Antimicrobial composition

Abstract

It is an object of the present invention to provide an antimicrobial composition that is suitable for use on hard surfaces. [Solution] The above problem is solved by an antimicrobial composition comprising (i) an antimicrobial component comprising at least one antimicrobial quaternary ammonium compound, (ii) a hydrophilic polymer, (iii) a polar solvent, (iv) at least one nonionic surfactant, and (v) a chelate, wherein the polymer comprises at least two of the following types of monomers: (1) a monomer having a permanent cationic charge or a monomer capable of forming a cationic charge by protonation; (2) an acidic monomer having an anionic charge or capable of forming an anionic charge; and (3) a neutral monomer.

Description

[Technical Field]

[0001] The present invention relates to antimicrobial compositions and formulations comprising the antimicrobial compositions. [Background technology]

[0002] Microorganisms are known to pose health hazards through infection or contamination. Microorganisms can also cause damage to items such as clothing and unpleasant odors. When present on the surface of a substrate, microorganisms can rapidly replicate and form colonies.

[0003] A number of antimicrobial agents are known that are capable of destroying microorganisms present in a wide range of environments, including healthcare, industrial, commercial, domestic and marine environments. Many of the known antimicrobial agents have previously been included in compositions for use in a variety of applications and environments.

[0004] Known antimicrobial agents and compositions containing these antimicrobial agents destroy microorganisms by several different mechanisms.

[0005] For example, many antimicrobial agents are toxic to microorganisms and therefore destroy them upon contact. Examples of this type of antimicrobial agent include hypochlorite (bleach), phenol and its compounds, and salts of copper, tin, and arsenic. However, some of these antimicrobial agents can be highly toxic not only to microorganisms but also to humans and animals. Therefore, handling these antimicrobial agents is dangerous and requires specialized handling, processing, and equipment for safe handling. Therefore, there can be many problems with the production and disposal of compositions containing this type of antimicrobial agent. There can also be problems associated with the use of compositions containing this type of antimicrobial agent, especially in consumer products, where it is difficult to ensure that they are used for their intended purpose.

[0006] As used herein, unless the context indicates otherwise, "toxicity" is intended to refer to toxicity to complex organisms such as mammals, and words referring to "toxicity" should be construed accordingly.

[0007] Once antimicrobials enter the environment, they can affect the health of forms of life that they were not intended to affect. Furthermore, antimicrobials are often quite stable, potentially causing long-term environmental problems.

[0008] Other antimicrobial agents currently in use include antibiotic-type compounds, which disrupt the biochemistry within microorganisms. Although effective, antibiotics are thought to be able to selectively allow the development of resistant strains of the species against which they are used.

[0009] Another method of microbial control is the use of oxidizing agents in substances such as household bleach, which can be based on hypochlorite or peroxides such as hydrogen peroxide. These substances are effective in moist environments for sterilization and cleaning, but cease to function immediately upon drying.

[0010] 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. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] U.S. Patent No. 6,569,261 [Patent Document 2] U.S. Patent No. 6,593,288 [Patent Document 3] U.S. Patent No. 6,703,358 [Patent Document 4] U.S. Patent No. 6,767,410 [Non-patent literature]

[0012] [Non-Patent Document 1] Biocidal Products Regulations (Directive 98 / 8 / EC) [Non-patent document 2] EPA (U.S. Environmental Protection Agency) Listing and Annex I Summary of the Invention [Problem to be solved by the invention]

[0013] There is a need to provide compositions for various applications and uses, such as cleaning applications, that have antimicrobial properties and address one or more of the above problems. However, achieving this is not easy. There are regulations, such as the Biocidal Products Regulations (Directive 98 / 8 / EC), that regulate the use of antimicrobial agents in terms of both the nature and amount of a given antimicrobial agent that may be used. Furthermore, the potential reactivity of an antimicrobial agent when present in a composition is important, as some antimicrobial agents are chemically inactivated. Even if an antimicrobial agent is not chemically inactivated, its activity may be inhibited by other components of the composition. [Means for solving the problem]

[0014] Surprisingly, the inventors have discovered that the aforementioned drawbacks can be overcome by certain combinations of ingredients. It has also been discovered that compositions containing these combinations of ingredients can possess several surprising and unexpected properties.

[0015] In particular, the present invention provides antimicrobial compositions suitable for a variety of consumer applications. The compositions of the present invention are particularly suitable for use on hard surfaces. Some compositions of the present invention are suitable for cleaning hard surfaces and also provide residual antimicrobial benefits.

[0016] The compositions of the present invention can be used in a variety of applications, and are particularly suitable for use on hard surfaces. They can be used on indoor hard surfaces, such as those found in domestic settings, offices, or public buildings such as hospitals, or on outdoor hard surfaces.

[0017] As used herein, the term cleaning refers to the removal of dirt, soap scum, limescale, and other soiling.

[0018] The compositions of the present invention comprise (i) an antimicrobial component comprising at least one quaternary ammonium compound, (ii) a polymer as defined below, (iii) a polar solvent, (iv) at least one nonionic surfactant, and (v) a chelate. The antimicrobial component (i) preferably contains at least two quaternary ammonium compounds.

[0019] The compositions of the present invention may consist of or consist essentially of the components listed in the paragraphs above, although it is contemplated that they may contain additional components described below and other components standard in the art.

[0020] For the avoidance of doubt, when the terms "comprising" or "comprises" are used herein, it means that the composition or formulation or component being described must contain the recited components, but may optionally contain additional components. When the terms "consisting essentially of" or "consists essentially of" are used, it means that the composition or formulation or component being described must contain the recited components, but may contain small amounts (e.g., up to 5% by weight, or up to 1% by weight, or 0.1% by weight) of other components, provided that any additional components do not affect the essential properties of the composition, formulation, or component. When the term "consisting of" is used, it means that the composition or formulation or component being described must contain only the recited components. These terms may similarly be applied to processes, methods, and uses.

[0021] By "substantially free," it is meant that the composition or formulation or ingredient being described contains less than 3% by weight of the described component, preferably less than 1% by weight, and more preferably 0.1% by weight or less. For example, a composition of the present invention that is substantially free of alcohol contains less than 3% by weight of alcohol, preferably less than 1% by weight, and more preferably 0.1% by weight or less of alcohol.

[0022] The term "antimicrobial" refers to a compound or composition that kills and / or inhibits the growth of microorganisms. The term "microbicidal" is used to refer to a compound or composition that kills microorganisms. The compositions of the present invention are antimicrobial and / or microbicidal.

[0023] A microorganism (or microbe) is a microscopic organism (too small to be seen with the naked eye). Examples of microorganisms include bacteria, fungi, yeast, mold, mycobacteria, algae, spores, archaea, and protists. Microorganisms are generally single cells or unicellular organisms. However, as used herein, the term "microorganism" also encompasses viruses.

[0024] The compositions of the present invention comprise at least one antimicrobial agent selected from antibacterial, antifungal, antialgal, antisporogenic, antiviral, antiyeast and antimold agents, and mixtures thereof. More preferably, the compositions of the present invention comprise at least one antibacterial, antiviral, antifungal and / or antimold agent.

[0025] As used herein, the terms antibacterial, antifungal, antialgal, antiviral, antiyeast and antimold are intended to refer to agents that inhibit the growth of, but do not necessarily kill, the respective microorganisms, and agents that do kill the respective microorganisms. Thus, for example, the term antibacterial agent includes within its scope agents that inhibit the growth of, but do not necessarily kill, bacteria, as well as bactericides that do kill bacteria.

[0026] As one skilled in the art will appreciate, the suffix "cidal," as used in, for example, "bactericidal" and "fungicidal," is used to refer to an agent that kills the microorganism being referred to. Thus, in these examples, bactericide refers to an agent that kills bacteria, and fungicide refers to an agent that kills fungi. Examples of bactericides include mycobactericides and tuberculocides. Preferably, the compositions of the present invention comprise at least one agent selected from bactericides, fungicides, algicides, sporicides, virucides, yeasticides, and moldicides, and mixtures thereof. More preferably, the compositions of the present invention comprise at least one bactericide, virucide, fungicide, and / or moldicide.

[0027] The compositions of the present invention are effective against a wide range of organisms, including gram-negative and gram-positive bacteria, fungi, yeasts, viruses and some spore-formers.

[0028] The antimicrobial component (i) can include (a) at least one, and preferably at least two, quaternary ammonium compounds having antimicrobial properties, and optionally (b) one or more additional antimicrobial agents. Commercially available blends of quaternary ammonium compounds having antimicrobial properties may be used.

[0029] The quaternary ammonium antimicrobial agents used in the present invention are typically water-soluble at room temperature and pressure.

[0030] Suitable antimicrobial quaternary ammonium compounds include compounds of formula (A):

[0031] [ka]

[0032] [In the formula, R 1 and R 2 are each independently a linear, unsubstituted, uninterrupted C 8~12 is an alkyl group, and X - is a halide anion such as chloride, bromide, fluoride, iodide, or sulfonate, saccharinate, carbonate, or bicarbonate; and a benzalkonium compound having the formula (B):

[0033] [ka]

[0034] wherein m is 8 to 18; and X -is a halide anion such as chloride, bromide, fluoride, iodide, sulfonate, saccharinate, carbonate, or bicarbonate. Compounds of formula (B) are commonly called benzalkonium compounds. Benzalkonium chloride is 8~18 Mixtures of alkyl groups, especially linear unsubstituted uninterrupted alkyl groups n-C8H 17 From nC 18 H 37 , mainly nC 12 H 25 (dodecyl), nC 14 H 29 (tetradecyl), and nC 16 H 33 (hexadecyl). Preferably, m is 8, 10, 12, 14 and / or 16. Most preferably, m is 12 to 16, e.g., 12, 14 and / or 16.

[0035] In the compound of formula (A), R 1 Groups and R 2 Each group is independently a linear, unsubstituted, uninterrupted C 8~12 An alkyl group, for example, an alkyl group containing 8, 9, 10, 11, or 12 carbon atoms. 1 Groups and R 2 The groups contain the same number of carbon atoms, but this is not essential; R 1 and R 2 Compounds containing different numbers of carbon atoms may be used.

[0036] The anion of each quaternary ammonium compound in the composition of the present invention may be the same or different. For example, the anion of the compound of formula (A) may be the same or different from the anion of the compound of formula (B). In one embodiment, the anion of each compound is chloride.

[0037] Examples of quaternary ammonium compounds of formula (A) include di-n-decyldimethylammonium chloride, octyldecyldimethylammonium chloride, and dioctyldimethylammonium chloride.

[0038] Examples of commercially available compounds of formula (A) include Acticide DDQ 50, Bardac 2250, 2280 and Maquat 4480E manufactured by Mason Chemical Company (USA).

[0039] Examples of quaternary ammonium compounds of formula (B) include N,N-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, N,N-dimethyl-N-benzyl-N-octadecylammonium chloride, and mixtures thereof.

[0040] Commercially available benzalkonium chlorides often contain mixtures of compounds with varying alkyl chain lengths. Examples of commercially available benzalkonium chlorides that can be used in the present invention are listed in the table below. It should be understood that other commercially available benzalkonium compounds may be used instead or in addition.

[0041] [Table 1]

[0042] It should be understood that a single CAS number often refers to a blend or mixture of multiple compounds. The CAS classification of a commercially available preparation typically includes a blend containing the specified compound in a defined range of amounts. The compositions with the CAS numbers cited above are merely examples of compositions with a given CAS number that can be used in the present invention.

[0043] The amount of component (i) in the compositions of the present invention will vary depending on several factors, including the intended use of the composition and the particular compound used as component (i).

[0044] When a mixture of quaternary ammonium compounds of Formula A and Formula B is used, the weight ratio of A to B is not limited and can be from about 1:10 to about 10:1, preferably from 1:5 to 5:1, or from about 1:4 to about 4:1, such as about 2:1, or from about 3:2 to about 2:3.

[0045] Examples of quaternary ammonium components are octyldecyldimethylammonium chloride and / or didecyldimethylammonium chloride and / or dioctyldimethylammonium chloride, and alkyl chlorides (C 14 , 50%;C 12 , 40%;C 16 , 10%) dimethylbenzylammonium. These compounds may be used together in any suitable ratio. One such weight ratio is about 2:1:1:2.7. A suitable mixture is commercially available from Mason Chemical as Maquat MQ 615M.

[0046] Component (i) may consist essentially of or consist of at least one or at least two compounds of formula (A), or may consist essentially of or consist of at least one or at least two compounds of formula (B).

[0047] In one embodiment, component (i) comprises, consists essentially of, or consists of at least one compound of formula (A) and at least one compound of formula (B). In this embodiment, the weight ratio of compounds of formula (A) to compounds of formula (B) is, for example, 10:1 to 1:10, or 4:1 to 1:4, such as 3:2 or 2:3.

[0048] In one embodiment, the quaternary ammonium antimicrobial component (i) may consist of (1) a component consisting essentially of a single compound of formula (A) and (2) a component consisting essentially of at least one benzalkonium compound having formula (B), wherein the weight ratio of (1) to (2) is from 10:1 to 1:10, or from 4:1 to 1:4, such as 3:2 or 2:3.

[0049] The quaternary ammonium compounds used in the present invention are typically not polymerized.

[0050] The compositions of the present invention must contain at least one, such as at least two, quaternary ammonium antimicrobial agents, and may further include any other suitable antimicrobial agents (b), such as those listed in the EPA (U.S. Environmental Protection Agency) Listing and Annex I and Annex 3 of the EC Biocides Directive.

[0051] Suitable antimicrobial agents (b) include antimicrobial agents that are not quaternary ammonium compounds. Preferably, these additional antimicrobial agents are water-soluble at room temperature and pressure.

[0052] Examples of suitable additional antimicrobial agents include, but are not limited to, polymeric biguanidines (e.g., polyhexamethylene biguanidine (PHMB)), non-polymeric biguanides (e.g., chlorhexidine), silver, octenidine HCl, amphoteric compounds, iodophors, phenolic compounds, amine antimicrobial agents, and nitrogen-based heterocyclic compounds, orthophenylphenol (OPP), and nitrobromopropanes (e.g., bronopol (INN), 2-bromo-2-nitropropane-1,3-diol), naturally derived biocidal compounds (e.g., honey and honey extracts, such as those containing methylglyoxal, flavenoid-based antimicrobial agents, essential oils, and organic acids, such as lactic acid or citric acid).

[0053] In one embodiment, the compositions of the present invention do not include inorganic antimicrobial agents, such as those containing silver. In this embodiment, the additional antimicrobial agent is an organic antimicrobial agent.

[0054] Preferred additional antimicrobial agents (b) include polymeric biguanidines. One preferred additional antimicrobial agent (b) is polyhexamethylene biguanidine (PHMB). PHMB is commercially available from Arch Biocides as Vantocil (technical grade quality) or Cosmocil (cosmetic grade quality, e.g., PHMB20 supplied by Thor).

[0055] Examples of amine antimicrobial agents that can be used in the compositions of the present invention are compounds of formula (C)

[0056] [ka]

[0057] [Wherein R is an unsubstituted C-C 18 Preferably, R is an unsubstituted C 10 ~C 14 , e.g. C 12 A preferred compound of formula (C) is dodecyldipropylenetriamine (N,N-bis(3-aminopropyl)-dodecylamine, CAS number 2372-82-9), available commercially from Lonzabac as Lonzabac 12, also known as Triameen YD12 (supplied by Akzo Nobel).

[0058] In one embodiment, the compositions of the invention are free of PHMB, or free of polymeric biguanides, or free of non-polymeric biguanidines, or free of biguanidines (e.g., free of polymeric and non-polymeric biguanides). In one embodiment of the invention, the antimicrobial compositions are free of any isothiazalone, and / or any nitrobromopropane, such as bronopol, and / or any hypochlorite.

[0059] In a particular embodiment, compositions of the invention comprising a compound of Formula (C), e.g., N,N-bis(3-aminopropyl)-dodecylamine, are PHMB-free, or polymeric biguanidine-free or biguanidine-free (e.g., polymeric biguanidine and non-polymeric biguanidine-free). However, compositions comprising a compound of Formula (C), e.g., N,N-bis(3-aminopropyl)-dodecylamine, and a biguanidine, such as a polymeric biguanidine or a non-polymeric biguanidine, e.g., PHMB, are also contemplated.

[0060] Exemplary compositions of the present invention are those in which component (i) is (a) at least one or at least two of the above-described quaternary ammonium compounds, e.g., compounds of formula (A) and / or compounds of formula (B), and (b) at least one polymeric biguanide such as PHMB, which can be the only additional antimicrobial component (b), or component (b) can contain additional antimicrobial components.

[0061] An example of a composition of the present invention is a composition in which component (i) comprises (a) at least one or at least two of the above-described quaternary ammonium compounds, such as a compound of formula (A) and / or a compound of formula (B), and (b) at least one compound of formula (C), such as N,N-bis(3-aminopropyl)-dodecylamine.

[0062] An example of a composition of the present invention is a composition in which component (i) comprises (a) at least one or at least two of the quaternary ammonium compounds described above, such as a compound of formula (A) and / or a compound of formula (B), but does not comprise an additional antimicrobial agent (b).

[0063] In one embodiment, component (b) is free of isothiazoles. In this embodiment, the compositions of the present invention are free of isothiazoles.

[0064] The compositions of the present invention can be provided in a concentrated form for dilution before use or in a ready-to-use form. The compositions of the present invention are preferably provided in a ready-to-use form, and unless otherwise stated, the amount data given herein (such as in % by weight or ppm) relate to the ready-to-use composition.

[0065] Typically, compositions of the present invention have a concentration of component (i) of about 100 ppm or 500 ppm to about 20000 ppm, such as about 2000 ppm to about 10000 ppm or 3000 ppm to 8000 ppm, although this is not essential.

[0066] Polymers suitable for use in the present invention are those containing the following types of monomers: (1) Monomers that have a permanent cationic charge or that can form a cationic charge by protonation; (2) an acidic monomer having or capable of forming an anionic charge; and (3) Neutral monomer The hydrophilic polymer contains at least two of the following:

[0067] These types of monomers can be used in any combination. For example, suitable polymers include, but are not limited to, those comprising, consisting of, or consisting essentially of at least one monomer of type (1) and at least one monomer of type (2), as well as polymers comprising, consisting of, or consisting essentially of at least one monomer of type (1) and at least one monomer of type (3), polymers comprising, consisting of, or consisting essentially of polymers comprising at least one monomer of type (2) and at least one monomer of type (3), and polymers comprising, consisting of, or consisting essentially of at least one of each of the three types of monomers.

[0068] The polymers used in the present invention can have a polyampholyte structure such that charge and surface adsorption are pH-dependent. For example, the polymer can be an amine-functional acrylate polymer. Examples of suitable hydrophilic polymers are described in U.S. Pat. Nos. 6,569,261, 6,593,288, 6,703,358, and 6,767,410, the disclosures of which are incorporated herein by reference. These references describe water-soluble or water-dispersible copolymers containing, in the form of polymerized units, (1) at least one amine-functional monomer, (2) at least one acidic hydrophilic monomer, and (3) optionally, at least one neutral hydrophilic monomer having ethylenic unsaturation. The copolymers include quaternized ammonium acrylamido acid copolymers.

[0069] Examples of cationic monomers (1) include, but are not limited to:

[0070] [ka]

[0071] Diallyldimethylammonium halides, such as diallyldimethylammonium chloride (DADMAC) or the corresponding bromide. Alternatively, the counterion may be a sulfate or phosphate. One or more of the CH3 groups may be C 2~12 , e.g. C 2~6 Similar monomeric units may be used, such as those substituted with alkyl groups, or those in which one or more of the CH groups are replaced with alkyl groups having from 2 to 12, e.g., from 2 to 6, carbon atoms. In other words, other similar commercially available monomers or polymers containing such monomers may be used.

[0072] [ka]

[0073] N,N,N-trimethyl-3-((2-methyl-1-oxo-2-propenyl)amino)-1-propanaminium halide, such as chloride (MAPTAC, also known as methacryl-amido(propyl)-trimethylammonium chloride).

[0074] Examples of acidic monomers (2) include, but are not limited to, acrylic acid and methylacrylic acid.

[0075] Examples of neutral monomers (3) include, but are not limited to:

[0076] [ka]

[0077] 2-(dimethylamino)ethyl methacrylate (DMAEMA),

[0078] [ka]

[0079] N-vinylpyrrolidone (NVP),

[0080] [ka]

[0081] N-vinylimidazole,

[0082] [ka]

[0083] acrylamide, and

[0084] [ka]

[0085] Methacrylamide.

[0086] Examples of polymers suitable for use in the present invention are polymers comprising, consisting of, or consisting essentially of DMAEMA, MAPTAC, and methylacrylic acid.

[0087] Suitable polymers include those sold under the trade name Mirapol available from Rhodia Novecare, for example Mirapol Surf-S110, Mirapol Surf-S200 or Mirapol Surf-S500.

[0088] Other suitable polymers include those comprising, consisting of, or consisting essentially of DADMAC and acrylamide, such as those sold by Surfacare under the trade name Polyquat 7 or PQ7 or by Lubrizol under the trade name Merquat S. Other suitable polymers include those comprising, consisting of, or consisting essentially of DADMAC and methacrylamide and / or acrylic acid or methacrylic acid.

[0089] Polymers comprising, consisting of, or consisting essentially of MAPTAC and acrylamide or methacrylamide are also suitable for use in the present invention. Polymers comprising, consisting of, or consisting essentially of MAPTAC and vinylpyrrolidone, such as Polyquat 28, are also suitable. Suitable polymers include those sold by BASF under the trade names Polyquart Pro (polyquat 28 plus silicone) and Polyquart Ampo 140.

[0090] Other suitable polymers include those sold under the trade name Polyquat Ampho, e.g., Polyquat Ampho 149, which are polymers comprising, consisting of, or consisting essentially of MAPTAC and acrylic or methacrylic acid.

[0091] Polymers comprising, consisting of, or consisting essentially of DMAEMA and vinylpyrrolidone are suitable for use in the present invention. An example of such a polymer is sold by BRB International under the name PQ11.

[0092] Other suitable polymers include those comprising, consisting of, or consisting essentially of DMAEMA and acrylamide, such as those sold under the trade name Polyquat 5.

[0093] Typically, the polymers used in the present invention are unmodified polymers, meaning that the polymers have not been modified by reactions such as, for example, grafting with functionalizing agents or hydrophobic materials.

[0094] The ratio of quaternary ammonium component (a) to polymer (ii) in parts per million (PPM) is typically 200:1 to 1:20, such as 1:1 to 20:1 or 10:1, for example, about 2:1 or about 4:1. In certain embodiments, the amount of component (a) in ppm is equal to or greater than the amount of polymer. For example, the ratio of component (a) to polymer (ii) can be about 5:1, or about 4:1, or about 3:1, or about 2:1, or about 1:1.

[0095] By way of example, the compositions of the present invention may contain from 500 ppm to 3000 ppm of polymer, such as from 1000 ppm to 2500 ppm or about 2000 ppm.

[0096] The compositions of the present invention may comprise a single polymer (a single combination of monomeric units), or two or more polymers may be used (polymers made up of two or more combinations of monomeric units).

[0097] The pH of the composition of the present invention can vary within wide limits.Typically, the pH of the composition of the present invention is similar to the pH of known compositions intended for the same or similar purpose as a given composition of the present invention.Formulations used for purposes such as kitchen or bathroom cleaning can have a low pH, such as a pH of 3 or less, for example, about 2, or a high pH, ​​such as a pH of 10 or more, for example, 11.

[0098] In one embodiment, the composition of the invention has a pH of 5 to 13, such as from about pH 5 to about pH 12, such as from about pH 5 to pH 9 or above, or a pH of 2.5 or above, such as 3.5 or above or 4 or 4.5 or above.

[0099] The composition of the present invention comprises at least one suitable nonionic surfactant, or a combination of surfactants comprising at least one nonionic surfactant (for example, at least one nonionic surfactant and at least one cationic surfactant and / or amphoteric surfactant, optionally combined).The choice of surfactant depends on the nature of the composition and the intended purpose.The surfactant suitable for use in the formulation for different purposes is within the knowledge of a person skilled in the art.Similarly, the selection of the appropriate amount of surfactant is also within the knowledge of a person skilled in the art.

[0100] Some compositions of the present invention contain amphoteric surfactants.When a combination of amphoteric surfactants and nonionic surfactants is used, the weight ratio of these two types of surfactants can vary within wide limits, for example, from 1% amphoteric surfactant to 99% nonionic surfactant to 99% amphoteric surfactant to 1% nonionic surfactant, based on the total weight of surfactants.For example, amphoteric surfactants and nonionic surfactants can be used in approximately equal amounts by weight.

[0101] In one embodiment, the composition is substantially free of or free of anionic surfactants. In another embodiment, the composition of the present invention is free of amphoteric surfactants.

[0102] The compositions of the present invention include component (iii) a polar solvent. Suitable polar solvents include, but are not limited to, water, alcohols, glycol ethers, and mixtures thereof.

[0103] Suitable alcohols include, but are not limited to, straight or branched chain C1-C5 alcohols such as methanol, ethanol, n-propanol, iso-propanol, a mixture of propanol isomers, n-butanol, sec-butanol, tert-butanol, iso-butanol, a mixture of butanol isomers, 2-methyl-1-butanol, n-pentanol, a mixture of pentanol isomers, and amyl alcohol (a mixture of isomers), and mixtures thereof.

[0104] Preferred polar solvents for use in the composition of the present invention include, but are not limited to, water, ethanol, n-propanol, isopropanol, ethylene glycol ether, propylene glycol ether, butyl diglycol (BDG), and dipropylene glycol methyl ether (trade name Dowanol DPM), and mixtures thereof.In one embodiment, the composition comprises water or a mixture of water and one or more alcohols selected from the alcohols listed above.In such a mixture, water is preferably the main component.The polar solvent can consist essentially of water or can consist of water.

[0105] When the compositions of the present invention include alcohol, the alcohol is typically present in an amount less than that required for the alcohol to provide an antimicrobial effect.

[0106] In one embodiment, the compositions of the present invention are substantially free of alcohol. For example, the compositions may contain 1% by weight or less of alcohol. For example, the compositions may contain less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight of alcohol, such as isopropanol. For example, the compositions of the present invention may be completely free of isopropanol, or may be completely free of alcohol.

[0107] The composition may comprise water or a mixture of water with one or more alcohols selected from those mentioned above, preferably with water being the major component in such a mixture.

[0108] Suitable nonionic surfactants include, but are not limited to, amine oxides, alkyl polyglucosides, linear and branched primary and secondary alcohol ethoxylates, nonylphenol ethoxylates, and ethoxylated / propoxylated (EOPO) block polymers.

[0109] Amine oxides suitable for use in the present invention have alkyl chain lengths of C8 to C 16 Amine oxides are suitable for use in the present invention because they can provide improved cleaning properties over some other surfactants and can reduce the degradative effects on certain plastic surfaces.

[0110] Examples of suitable amine oxide compounds include C8 amine oxide surfactants such as those sold under the trade name Macat AO-8 (Mason Chemical Company); Euroxide D40 (EOC Group) and Mackayamine C 10 C, such as those sold by Rhodia Novecare 10 Amine oxide; C 12Longer chain glucosides such as amine oxides, for example those sold under the trade names Eurooxide LO / A (EOC Group), Ammonyx LO (Stepan Chemicals), and Surfac AO30 (Surfachem); and C such as those sold under the trade name Ammonyx C (Stepan Chemicals). 10 ~C 16 These include, but are not limited to, amine oxides.

[0111] Alcohol alkoxylates suitable for use in the present invention include C6-C alkoxylates having 2 to 20 EO units, such as 7 to 12 EO units. 18 Included are linear and branched primary and secondary alcohol ethoxylates, such as alcohol ethoxylates. Preferred linear primary alcohol alkoxylates include C9 to C12 alkoxylates having 5 to 12 EO units, such as 7 to 12 EO units. 11 Examples of suitable alcohol ethoxylates include alcohol ethoxylates. These surfactants are commercially available under the name Neodol (Shell Chemical Company). Examples of C12-15 secondary alcohol ethoxylates include those having about 3 to about 10 EO units, such as those available under the Tergitol series (Dow), particularly those available under the Tergitol 15-S series. Examples of suitable branched alcohol ethoxylates include C10 Guerbet alcohols containing 3 to 14 EO units, such as the Lutensol XL and XP series (BASF). Alcohol ethoxylates containing a mixture of EO and PO units are also suitable, including linear and branched alcohol ethoxylates with PO-EO units, such as ECOSURF™ EH surfactants (DOW) and Plurafac D250 (BASF). Alkylphenol ethoxylate (APE) surfactants can also be used.

[0112] Another group of nonionic surfactants that can be used are compounds based on alkoxy block copolymers, in particular ethoxy / propoxy block copolymers. Block copolymers of polymeric alkylene oxides include block polymers C 2~4 Nonionic surfactants comprised primarily of alkylene oxides include those commercially available under the Pluronic trademark, particularly the Pluronic F, L, P, and R series.

[0113] Another group of suitable nonionic surfactants are alkyl polyglucosides or glucosides. Suitable examples include capryl glucoside, Surface APG, available from Surfachem, and the Glucopon series (Glucopon 425N / HH (C8-14), Glucopon 215 (C8-10), and Glucopon 600 (C12-14) alkyl polyglucosides) available from BASF.

[0114] In one embodiment of the present invention, the compositions of the present invention may be free of alcohol alkoxylates. For example, compositions of the present invention containing a compound of formula (C) as defined herein, such as those containing N,N-bis(3-aminopropyl)-dodecylamine, may be free of alcohol alkoxylates.

[0115] Compositions of the invention may alternatively or additionally be free of alkyl polyglucosides. For example, compositions of the invention containing compounds of formula (C) as defined herein, such as those containing N,N-bis(3-aminopropyl)-dodecylamine, may be free of alkyl polyglucosides (APGs).

[0116] Typically, component (iv) is present in the compositions of the present invention in an amount of about 500 ppm to 35,000 ppm. The amount of surfactant (iv) depends on several factors, such as the pH of the composition and the intended use of the composition. Typically, the higher the pH of the composition, the higher the concentration of nonionic surfactant required. A preferred range for the amount of surfactant (iv) in compositions having a pH of 8 to 10.5 is 2,000 ppm to 13,500 ppm.

[0117] Suitable amphoteric surfactants include C6-C 20 Alkyl amphoacetates or amphodiacetates (e.g., cocoamphoacetate), C 10 ~C 18 Alkyl dimethyl betaine, C 10 ~C 18 Examples include, but are not limited to, alkylamidopropyl dimethyl betaine. Examples include, but are not limited to, the coconut oil-based amphoteric surfactant cocoamidopropyl betaine (CAPB) (Surfac B4, CAS 61789-40-9), cocoimidazoline betaine, oleamidopropyl betaine, and tall oil imidazoline.

[0118] Without being bound by any particular theory, it has been found that surfactant components can have some influence on the properties of the composition of the present invention.The presence of nonionic surfactants can improve the cleaning ability of the composition, i.e., can improve the removal of dirt and mud.It has been found that the use of alcohol alkoxylates in combination with amine oxides can improve cleaning performance in some situations.In addition, the inclusion of nonionic surfactants can improve the stability of the composition of the present invention.

[0119] Surprisingly, the inventors have found that by using the combinations described herein, stable compositions are obtained that provide residual antimicrobial performance.

[0120] In one embodiment, the compositions of the present invention are free of glycol ethers, for example, free of propylene glycol n-butyl ether, and / or free of binary solvent combinations of glycols and linear primary alcohols.

[0121] The compositions of the present invention contain a chelate. Any suitable chelate may be used. Suitable chelates include, but are not limited to, EDTA (ethylenediaminetetraacetic acid), gluconate, GLDA (glutamic acid diacetate) - trade name Dissolvine GL, EDDS (ethylenediamine-N,N'-disuccinic acid), DPTA (diethylenetriaminepentaacetic acid), HEDTA (hydroxyethylethylenediaminetriacetic acid), MGDA (methylglycine diacetate) - trade name Trilon M, PDTA (1,3-propylenediaminetetraacetic acid), and EDG (ethanol diglycinate), and mixtures thereof. When the chelate contains a counterion, it is preferred that the counterion be metallic. Suitable metal counterions include, but are not limited to, Na, Ca, Fe, K, Zn, Mg, and Mn.

[0122] Preferred chelates are GLDA (Dissolvine) and EDTA.

[0123] The chelate is typically present in an amount of about 100 ppm to 10,000 ppm, preferably about 400 ppm to 3,000 ppm, for example about 500 ppm to 2000 ppm.

[0124] It should be understood that the compositions of the present invention may contain other components commonly used in the art. The nature of any other components used will depend on the nature and intended purpose of the composition. Those skilled in the art will understand which additional components are suitable for use in compositions for different applications.

[0125] The additional components that can be used in the composition of the present invention include, but are not limited to, buffering agents.Buffering agents include, but are not limited to, hydrophobic substances such as siloxanes, bicarbonates such as sodium bicarbonate, sodium chloride, potassium chloride, triethylamine, triethylenetetraminetetraethylethylenediamine, tetramethylenediamine, piperazine, histidine, imidazole, morpholine, amino alcohols such as 2-aminoethanol, 2-amino-2-methyl-1-propanol (AMP) and triethanolamine, phosphate buffers, citrate buffers, and salts thereof, and mixtures thereof.

[0126] Complexing agent can be used.For example, complexing agent can be used to help form clear composition even when the composition of the present invention is used with hard water.Suitable complexing agent includes but is not limited to methanediphosphonic acid, hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, amino-trimethylenephosphonic acid, ethylenediamine-tetra(methylenephosphonic acid), diethylenetriamine-penta(methylenephosphonic acid), 2-phosphonobutanebutane-1,2,4-tricarboxylic acid, and sodium salt of nitrilotriacetic acid (NTA), citrate and gluconate, or salts of glutaric acid, adipic acid and succinic acid, and mixtures thereof.

[0127] pH adjuster can be used.Suitable pH adjuster includes, but is not limited to, acids such as citric acid, sulfamic acid, hydrochloric acid, phosphoric acid, nitric acid, lactic acid, formic acid, acetic acid, glycolic acid, or gluconic acid, or other inorganic or organic acids, or bases such as sodium or potassium hydroxide and sodium or potassium carbonate, and mixtures thereof.The composition of the present invention can alternatively or additionally contain salts such as alkali metal or alkaline earth metal halides, such as NaCl or KCl.In some circumstances, the use of salts can facilitate the formation of stable compositions.

[0128] Some compositions of the present invention are free of or substantially free of acids or bases. For example, some compositions of the present invention are free of citrate or citric acid or lactic acid. Other compositions may contain acids or bases appropriate for their intended use. In one embodiment of the present invention, the composition contains no more than 0.5% by weight of formic acid or is free of formic acid.

[0129] Siloxanes suitable for use in the present invention include those of the formula (H3C)[SiO(CH3)2] n Si(CH3)3 and the formula (H3C)[SiO(CH3)H] n Si(CH3)3, and mixtures thereof, where n is an integer from 1 to 10, more preferably from 1 to 6, and most preferably from 1 to 4; for example, n can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and particularly 1, 2, 3, or 4. Examples of preferred (poly)dimethylsiloxanes are hexamethyldisiloxane (CAS#107-46-0), octamethyltrisiloxane (CAS#107-51-7), decamethyltetrasiloxane (CAS#141-62-8), and dodecamethylpentasiloxane (CAS#141-63-9). Commercially available siloxanes that can be used include those offered by Xiameter under the trade names PMX 200 and PMX-1184.

[0130] In certain embodiments of the present invention, the compositions of the present invention are free or substantially free of hydrophobic materials, for example, free or substantially free of siloxanes, silicones, polysiloxanes such as polydimethylsiloxanes.

[0131] The compositions of the present invention may also contain other components standard in the art such as colorants, fragrances, emollients, antioxidants, thickeners and corrosion inhibitors, and mixtures thereof.

[0132] Typically, component (i) is present in the compositions of the present invention in an amount of from about 0.05% to about 2% by weight, such as from about 0.2% or about 0.5% to about 1.5% or about 1.0% by weight of the composition.

[0133] The weight ratio of component (a) to additional antimicrobial agent (b) is typically from about 1:10 or about 1:2 or about 1:1 to about 50:1 or 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 from 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 3:1 or 4:1.

[0134] Typically, the polar solvent component (iii) is present in the compositions of the present invention in an amount of from about 10% to about 99.999% by weight, such as from about 50% to about 99.999% by weight of the composition, for example from about 80% to about 99.99% by weight, preferably from about 90% to about 99.9% by weight, more preferably from about 95% to about 99.8% by weight (e.g., 97% to 99.7% by weight or 97.5% to 99.6% by weight).

[0135] Typically, the additional antimicrobial component (b) is present in the composition in an amount of from about 0.001% to about 10% by weight, such as from about 0.005% to about 5% by weight of the composition, for example from about 0.01% to about 2% by weight, preferably from about 0.05% to about 1% by weight (e.g., 0.1% to 0.5%).

[0136] An example of a composition of the present invention is a composition comprising: (i) may be present in a weight ratio of about 1:10 to 10:1, e.g., about 4:1 (C 10 H 21 )2(CH3)2N + Cl - and benzalkonium chloride; (ii) Polymers as defined above, such as polymers comprising DMAEMA, MAPTAC and methylacrylic acid, or DADMAC and acrylamide, methacrylamide, acrylic acid or methacrylic acid, or MAPTAC and acrylamide or methacrylamide, or MAPTAC or DMAEMA and vinylpyrrolidone, or MAPTAC and acrylic acid or methacrylic acid, or DMAEMA and acrylamide; (iii) water; (iv) a nonionic surfactant such as an alcohol ethoxylate or an amine oxide or a mixture thereof; and (v) Chelates such as EDTA or GLDA. The composition has a pH of at least 2.5, such as at least 3.5.

[0137] Preferably, the polymer comprises DMAEMA, MAPTA, and methylacrylic acid, a commercially available example of which is sold under the trade name Mirapol Surf-S 110.

[0138] Without wishing to be bound by any particular theory, the inventors have discovered that there are very significant advantages associated with the compositions of the present invention.

[0139] During use, the compositions of the present invention have been found to exhibit advantageous antimicrobial effects. For example, such compositions exhibit antimicrobial effects when initially applied to a surface (a so-called "wet kill") and can also exhibit residual antimicrobial effects in that they control, reduce, or prevent the formation of new microbial colonies on the surface (a so-called "dry kill").

[0140] The compositions of the present invention are also resistant to washing with water and wiping, which results in the compositions of the present invention providing residual antimicrobial benefit even when the treated surface is subsequently wiped and / or washed or rinsed with water.

[0141] The compositions of the present invention provide residual antimicrobial efficacy, even after undergoing the residual efficacy tests described herein. That is, these compositions achieve a reduction in microorganisms when subjected to three abrasion cycles on non-porous stainless steel, glass, or plastic substrates, typically achieving a 3-log reduction or greater over a 24-hour period. This means that 24 hours after applying the compositions of the present invention to the surface, if microorganisms are applied to the surface (without further addition of the compositions of the present invention or another antimicrobial agent), a reduction of at least 3 logs of those microorganisms is achieved.

[0142] The advantage of the present invention is that it is possible to prevent a wide range of microorganisms from adhering and attaching to surfaces, and thus preventing the formation of biofilms. The formation of large, numerous colonies is also substantially prevented. Thus, the growth ability of the colonies is substantially reduced or even prevented. The present invention is therefore general in the control of microorganisms.

[0143] Typically, the compositions of the present invention need not contain components that are highly toxic to mammals. The antimicrobial agents used in the antimicrobial compositions are typically well-known, widely understood, and tested. The effectiveness of known antimicrobial agents is amplified in the formulations of the present invention. Thus, less toxic antimicrobial agents can be used in the antimicrobial compositions. Conversely, in the known art of sanitization, many "new" antimicrobial agents are "stronger," more toxic, and / or less tested.

[0144] The antimicrobial compositions of the present invention do not contain materials that produce persistent residues or rinses, or products that contain heavy metals and their salts, thus greatly reducing the risk of long-term hazards.

[0145] The antimicrobial compositions of the present invention do not interfere with the biochemical reproductive pathways of the microorganisms they control, therefore reducing the risk of developing resistance and the development of resistant strains.

[0146] The antimicrobial compositions of the present invention can be dual effective in that they not only provide antimicrobial benefit during use, but also provide a preservative effect to the composition, which typically eliminates the need to include additional preservatives in the formulations of the present invention.

[0147] The compositions of the present invention do not typically impart a greasy feel to the surface to which they are applied.

[0148] According to another aspect of the present invention there is provided the use of the composition of the present invention to control, reduce or prevent the formation of microbial colonies on a surface to which the composition of the present invention has been applied.

[0149] The present invention provides a method for providing a residual antimicrobial effect to a surface, such as a hard surface or skin, comprising applying a composition as defined herein to the surface. The composition can be applied to the surface by spraying the composition onto the surface or by rubbing the composition onto the surface. In one method of the present invention, the method need not include any steps other than simply applying the composition to the surface. Thus, there is provided a method that consists essentially of or consists of applying a composition to a surface.

[0150] It should be understood that wiping or scrubbing the surface may also be necessary to achieve cleaning. Accordingly, the present invention also provides a method of wiping or scrubbing the surface when applying the composition of the present invention to the surface.

[0151] The compositions of the invention can be used in ready-to-use form or can be diluted with water before use. Thus, the invention also provides methods such as those defined above, in which the compositions of the invention are diluted before use.

[0152] Compositions of the present invention that include compounds of formula (C), such as N,N-bis(3-aminopropyl)-dodecylamine, are particularly useful for controlling or reducing or preventing the formation of fungi.

[0153] The antimicrobial compositions of the present invention typically degrade upon immersion in water, allowing for rinse / leachate with low toxicity and short residence time in the environment.

[0154] The mobility of the product allows frequently washed or rinsed materials to be "recharged" with the antimicrobial composition during routine cleaning or maintenance procedures.

[0155] Typically, antimicrobial compositions are incorporated into simple regular detergent solutions or added to the "final rinse" during cleaning. Due to the presence of hydrophobic elements, the antimicrobial composition is drawn to the surface of the product being "refilled." Thus, the sanitizing properties of the formulation are restored without the need for remanufacturing or difficult processing methods.

[0156] Any such refill solution and any waste wash or rinse solution containing the water-diluted antimicrobial composition or formulation will rapidly separate into the biodegradable components described above.

[0157] According to another aspect of the present invention there is provided the use of the antimicrobial composition of the present invention to reduce or prevent microbial colonisation on a surface to which the antimicrobial composition of the present invention has been applied.

[0158] The antimicrobial compositions of the present invention are typically made in the manner described below.

[0159] 1. Weigh out the majority of the water (approximately 50 to 75% of the total water usage) into a suitable container. 2. Add the chelate to the water and stir until homogeneous. 3. Optionally, if a polar solvent is used in addition to water, add it and stir until the mixture is homogeneous. 4. In a separate container, prepare a combination of nonionic and amphoteric surfactants (if used) and fragrance (if used), then add to the mixture from step 3 and stir until the mixture is homogenous. 5. If using any cationic surfactants, add them and stir the mixture until homogeneous. 6. Add the quaternary ammonium compound and stir until the mixture is homogeneous. 7. Add the polymer and stir until the mixture is homogeneous. 8. Add water to 100% and stir the mixture.

[0160] Those skilled in the art will understand how to adjust the pH of a composition. For example, if this method is being used to produce a high pH composition, sodium carbonate and / or sodium bicarbonate and / or other suitable pH adjusters can be added in step 2. If this method is being used to produce a low pH composition, the pH can be adjusted by adding an acid to the composition between steps 7 and 8.

[0161] If the composition desires to include an additional antimicrobial agent, such as PHMB, add it between steps 6 and 7.

[0162] The composition may be prepared in a concentrated form (ie, containing little or no polar solvent) and diluted with a polar solvent (eg, water) at the time of use.

[0163] The present invention provides a composition obtainable by the above method. [Brief explanation of the drawings]

[0164] [Figure 1] FIG. 1 shows the results of the cleaning test reported in Example 6. [Figure 2] FIG. 1 shows the results of the cleaning test reported in Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0165] The invention will now be illustrated by the following non-limiting examples.

[0166] Experimental Residual Efficacy Testing Objective: A study was conducted to determine the residual sanitizing efficacy of antimicrobial products against certain microorganisms on non-porous stainless steel surfaces using an abrasion process and microbial challenge over a 24 hour period.

[0167] Equipment Stainless steel coupon, 2cm diameter, Grade 304 / 1.4301, Grade 2B finish (verified to EN13697:2001) Tryptone Soy Agar (TSA) for antibacterial efficacy testing Malt extract agar (MEA) for antifungal efficacy testing Tryptone-saline diluent (verified by EN1276-2009) Bovine albumin (fraction V) Vortex Validated Neutralization Solution Sterile plastic containers, diameter >3cm and <5cm forceps 50ml centrifuge tube, weight up to approximately 200g Sterile Petri dishes Inoculation Loop 70% (v / v) isopropanol Balance with at least two decimal places LAF Class 2 Biological Safety Cabinet Deionized water Hard Surface Polypropylene Wipes Standard hard water (as specified in en1276:2009) Incubator capable of maintaining temperature at 37°C ± 1°C

[0168] method Preparation of steel coupons Steel coupons (stainless steel disks) were rinsed thoroughly with clean, hot tap water to remove contaminating mud from the surface, then rinsed for several seconds with fresh deionized water. The cleaned coupons were sanitized by immersing them in 70% (v / v) isopropanol for 15 minutes. Using sterile forceps, the coupons were transferred to sterile Petri dishes and allowed to evaporate dry under laminar airflow with the lid slightly ajar. Five replicates were used for each time point collected, plus a control set.

[0169] Abrasive Cycle A 50 ml centrifuge tube was weighed to approximately 200 g (± 20 g). A professional care wipe was folded twice (four layers) and wrapped around the entire lid of the centrifuge tube to create a smooth covering. The abrasive cycle consisted of a dry wipe followed by a bacterial challenge and a wet wipe followed by a bacterial challenge (detailed below).

[0170] a) Wet wipes This consisted of wrapping a polypropylene hard surface wipe around the entire lid of a 50 ml centrifuge tube. The wipe was moistened by spraying a mist of standard sterile hard water using a trigger spray (two sprays, approximately 50 cm from the wipe). The centrifuge tube was wiped across the stainless steel coupon in a back-and-forth motion for 2-3 seconds, allowing all of the downward pressure to be applied to the coupon surface by the weight of the centrifuge tube. The wiped disk was then allowed to dry before a dry wipe was performed.

[0171] b) Dry wipes Similar mechanism to the wet wipe cycle, but the wipe was not moistened.

[0172] c) Bacterial challenge The required concentration of the bacterial suspension containing the interfering substance was then adjusted to 10 6 CFU / ml (midpoint / wear point) or concentration 10 8 The discs were subjected to a bacterial challenge (see below for bacterial challenge preparation) using CFU / ml (0 and final wear cycle).

[0173] Bacterial challenge preparation Bacterial suspensions were freshly prepared from secondary subcultures in TSA (subcultures prepared as specified in EN13697:2001). Tryptone saline was used to dilute the bacterial suspension as needed to a cell concentration of approximately 10 8A suspension of CFU / ml was obtained. The concentration of the bacterial suspension was determined using a colorimeter. The suspension was mixed 1:1 with bovine albumin solution (0.6%) before use to obtain a final concentration of 0.3% bovine albumin solution in the bacterial suspension. 8 CFU / ml bacterial suspension was used for the initial and final bacterial challenge of the study.

[0174] For reinoculation (included in the ablation step), tryptone saline solution was used to 8 CFU / ml suspension for another 10 6 CFU / ml. 6 The CFU / ml suspension was mixed 1:1 with bovine albumin solution (0.6%) before use to obtain a final concentration of 0.3% bovine albumin solution in the bacterial suspension.

[0175] Testing Methodology (All tests were performed using five replicates) 1. Time 0: 100 μl of the product to be tested or sterile hard water (for control coupons) was pipetted onto the sterile coupons and the product was spread with an inoculating loop so that the entire surface was covered. The coupons were left to dry at ambient temperature (21-23°C) on a level surface in a biological safety cabinet until completely dry.

[0176] 2. (0 wear) Control steel discs were evaluated for initial antibacterial efficacy - bacterial suspension (10 8 Ten microliters of 10 μL of 10 CFU / ml was added to a steel disk, and after a contact time of 5 minutes, the disk was dropped using sterile forceps into a vial containing 10 ml of neutralizer solution. The vial was briefly shaken to mix, then allowed to stand for 5 minutes, after which the vial was vortexed for 30 seconds. Serial dilutions (10 -4 ) was prepared in neutralizing solution and incubated. Molten TSA was poured into the plate, allowed to solidify, and then incubated at 37°C for 48 hours.

[0177] 3. Ablation Sample First abrasive wear cycle - After complete dehydration (at least 3 hours) of 100 μl of product, the steel coupons were subjected to the first abrasive wear cycle. 6 The tests consisted of a dry wipe followed by a bacterial challenge and a wet wipe followed by a bacterial challenge using a bacterial suspension of 10 CFU / ml (0.3% bovine albumin concentration). 6 Ten microliters of the bacteria / bovine albumin suspension at CFU / ml was applied to the center of the disk and gently spread using a sterile disposable loop. The disk was left to dry in the petri dish in a safety cabinet. Once dry, the lid was replaced and the disk was left undisturbed until the next abrasive cycle was required.

[0178] 2nd abrasive wear cycle - exactly the same as above Third abrasive wear cycle (24 hours). After a dry wipe and subsequent re-inoculation, the discs were given a final wet wipe and were then washed for 10 minutes as follows: 8 Antibacterial efficacy was determined using CFU / ml bovine albumin bacterial suspension as well as initial activity (0 wear).

[0179] 10 8 10 μl of the CFU / ml bacteria / bovine albumin suspension was added to the disk, and after a contact time of 5 minutes, the disk was placed using sterile forceps into another vial containing 10 ml of neutralizer solution. The vial was briefly shaken to mix, then allowed to stand for 5 minutes, after which the vial was vortexed for 30 seconds. -4 Serial dilutions (up to 100%) were prepared in neutralizing solution and incubated. Molten TSA was poured onto the plates, allowed to solidify, and then incubated at 37°C for 48 hours.

[0180] Neutralizer validation A new batch of bacterial suspension was prepared in tryptone saline solution from the secondary culture in TSA (10 8 CFU / ml). The suspension was mixed 1:1 with 0.6% bovine albumin solution to obtain a final concentration of 0.3% bovine albumin solution in the bacterial suspension.

[0181] For each product under test, 100 μl of product was pipetted into a sterile container containing 10 ml of neutralizing agent, mixed gently, and allowed to stand for 5 minutes. After neutralization, 10 8 10 μl of CFU / ml of antimicrobial test suspension was inoculated, transferred to a vial, mixed thoroughly, and the vial was allowed to stand for 5 minutes and vortexed for 30 seconds. -4 Serial dilutions up to 100% were prepared in neutralizing solution and incubated. Molten TSA (tryptone soy agar) was poured onto plates, allowed to solidify, and then incubated at 37°C for 48 hours. TVC (total viable count of bacteria grown in agar) was obtained from the products, and the log 10 bacterial reduction / was calculated from a hard water-treated disk as a control.

[0182] A tested composition was considered to have passed the test and provided residual antimicrobial efficacy if it showed a log 3 or greater reduction in bacteria at the end of the test. [Example]

[0183] Simple formulations, Quats / Chelating / Surfactants with or without polymers (Mirapol)

[0184] [Table 2]

[0185] These results demonstrate that formulations that do not contain the polymer (Mirapol Surf S110) do not provide residual antimicrobial performance against either Pseudomonas or E. coli. These results also demonstrate that formulations that contain all of the essential components of the compositions of the present invention provide residual antimicrobial performance.

[0186] Experimental section Quat Blend Concentrate - RSH008 / 100A To a suitable sized container, deionized water (760.00 g) was added, followed by DDQ (Acticide DDQ40) (200.00 g), and the mixture was stirred with a magnetic stirrer for 10 minutes. BAC (Acticide BAC50M) (40.00 g) was then added and stirred for an additional 30 minutes.

[0187] Preparation of 12E To an appropriately sized container, deionized water (90.00 g) was added, followed by tetrasodium EDTA (Surfac Na4 EDTA Liquor-Surfachem) (0.2 g), and the mixture was stirred with a magnetic stirrer for 15 minutes. C9-11 alcohol ethoxylate (Surfac UN9090-Surfachem) (0.11 g) was then added, and the mixture was stirred for an additional 15 minutes. Quat blend (RSH008 / 100A-Byotrol) (7.00 g) was then added, and the mixture was stirred for an additional 10 minutes. The pH was then checked and adjusted to approximately pH 4 using 88% lactic acid sol (Fisher) (0.1 g). Deionized water was then added until the sample reached 100 g (4.61 g), and the mixture was then stirred for an additional 15 minutes. [Example]

[0188] Low pH mixed surfactant formulation Residual performance against Pseudomonas spp.

[0189] [Table 3]

[0190] These results demonstrate that compositions without polymer do not achieve the desired level of residual antimicrobial performance. It is known that adding high levels of surfactant relative to the amount of quaternary ammonium compound can affect the antimicrobial performance of a composition. However, the Sharp 3E results demonstrate the following effect: The addition of component (ii) polymer and chelate (v) produces formulations that exhibit desirable levels of residual antimicrobial performance (>3 logs).

[0191] Sharp Series: Sharp 3B Experiment To an appropriately sized container, approximately 78.35 g of deionized water was added, followed by 0.2 g of Dissolvine GL-47 (Brenntag). The mixture was then stirred with a magnetic stirrer for 10 minutes. Then, 0.50 g of alcohol ethoxylate (Surfac UN9090 - Surfachem) and 1.0 g of C10 amine oxide (Euroxide D40 - EOC) were added and stirred for an additional 15 minutes. After this, 14.0 g of Quat blend (a 4:1 blend of DDAC and BAC) was added and the mixture was stirred for an additional 10 minutes. 0.95 g of Mirapol Surf S110 (Rhodia) was then added and stirred for an additional 10 minutes. The pH was then checked and adjusted to approximately pH 4 using 4.14 g of 8.8% lactic acid sol (Fisher). Deionized water was then added to a final volume of 100 g, followed by stirring for an additional 15 minutes.

[0192] Samples Sharp 3A, 3C and 3E were prepared using the same procedure as for Sharp 3B, except that the components specified in the table were omitted. [Example]

[0193] Low pH mixed surfactant formulations containing various chelates - Residual performance against Pseudomonas spp.

[0194] [Table 4]

[0195] Project Sharp 4: Sharp 4A To an appropriately sized container, deionized water (75 g) was added, followed by alcohol ethoxylate (Surfac UN9090 - Surfachem) (0.50 g), followed by C10 amine oxide (Euroxide D40 - EOC) (1.0 g), and the mixture was allowed to stir for 15 minutes. After this, Quat blend (a 4:1 blend of DDAC and BAC) (14.0 g) was added, and the mixture was allowed to stir for an additional 10 minutes. Mirapol Surf S110 (Rhodia) (0.95 g) was then added, and the mixture was allowed to stir for an additional 10 minutes. Tetrasodium EDTA (Surfac Na4EDTA Liquor) (0.4 g) was then added, and the mixture was allowed to stir for an additional 15 minutes. The pH was then checked and adjusted to approximately pH 4 using 88% lactic acid sol (Fisher) (0.5 g). Deionized water (7.65 g) was then added to 100 g, and the mixture was allowed to stir for an additional 15 minutes.

[0196] All other formulations were prepared in the same manner as Sharp 4A using alternative chelates. [Example]

[0197] High pH formulation - residual performance against Pseudomonas spp.

[0198] [Table 5]

[0199] These results demonstrate that chelates can improve formulation clarity in addition to improving residual antimicrobial performance at high pH, ​​which is particularly important in achieving an aesthetically pleasing product.

[0200] The inventors have found that when formulated with polymers of the type described herein, the chemistry of the monomers can also cause clarity problems at higher pH (>4.5). Selection of surfactants, chelates, and the amounts of these components can improve the clarity of the composition.

[0201] Project Sharp 2: Experimental section of Sharp 2A (RSH008 / 96A) To an appropriately sized container, deionized water (75 g) was added, followed by sodium carbonate (Fisher) (0.36 g) and sodium bicarbonate (Fisher) (0.10 g). The mixture was stirred with a magnetic stirrer for 15 minutes. After this, alcohol ethoxylate (Surfac UN9090 - Surfachem) (0.5 g) and C10 amine oxide (Euroxide D40 - EOC) (2.00 g) were added and stirred for an additional 30 minutes. Next, Quat blend (4:1 blend of DDAC:BAC) (14.00 g) was added and stirred for an additional 10 minutes. Next, Mirapol Surf S110 (Rhodia) (0.95 g) was added and stirred for an additional 10 minutes. The solution became cloudy at this point. Tetrasodium EDTA chelate (Surfac Na4 EDTA Liquor - Surfachem) (0.4 g) was then added and stirred for an additional 15 minutes. The solution became clear upon addition of EDTA. The pH was then checked. Specification pH 9.50-10.00. Deionized water (6.69 g) was then added to 100 g, and the mixture was then stirred for an additional 15 minutes. Sharp 2F was made in the same manner, omitting the chelate.

[0202] At high pH, ​​stability and clarity issues can exist. The use of a chelate can help improve the clarity and subsequent stability of the composition. Absence of the chelate (EDTA) can have an adverse effect on microbiological performance.

[0203] [Table 6]

[0204] These results demonstrate that the use of polar solvents in addition to water can help improve the stability of compositions, especially when the composition contains a fragrance. The inclusion of such solvents does not have a detrimental effect on residual antimicrobial performance. All of the compositions tested in this example passed the test for residual antimicrobial efficacy.

[0205] Experimental section Compositions Sharp 2E, 2G, and 2H were prepared in the same manner as described for Composition Sharp 2A, with the addition of a solvent added after the surfactant. [Example]

[0206] High pH formulations with or without polymers (Mirapol), with or without chelates, residual performance against Pseudomonas spp.

[0207] [Table 7]

[0208] These results demonstrate that the absence of a chelate and / or polymer can result in reduced residual antimicrobial efficacy. They also demonstrate that compositions containing both a polymer and a chelate pass the test for residual antimicrobial efficacy. Formulation Sharp 11B contained no surfactant and resulted in an opaque solution, which is undesirable. While desirable residual performance was achieved, the sample that did not contain surfactant exhibited poor cleaning performance, which is undesirable. Formulation Sharp 2A demonstrates that a composition containing all four essential components required by the present invention has desirable residual antimicrobial performance and desirable cleaning capabilities (see Example 6).

[0209] Experimental section The compositions were prepared as described above for the Sharp 2 series. [Example]

[0210] Comparison of cleaning properties of high and low pH formulations with and without surfactants The results of this experiment are shown in FIG. Line 1 - Sharp 2A - High pH formulation with surfactant Line 2 - Sharp 11B - surfactant-free high pH formulation Line 3 - Sharp 3A - surfactant-free low pH formulation Line 4 - Sharp 3B - Low pH formulation with surfactant

[0211] The results show that surfactants are essential for cleaning, and that high pH compositions can provide slightly better cleaning than low pH compositions. Mixed surfactants can improve cleaning performance, especially on a wide range of soils.

[0212] Cleanliness test procedure (using wet abrasive scrub tester Re 903PG) A white acrylic panel coated with a simulated bathtub soil composition (a combination of calcium carbonate, soap, and grease) was placed on the wet abrasive scrub tester with the coated side facing up. Four sponges, labeled 1 through 4, were immersed in cold water and then squeezed between two tiles. Two grams of each product was added to the sponge, and the product added to each sponge was recorded. The sponges were placed in sponge holders 1 through 4 of the wet abrasive scrub tester. 300 grams of extra weight was added to each sponge holder. The tester was set for 100 abrasion cycles and then started. Upon completion of the run, the panel was removed from the tester, and the level of soil removal was evaluated using tracks 1 through 4. The tracks were then scored between 0 and 10, with 0 corresponding to no soil removal and 10 corresponding to complete soil removal.

[0213] Series 6: High pH and the presence or absence of surfactants

[0214] [Table 8]

[0215] Series 6: Low pH with or without surfactants

[0216] [Table 9] [Example]

[0217] Cleaning performance

[0218] [Table 10]

[0219] The results of this experiment are shown in FIG. Line 1 - Sharp 8A - Low pH formulation with polymer, no surfactants, no chelates Line 2 - Sharp 8B - Low pH formulation containing polymers and chelates, no surfactants Line 3 - Sharp 8C - Low pH formulation, no surfactants, no polymers, no chelates Line 4 - Sharp 8D - Low pH formulation containing surfactants, chelates and polymers

[0220] The results show that surfactants aid in cleaning.

[0221] Experimental section: Sharp 8D To an appropriately sized container, 85 g of deionized water was added, followed by 7.0 g of Quat blend (RSH008 / 100A-Byotrol). The mixture was then stirred with a magnetic stirrer for 10 minutes. After this, 0.95 g of Mirapol Surf S110 (Rhodia) was added and stirred for an additional 10 minutes. 0.20 g of Dissolvine GL-47 (Brenntag) was then added and stirred for an additional 10 minutes. 1.0 g of C10 amine oxide (Euroxide D40-EOC) and 0.5 g of C9-11 alcohol ethoxylate (Surfac UN90 90-Surfachem) were then added, and the mixture was stirred for an additional 15 minutes. The pH was then checked and adjusted to approximately pH 3.5 using 0.60 g of 88% lactic acid sol (Fisher). Deionized water (5.75 g) was then added to 100 g and the mixture was stirred for a further 15 minutes.

[0222] Compositions Sharp 8A, Sharp 8B and Sharp 8C were made using the same procedure except for omitting the indicated component.

Claims

1. (i)(I) Formula (A): 【Chemical Formula 1】 [In the formula, R 1 and R 2 are each independently a linear, unsubstituted, uninterrupted C 8～12 is an alkyl group, and X - is chloride, bromide, fluoride, or iodide] and at least one quaternary ammonium compound of (II) A compound of formula (B): 【Chemistry 2】 wherein m is 8 to 18; and X - is chloride, bromide, fluoride, or iodide] or benzethonium chloride, an antimicrobial component comprising a quaternary ammonium component (a), (ii) a hydrophilic polymer; (iii) a polar solvent, (iv) nonionic surfactants, including alcohol ethoxylates and amine oxides; and (v) containing a chelating agent; The polymer is (1) a monomer which is diallyldimethylammonium chloride; and (2) Acrylic acid as an acidic monomer Including, having a pH of 4 or greater; An antimicrobial composition that is alcohol-free, or that contains less than 1% by weight alcohol, or less than 0.5% by weight alcohol, or less than 0.1% by weight alcohol.

2. 10. The composition of claim 1, which is free of glycol ethers.

3. 3. The composition of claim 1 or 2, wherein the polar solvent consists of or is water.

4. (i) The benzalkonium compound of formula (B) is selected from the group consisting of benzyldimethyl-n-tetradecyl-ammonium chloride, benzyldimethyl-n-dodecyl-ammonium chloride, benzyl-C 12 ~C 16 -alkyl-dimethyl-ammonium or benzyl-cocoalkyl-dimethyl-ammonium chloride, and / or (ii) The composition of any one of claims 1 to 3, wherein the compound of formula (A) is di-n-decyldimethylammonium chloride, octyldecyldimethylammonium chloride, or dioctyldimethylammonium chloride.

5. 5. The composition of claim 1, wherein the chelating agent is selected from EDTA (ethylenediaminetetraacetic acid), gluconate, GLDA (glutamic acid diacetate), EDDS (ethylenediamine-N,N'-disuccinic acid), DPTA (diethylenetriaminepentaacetic acid), HEDTA (hydroxyethyl-ethylenediaminetriacetic acid), MGDA (methylglycine diacetate), PDTA (1,3-propylenediaminetetraacetic acid), and EDG (ethanol diglycine), and mixtures thereof.

6. 6. The composition of claim 1, having a pH of 4.5 or greater.

7. 7. The composition of any one of claims 1 to 6, comprising 2000 ppm to 10000 ppm of component (i).

8. 8. The composition of claim 1, comprising from 500 ppm to 3000 ppm of the hydrophilic polymer.

9. 9. The composition of claim 1, comprising 400 ppm to 3000 ppm of a chelating agent.

10. 10. The composition of claim 1, comprising from 2000 ppm to 13500 ppm of nonionic surfactant.

11. 11. The composition of claim 1, which does not contain alkyl polyglucosides.

12. 12. The composition of any one of claims 1 to 11, comprising an additional antimicrobial component (b).

13. 13. The composition of claim 12, wherein the additional antimicrobial agent (b) is selected from polymeric and non-polymeric biguanidines, silver, octenidine HCl, amphoteric compounds, iodophors, phenolic compounds, isothiazalone, nitrobromopropane, nitrogen-based heterocyclic compounds, alkylbetaines, alkylamine oxides, arginine-based cationic surfactants, anionic amino acid-based surfactants, and amine antimicrobial agents, and mixtures thereof.

14. The additional antimicrobial agent is polyhexamethylene biguanidine or a compound of formula (C) 【Chemistry 3】 wherein R is an unsubstituted C 8 ~C 18 The composition of claim 13, wherein:

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

16. 16. The composition of claim 1, comprising no more than 0.5% by weight of formic acid.

17. 17. The composition of any one of claims 1 to 16, which is also a cleaning composition.

18. (i) (C 10 H 21 ) 2 (CH 3 ) 2 N + Cl - and benzalkonium chloride; (ii) a polymer containing DADMAC and acrylic acid; (iii) water; (iv) nonionic surfactants that are alcohol ethoxylates and amine oxides; and (v) a chelating agent that is EDTA or GLDA 10. The composition of claim 1, comprising:

19. 19. The composition according to any one of claims 1 to 18, for use on hard surfaces.

20. 20. A method of cleaning a hard surface and providing a residual antimicrobial benefit to the hard surface, the method comprising applying to the hard surface a composition according to any one of claims 1 to 19.

21. 20. Use of a composition according to any one of claims 1 to 19 to reduce or control the formation of microbial colonies on or near hard surfaces.

22. 20. A method of reducing or controlling the formation of microbial colonies on or near a hard surface, comprising applying to said surface a composition according to any one of claims 1 to 19.

23. 20. A method of disrupting, preventing or reducing the adhesion and / or attachment of microorganisms to a hard surface, the method comprising applying to the surface a composition according to any one of claims 1 to 19.

Images