WO2014060755A1

WO2014060755A1 - Cleaning, sanitizing and sterilizing preparations

Info

Publication number: WO2014060755A1
Application number: PCT/GB2013/052707
Authority: WO
Inventors: Gregor GSCHWANDTNER; George Victor Garner
Original assignee: Arcis Biotechnology Holdings Limited
Priority date: 2012-10-17
Filing date: 2013-10-16
Publication date: 2014-04-24

Abstract

An antimicrobial cleansing composition comprising an alcohol and at least one cationic microbiocide wherein the composition comprises less than 2 wt% of non-ionic surfactant.

Description

Cleaning, Sanitizing and Sterilizing Preparations

The present invention relates to enhancement and optimization in cleaning, sanitizing and sterilizing surfaces, and more particularly, the present invention relates to antimicrobial compositions formulated for the disinfection and sterilization of materials, commodities and surfaces contaminated with one or more species of micro-organisms including bacteria, fungi, algae, yeasts, bacterial and fungal spores and viruses including both enveloped and non- enveloped viruses. It is now well recognized that many contagious diseases are transmitted through contact with unsanitized surfaces, and that some disease-causing microorganisms are able to survive on some surfaces for up to five weeks. There has been a longstanding need for antimicrobial agents having improved antimicrobial efficacy and improved speed of action. The specific requirements for such agents vary according to the intended application (e.g., sanitizer, disinfectant, sterilant, etc.) and the applicable public health requirements.

Human health is impacted by a variety of microbial organisms. As such, there has been a thrust by the medical community to persuade the general public to wash any areas which generally come in contact with infected surfaces like body parts (e.g. hand washing), foods (e.g., uncooked meat, vegetables, fruits, etc.), cooking utensils, cooking surfaces (e.g., counter tops, sinks, etc.), medical equipment (e.g..tables, instruments, and other surfaces in medical facilities), surfaces accessible to children in daycare facilities (e.g., toys, bathroom facilities), etc. It has been found that such methods are important in attempts to remove pathogenic microorganisms from human skin as well as other contacting surfaces.

The types of microorganisms which can be found to be available for contact with humans include viruses, bacteria, and fungi. With regard to bacteria, there are two types, those being, resident and transient bacteria. Resident bacteria are usually Gram positive bacteria which are established as permanent microcolonies on the surface and outermost layers of mammalian skin. Such bacteria play an important role in preventing the colonization of other more harmful bacteria and fungi. Transient bacteria, however, are not part of the normal resident flora of the skin but they can be deposited when airborne contaminated material lands on the skin or when contaminated material is brought into physical contact with it. Transient bacteria are typically divided into two subclasses: Gram positive and Gram negative. Gram positive bacteria include pathogens such as Staphylococcus aureus, Streptococcus pyogenes and Clostridium botulinum. Gram negative bacteria include pathogens such as, Salmonella, Escherichia coli, Klebsiella, Haemophilus, Pseudomonas aeruginosa, Proteus and Shigella dysenteriae. As with bacteria, the types of viruses that can infect humans and other mammals are innumerable. Viruses can be divided into enveloped and non-enveloped types. Enveloped viruses include an outer lipophilic envelope surrounding the capsid. When a virus is lacking the outer envelope, they are referred to as "non-enveloped viruses."

Enveloped viruses include influenza, smallpox and Human Immunodeficiency Virus (HIV). Non-enveloped viruses can persist in the environment for long periods of time and are therefore more contagious and harder to eradicate. In general, virologists agree that non- enveloped type viruses, such as, rhinoviruses, influenza viruses, and adenoviruses are very difficult to inactivate and likely to be the most relevant viruses that cause respiratory diseases. It is believed that rhinoviruses, in particular, are responsible for acting as the primary cause for the common cold. Rhinoviruses are members of the picornavirus family. Other examples of nonenveloped viruses include norovirus, rotavirus and human papillomavirus (HPV), feline calicivirus (FCV), and murine norovirus 1 (MNV-1).

Sterilization and/or disinfection of microorganisms, such as viruses, fungi and bacteria can be achieved physically, chemically and biochemically. Physical sterilization and/or disinfection schemes include heating, drying, freezing, ionizing irradiation and filtration, etc. These physical sterilization and/or disinfection schemes are relatively constrained in terms of factors such as characteristics of environments in which to perform such processing. Chemical and biochemical sterilization and/or disinfection schemes are thus more practically applicable for control of microorganisms.

Materials and substances generally used as chemical sterilants and/or disinfectants include acids, alkalis, alcohols, aldehydes, surfactants, halogens, heavy metals, etc. to achieve microorganism disinfection. Combinations of chemicals have been found to be particularly effective as they have been observed to lead to enhanced microbiocidal action especially in cleaning preparations; some prior art provides several cleaning compositions as follows:

Baugh et al., (U.S. Patent No.: 6,656,919) describes a microbiocidal solution that can range from a simple solution of a single component such as aqueous formaldehyde to complex mixtures of microbiocides and various adjuncts including microbiologically active components such as germination promoters or other inert material that displays surfactant properties. The microbiocidal properties of cationic surfactants such as quaternary ammonium compounds (QAC) and biguanidinium salts are well known and authenticated.

Spooner et al., (WO98/20738) describes microbiological activity which was found to be enhanced when bis(biguanide) microbiocides were combined with polymeric biguanides in contact lens cleaning solutions. Van Buskirk et al., (U.S. Patent No.: 5,856,290) describes the combination of QAC and N- alkylpropylenediamine microbiocides with a mixture of non-ionic surfactants that was observed to lead to a noticeable improvement in microbiocidal efficacy.

Lehman et al., (U.S. Patent No.: 4,920,100) describes bactericidal alcohols and carboxylic acids that were also observed to demonstrate potentiated effects when mixed with certain non- ionic surfactants. Biermann et al., (U.S. Patent No.: 4,748,158) describes potentiation in dental cleaning applications of mixtures of chlorhexidine salts and alkylpolyglucosides.

Toshiyuki et al., JP57009717 describes synergistic germicidal activity in mixtures of chlorhexidine salts or polyhexamethylenebiguanide and polyoxyethylene alkyl ethers in the proportions 1 :1 .

European Patent Application No. EP05252443.6 suggests the formation of a transient intermediate to explain the observed improvement in minimum inhibitory concentration data for chlorhexidine salts when mixed with various non-ionic surfactants, and until that time a mechanism explaining the origin of such improved microbiocidal efficacy had not been defined.

WO 2009/1 17299 described a novel combination of cationic microbiocides with non-ionic surfactants and other co-formulants that demonstrated excellent cleaning properties together with outstanding microbiocidal activity against bacteria and fungi. A crucial element of this strategy was the omission of ingredients that compromised the generation of the most microbiocidally active supramolecular assemblies. Although this combination was effective against enveloped viruses as well as a broad range of bacteria and fungi, it presented little or no action against non-enveloped types. However, all the above discussed compositions fail to provide the most efficient and effective cleaning, sanitizing and sterilizing compositions. Thus, a need exists for antimicrobial compositions that provide not only improved anti-viral, antifungal and/or antibacterial efficacy but also improved residual efficacy. According to the present invention, antimicrobial compositions may be prepared using microbiocides provided that they are mixed in such a way that chemical species that interfere with said preparation are avoided and/or destroyed. In order to achieve an improvement in activity, two themes have been developed: in one, the chaotropic approach, cationic microbiocides are combined to provide optimum generation of the supramolecular assemblies without the inclusion of interfering substances or dilution by the presence of high concentrations of non-ionic surfactants. Changes in solvent medium and pH have also been found to be beneficial. The other approach involves the incorporation of chemical species that could possibly stabilise peroxy species thereby providing additional reactive chemicals to the existing chaotropic affects. These stabilising chemicals may also provide a low-volatility phase similar to polysiloxanes in which the cationic microbiocides can become concentrated.

According to a first aspect of the present invention there is provided an antimicrobial cleansing composition comprising an alcohol and at least one cationic microbiocide wherein the composition comprises less than 2 wt% of non-ionic surfactant.

According to a second aspect of the present invention there is provided a process of reducing microbial populations on a contaminated surface, the process comprising contacting the surface with a composition of the first aspect.

The composition of the first aspect may be provided as a concentrated composition or as a ready to use composition.

The method of the second aspect preferably comprises contacting the surface with a ready to use composition.

Suitably a concentrated composition may be diluted to provide a ready to use (or end use) composition

In one embodiment, the present invention provides an aqueous alkaline antimicrobial cleaning composition comprising an alcohol, at least one cationic microbiocide, and an alkaline base, wherein the composition comprises less than 2 wt% of non-ionic surfactant.

The composition can be in the form of a concentrate or can be diluted to an end use composition.

The composition may be prepared as a ready to use composition

A further aspect of the present invention is the novel, antimicrobial concentrate composition which is capable of being diluted with a major proportion of water or other aqueous based liquid to form a use solution. A still further aspect of the present invention is an aqueous antimicrobial use solution which is particularly suited for "in-place" cleaning applications. Yet another aspect of the present invention is a process of employing the composition of the present invention in the reduction of microbial populations on various contaminated surfaces. Another aspect of the present invention is a method of employing the composition of the present invention in the reduction of microbial populations on various process facilities or equipment as well as other surfaces.

The composition of the first aspect of the present invention preferably comprises less than 1 wt% non-ionic surfactants, preferably less than 0.5 wt% non-ionic surfactants, more preferably less than 0.1 wt% non-ionic surfactants. In some embodiments the composition may comprise less than 0.01 wt% non-ionic surfactants or less than 0.001 wt%. The composition may be free of any non-ionic surfactant.

By non-ionic surfactant we mean to refer to uncharged compounds including a hydrophilic portion and a polar head group. Compounds of this type will be known to the person skilled in the art and include fatty alcohol ethoxylates and polyglycosides.

The cationic microbiocides of the present invention may be selected from among (a) guanidine salts and (b) positive non-metallic salts which include preferably quaternary ammonium salts. The cationic microbiocides are included in an amount from about 5 wt% to about 15 wt%, and more preferably, from about 9 wt% to about 12 wt% in the concentrate versions.

In some embodiments the composition may contain a mixture of cationic microbiocides, for example a guanidine salt and a positive non-metallic salt.

Both guanidine salts and quaternary ammonium salts may be combined in a ratio of 1 :3 to 1 :1 .6, or from about 1 :1 .2 to about 1 : 1 .4.

In one embodiment, the inventive antimicrobial cleaning composition comprises the alcohol in an amount from about 5 wt % to about 50 wt%, and more preferably from about 8 wt% to about 40 wt % in the concentrate versions.

The alcohol may be selected from the group consisting of methanol, ethanol, n-propanol, n- butanol, isopropanol, sec-butanol, tert-butanol and combinations thereof. Preferably, ethanol or isopropanol is used as the alcohol component. Most preferably the alcohol is ethanol.

One aspect of the present invention provides a process of reducing microbial populations on contaminated surfaces including the steps of: selecting a diluted antimicrobial composition prepared from a concentrate comprising about 5% wt% to about 15 wt% and more preferably from about 9 wt% to about 12 wt% of at least one cationic microbiocide and about 10 wt % to about 30 wt%, and more preferably from about 15 wt% to about 25 wt % of a short chain alcohol, wherein the antimicrobial composition comprises less than 2 wt% of a non-ionic surfactant; and contacting the contaminated surface with the composition.

The cationic microbiocides may be selected from (a) guanidine salts or (b) positive non- metallic salts, wherein the positive non-metallic salts may be selected from the group consisting of quaternary ammonium salts, phosphonium salts and sulfonium salts. The guanidine salts may be selected from the group consisting of chlorhexidine digluconate, dihydrochloride and diacetate; hexamethylenebis(ethylhexyl)biguanide dihydrochloride, oxocyclohexadienylideneaminoguanidine thiosemicarbazone, bis(chlorophenylamidino)piperazinedicarboxamidine dihydrochloride, polymeric biguanidinium chloride and polyhexamethylenebiguanidine hydrochloride.

Thus cationic microbiocides of the present invention may be selected from among (a) guanidine salts and (b) positive non-metallic salts, preferably quaternary ammonium salts. The guanidine salts of the present invention may be guanidine salts per se, biguanidinium salts, guanide salts, biguanidine salts or biguanide salts, and all the above are standing for the same molecules.

The guanidine salts of the present invention may be selected from among the following salts, however they are not restricted thereto: chlorhexidine digluconate, dihydrochloride and diacetate; hexamethylenebis(ethylhexyl)biguanide dihydrochloride; oxocyclohexadienylideneaminoguanidine thiosemicarbazone; bis(chlorophenylamidino)piperazinedicarboxamidine dihydrochloride and polyhexamethylenebiguanidine hydrochloride.

The positive non-metallic salts may be selected from among quaternary ammonium salts, phosphonium salts and sulfonium salts. The quaternary ammonium salts of the present invention may be selected from among the following salts, however they are not restricted thereto: quaternary salts containing either or both aliphatic or aromatic moieties; aliphatic groups including alkoxy groups which may contain from one to 30 carbon atoms in linear or branched arrangements; alicyclic groups which may be cyclohexyl and its alkylated and alkoxylated derivatives. The preferred quaternary ammonium salt of the present invention is didecyldimethylammonium chloride. The counter ions of the guanidine and quaternary ammonium salts may be selected from among halides, preferably chloride; bicarbonate, borate, carbonate, fluoborate, fluoride, phosphate, and sulphate. In a preferred embodiment of the present invention, the cationic microbiocides of the present invention consist of a mixture of polymeric biguanidinium chloride or polyhexamethylenebiguanidine hydrochloride and didecyldimethylammonium chloride in the ratio of between 1 :1 and 1 :1 .4. The cationic microbiocide may in some embodiments comprise a quaternary ammonium salt.

The composition of the present invention may optionally further contain a cationic surfactant. In some embodiments the cationic surfactant may be a quaternary ammonium salt. This may suitably be present in addition to a quaternary ammonium salt which is present as a cationic microbiocide.

The cationic surfactant may also have antimicrobial properties.

The cationic surfactant may be selected from the group consisting of an alkylbenzyldimethylammonium chloride, alkyl(C12-16) dimethylbenzyl ammonium chloride, benzylhexyldimethylammonium chloride, benzyloctyldimethylammonium chloride, benzyldecyldimethylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltetradecyldimethylammonium chloride, benzyloctadecyldimethylammonium chloride, and similar species in which the benzyl moiety is replaced by tolyl- and xylyl moieties.

Suitably, the antimicrobial compositions of the present invention may comprise one or more further cationic surfactants such as alkylbenzyldimethylammonium chloride, alkyl(C12- 16)dimethylbenzylammonium chloride and any other cationic surfactants, preferably with an aromatic moiety selected among but not restricted to benzylhexyldimethylammonium chloride, benzyloctyldimethylammonium chloride, benzyldecyldimethylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltetradecyldimethylammonium chloride, benzyloctadecyldimethylammonium chloride, and similar species in which the benzyl moiety is replaced by tolyl- and xylyl- (ie methylbenzyl- and dimethylbenzyl-) moieties. Said cationic surfactant may be used also as a cleaning agent.

The ratio of the total amount of quaternary ammonium compounds to the amount of guandine compounds in the compositions of the present invention is preferably from 1 :1 to 2:1 , for example from 1 .2:1 to 1 .8:1 The antimicrobial solutions of the present invention further comprise one or more solubilizing agents and among these, in particular, an alcohol, wherein the alcohol may be selected from methanol, ethanol, n-propanol, i-propanol or n-, i-, s- or t-butanol. Other components that may be included in the compositions include organic acids, including propanoic acid, glycolic acid, lactic acid; and common salts of Group 1 & 2 metals such as potassium and sodium cations with any of the following anions: halides such as chloride, fluoride, bromide, iodide; phosphate, carbonate, bicarbonate, citrate, lactate, phosphate and sulphate; and combinations thereof.

The composition of the present invention may comprise conventional auxiliary substances for cleaning including fragrances, aromatics, dyestuffs, foam inhibitors, viscosity adjusters and agents for regulating the pH. Such a fragrance material may be any commercial material such as: SAFA 30472 of Parfex S.A., in any desired amount such as 0.1 wt % to 5 wt%. Preferred pH agents include sodium hydroxide and alkanolamines.

Viscosity agents may be used to retain components dispersed in the composition. Examples of suitable agents include silicas, vegetable gums such as xanthans, polymeric gelling agents such as polymers containing carboxyl groups.

In some preferred embodiments the composition of the present invention comprises a base. Preferred bases include alkali metal hydroxides. Most preferred are sodium hydroxide and potassium hydroxide. Sodium hydroxide is especially preferred. In some preferred embodiments the composition of the present invention comprises a halide salt, especially a fluoride salt. Preferred are alkali metal halide salts. One especially preferred salt is sodium fluoride.

In one embodiment the present invention provides a concentrated cleaning composition comprising:

- from 5 to 50 wt%, preferably from 15 to 25 wt% of an alcohol, preferably ethanol;

- from 1 to 20 wt%, preferably from 2 to 10 wt% of a guanidine salt, preferably polyhexamethylene biguanidine hydrochloride;

- from 1 to 20 wt%, preferably from 2 to 10 wt% of a first quaternary ammonium salt, preferably didecyldimethyl ammonium chloride;

- from 0.1 to 10 wt%, preferably from 0.5 to 2.5 wt% of a second quaternary ammonium salt, preferably an alkylbenzyl dimethyl ammonium chloride; - from 0.0001 to 1 wt%, preferably from 0.001 to 0.5 wt% of an alkali metal hydroxide, preferably sodium fluoride;

- from 0.01 to 5 wt% of a base, preferably from 0.1 to 1 wt% of an alkali metal hydroxide, preferably sodium hydroxide; and water.

The concentrated composition is suitably diluted with water between 10 and 100 times, preferably between 15 and 40 times, for example between 20 and 30 times to provide a ready to use cleaning composition.

A further aspect of the present invention provides a diluted antimicrobial composition comprising a mixture of cationic microbiocides, cationic surfactant, an alcohol and non-ionic surfactants in an aqueous matrix, and further comprising at least one additional component having a stabilizing effect on the composition including hydrogen peroxide, allylanisole, triethyl citrate, citric acid and triethyl O-acetylcitrate. Notably if hydrogen peroxide is included, citric acid forms a peroxy derivative with the hydrogen peroxide thereby providing a stable peroxy compound due to intramolecular H-bonding with the adjacent carboxyl groups. Stabilization is further enhanced by using an O-acetylcitrate analogue.

Further compositions of the present invention comprise an alcohol, at least one non-ionic surfactant, at least one cationic surfactant, at least one cationic microbiocide, allylanisole, citric acid, sodium fluoride and optionally triethyl citrate. For example, a preferred composition comprises an alcohol in an amount from about 8 wt % to about 40 wt %, at least one non-ionic surfactant in an amount from about 5 wt % to about 10 wt %, at least one cationic microbiocide in an amount from about 5 wt % to about 15 wt %, at least one cationic surfactant in an amount from about 1 wt % to about 8 wt %, triethyl citrate from about 5 wt % to about 10 wt %, allylanisole from about 0.5 wt % to about 2 wt %, citric acid in an amount from about .01 wt % to about 1 wt % and sodium fluoride in an amount from about 0.01 wt % to about 0.1 wt %.

Other antimicrobial compositions of the present invention comprise at least one cationic surfactant, at least one cationic microbiocide, hydrogen peroxide, a stabilizer component for stabilizing the hydrogen peroxide including citric acid, triethyl citrate or triethyl O-acetylcitrate and optionally at least one non-ionic surfactant. For example, a preferred composition comprises at least one cationic microbiocide in an amount from about 1 wt % to about 5 wt %, at least one cationic surfactant in an amount from about 0.5 wt % to about 8 wt %, hydrogen peroxide in an amount from about 0.4 wt % to about 5 wt %, a stabilizer for stabilizing the hydrogen peroxide in an amount from 0.5 wt% to about 10 wt % and optionally at least one non-ionic surfactant in an amount from about 0.5 wt % to about 3 wt %. The non-ionic surfactacts may be selected from the group consisting of primary and secondary alcohol ethoxylates and condensates with oligoglycosides, the alkanol containing about 8 to 18 carbon atoms in either straight chain or branched arrangements condensed with six to ten moles of ethylene oxide or four to six moles of a monosaccharide. For example, the non-ionic surfactants may be an alkylpolyglucoside, an alkylethoxylate; a C₉-C ₀alkyltetraglucoside, a Cg-C alkylhexaethoxylate, or a C_8-11 alcoholethoxylate.

It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a "surfactant" includes two or more such surfactants.

In the application, effective amounts are generally those amounts listed as the ranges or levels of ingredients in the descriptions, which follow hereto. Unless otherwise stated, amounts listed in percentage ("%'s") are in weight percent (based on 100% active) of the cleaning composition.

The antimicrobial cleaning preparations of the present invention may be used for cleaning and/or for sanitizing and/or for sterilizing. The compositions in accordance with the present invention may be used for the disinfection and sterilization of materials, commodities and surfaces contaminated with one or more species of micro-organisms including Gram negative bacteria, Gram positive bacteria, viruses (e.g., rhinoviruses, adenoviruses, rotaviruses, herpes viruses, respiratory syncytial viruses, coronaviruses, parainfluenza viruses, enteroviruses, influenza viruses, etc.), and the like and are also able to provide residual anti-viral and antibacterial effectiveness against such microorganisms. The components of the present invention may be used in sterilizing compositions for killing and rendering spores lifeless and also may affect the necromass so formed in such a way that it becomes easily removable by water rinsing hence reducing the likelihood of biofilm formation.

For clarity's sake it should be noted that when referring to antimicrobial compositions it refers to cleaning, sanitization and sterilization compositions per se or to any other compositions from said group such as disinfecting preparations, compositions for use in hygiene (disinfecting), compositions for use in hygiene (sterilizing), disinfectants, anti-bacterial preparations, antibacterial compositions for medical use, detergents for medical use, detergents for medical use having anti-bacterial properties, disinfectants for hygiene purposes, disinfectants for medical and veterinary use, disinfectants for hygiene purposes or for medical and veterinary use having anti-bacterial properties, Bactericidal preparations, Virucididal preparations, Fungicidal preparations, Tuberculocidal preparations, Sporicidal preparations, Biocides, chemicals having antimicrobial properties (medical or veterinary), cleaning and sanitizing solutions and compositions for medical use, rinse and drying aids for use in medical washing applications, chemicals for use in cleansing, disinfecting and/or decontamination applications in the medical field, medical scrubs (sterilizing or disinfecting, scrubs preparations) for medical use, surface hygiene products, medicated anti-bacterial washes, anti-bacterial cleansers. According to the present invention, the cleaning, sanitizing and sterilizing solutions, as described herein, can be prepared using microbiocides provided that they are mixed in such a way that transient supramolecular assemblies can be formed and that chemical species which interfere with this molecular organisation can be avoided. A preferred embodiment of the present invention comprises an aqueous preparation which may be diluted to form the required strength of the preparation consisting essentially of the following components: ethanol, didecyldimethylammonium chloride, polyhexamethylenebiguanidine HCId, alkylbenzyldimethylammonium chloride, sodium hydroxide and optionally sodium fluoride.

According to a further embodiment, the composition may further comprise one or more activators, which are understood as meaning precursors of peroxycarboxylic acids. Peroxycarboxylic acids have good disinfecting action and may be formed in-situ from the activators and hydrogen peroxide. Thus, adding hydrogen peroxide and an activator provides increased disinfecting actions. Suitable activators include O-acylated activators such as glycerol triacetate, triethyl acetylcitrate, and ethylene glycol diacetate.

In one embodiment the present invention may provide an aqueous cleanining composition comprising a cationic surfactant, a cationic microbiocide, an organic acid and a peroxide compound.

Suitable cationic surfactants are as previously described herein. A preferred cationic surfactant is alkylbenzyl dimethyl ammonium chloride. Suitable cationic microbiocides are as previously described herein. Preferred are guanidine compounds, especially polyhexamethylene biguanidine hydrochloride.

Preferred organic acids include polycaroxylic acids. A preferred organic acid is citric acid.

Suitable peroxide compounds include hydrogen peroxide and alkyl hydroperoxides. A preferred peroxide compound is tert-butyl hydroperoxide. A ready-to-use composition may be provided comprising from 0.1 to 5 wt%, preferably from 0.25 to 2 wt% of a cationic surfactant; from 0.1 to 10 wt%, preferably from 0.5 to 5 wt% of a cationic microbiocide; from 0.01 to 2.5 wt%, preferably from 0.1 to 1 wt% of an organic acid; and from 0.1 to 20 wt%, preferably from 0.5 to 10 wt% of a peroxide compound.

One embodiment of the present invention comprises the following components in an aqueous composition in the following concentration as shown in Table I (in order of decreasing abundance) and expressed as weight per cent: Table I (examples 1 , 2 & 3 as both concentrates'⁰' and diluted preparations ready for use^(d>) (Sa = Sample Composition)

Component from to Sa1^(c) Sa2^(c) Sa3^(d)

Ethanol 1 40 20 20 2

Isopropanol 0 40 0 0 2

Didecyldimethylammonium chloride 0.3 15 4.7 4.7 1

Polyhexamethylenebiguanidine HCId 0.03 9 4.33 4.33 0.5

Alkylbenzyldimethylammonium chloride 0.01 8 1 .55 1 .55 0.5

Sodium hydroxide 0 0.3 0 0.15 0.015

Sodium fluoride 0 0.1 0.012 0.012 0

Total cation ics 1 15 10.58 10.58 2.0

*P/D ratio 1 :1 .1 1 :1 .1 1 :2

*P/D+B ratio 1 :1 .4 1 :1 .4 1 :3 *(P/D ratio = Polyhexamethylenebiguanidine HCId:Didecyldimethylammonium chloride ratio) *(P/D+B ratio = Polyhexamethylenebiguanidine HCId:Didecyldimethylammonium chloride + alkylbenzyldimethylammonium chloride)

A further embodiment of the present invention comprises the following components in an aqueous composition in the following concentration as shown in Table II (in order of decreasing abundance) and expressed as weight per cent:

Table II (examples 4, 5, 6 & 7 as both concentrates'⁰' and diluted preparations ready for use^(d)) (Sa = Sample Composition)

Component from to Sa4^(c) Sa5^(c) Sa6^(c) Sa7^(c)

Ethanol 0 40 0 0 0 40

Isopropanol 0 10 8.25 8.25 8.25 0 Alcoholethoxylate 0.4 10 7 6 6 6

Triethyl citrate 0.5 10 0 0 7 0

Didecyldimethylammonium chloride 0.3 15 4.7 4.7 4.7 4.7

Polyhexamethylenebiguanidine HCId 0.03 9 4.33 4.33 4.33 4.33

Alkylbenzyldimethylammonium chloride 0.01 8 1 .55 1 .55 1 .55 1 .55

Alkylpolyglucoside 0.06 1 0.75 0.75 0.75 0.75

Allylanisole 0.04 2 0.5 2 2 2

Citric acid 0 0.1 0.1 0.1 0.1 0.1

Sodium fluoride 0 0.1 0.012 0.012 0.012 0.012

Total cation ics 1 15 10.58 10.58 10.58 10.58

*P/D ratio 1 :1 .1 1 :1 .1 1 :1 .1 1 :1 .1

*P/D+B ratio 1 :1 .4 1 :1 .4 1 :1 .4 1 :1 .4

*(P/D ratio = Polyhexamethylenebiguanidine HCId:Didecyldimethylammonium chloride ratio) *(P/D+B ratio = Polyhexamethylenebiguanidine HCId:Didecyldimethylammonium chloride + alkylbenzyldimethylammonium chloride)

A still further embodiment of the present invention comprises the following components in an aqueous composition in the following concentrations as shown in Table III (in order of decreasing abundance) and expressed as weight per cent:

Table III (examples 8, 9, 10 & 11 as both concentrates'⁰' and diluted preparations ready for use^(d)) (Sa = Sample Composition)

Component from to Sa8^(d) Sa9^(d) Sa10 [c)_{Sa1 1} (d,

Alcoholethoxylate 0 1 0.5 0 0 0

Triethyl citrate 0 10 0 0 7 0

Triethyl O-acetylcitrate 0 2 0 0 0 1

Polyhexamethylenebiguanidine HCId 0.03 9 2 2.5 4.33 2.5

Alkylbenzyldimethylammonium chloride 0.01 8 1 1 .5 6.25 1 .5

Citric acid 0 2 1 1 0 0

Hydrogen peroxide (as 30% aq) 0.4 5 1 1 .5 4.5 1 .5

Total cation ics 0.8 15 3 4 10.58 4

*P/B ratio 1 :0.5 1 :0.6 1 :1 .4 1 :0.6

*(P/D ratio = Polyhexamethylenebiguanidine HCId:Didecyldimethylammonium chloride ratio)

In yet another embodiment of the present invention, Example 2, Table I, a composition comprises an aqueous concentrated solution having the following components in terms of weight percent: Ethanol in the amount of 20.00, Didecyldimethylammonium chloride in the amount of 4.7; Polyhexamethylenebiguanidine HCId or polymeric biguanidinium chloride in the amount of 4.33; Alkylbenzyldimethylammonium chloride in the amount of 1 .55; Sodium Hydroxide in the amount of 0.150 and Sodium fluoride in the amount of 0.012. The remaining amount is water. The composition is free of a non-ionic surfactant.

In yet another embodiment, the composition comprises an equal amount of both ethanol and isopropanol in combination with sodium fluoride, Didecyldimethylammonium chloride, Polyhexamethylenebiguanidine HCId and Alkylbenzyldimethylammonium chloride.

In another embodiment the present invention, the process for the manufacture of the antimicrobial composition comprises the step of combining the components at any ambient temperature. In a further embodiment of the present invention, the process for manufacture of the antimicrobial composition comprises the following steps:

a. dissolving in water sodium hydroxide and sodium fluoride, if any, wherein the water preferably has less than 500 ppm of CaC0₃ to reduce competing ion effect with quaternaries in the preparation;

b. add the Didecyldimethylammonium chloride and alkylbenzyldimethylammonium chloride; c. adding the ethanol; and

d. adding Polyhexamethylenebiguanidine HCId

In a still further embodiment, the antimicrobial composition is manufactured by combining the following components, as shown in Table IV, in the order given at ambient temperature, ranging from about 20 to 25°C. Quantities are in parts by weight.

Table IV

Ingredient by wt soln cone ght per cent

Didecyldimethylammonium chloride 100 as 50% solution 10

Alkylbenzyldimethylammonium chloride 30 as 50% solution 3

Sodium fluoride 1 in 40 parts water 0.1

Ethanol 160 neat 20

Polyhexamethylenebiguanidine HCId 80 as 20% solution 8

Several compositions, as described above in Tables I and II have been prepared and tested for antimicrobial activity, as shown below in Table V:

Table V (Data results from microbiological tests composition test/lab organism contact time result

Example 1 EPA Initial Feline no residual virus

(Table I) Virucidal Efficacy calicivirus

Sample 2 2838. FCV

MIKROLAB

Example 2 EPA966.04 B. subtilis 1 & 5 mins No growth of

(Table II) ATCC6633 bacteria

Sample 4

Example 3 EPA966.04 B. subtilis 1 & 5 mins No growth of

(Table II) ATCC6633 bacteria

Sample 5

Example 4 EPA966.04 B. subtilis 1 & 5 mins No growth of

(Table II) ATCC6633 bacteria

Sample 6

Example 5 EPA966.04 B. subtilis 1 & 5 mins No growth of

(Table II) ATCC6633 bacteria

Sample 7

It is evident that compositions of the present invention are effective as antimicrobial agent and inhibit the growth of microbes, including bacteria and viruses. The present invention optimizes the activity of quaternary ammonium and biguanidine microbiocides when combined with ethanol in aqueous media. The present invention demonstrates excellent cleaning properties, including soil lift and suspension, as well as exceptional sporicidal activities. In a further embodiment of the present invention, the antimicrobial cleaning composition is manufactured as a super-concentrate which is diluted with water to form a concentrate for transportation to the site of use where it is diluted further with water to prepare the required solution, i.e. for cleaning and/or for rinsing and/or for sanitization and/or for sterilization by appropriate dilution.

The present invention thus provides various compositions of differing concentrations, e.g. as a super-concentrate, as a concentrate, as a diluted solution for the manufacture of fabric wipes, as another diluted solution for use as a spray, as a soaking solution of various strengths, as a final rinse aid solution etc.

As discussed above, the compositions of the present invention are useful in the cleaning and reduction of microbial population of various surfaces including floors, counters, furniture, architectural surfaces, porous surfaces (e.g., textiles, wall paper, carpeting, etc.), medical tools and equipment, food service wares, skin, animal enclosures, feeding stations, veterinarian surgical or examination areas, etc.

Preferably, the compositions of the present invention possess several properties in addition to antimicrobial efficacy. The compositions are preferably no rinse after application, and have residual antimicrobial activity. Residual activity implies a film of sanitizing material which will continue to have antimicrobial effect if the treated surface is contaminated by microorganisms during a period after application of the composition. A method of reducing microbial population of surfaces comprises the following steps. The composition of the present invention, being a solution formulated for the specific surface and concentration, is introduced onto the surface at a temperature in the range of about 0 to 100°C, and more preferably from about 10 to 25°C. After introduction of the composition, the solution is allowed to remain on the surface for a time sufficient to be effective in reducing the microbial population of the surface (i.e., to kill undesirable microbes). After sufficient time for microbial reduction, the use solution is removed. Preferably, the compositions of the invention provide greater than a 99% reduction (2-log order reduction) and more preferably greater than a 99.99% reduction (4-log order reduction) in such microbial population within 5 to 30 minutes at the temperature of treatment.

A method of treating substantially "fixed in-place" equipment comprises: introducing a composition of the present invention into the equipment at a temperature in the range of about 0 to 100°C, and more preferably form about 10 to about 25°C. After introduction of the antimicrobial composition, either diluted or as a concentrate, the antimicrobial composition is circulated throughout the equipment for a time sufficient for reduction in microbial population therein. After the equipment has been treated with the antimicrobial composition, any remaining composition may be drained therefrom. The antimicrobial composition can be circulated through the equipment for a period of time which can be varied according to treatment conditions, for example it may be 15 minutes or less.

The antimicrobial composition may also be employed by dipping equipment into the composition, soaking the equipment for a time sufficient to reduce the microbial population from the equipment, or spraying or wiping the equipment. In general, the antimicrobial composition should stay in contact with the equipment for a time sufficient to reduce the microbial population of the surfaces. Excess composition is removed by wiping, vertically draining, vacuuming, etc. Suitable soaking times are generally under 10 minutes but may range up to an hour or more depending on the concentration of the components of the composition, as discussed herein. Further aspects and features of the present invention will now be described.

The present invention may provide an antimicrobial composition comprising at least one cationic microbiocide and an alcohol, wherein the composition is free of non-ionic surfactants. The at least one cationic microbiocide may be present in an amount from about 5 wt% to about 15 wt% and the alcohol may be present in an amount from about 10 wt% to about 30 wt% in an aqueous matrix. The at least one cationic microbiocide may be selected from the group consisting of (a) guanidine salts and (b) positive non-metallic salts.

Suitable guanidine salts may be selected from among: chlorhexidine digluconate, dihydrochloride and diacetate; hexamethylenebis(ethylhexyl)biguanide dihydrochloride; oxocyclohexadienylideneaminoguanidine thiosemicarbazone; bis(chlorophenylamidino)piperazinedicarboxamidine dihydrochloride and polyhexamethylenebiguanidine hydrochloride.

Suitable positive non-metallic salts may be selected from among quaternary ammonium salts, phosphonium salts and sulfonium salts.

The quaternary ammonium salts may be selected from quaternary salts containing either or both aliphatic or aromatic moieties; aliphatic groups including alkoxy groups from one to 30 carbon atoms in linear or branched arrangements; and alicyclic groups selected among cyclohexyl and its alkylated and alkoxylated derivatives.

The quaternary ammonium salt may be didecyldimethylammonium chloride.

The counter ions of the quaternary ammonium salts may be selected among halides, chloride; bicarbonate, borate, carbonate, fluoborate, fluoride, phosphate, and sulphate.

The cationic microbiocides may consist of a mixture of polymeric biguanidinium chloride or polyhexamethylenebiguanidine hydrochloride; and didecyldimethylammonium chloride. The ratio between polymeric biguanidinium chloride or polyhexamethylenebiguanidine hydrochloride and didecyldimethylammonium chloride may be between 1 :1 and 1 :1 .6.

The alcohol may be selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and combinations thereof.

The antimicrobial composition may further comprise additional components comprising at least one of the following selected from the group consisting of organic acids selected from among, propanoic acid, glycolic acid, lactic acid and citric acid; and common salts of Group 1 & 2 metals selected among potassium and sodium cations with any of the following anions: halides selected among chloride, fluoride, bromide, iodide; phosphate, carbonate, bicarbonate, citrate, lactate, phosphate and sulphate; and combinations thereof.

The antimicrobial composition may further comprise sodium fluoride.

The antimicrobial composition may further comprise at least one cationic surfactant. The at least one cationic surfactant may be a cationic surfactant with an aromatic moiety. The cationic surfactants may be selected from among an alkylbenzyldimethylammonium chloride, alkyl(C12-16)dimethylbenzylammonium chloride; benzylhexyldimethylammonium chloride, benzyloctyldimethylammonium chloride, benzyldecyldimethylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltetradecyldimethylammonium chloride, benzyloctadecyldimethylammonium chloride, and similar species in which the benzyl moiety is replaced by tolyl- and xylyl- (ie methylbenzyl- and dimethylbenzyl-) moieties.

The antimicrobial composition may comprise an aqueous preparation which is diluted to form the required strength comprising the following components: Ethanol; Didecyldimethylammonium chloride; Polyhexamethylenebiguanidine HCId; Alkylbenzyldimethylammonium chloride; Sodium Hydroxide and optionally Sodium Fluoride.

The antimicrobial composition may comprise an aqueous preparation, in terms of weight per percent, having the following components: Ethanol in an amount from 1 to about 40; Didecyldimethylammonium chloride in an amount from about 0.1 to about 10; Polyhexamethylenebiguanidine HCId or polymeric biguanidinium chloride in an amount from about 0.08 to about 9; Alkylbenzyldimethylammonium chloride in an amount from about 0.03 to about 4; Sodium Hydroxide in an amount from about 0.002 to about 0.4 and Sodium Fluoride in an amount from about 0 to about 0.1 . The antimicrobial composition may comprise an aqueous preparation, in terms of weight per percent, having the following components: Ethanol in an amount from 1 to about 40; Didecyldimethylammonium chloride in an amount from about 0.1 to about 10; Polyhexamethylenebiguanidine HCId or polymeric biguanidinium chloride in an amount from about 0.09 to about 9; Alkylbenzyldimethylammonium chloride in an amount from about 0.04 to about 4; Sodium Hydroxide in an amount from about 0.004 to about 0.4 and Sodium Fluoride in an amount from about 0.5 to about 0.1 .

The antimicrobial composition may comprise an aqueous preparation, in terms of weight per percent, having the following components: Ethanol in an amount from 1 to about 40; Didecyldimethylammonium chloride in an amount from about 0.1 to about 10; Polyhexamethylenebiguanidine HCId or polymeric biguanidinium chloride in an amount from about 0.08 to about 8; Alkylbenzyldimethylammonium chloride in an amount from about 0.03 to about 3; Sodium Hydroxide in an amount from about 0.002 to about 0.2 and Sodium Fluoride in an amount from about 0.001 to about 0.1 .

The antimicrobial composition may comprise an aqueous preparation, in terms of weight per percent, having the following components: Ethanol in an amount of about 20; Didecyldimethylammonium chloride in an amount of about 4.7; Polyhexamethylenebiguanidine HCId or polymeric biguanidinium chloride in an amount of about 4.33; Alkylbenzyldimethylammonium chloride in an amount of about 1 .55; Sodium Hydroxide in an amount of about 0.150 and Sodium Fluoride in an amount of about 0.012.

The present invention may provide a process for manufacture of the antimicrobial composition as described in the preceding four paragraphs the method comprising:

a. dissolving in water sodium hydroxide and sodium fluoride, if any;

b. adding the didecyldimethylammonium chloride and alkylbenzyldimethylammonium chloride;

c. adding the ethanol; and

d. adding the polyhexamethylenebiguanidine HCId

The present invention may provide an antimicrobial composition including differing concentrations selected among super-concentrate, concentrate, diluted solution for the manufacture of fabric wipes, diluted solution for use as a spray, soaking solutions of various strengths and a final rinse aid solution.

The present invention may provide a method for cleaning, sanitizing and/or sterilizing a surface, the method comprising contacting the surface in need of such cleaning, sanitizing and/or sterilizing with an antimicrobial composition as defined herein.

In the method the surface may be contaminated with one or more species of micro-organisms including bacteria, viruses, fungi, algae and their associated spores.

The surface may be on equipment in the human and animal healthcare sector. The present invention may provide an antimicrobial composition comprising a mixture of cationic microbiocides, cationic surfactant, an alcohol, at least one non-ionic surfactant and at least one stabilizer component having a stabilizing effect on the composition.

The antimicrobial composition may further comprise a cationic surfactant. The at least one stabilizer component may be selected from hydrogen peroxide, allylanisole, triethyl citrate, citric acid, glycerol triacetate, triethyl O-acetylcitrate, ethylene glycol diacetate. Hydrogen peroxide may be combined with glycerol triacetate, triethyl O-acetylcitrate, triethyl citrate, and ethylene glycol diacetate to form peroxycarboxylic acids.

The cationic microbiocides may be selected from (a) guanidine salts or (b) positive non- metallic salts, wherein the positive non-metallic salts are selected from the group consisting of quaternary ammonium salts, phosphonium salts and sulfonium salts.

The guanidine salts may be selected from the group consisting of chlorhexidine digluconate, dihydrochloride and diacetate; hexamethylenebis(ethylhexyl)biguanide dihydrochloride, oxocyclohexadienylideneaminoguanidine thiosemicarbazone, bis(chlorophenylamidino)piperazinedicarboxamidine dihydrochloride, polymeric biguanidinium chloride and polyhexamethylenebiguanidine hydrochloride.

The non-ionic surfactant is selected from the group consisting of primary and secondary alcohol ethoxylates and condensates with oligoglycosides; alkanol containing about 8 to 18 carbon atoms in either straight chain or branched arrangements condensed with six to ten moles of ethylene oxide or four to six moles of a monosaccharide.

The non-ionic surfactant is an alkylpolyglucoside, an alkylethoxylate; a C₉- C ₀alkyltetraglucoside, a Cg-C alkylhexaethoxylate, or a C_8-11 Alcoholethoxylate.

The cationic surfactant may be selected from the group consisting of an alkylbenzyldimethylammonium chloride, alkyl(C12-16)dimethylbenzyl Ammonium Chloride, benzylhexyldimethylammonium chloride, benzyloctyldimethylammonium chloride, benzyldecyldimethylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltetradecyldimethylammonium chloride, and benzyloctadecyldimethylammonium chloride.

The alcohol may be selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secbutanol, tertbutanol and combinations thereof.

The antimicrobial composition may, further comprise additional components comprising at least one of the following selected from the group consisting of organic acids selected from among, propanoic acid, glycolic acid, lactic acid and citric acid; and common salts of Group 1 & 2 metals selected among potassium and sodium cations with any of the following anions: halides selected among chloride, fluoride, bromide, iodide; phosphate, carbonate, bicarbonate, citrate, lactate, phosphate and sulphate; and combinations thereof.

The present invention may provide a cleaning composition comprising alcohol, at least one non-ionic surfactant, at least one cationic surfactant, at least one cationic microbiocide, allylanisole, citric acid, sodium fluoride and optionally triethyl citrate.

The present invention may provide a cleaning concentrate composition comprising an alcohol in an amount from about 8 wt % to about 40 wt %, at least one non-ionic surfactant in an amount from about 5 wt % to about 10 wt %, at least one cationic microbiocide in an amount from about 5 wt % to about 15 wt %, at least one cationic surfactant in an amount from about 1 wt % to about 8 wt %, triethyl citrate from about 5 wt % to about 10 wt %, allylanisole from about 0.5 wt % to about 2 wt %, citric acid in an amount from about .01 wt % to about 1 wt % and sodium fluoride in an amount from about 0.01 wt % to about 0.1 wt %.

The present invention may provide a cleaning compositions comprising at least one cationic surfactant, at least one cationic microbiocide, hydrogen peroxide, a stabilizer component for stabilizing the hydrogen peroxide including citric acid, triethyl citrate or triethyl O-acetylcitrate and optionally at least one non-ionic surfactant.

The present invention may provide a cleaning composition comprising at least one cationic microbiocide in an amount from about 1 wt % to about 5 wt %, at least one cationic surfactant in an amount from about 0.5 wt % to about 8 wt %, hydrogen peroxide in an amount from about 0.4 wt % to about 5 wt %, a stabilizer for stabilizing the hydrogen peroxide in an amount from 0.5 wt% to about 10 wt % and optionally at least one non-ionic surfactant in an amount from about 0.5 wt % to about 3 wt %.

Claims

Claims:

1 . An antimicrobial cleansing composition comprising an alcohol and at least one cationic microbiocide wherein the composition comprises less than 2 wt% of non-ionic surfactant.

2. A composition according to claim 1 which comprises an alcohol, at least one cationic microbiocide, and an alkaline base, wherein the composition comprises less than 2 wt% of non-ionic surfactant.

3. A composition according to claim 1 or claim 2 which comprises less than 0.1 wt% non- ionic surfactants.

4. A composition according to any preceding claim wherein the cationic microbiocide is selected from among (a) guanidine salts and (b) positive non-metallic salts.

5. A composition according to any preceding claim, wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol, n-butanol, isopropanol, sec- butanol, tert-butanol and combinations thereof.

6. A composition according to any preceding claim which further comprises a cationic surfactant.

7. A composition according to claim 6 wherein the cationic surfactant is selected from the group consisting of an alkylbenzyldimethylammonium chloride, alkyl(C12-16) dimethylbenzyl ammonium chloride, benzylhexyldimethylammonium chloride, benzyloctyldimethylammonium chloride, benzyldecyldimethylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltetradecyldimethylammonium chloride, benzyloctadecyldimethylammonium chloride, and similar species in which the benzyl moiety is replaced by tolyl- and xylyl moieties.

8. A composition according to any preceding claim which comprises an alkali metal hydroxide.

9. A composition according to any preceding claim which comprises a fluoride salt.

10. A composition according to any preceding claim which comprises an aqueous preparation, in terms of weight per percent, having the following components: Ethanol in an amount from 1 to about 40; Didecyldimethylammonium chloride in an amount from about 0.1 to about 10; Polyhexamethylenebiguanidine HCId or polymeric biguanidinium chloride in an amount from about 0.08 to about 9; Alkylbenzyldimethylammonium chloride in an amount from about 0.03 to about 4; Sodium Hydroxide in an amount from about 0.002 to about 0.4 and Sodium Fluoride in an amount from about 0 to about 0.1 .

An aqueous cleaning composition comprising a cationic surfactant, a cationic microbiocide, an organic acid and a peroxide compound.

12. A process of reducing microbial compositions on a contaminated surface, the process comprising contacting the surface with a composition as claimed in any preceding claim.