol, mixtures of butanol isomers 2-methyl-1- butanol, n-pentanol, mixtures of pentanol isomers and amyl alcohol (mixture of isomers), and mixtures thereof. Preferred polar solvents for use in the anti-microbial compositions include, but are not limited to, water, ethanol, n-propanol, isopropanol, ethylene glycol ethers, propylene glycol ethers, butyl diglycol (BDG) and dipropylene glycol methyl ether (Trade name Dowanol DPM) and mixtures thereof. In one aspect, the composition comprises water or a mixture of water and one or more alcohols selected from the alcohols described above. In such mixtures, water is preferably the major component. The polar solvent may consist essentially of water or consist of water. If the compositions of the invention comprise an alcohol, the alcohol is typically present in an amount lower than the amount necessary for the alcohol to provide an antimicrobial effect.

In one aspect, the compositions of the invention are substantially free of alcohol. For example, the compositions may contain 1% or less by weight alcohol. For example, the compositions may contain less than 1% or less than 0.5% by weight or 0.1% by weight or less of an alcohol such as isopropanol. As an example, compositions of the invention may comprise no isopropanol or may comprise no alcohol.

The anti-microbial compositions may contain components in addition to components (i), (ii), (iii) and (iv) set out above.

The compositions of the invention may optionally comprise one or more of ethylene glycol, propylene glycol, 1,3-butylene glycol, 1 ,4-butylene glycol, hexylene glycol, butyl diglycol, diethylene glycol, triethylene glycol and dipropylene glycol, and mixtures thereof, particularly one or more of diethylene glycol and/or dipropylene glycol. In this invention, these ingredients are not considered to be polar solvents.

The anti-microbial compositions of the invention are typically made by a process which comprises the steps of (I) mixing component (i) and component (ii); (II) adding the polar solvent to the mixture formed in step (I); and (III) agitating the resulting mixture until a clear solution is formed.

If one of the compounds in component (i) is a solid, step (I) can be carried out in sufficient polar solvent to dissolve component (i). Alternatively, some materials which may be used a component (i) are commercially available in solution. In this case, these materials can be used in step (I) in their commercially available form. Typically, the mixture used in step (I) comprises from about 1 to about 25% by weight of a polar solvent, more preferably from about 2 to about 8% by weight polar solvent. The person of ordinary skill in the art could readily determine an appropriate amount of solvent to use. If too much solvent is used the initial cloudy solution will not become clear. The polar solvent typically use in step (I) is water, although other polar solvents may be used alternatively or additionally.

The one or more additional antimicrobial agents (iv) may be introduced in step (I) or they may be added in step (II).

Typically, the process to produce the compositions is carried out at room temperature with stirring. In step (I) the mixture is initially cloudy because the component (ii) is insoluble in the polar solvent.

Typically step (I) is complete when the solution becomes clear.

If an antimicrobial agent that is not soluble in the polar solvent is used, it should be added in step (I).

In step (I) the components may be mixed in any suitable manner. This may be achieved by slow addition of a component (i) to component (ii) or visa versa and then mixing (for example stirring overnight). It would be a routine matter for the person of ordinary skill in the art to determine a suitable rate of addition. The mixing/blending steps can also use techniques ultrasonic mixing/blending.

The compositions may be prepared in a concentration form (i.e. with little or no polar solvent) and diluted with polar solvent (e.g. water) when used. Typically, the ratio by weight of the component (I) to the component (ii) in the anti-microbial compositions ranges from about 100:1 to 5.1, preferably from about 90:1 to about 8:1, more preferably from about 80:1 to about 15:1, still more preferably from about 50:1 or about 40:1 to about 20:1, for example about 20:1 to about 40:1 , such as about 20:1 or about 27:1 or about 29:1 or about 38:1. The ratio by weight of the component (I) to the additional anti-microbial agent (II) is typically from about 1:10 or about 1 :2 or about 1:1 to about 50:1, or to about 30:1, for example, from about 1:1 or about 2:1 or about 3:1 to about 20:1 or about 10:1 or about 6:1 or from about 0.4:1 to about 4:1, such as about 0.55:1 to about 3.16:1, for example about 1:1, or about 2:1, or about 2.75: 1 or about 3.17:1

In a typical composition, the total weight ratio of (I) and (II) to the component (ii) is from about 5:1 to about 100:1, for example from about 10:1 to about 60:1, e.g. about 50:1 or about 40:1. Typically, component (I) is present in an amount of from about 0.01 to about 50 % by weight of the composition, such as from about 0.02 to about 40 %, for example from about 0.05 to about 30 %, preferably from about 0.1 to about 20 % (e.g. from 0.2 to 15 % or 0.5 to 10 %).

Typically, component (ii) is present in an amount of from about 0.001 to about 10 % by weight of the composition, such as from about 0.002 to about 5 %, for example from about 0.003 to about 2 %, preferably from about 0.005 to about 1 % (e.g. from 0.008 to 0.8 % or 0.1 to 0.5 %). The amount of component (ii) will vary depending on a number of factors such as the viscosity and/or volatility of the compound used. Typically, the polar solvent component (iii) is present in an amount of from about 10 to about 99.999 % by weight of the composition, such as from about 50 to about 99.999 %, for example from about 80 to about 99.99 %, preferably from about 90 to about 99.9 %, more preferably from about 95 to about 99.8 % (e.g. from 97 to 99.7 % or 97.5 to 99.6 %). Typically, the additional anti-microbial agent(s), such as PHMB, is present in the compositions in an amount of from about 0.001 to about 10 % by weight of the compositions, such as from about 0.005 to about 5 %, for example from about 0.01 to about 2 %, preferably from about 0.05 to about 1 % (e.g. from 0.1 to 0.5 %). Examples of compositions of the invention include:

Composition 1

A composition comprising:

(i) (I) (C ₀H₂i)₂(CH₃)₂N⁺C and a benzalkonium chloride in a ratio in terms of the weight from about 1:1 to about 3:1, for example about 3:2 and (II) PHMB in an amount such that the ratio of component (I) to PHMB in terms of weight is from about 1 :3 to 3:1, for example about 1:1;

(ii) a siloxane such a hexamethyldisiloxane or dodecamethylpentasiloxane;

(iii) water;

(iv) a non-ionic surfactant such as a C_8-10 alkyl glucoside or an alcohol ethoxylate, such as a Cg.₁₁ alcohol ethoxylate;

wherein the ratio of (iv) to (i) in terms of ppm is no more than 20:1 , such as from 1 :1 to 10:1.

Composition 2

A composition comprising:

(i) (I) (C₁₀H₂i)₂(CH₃)₂N⁺C and a benzalkonium chloride in a ratio in terms weight from about 1 :1 to about 3:1, for example about 1.5:1 , eg 1.53:1 and (II) PHMB in an amount such that the ratio of component (I) to PHMB in terms of the number of molecules is about 1:1 to about 5: 1 , for example about 3: 1 , eg 3.17: 1 ;

(ii) a siloxane such a hexamethyldisiloxane or dodecamethylpentasiloxane;

(iii) water;

(iv) a non-ionic surfactant such as a C_8-io alkyl glucoside or an alcohol ethoxylate, such as a C_9-1 alcohol ethoxylate;

wherein the ratio of (iv) to (i) in terms of ppm is no more than 20:1, such as from 1 :1 to 10:1.

Composition 3

A composition comprising:

(i) (I) (C₁₀H₂i)₂(CH₃)₂ ⁺Cr and a benzalkonium chloride in a ratio in terms weight from about 1:1 to about 8:1, for example about 4:1, and (II) PHMB in an amount such that the ratio of component (I) to PHMB in terms of weight from about 1 :1 to about 3:1, for example about 2:1;

(ii) a siloxane such a hexamethyldisiloxane or dodecamethylpentasiloxane;

(iii) water;

(iv) a non-ionic surfactant such as a C₈.io alkyl glucoside or an alcohol ethoxylate, such as a Cg-n alcohol ethoxylate;

Composition 4

A composition comprising:

(i) (I) (C ₀H₂₁)₂(CH₃)₂N⁺C and a benzalkonium chloride in a ratio in terms of weight from about 1 :1 to about 8:1 , for example about 4:1, and (II) PHMB in an amount such that the ratio of component (i) to PHMB in terms of weight is from about 1:1 to about 4:1 , for example about 2:1 or about 3:1 , eg about 2.75:1;

(ii) a siloxane such as hexamethyldisiloxane or dodecamethylpentasiloxane;

(iii) water;

(iv) a non-ionic surfactant such as a C_8-i₀ alkyl glucoside or an alcohol ethoxylate, such as a C_9-ii alcohol ethoxylate;

Composition 5

A composition comprising:

(i) (I) at least one compound of formula A and at least one compound of formula B, for example (C₁₀H2i)2(CH3)₂N⁺c and benzalkonium chloride in a ratio as stated above for any one of compositions 1,2,3 or 4, and at least one compound of formula (C), such as N,N- bis(3-aminopropyl)-dodecylamine;

(ii) a siloxane as defined herein such as hexamethyldisiloxane or dodecamethyl pentasiloxane;

(iii) water;

(iv) a non-ionic surfactant such as a C₈-C₁₀ alkyl glucoside or an alcohol ethoxylate, such as a C9.11 alcohol ethoxylate and/or a cationic surfactant;

wherein the ratio of (iv) to (i) in terms of ppm is no more than 20: 1 , such as from 1 : 1 to 10: 1.

In composition 5, the ratio by weight of component (I) (total weight of the compound of formula A and the compound of formula B) to the compound of formula (C) is preferably from 1:1 to 10:1, for example about 4:1. In one aspect, the ratio of component (i) to N,N-bis(3- aminopropyl)-dodecylamine is from 1 : 1 to 10: 1 , for example about 4: 1.

In these compositions the ratio of component (ii) to the total amount of anti-microbial agents is preferably about 1:40 or 1:50 by weight. These compositions may optionally comprise butyl diglycol. These compositions may optionally comprise one or more additional ingredients, for example one or more of a fragrance, a builder (for example a carbonate, a bicarbonate or citric acid), and/or a chelating agent such as EDTA. The compositions of the invention may comprise compatible ingredients which are commonly used in the art in compositions for a particular purpose. For example, ingredients that are commonly used in a washing up liquid could be used in combination with the essential ingredients of the compositions of the invention to provide a composition that has the necessary cleaning properties together with anti-microbial properties. When the compositions of the invention contain ingredients, which make the composition suitable for a particular purpose, such as ingredients that are standard in the art for detergent compositions such as washing up liquid or personal care compositions, the compositions of the invention can be made by introducing an amount of an anti-microbial composition as described above into a pre-prepared initial formulation. For example, an anti-microbial composition could be introduced into a suitable commercially available detergent composition.

Alternatively, an anti-microbial composition of the invention may be incorporated into a formulation by addition during one of the steps in the process for making the formulation or a method in which an initial composition according to the invention is not formed before mixing with other ingredients.

Without wishing to be bound by theory, the inventors have found that there are very significant advantages associated with the compositions of the invention.

In use, the compositions of the invention act to substantially reduce or control the formation of microbial colonies on or at the surface to which they are applied. This means that not only do the compositions of the invention kill any microorganisms that are present on a surface when they are applied to that surface (so called "wet kill"), they also have a residual effect in that they prevent the formation of new microbial colonies at the surface (so called "dry kill").

The compositions of the invention are also resistant to washing with water and to wiping. This means that the compositions of the invention provide a residual anti-microbial effect even when the surface which has been treated is subsequently wiped and/or washed or rinsed with water.

The compositions of the invention provide a residual antimicrobial effect and provide an antimicrobial effect even after being subjected to the residual efficacy test described herein. That is, these compositions provide a reduction in microorganisms when subjected to a three wear cycle test on a non-porous stainless steel, glass or plastics substrate and typically provide a 3 log or greater reduction over a 24 hour period. By this we mean that 24 hours after application of the composition of the invention to the surface, if micro-organisms are applied to that surface (without the further addition of a composition of the invention or another anti-microbial agent) at least a 3 log reduction in those micro-organisms will be achieved.

The present invention provides a method for providing a residual antimicrobial benefit to a surface such as a hard surface or skin, which method comprises applying a composition as defined herein to that surface. The composition may be applied to the surface by spraying the composition on the surface or wiping the composition onto the surface. In one method of the invention, it is not necessary for the method to include any steps in addition to simply applying the composition to the surface. Thus, a method that consists essentially of or consists of applying the composition to the surface is provided.

It will be appreciated that in order to also provide cleaning it may also be necessary to wipe or scrub the surface. Thus, the invention also provides a method in which the surface is wiped or scrubbed when the composition of the invention is applied to the surface.

The compositions of the invention can be used in the form in which they are provided or can be diluted with water before use. Thus, the invention also provides a method, such as a method as defined above, in which a composition of the invention is diluted before use.

An advantage of the invention is that it is possible to prevent a broad range of microorganisms from adhering and attaching to the surface, and, therefore, from forming a biofilm. Large numerous colonies are also substantially prevented from forming. Thus, the ability of the colony to grow is substantially reduced or even prevented. The invention is therefore general in its control of microorganisms.

Typically, the compositions of the invention do not need to contain materials that are highly toxic to mammals. The anti-microbial agents used in the anti-microbial compositions are typically well known and widely understood and tested anti-microbial agents. The efficacy of the known anti-microbial agents is amplified in the formulations of the invention. Therefore, anti-microbial agents that have a low toxicity can be used in the anti-microbial compositions. In contrast, many "new" anti-microbial agents for known techniques of sanitization use "stronger", more toxic and/or little tested materials. The anti-microbial compositions of the invention do not contain materials that produce highly persistent residues or rinsates or products that contain heavy metals and their salts. Thus, there is a greatly reduced risk of long term hazards. The anti-microbial compositions of the invention do not interfere with the biochemical reproductive pathways of the micro-organisms they control. The risk of resistance build up and the development of resistant strains is, therefore, low.

The anti-microbial compositions of the invention can have a duel effect in that not only do they provide an anti-microbial effect in use but they can also have a preservative effect on the composition. This means that it is typically not necessary to include additional preservatives in the formulations of the invention.

The compositions of the invention do not typically give surfaces to which they are applied a greasy feel.

The anti-microbial compositions of the invention can provide a very good hand feel, which is important in formulations for personal care and hand sanitizing. Products for use on the skin can provide anti-fungal, anti-microbial, odour prevention, reduced risk of infection and/or enhanced healing benefits. Hair care products of the invention can be used to prevent/reduce scalp odour. Food sprays can reduce/prevent spoilages of food by preventing microbial build up. The compositions of the invention are particularly suitable for surface treatment applications. For example, compositions of the invention comprising a compound of formula (C) such as N,N-bis(3-aminopropyl)-dodecylamine are particularly suitable for surface treatment applications. According to a further aspect of the invention, there is provided the use of composition of the invention to control, reduce or prevent the formation of colonies of micro-organisms on a surface at which it is provided.

The compositions of the invention that comprise a compound of formula (C) such as N,N- bis(3-aminopropyl)-dodecylamine are particularly useful for controlling or reducing or preventing the formation of fungi. The anti-microbial compositions of the invention can typically degrade when submersed in water, to provide a rinsate/leachate of low toxicity and which has a short residence time in the environment.

The property of mobility of the product permits materials that are frequently washed or rinsed to be "recharged" with the anti-microbial composition during a routine act of cleaning or maintenance. Typically, the anti-microbial composition is incorporated into a simple conventional detergent solution or added to a "final rinse" during cleaning. The anti-microbial composition will be drawn, due to the presence of its hydrophobic elements, into the surface of the product to be "recharge". The sanitization properties of the formulation are, therefore, restored without the need for re-manufacture or difficult treatment processes.

Any wash off or rinsates containing the anti-microbial composition or formulation diluted by such a re-charging solution and water would quickly dissociate into the biodegradable components as previously discussed. Brief description of the figures:

Figure 1 shows the results of the cleaning test reported in Example 11.

Figure 2 shows the results of the cleaning test reported in Example 12.

The invention will now be illustrated by the following non-limiting Examples. The following ingredients were used in the Examples described below. Residual Efficacy Testing

Aim

Testing was carried out to determine the residual sanitising efficacy of antimicrobial products on non-porous stainless steel surface against certain microorganisms using abrasion steps and microbial challenges (3 log reduction) over a 24 hour period.

Equipment Stainless steel coupons 2cm diameter, grade 304/1.4301 with grade 2B finish.

Tryptone soya agar (TSA)

Sabouraud's agar (SAB)

Tryptone diluent

Bovine albumin

Vortex

Validated neutraliser

Sterile plastic containers > 3cm and < 5cm in diameter

Forceps

50ml centrifuge tube weighted to 200g

Sterile petri dishes

Inoculating loops

70% (v/v) iso-propanol

Balance to at least 2 decimal places

LAF cabinet

Deionised water

Professional care wipes (Wipertec Ltd)

Hard water Method

Preparation of steel coupons

Steel coupons were rinsed thoroughly with clean water (tap water) to remove any surfactant from the surface then rinsed for a few seconds with freshly deionised water. The cleaned coupons were sterisilised by submerging in 70% (v/v) iso-propanol for 15 minutes. Using sterile forceps the coupons were transferred to sterile Petri dishes and dried by evaporation under laminar air flow by leaving the lid slightly ajar. Three replicates were used for each time point sampled plus a control set.

Abrasive Cycle

A 50ml centrifuge tube was weighted so that it weighed approximately 200g (+/- 20g). A professional care wipe was folded twice (4 layers) and wrapped over the lid of the centrifuge tube ensuring a smooth cover. An abrasive cycle consisted of a wet and dry wipe followed by a bacterial challenge as detailed below. a) Wet Wipe

This constitutes an abrasion with a professional care wipe wrapped over the lid of a 50 ml centrifuge tube. The wipe was dampened by spraying a mist of standard sterile hard water, using a trigger spray (2 sprays, approximately 50 cm distance from the wipe). The tube was wiped in a forward and backward motion across the stainless steel coupon taking 2-3 seconds, allowing all the downward pressure to be provided by the weight of the centrifuge tube on the coupon surface. The wiped discs were then allowed to dry before the dry wipe cycle was carried out. b) Dry Wipe

Mechanism as in the wet wipe cycle however the wipe was not wetted. c) Bacterial challenge

The discs were then subject to a bacterial challenge using either a 10⁶ CFU/ml (intermediate time/ wear points) or 10⁸ CFU/ml (0 and final wear cycles) concentration of the required bacterial suspension with an interferring substance. (See below for bacterial challenge preparation).

Bacterial Challenge Preparation

A bacterial suspension was prepared fresh from a secondary subculture on TSA. The bacterial suspension was diluted as necessary using tryptone saline, to give a cell concentration of approximately 10⁸ CFU/ml suspension. The concentration of the bacterial suspension was determined by spectrophotometry. The suspension was mixed 1:1 with bovine albumin soluion (0.6%) before use to achive a final concentration of 0.3% bovine albumin solution in the bacterial suspension. The 10⁸ CFU/ml concentration of bacterial suspension was used for the initial and final bacterial challenges in the testing.

For re-innoculations (included in the abrasion steps) the 10⁸ CFU/ml suspension was further diluted to 10⁶ CFU/ ml using tryptone-saline solution. The 10⁶ CFU/ml suspension was mixed 1 :1 with bovine albumin soluion (0.6%) before use to achive a final concentration of 0.3% bovine albumin solution in the bacterial suspension.

Test Method (All testing carried out in triplicate)

1. Time Ohr: 100μΙ of the product being tested or sterile hard water was pipetted onto sterile coupons, ensuring the entire surface was covered by spreading the product with an inoculating loop the coupon was left to dry on a level surface in a biological safety cabinet until completely dry at ambient temperature (21-23°C). 2. A control of 0 abrasive wears was sampled for antibacterial efficacy - 10 μΙ of the bacterial suspension (10⁸ CFU/ml) containing 0.3% bovine albumin was added to the steel disc and after 5 minutes contact time, using sterile tweezers, the disc was placed into a vial containing 10ml neutraliser solution. The vial was shaken briefly to allow mixing, then left to stand for 5 minutes, after which time the vial was vortexed for 30 seconds. Serial dilutions (10^) were then prepared in the neutralisation solution and plated out. Molten TSA was poured into the plates and allowed to set before incubation at 37°C for 48 hours.

3. Abrasion samples.

1 wear - Following the complete desiccation of the 100 μΙ of product (at least 3 hours) the steel coupons were subjected to their first abrasion cycle. This consisted of a wet and dry cycle followed by a bacterial challenge using a 10⁶ CFU/ ml concentration of the bacterial suspension (0.3% bovine albumin concentration). 10 μΙ of the suspension was applied to the centre of the disc and gently spread using a sterile disposable loop. The discs were left to dry in a Petri dish in a safety cabinet. Once dried the lids were replaced and the discs left to stand until the next abrasive cycle was required.

2 wears - exactly as above 3 wears (24 hours). A wet and dry wear cycle was carried out on the discs and the antibacterial efficacy was determined as in the 0 wears samples using the 10⁸ CFU/ml bovine albumin bacterial suspension as follows.

10ul of the 10⁸ CFU/ml bacterial suspension was added to the discs and after 5 minutes contact time, using sterile tweezers, the discs were placed into separate vials containing 10ml neutraliser solution. The vials shaken briefly to allow mixing, then left to stand for 5 minutes, after which time the vials were vortexed for 30 seconds. Serial dilutions (10^" ) were then prepared in the neutralisation solution and plated out. Molten TSA was poured into the plates and allowed to set before incubation at 37°C for 48 hours.

Neutraliser Validation:

A fresh batch of bacterial suspension was prepared (10⁸ CFU/ml) in tryptone-saline solution from a secondary culture on TSA. The suspension was mixed 1:1 with 0.6% bovine albumin solutions to achieve a final concentration of 0.3% bovine albumin solution in the bacterial suspension. For each product under test, 50 μΙ of product was pipette into a sterile container with 10 ml of neutraliser and gently mixed, left for 5 minutes. After the neutralisation the disc was inoculated with 10 μΙ of 108 CFU/ml of the antimicrobial test suspension and transferred to a vial and mixed well, the vial was allowed to stand for 5 minutes and vortexed for 30 seconds. Serial dilutions (10^" ) were prepared in the neutraliser solution and plated out. Molten TSA (Tryptic Soy Agar) was poured into the plate and allowed to set before being incubated at 37°C for 48 hours. TVC's (total viable counts of the bacteria grown in the agar) were obtained from the products and compared with the hard water controls. Compositions Used in Examples

BAC is benzalkonium chloride

DDAC is dodecyl dimethyl ammonium chloride

PHMB is poly hexamethylene biguanide Example 1 - Comparison of the Residual Efficacy of a single Quaternary Ammonium Compound (Benzalkonium Chloride) and the G32 Composition of the Invention (No surfactant)

An experiment was carried out to show the synergistic effect of using an antimicrobial combination as defined herein in comparison to using a single antimicrobial agent . No surfactant was included in the formulations at this stage as the objective was show the difference between the actives only and no assessment was made on their cleaning performance.

A residual efficacy test using P. aeruginosa was carried out in accordance with the method described herein. The results of this test are shown in the following table

* Log challenge 4.54 cfu/ml The results show that the formulation comprising an antimicrobial component as used in the compositions of the invention have residual efficacy against P. aeruginosa and superior performance compared to a composition comprising a single quaternary ammonium compound, highlighting the synergistic effect of the ingredients of the antimicrobial component (i).

Formulation Experimental: Preparation of 1 kg of G32N100 - (100,000 ppm)

In a suitably sized vessel DDAC (Lonzabac 2240) (75g) was added and stirred followed by the addition of Silicone (PMX 200) (2.5g), the mixture was left to stir for at least an hour (the mixture was cloudy at first but became clear after 10 minutes). The mixture was left to stand overnight. Water was added to the DDAC / Silicone mixture whilst stirring. The following ingredients were added, BAC (Acticide BAC50) (40g) and PHMB (Vantocil TG) (250g) and stirring was continued for 30 minutes until everything had dissolved. A subsequent dilution of G32 to 5000 ppm was made using deionised water.

Example 2: Comparison of the Residual Efficacy of Quaternary Ammonium Compound Mixtures and those containing the additional antimicrobial agent (PHMB or N,N-bis(3- aminopropyl)-dodecylamine)

As in Example 1 , no surfactant was included in the formulations tested as the purpose of the experiments was to illustrate the advantages of using the combination of antimicrobials used in the invention.

A residual efficacy test using Pseudomonas aeruginosa was carried out in accordance with the method described herein. The results of this test are shown in the following Table.

Residual Testing vs Pseudomonas 3 wears

• Log challenge 6.96 cfu/ml

• TNTC = Too numerous to count The results show that the composition comprising a mixture of quaternary ammonium compounds alone did not show acceptable residual performance, but the addition of either PHMB or Triameen was able to deliver the required at least 3 log reduction. Formulation Experimental Formulations TJM003/11A and TJM003/13B were made as in Example 1 using the indicated ppm levels of biocides.

TJ 003/13C - In a suitable sized vessel Deionised Water (96.67g) was added, followed by the addition of Lonzabac 1230 (Lonza) (3.33g), the mixture was then stirred on a magnetic stirrer for 30 minutes.

TJM003/13A - In a suitable sized vessel Acticide DDQ40 (Thor) (98.52g) was added, followed by the addition of Silicone (PMX200 - Xiameter) (1.48g) the mixture was then stirred for an hour on a magnetic stirrer. The solution was left to stand overnight and stirred before use to give solution (1).

In a separate vessel Deionised Water (98.0g) was added, followed by the addition of Acticide BAC50M (Thor) (2.0g), the mixture was then stirred on a magnetic stirrer for 30 minutes to give solution (2).

In suitably sized vessel Deionised Water (95.80g) was added, followed by the addition of solution (1) (0.2g), the mixture was then stirred on a magnetic stirrer for 15 minutes. Solution (2) (2.0g) was then added and stirred for a further 15 minutes and finally TJM003/13C (2.0g) was then added and stirred for a further 15 minutes to give TJM003/13A.

Example 3: Comparison of the Antimicrobial Efficacy of Quaternary Ammonium Compound Mixtures and those containing the additional antimicrobial agents (PHMB or N,N-bis(3-aminopropyl)-dodecylamine)

The testing was carried out as in the British Standard test EN 1276:2009 (bacteria standard: 'Chemical disinfectants and antiseptics— Quantitative suspension test for the evaluation of bactericidal activity of chemical disinfectants and antiseptics used in food, industrial, domestic, and institutional areas— Test method and requirements (phase 2, step 1)'

The results show that the composition comprising a mixture of quaternary ammonium compounds alone did not show acceptable performance against all the standard bacteria in the suspension test, especially against Pseudomonas aeruginosa. The addition of either PHMB or Triamine was able to deliver a 5 log reduction. A 5 log reduction is required to pass the British Standard test EN 1276:2009.

Formulation Experimental

Formulations were prepared as in Examples 1 and 2 using the respective concentrations (ppm) of antimicrobial agents.

Examples 1-to 3 show that the use of either a single or mixed Quaternary Ammonium Salt mixture does not provide the necessary antimicrobial effect but that desirable antimicrobial performance can be obtained if a combination of biocides as defined in the present invention is used. The formulations tested in the following Examples contained a surfactant.

Example 4: Testing for Residual Efficacy of a PHMB and N,N-bis(3-aminopropyl)- dodecylamine formulation containing non-ionic surfactants against S. aureus.

The residual efficacy of the formulations was tested using the residual method described herein. The results of this testing are shown below.

Log challenge 4.67 cfu/ml

These results show that compositions of the invention containing non-ionic surfactants for example alcohol ethoxylates (Neodol 91-8) possess residual efficacy against S. aureus. Testing was also carried out on Pseudomonas aeruginosa as an alternative bacteria and showed similar results.

Formulation Experimental

The formulations were prepared as in Examples 1 and 2 using the respective concentrations (ppm) of antimicrobial agents. The surfactant was added as the final step with a further 15 minutes of stirring. Example 5: Residual Efficacy vs Pseudomonas - Compositions comprising various solvents

An experiment was carried out to show that a variety of different of surfactant could be used with G32 to improve the cleaning performance and still retain the necessary at least 3 log reduction in the residual antimicrobial test disclosed within.

The results obtained in this experiment show that when the ratio of the antimicrobial component (i) to the surfactant component (iv) is about 1:1 the compositions of the invention pass the residual antimicrobial efficacy test described herein. It is accepted by those in the field that different surfactants exhibit different abilities to clean different soils. The results of these experiments which show that long lasting antimicrobial performance can be achieved using compositions containing a different types of surfactant was extremely surprising to the inventors. Formulation Experimental

In a suitably sized vessel Deionised Water (97.8g) was added, followed by G32N100 (2.0g), the mixture was left to stir for 15 minutes on a magnetic stirrer. Plurafac D250 (BASF) (0.2g) was then added and the mixture stirred for a further 15 minutes, until a homogenous solution was achieved.

The remaining samples were prepared in the same way using the different non-ionic surfactants as indicated in the table.

Example 6: Residual Efficacy vs Pseudomonas for compositions containing different ratios of antimicrobial component (i) to surfactant component (iv), using the alcohol ethoxylate surfactant sold under the trade name Neodol 91-8

Residual antimicrobial performance was measures as described within.

These results show that compositions comprising components (i) and (iv) in a ratio of 1:20 or less pass the residual efficacy test while compositions containing a higher proportion of surfactant do not. In other words, the addition of a surfactant to a biocidal formulation can have a negative impact on antimicrobial performance. It is therefore important to formulate antimicrobial compositions with the optimal level of surfactant to balance the cleaning capabilities on hard surfaces and skin. The inventors have found that ratio to be less than 1:20 (Antimicrobial component (eg: actives in G32): Surfactant).

Formulation Experimental

RSH009/70A - In a suitably sized vessel Deionised Water (99.3g) was added, followed by G32N100 (0.5g) the mixture was left to stir for 15 minutes on a magnetic stirrer. The Neodol 91-8 (Shell) (0.2g) was then added and the mixture stirred for a further 15 minutes, until a homogenous^'solution was achieved.

The other samples were prepared in the same way using different levels of Neodol 91-8 and water.

Example 7: Residual Efficacy vs Pseudomonas for a composition containing the surfactant APG

Residual analysis on a formulation containing an alternative surfactant was also carried out.

This result shows that when the surfactant is an APG and the ratio of the antimicrobial component (i) to the surfactant is within a range defined herein the composition passes the residual efficacy test.

Formulation Experimental

RSH009/70E - In a suitably sized vessel Deionised Water (99.17g) was added, followed by G32N100 (0.5g) the mixture was left to stir for 15 minutes on a magnetic stirrer. Surfac APG-PC (Surfachem) (0.33g) was then added and the mixture stirred for a further 15 minutes, until a homogenous solution was achieved.

Example 8: Residual efficacy testing for compositions comprising Triamine with and without surfactant

An experiment was carried out to show the residual performance of a Quats and Lonzabac 1230 (Bis-(3-Aminopropyl) Dodecylamine) formulation with the addition of a cationic surfactant. % Cationic Surfactant 0.6%

Lab Code TTG001/46A

Quats (4:1 DDQ: BAC) 1000

Triamine 200

Praepagen HY (Cationic) 6000

pH (Paper) 9-9.5

Ratio (Actives: Surfactant) 1:6

Microbiological results >3.54 (0.17)

The result again shows that if the addition of a surfactant is within the ratio specified then a good residual antimicrobial performance is achieved.

Formulation Experimental

TTG001/46C - Prepared as TJM003/13A (Example 2) but with the addition of Praepagen HY (Clariant) (1.5g). Example 9: Initial antimicrobial efficacy against S. aureus using compositions containing an amine oxide surfactant

This test was carried out as in the British Standard test EN 13697:2001 (bacteria standard: 'Chemical disinfectants and antiseptics — Quantitative non-porous surface test for the evaluation of bactericidal activity of chemical disinfectants used in food, industrial, domestic, and institutional areas— Test method and requirements without mechanical action (phase 2, step 2)'.

The results show that an amine oxide can be used as a surfactant in the formulations when used within the ratio specified and still maintain a high level of antimicrobial efficacy. A 4 log reduction is required to pass the British Standard test EN 13697:2001.

Formulation Experimental

TTG001/17A - In a suitably sized vessel Deionised Water (95.15g) was added, followed by the addition of G32N100 (3.75g) the mixture was left to stir for 15 minutes on a magnetic stirrer. The Ammonyx LO (Stepan Chemicals) (1.00g) was then added and the mixture stirred for a further 15 minutes, until a homogenous solution was achieved. Sodium Carbonate (Fisher) (0.06g) and Sodium Bicarbonate (Univar) (0.04g) were then added and stirred for a further 15 minutes, to increase the pH to 9-10.

TTG001/17B - In a suitably sized vessel Deionised Water (94.65g) was added, followed by the addition of G32N200 (3.75g) the mixture was left to stir for 15 minutes on a magnetic stirrer. The Ammonyx LO (Stepan Chemicals) (1.50g) was then added and stirred for a further 15 minutes, until a homogenous solution is achieved. Sodium Carbonate (Fisher) (0.06g) and Sodium Bicarbonate (Univar) (0.04g) were then added and stirred for a further 15 minutes, to increase the pH to 9-10.

Example 10 - Modified EN 13697 carried out Human skin for residual analysis

The Examples above show the effect of formulations of the invention on hard surfaces. Formulations on the invention are also suitable for use on skin - for example as hand sanitizers.

A modified residual method similar to that described above was carried out on a human skin model. No abrasions were performed and the residual activity was measured after 8 hours against various bacteria using isopropanol as the control.

Treatment of human skin with B1919 (TJM003/60) in comparison with isopropanol showed microbial effect with a >3.0 mean log reduction up to 8 hours against Escherichia coli, Staphylococcus aureus, Salmonella enterica and Pseudomonas aeruginosa.

The results showed that a G32 formulation containing non-ionic surfactant (2:1) ratio is able to obtain a much higher residual performance than a single biocide (alcohol) on skin. Formulation Experimental

RSH003/87A - In a suitably sized vessel Deionised Water (99.45g) was added, followed by G32N100 (0.3g) the mixture was left to stir for 15 minutes on a magnetic stirrer. Surfac APG- PC (Surfachem) (0.25g) was then added and the mixture stirred for a further 15 minutes, until a homogenous solution was achieved.

Example 11: Cleaning performance (APG)

The compositions tested contained G32 and various levels of an alkyl polyglucoside surfactant.

Samples

1. RSH009/96A 7500 ppm G32

2. RSH009/96B 7500 ppm G32 : 750 APG-PC (10:1)

3. RSH009/96C 7500 ppm G32 : 7500 APG-PC (1:1)

4. RSH009/96D 7500 ppm G32 : 75,000 APG-PC (1 :10)

Experimental Cleaning Test

A white acrylic panel dosed with a simulated bath soil (a combination of calcium carbonate, soap and grease) was loaded onto the Wet Abrasion Scrub Tester with the soiled side facing up. 4 sponges labelled 1-4, were soaked in cold water then squeezed out between 2 tiles. For each product 2 grams of solutions RSH009/96 A-D was dosed onto a sponge, recording which product was on which sponge. The sponges were the loaded into the wet abrasion scrub tester in sponge holders 1-4. 200grams of extra weight was added to each sponge holder. The machine was set to 100 hundred wear cycles, and then started. The number of wares was continued until a total of 600 wares had been completed. The panel was removed from the machine and the level of soil removal assessed on tracks 1-4. (The results of this experiment are shown in Figure 1.) The results show that a small improvement in soil removal is seen with the addition of surfactant to G32 (10:1 ratio) track 2. Track 3 provides good cleaning as does the higher level of surfactant in track 4. Formulation Experimental:

Preparation of 1 kg of G32N200

In a suitably sized vessel DDAC (Acticide DDQ40) (150g) was added and stirred followed by the addition of Silicone (PMX 200) (5.0g) the mixture was left to stir for at least an hour on a magnetic stirrer (the mixture was cloudy at first but became clear after 10 minutes). The mixture was left to stand overnight. Water was added to the DDAC / Silicone mixture whilst stirring. The following ingredients were added, BAC (Acticide BAC50) (80g) and PHMB (Vantocil TG) (500g) and stirring was continued for 30 minutes until everything had dissolved.

Preparation of RSH009/96B

In a suitably sized vessel Deionised Water (96.125g) was added, followed by the addition of G32N200 (3.75g) the mixture was left to stir for 15 minutes, The Surfac APG-PC (Surfachem) (0.125g) was then added and left to stir for a further 15 minutes until a homogenous solution was achieved.

RSH009/96A-D made as preparation RSH009/96B using the following,

Example 12: Cleaning performance (Neodol 91-8)

The compositions tested contained G32 and various levels of an alcohol ethoxylate (Neodol 91-8) surfactant.

Line 1 - 7500 ppm G32 0 Surfactant

Line 2 - 7500 ppm G32 750 ppm Surfactant (Ratio 10:1)

Line 3 - 7500 ppm G32 7500 ppm Surfactant (Ratio 1:1)

(The results of this experiment are shown in Figure 2.)

The results show that compositions comprising 1 :1 G32:Surfactant gave particularly good cleaning performance. As illustrated in the Examples above, this ratio also provides desirable antimicrobial performance. Experimental

The formulation were prepared using the method described in Example 11 and the cleaning testing was carried out using the method described in Example 11, except Neodol 91-8 replaced APG-PC.

Claims

1. An antimicrobial composition comprising:

(a) a component consisting essentially of a single compound of formula (A)

wherein R¹ and R² are each independently a straight chain, unsubstituted and uninterrupted Ca_₁₂ alkyl group and X^" is chloride, bromide, fluoride, iodide sulphonate, carbonate or bicarbonate and

(ii) at least one siloxane selected from those having the formula (H₃C)[SiO(CH₃)₂]_nSi(CH₃)₃₎ and (H₃C)[SiO(CH₃)H]_nSi(CH₃)3 wherein n is an integer of from 1 to 10;

(iii) a polar solvent;

(iv) at least one surfactant;

wherein in terms of parts per million (ppm) the amount of component (iv) is no more than 20 times the amount of component (i); and

2. A composition according to claim 1 , wherein, in terms of ppm, the ratio of component (iv) to component (i) is from 0.1 : 1 to 20: 1 , or from 1 : 1 to 10: 1.

3. A composition according to claim 1 , wherein the surfactant component (iv) comprises at least one non-ionic surfactant and/or at least one amphoteric surfactant.

4. A composition according to any one of the preceding claims, which does not comprise an anionic surfactant.

5. A composition according to any one of the preceding claims, wherein the benzalkonium compound of formula (B) is benzethonium chloride, benzyldimethyl-n- tetradecyl-ammonium chloride, benzyldimethyl-n-dodecyl-ammonium chloride, benzyl-C ₂- C₁₆-alkyl-dimethyl-ammonium chloride, or benzyl-cocoalkyl-dimethyl-ammonium chloride, Ν,Ν-benzyldimethyloctylammonium chloride, Ν,Ν-benzyldimethyldecylammonium chloride, N-dodecyl-N-benzyl-N,N-dimethylammonium chloride, N-tetradecyl-N-benzyl-N,N- dimethylammonium chloride, N-hexadecyl-N,N-dimethyl-N-benzylammonium chloride, N,N- dimethyl N-benzyl N-octadecyl ammonium chloride or a mixture thereof.

6. A composition according to any one of the preceding claims, wherein the compound of formula (A) is di-n-decyldimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride or dioctyl dimethyl ammonium chloride.

7. A composition according any one of the preceding claims, wherein the ratio by weight of component (i) to component (ii) is from about 50:1 to about 20:1.

8. A composition according to any one of the preceding claims wherein the siloxane comprises at least one of hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane and dodecamethyl pentrasiloxane.

9. A composition according to any of the preceding claims, wherein the polar solvent is selected from water, ethanol, n-propanol, isopropanol, diethyiene glycol and dipropylene glycol and mixtures thereof.

10. A composition according to any one of the preceding claims that is substantially free of alcohol.

11. A composition according to any one of the preceding claims, wherein the least one additional anti-microbial agent (II) is selected from polymeric and non-polymeric biguanidines, silver, octenidine HCI, amphoteric compounds, iodophores, phenolic compounds, isothiazalones, nitro bromopropanes, nitrogen based heterocyclic compounds, alkyi betaines, alkyi amine oxides, arginine-based cationic surfactants, anionic amino acid based surfactants and amine anti-microbial agents and mixtures thereof.

12. A composition according to claim 11, wherein the additional anti-microbial agent is polyhexamethylene biguanidine.

13. A composition according to claim 12, which does not comprise a nitrobromopropane.

14. A composition according to claim 11, wherein the additional anti-microbial agent is a compound of formula (C)

^ (CH₂)₃- NH₂

R - N

(CH₂)₃- NH₂

where R is unsubstituted C₈-C₁₈ alkyi.

15. A composition according to claim 14, wherein the compound of formula (C) is N,N- bis(3-aminopropyl)-dodecylamine.

16. A composition according to claim 14 or 15, which additionally comprises polyhexamethylene biguanidine.

17. A composition according to any one of the preceding claims wherein the ratio by weight of the total amount of component (I) to component (II) is from 1:1 to 10:1, such as about 4:1 or 5:1.

18. A composition according to any one of claims 1 to 11 , 14, 15 and 17, which does not comprise a biguanidine compound.

19. A composition according to any one of the preceding claims, wherein the surfactant component (iv) comprises an amine oxide.

20. A composition according to any one of the preceding claims, which is also a cleaning composition.

21. A composition according to any one of the preceding claims that in use provides a residual antimicrobial effect.

22. A composition according to any one of the preceding claims for use on hard surfaces.

23. A composition according to any one of the preceding claims for use on skin.

24. A composition according to any one of the preceding claims which on application to a surface acts to substantially reduce or control the formation of microbial colonies on or at the surface.

25. A method of cleaning a hard surface and providing a residual antimicrobial effect to that hard surface, which method comprises applying a composition according to any one of claims 1 to 22 and 24 to the hard surface.

26. A method of cleaning skin and providing a residual antimicrobial effect to that skin, which method comprises applying a composition according to any one of claims 1 to 21, 23 and 24 to the skin.

27. The use of a composition according to any one of claims 1 to 24 to substantially reduce or control the formation of microbial colonies on or at a surface.

28. A method of substantially reducing or controlling the formation of microbial colonies on or at a surface, which method comprises applying a composition according to any one of claims 1 to 24 to that surface.

29. A method of disrupting, preventing or reducing the adhesion and/or attachment of micro-organisms to a surface, which method comprises applying a composition according to any one of claims 1 to 24 to that surface.

30. The use of claim 27 or the method of claim 25, 26, 28 or 29, which provides a reduction in micro-organisms when subjected to a three wear cycle test on a non-porous stainless steel, glass or plastics substrate produces a 3 log reduction after 24 hours.

31. A composition, use or method generally as herein described.

32. A composition, use or method generally as herein described with reference to the Examples.