JP2023021253A - antimicrobial composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antimicrobial composition suitable for use in a hard surface.

SOLUTION: A composition contains (i) an antibacterial component containing at least one kind of antibacterial quaternary ammonium compound, (ii) a hydrophilic polymer, (iii) a polar solvent, (iv) at least one kind of nonionic surfactant and (v) a chelate, where the polymer contains 2 kinds of the following type monomers: (a) a monomer having a perpetual cation charge or a monomer capable of forming a cation charge by proton addition, (2) an acidic monomer having an anion charge or capable of forming the anion charge and (3) a neutral monomer.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to antimicrobial compositions and formulations containing antimicrobial compositions.

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

Many antimicrobial agents are known that are capable of destroying microorganisms present in a wide variety of environments, including medical, industrial, commercial, domestic and marine environments. Many of the known antimicrobial agents have previously been included in compositions for use in various applications and environments.

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

For example, many antimicrobial agents are toxic to microorganisms and therefore destroy them upon contact with them. 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 to humans and animals as well as microbes. Therefore, handling these antimicrobial agents is hazardous and therefore requires specialized handling, processing and equipment for safe handling. Therefore, there can be many problems in manufacturing and disposing 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 consumables that are difficult to ensure are used for their intended purpose.

As used herein, unless the context indicates otherwise, "toxicity" is intended to refer to toxicity to complex organisms such as mammals. The word "toxic" should be construed accordingly.

When antimicrobials enter the environment, they can affect the health of lifestyles that were not intended to affect them. Furthermore, antimicrobial agents are often quite stable and can cause long-term environmental problems.

Other antimicrobial agents currently in use include antibiotic-type compounds. Antibiotics disrupt the biochemistry within microorganisms. Although antibiotics are effective, it is believed that they can selectively allow the development of resistant strains of the species in which they are used.

An alternative 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 materials are effective in moist environments for sterilization and cleaning, but stop working immediately after drying.

The listing or discussion herein of an apparently previously published document should not necessarily be construed as an admission that the document is part of the state of the art or common general knowledge.

U.S. Patent No. 6,569,261 U.S. Patent No. 6,593,288 U.S. Patent No. 6,703,358 U.S. Patent No. 6,767,410

Biocidal Products Regulations (Directive 98/8/EC) EPA (U.S. Environmental Protection Agency) Listing and Annex I

There is a need to provide compositions that have antimicrobial properties and that address one or more of the above problems for a variety of applications and uses, such as cleaning applications. However, it is not easy to achieve this. There are regulations such as the Biocidal Products Regulations (Directive 98/8/EC) that regulate the use of antimicrobials in terms of both the nature and amount of a given antimicrobial that may be used. Additionally, potential reactivity when the antimicrobial is present in the composition is important, as some antimicrobials are rendered inactive by chemical reactions. Even if the antimicrobial agent is not chemically inactivated, its activity may be inhibited by other components of the composition.

Surprisingly, the inventors have found that the aforementioned drawbacks can be overcome by certain combinations of ingredients. It has also been found that compositions containing these combinations of ingredients can have some surprising and unexpected properties.

In particular, the present invention provides antimicrobial compositions suitable for various consumer uses. The compositions of the 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.

The compositions of the invention can be used in a variety of applications and are particularly suitable for use on hard surfaces. The compositions of the present invention 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.

As used herein, the term cleaning means removing dirt, such as dirt, soap scum, and scale.

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 and (v) chelates. Antimicrobial component (i) preferably contains at least two quaternary ammonium compounds.

The compositions of the present invention consist of the ingredients listed in the paragraph above, although it is envisioned that they may contain additional ingredients as described below and other ingredients that are standard in the art. well or may consist essentially of them.

For the avoidance of doubt, when the term "comprising" or "comprises" is used herein, the composition or formulation or ingredient being described does not include the listed components. It is meant to contain, but may optionally contain additional components. When the terms “consisting essentially of” or “consists essentially of” are used, the composition or formulation or ingredient being described is enumerated. other components in minor amounts (e.g., up to 5% by weight) provided that any additional component does not affect the essential properties of the composition, formulation or ingredient. , or up to 1% or 0.1% by weight). When the term "consisting of" is used, it is meant that the composition or formulation or ingredient being described must contain only the listed components. These terms may apply to processes, methods and uses as well.

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

The term "antimicrobial" means a compound or composition that kills and/or inhibits the growth of microbes (microorganisms). The term "microbicidal" is used to refer to compounds or compositions that kill microorganisms. The compositions of the invention are antimicrobial and/or microbicidal.

Microorganisms or microbes are organisms that are visible only under a microscope (too small to be seen with the naked eye). Examples of microorganisms include bacteria, fungi, yeasts, molds, mycobacteria, algae, spores, archaea and protists. Microorganisms are generally single-celled or single-celled organisms. However, as used herein, the term "microorganism" also includes viruses.

The composition of the present invention comprises at least one antimicrobial agent selected from antibacterial agents, antifungal agents, antialgal agents, antispore agents, antiviral agents, antiyeast agents and antifungal agents, and mixtures thereof. including. More preferably, the compositions of the invention comprise at least one antibacterial, antiviral, antifungal and/or antifungal agent.

As used herein, the terms antibacterial agent, antifungal agent, antialgal agent, antiviral agent, antiyeast agent and antifungal agent inhibit the growth of, but do not necessarily kill, the respective microorganisms. It is intended to refer to agents that are free from bacteria and agents that kill the respective microorganism. Thus, for example, included within the scope of the term anti-bacterial agent are agents that inhibit the growth of bacteria, but do not necessarily kill them, and bactericides that do kill bacteria.

As those skilled in the art will appreciate, the ending "cidal" as used, for example, in "bactericidal" and "fungicidal" refers to an agent that kills the microorganisms referred to. used for Thus, in these examples, bactericides refer to agents that kill bacteria, and fungicides refer to agents that kill fungi. Examples of bactericides include mycobactericides and tuberculicides. Preferably, the compositions of the present invention contain at least one bactericide selected from bactericides, fungicides, algicides, sporicides, viricides, yeasticides and fungicides, and mixtures thereof. Contains active agents. More preferably, the composition of the invention comprises at least one bactericide, viricide, fungicide and/or fungicide.

The compositions of the invention are effective against a wide range of organisms including Gram-negative and Gram-positive bacteria, fungi, yeast, viruses and some spore formers.

Antimicrobial component (i) comprises (a) at least one, preferably at least two quaternary ammonium compounds with antimicrobial properties, and optionally (b) one or more additional antimicrobial agents. can contain. Commercially available blends of quaternary ammonium compounds with antimicrobial properties may be used.

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

Suitable antimicrobial quaternary ammonium compounds include compounds of formula (A)

[wherein R ¹ and R ² are each independently a linear unsubstituted uninterrupted C _8-12 alkyl group, and X ^- is a halogen such as chloride, bromide, fluoride, iodide, etc.] compound anion or a sulfonate, saccharinate, carbonate or bicarbonate] and a benzalkonium compound having the formula (B)

[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 referred to as benzalkonium compounds. Benzalkonium chloride is a mixture _{of C8-18} alkyl groups, especially linear unsubstituted uninterrupted alkyl groups _nC8H17 to _nC18H37 , predominantly _nC12H25 ( _dodecyl ) _{, nC14.} Provided and/or used as a mixture of _H29 (tetradecyl), and _nC16H33 ( _hexadecyl ). Preferably m is 8, 10, 12, 14 and/or 16. Most preferably m is from 12 to 16, such as 12, 14 and/or 16.

In compounds of formula (A), the R ¹ and R ² groups are each independently linear unsubstituted uninterrupted C _8-12 alkyl groups, such as 8, 9, 10, 11 or It is an alkyl group containing 12 carbon atoms. In one embodiment, the R ¹ and R ² groups contain the same number of carbon atoms, although this is not essential and compounds in which R ¹ and R ² contain different numbers of carbon atoms can be used.

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

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

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

Examples of quaternary ammonium compounds of formula (B) include 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-dimethylN-benzyl N-octadecylammonium chloride, and their mixtures.

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 shown in the table below. It should be understood that other commercially available benzalkonium compounds may alternatively or additionally be used.

It should be understood that one CAS number often refers to multiple blends or mixtures. The CAS classification of commercial preparations typically includes blends containing the specified compounds in amounts within defined ranges. The compositions with CAS numbers cited above are only examples of compositions with given CAS numbers that can be used in the present invention.

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).

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 is about 1:10 to about 10:1, preferably 1:5 to 5:1, or about 1:4 to about 4:1, such as about 2:1, or about 3:2 to about 2:3.

Examples of quaternary ammonium moieties are octyldecyldimethylammonium chloride and/or didecyldimethylammonium chloride and/or dioctyldimethylammonium chloride, and alkyl chlorides ( _C14 , 50%; _C12 , 40%; _C16 , 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 available from Mason Chemical as Maquat MQ 615M.

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

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 compound of formula (A) to compound of formula (B) is, for example, 10:1 to 1:10, or 4:1 to 1:4, such as 3:2 or 2:3.

In one embodiment, the quaternary ammonium antimicrobial component (i) comprises (1) a component consisting essentially of a single compound of formula (A) and (2) at least one benzalkonium compound having formula (B). a component consisting essentially of the compound, 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 .

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

Compositions of the present invention must contain at least one, such as at least two, quaternary ammonium antimicrobial agents. They may additionally contain any other suitable antimicrobial agents (b) such as those listed in the EPA (US Environmental Protection Agency) Listing and Annex I and Annex 3 of the EC Biocide Directive.

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.

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

In one aspect, the compositions of the present invention are free of inorganic antimicrobial agents, such as those containing silver. In this aspect, the additional antimicrobial agent is an organic antimicrobial agent.

Preferred additional antimicrobial agents (b) include polymeric biguanidines. One preferred additional antimicrobial agent (b) is polyhexamethylenebiguanidine (PHMB). PHMB is commercially available from Arch Biocides as Vantocil (industrial grade quality) or Cosmocil (cosmetic grade quality, eg PHMB20 supplied by Thor).

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

[In the formula, R is an unsubstituted C ₈ -C ₁₈ alkyl group. Preferably, R is an unsubstituted C ₁₀ -C ₁₄ , eg C ₁₂ alkyl group]. A preferred compound of formula (C) is dodecyldipropylenetriamine (N,N-bis(3-aminopropyl)-dodecylamine, CAS number 2372-82-9) commercially available from Lonzabac as Lonzabac 12, Triameen Also called YD12 (provided by Akzo Nobel).

In one embodiment, the compositions of the present invention may be free of PHMB, or free of polymeric biguanides, or free of non-polymeric biguanidines, or free of biguanidines (e.g., polymeric biguanides and non-polymeric biguanides). may be free of polymeric biguanides). In one aspect of the invention, the antimicrobial composition does not comprise any isothiazalone, and/or any nitrobromopropane such as bronopol, and/or any hypochlorite.

In one particular embodiment, the compositions of the invention comprising a compound of formula (C), such as N,N-bis(3-aminopropyl)-dodecylamine, are free of PHMB, or free of polymeric biguanidine or biguanidine. (eg, polymeric biguanidine and non-polymeric biguanidine). However, compositions comprising a compound of formula (C), eg N,N-bis(3-aminopropyl)-dodecylamine and a biguanidine such as polymeric or non-polymeric biguanidine, eg PHMB, are also envisioned.

Examples of compositions of the invention are those wherein component (i) is (a) at least one or at least two quaternary ammonium compounds as described above, such as compounds of formula (A) and/or compounds of formula (B) and (b) at least one polymeric biguanide such as PHMB, which may be the only additional antimicrobial component (b), or a composition in which component (b) may contain additional antimicrobial components.

Examples of compositions of the invention are those wherein component (i) is (a) at least one or at least two quaternary ammonium compounds as described above, such as compounds of formula (A) and/or compounds of formula (B) and (b) at least one compound of formula (C), such as N,N-bis(3-aminopropyl)-dodecylamine.

Examples of compositions of the invention are those wherein component (i) is (a) at least one or at least two quaternary ammonium compounds as described above, such as compounds of formula (A) and/or compounds of formula (B) and without an additional antimicrobial agent (b).

In one embodiment, component (b) is free of isothiazole. In this embodiment, the composition of the invention does not contain isothiazole.

Compositions of the invention may be provided in concentrated or ready-to-use form for dilution prior to use. The compositions of the present invention are preferably provided in a ready-to-use form and, unless otherwise stated, data for amounts (such as % by weight or ppm) given herein are for ready-to-use compositions. Regarding.

Typically, but not essential, compositions of the present invention will have a concentration of component (i) from about 100 ppm or 500 ppm to about 20000 ppm, such as from about 2000 ppm to about 10000 ppm or from 3000 ppm to 8000 ppm.

Polymers suitable for use in the present invention are monomers of the following types:
(1) a monomer that has a permanent cationic charge or a monomer that can form a cationic charge upon protonation;
(2) an acidic monomer that has an anionic charge or is capable of forming an anionic charge; and
(3) It is a hydrophilic polymer containing at least two kinds of neutral monomers.

These types of monomers can be used in any combination. For example, suitable polymers include, consist of, or consist essentially of at least one monomer of type (1) and at least one monomer of type (2); and polymers comprising, consisting of, or consisting essentially of at least one monomer of type (1) and at least one monomer of type (3), at least one of type (2) A polymer comprising, consisting of, or consisting essentially of a monomer of type (3) and at least one monomer of type (3), and at least of each of the three types of monomer Polymers comprising, consisting of, or consisting essentially of one species include, but are not limited to.

The polymers used in the present invention can have an amphoteric polyelectrolyte structure such that charge and surface adsorption are pH dependent. For example, the polymer can be an amine acrylate functional polymer. Examples of suitable hydrophilic polymers are described in US Pat. No. 6,569,261, US Pat. No. 6,593,288, US Pat. No. 6,703,358 and US Pat. No. 6,767,410, the disclosures of which are incorporated herein by reference. incorporated into the book. These references describe (1) at least one amine-functional monomer, (2) at least one acidic hydrophilic monomer, and (3) optionally at least one having ethylenic unsaturation. Water-soluble or water-dispersible copolymers containing one neutral hydrophilic monomer in the form of polymerized units are described. Copolymers include quaternized ammonium acrylamic acid copolymers.

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

Diallyldimethylammonium halides such as diallyldimethylammonium chloride (DADMAC) or the corresponding bromides. Alternatively, the counterion can be sulfate or phosphate. a monomeric unit in which one or more of the _CH3 groups are substituted with a _C2-12 , such as a _C2-6 alkyl group, or one or more of the _CH2 groups is from 2 to 12, such as 2 Similar monomeric units may be used, such as monomeric units substituted with alkyl groups having 6 carbon atoms from . In other words, other similar commercially available monomers or polymers containing such monomers may be used.

N,N,N-trimethyl-3-((2-methyl-1-oxo-2-propenyl)amino)-1-propanamide, such as the chloride (MAPTAC, also called methacryl-amido(propyl)-trimethylammonium chloride) nium halide.

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

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

2-(dimethylamino)ethyl methacrylate (DMAEMA),

N-vinylpyrrolidone (NVP),

N-vinylimidazole,

acrylamide, and

methacrylamide.

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

Suitable polymers include those sold under the trade name Mirapol available from Rhodia Novecare, eg as Mirapol Surf-S110, Mirapol Surf-S200 or Mirapol Surf-S500.

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

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

Other suitable polymers include those sold under the trade name Polyquat Ampho, such as Polyquat Ampho 149, polymers comprising, consisting of, or consisting essentially of MAPTAC and acrylic acid or methacrylic acid. mentioned.

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 that sold by BRB International under the name PQ11.

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

Typically the polymers used in the present invention are unmodified polymers. This means that the polymer has not been modified by reactions such as grafting with functionalizing agents or hydrophobic agents.

The ratio in parts per million (PPM) of quaternary ammonium component (a) to polymer (ii) is typically from 200:1 to 1:1, such as from 1:1 to 20:1 or 10:1. 20, such as about 2:1 or about 4:1. In certain embodiments, the amount in ppm of component (a) is greater than or equal to 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.

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

The compositions of the invention may comprise a single polymer (only one combination of monomeric units) or two or more polymers may be used (two or more combinations of monomeric units). (a polymer composed of

The pH of the compositions of the invention can vary within wide limits. Typically, the pH of the compositions of the invention will be similar to that of known compositions intended to be used for the same or similar purposes as a given composition of the invention. Formulations used for purposes such as kitchen or bathroom cleaning can have a low pH, such as a pH of 3 or less, such as about 2, or can have a high pH, such as a pH of 10 or more, such as a pH of 11.

In one embodiment, the composition of the invention has a pH of 2.5 or higher, such as about pH 5 to about pH 12, such as about pH 5 to pH 9 or higher, such as pH 5 to 13, such as pH 5 to pH 9 or higher, such as pH 2.5 or higher, such as 3.5 or higher or 4 or higher or 4.5 or higher. have

The compositions of the present invention comprise at least one suitable nonionic surfactant or a combination of surfactants comprising at least one nonionic surfactant (e.g. at least one nonionic surfactant agent and at least one cationic surfactant and/or amphoteric surfactant, optionally in combination). The choice of surfactant will depend on the nature and intended purpose of the composition. Suitable surfactants for use in formulations for different purposes are within the knowledge of those skilled in the art. Likewise, selecting the appropriate amount of surfactant is within the knowledge of one skilled in the art.

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

In one aspect, the composition is substantially free or free of anionic surfactants. In another aspect, the compositions of the present invention are free of amphoteric surfactants.

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

Suitable alcohols include methanol, ethanol, n-propanol, iso-propanol, mixture of propanol isomers, n-butanol, sec-butanol, tert-butanol, iso-butanol, mixture of butanol isomers, 2-methyl- Linear or branched C ₁ -C ₅ alcohols such as 1-butanol, n-pentanol, mixtures of pentanol isomers, and amyl alcohol (mixtures of isomers), and mixtures thereof. is not limited to

Preferred polar solvents for use in the compositions of the present invention include water, ethanol, n-propanol, isopropanol, ethylene glycol ethers, propylene glycol ethers, butyl diglycol (BDG) and dipropylene glycol methyl ether (trade name Dowanol). DPM), and mixtures thereof. In one embodiment, the composition comprises water or a mixture of water and one or more alcohols selected from the alcohols mentioned above. Water is preferably the major component in such mixtures. The polar solvent can consist essentially of water, or it can consist of water.

When the composition of the present invention contains alcohol, the alcohol is typically present in an amount less than that required for the alcohol to provide antimicrobial efficacy.

In one aspect, the compositions of the present invention are substantially free of alcohol. For example, the composition may contain up to 1% by weight of alcohol. For example, the composition may contain less than 1%, or less than 0.5%, or less than 0.1% by weight of an alcohol such as isopropanol. By way of example, the compositions of the present invention may contain no isopropanol or may contain no alcohol.

The composition may comprise water or a mixture of water and one or more alcohols selected from the alcohols mentioned above. Water is preferably the major component in such mixtures.

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

Amine oxides suitable for use in the present invention are those having an alkyl chain length of C ₈ to C ₁₆ . Amine oxides are suitable for use in the present invention because they can improve cleaning properties over some other surfactants and can reduce the degrading effects on the surface of certain plastics. .

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); the trade names Euroxide D40 (EOC Group) and Mackamine _C10 ( _C10 amine oxides such as those sold by Rhodia Novecare); longer chain glucosides such as _C12 amine oxides such as the trade names Euroxide LO/A (EOC Group), Ammonyx LO (Stepan Chemicals) and Surfac AO30 (Surfachem). ); and C ₁₀ -C ₁₆ amine oxides such as those sold under the trade name Ammonyx C (Stepan Chemicals).

Alcohol alkoxylates suitable for use in the present invention include linear and branched alcohol ethoxylates such as _C6 - _C18 alcohol ethoxylates having 2 to 20 EO units, such as 7 to 12 EO units. primary and secondary alcohol ethoxylates of Preferred linear primary alcohol alkoxylates include C _9-11 alcohol ethoxylates having 5 to 12 EO units, such _as 7 to 12 EO units. These surfactants are offered under the commercial name Neodol series (manufactured by Shell Chemical Company). Examples of C12-15 secondary alcohol ethoxylates having from about 3 to about 10 EO units such as those provided in the Tergitol series (Dow), particularly those provided in the Tergitol 15-S series. include those that have Examples of suitable branched alcohol ethoxylates include C10 Guerbet alcohols containing 3 to 14 EO units such as the Lutensol XL and XP series (provided by BASF). Alcohol ethoxylates with mixtures of EO and PO are also suitable, including linear and branched surfactants with PO-EO units such as ECOSURF™ EH surfactants (DOW) and Plurafac D250 (BASF). Includes alcohol ethoxylates. Alkylphenol ethoxylate (APE) surfactants may also be used.

Another group of nonionic surfactants that can be used are compounds based on alkoxy block copolymers, especially ethoxy/propoxy block copolymers. Block copolymers of polymeric alkylene oxides include nonionic surfactants composed predominantly of block polymeric C _2-4 alkylene oxides. Specific examples include surfactants marketed under the trade name Pluronic, particularly the Pluronic F series, Pluronic L series, Pluronic P series and Pluronic R series.

Another group of suitable nonionic surfactants are the alkylpolyglucosides or glucosides. Suitable examples are Surface APG, a capryl glucoside from Surfachem and the Glucopon series from BASF (Glucopon 425N/HH (C8-14), Glucopon 215 (C8-10) and Glucopon 600 (C12 -14) Alkyl polyglucoside).

In one aspect of the invention, the compositions of the invention may be free of alcohol alkoxylates. Compositions of the invention containing compounds of formula (C) as defined herein, for example those containing N,N-bis(3-aminopropyl)-dodecylamine, must be free of alcohol alkoxylates. good.

Compositions of the invention may alternatively or additionally be free of alkyl polyglucosides. Compositions of the invention containing compounds of formula (C) as defined herein, such as, for example, those containing N,N-bis(3-aminopropyl)-dodecylamine, contain alkyl polyglucosides (APG). It does not have to be included.

Typically component (iv) is present in the compositions of the present invention in an amount from about 500 ppm to 35000 ppm. The amount of surfactant (iv) will depend 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 2000 ppm to 13500 ppm.

Suitable amphoteric surfactants include C6 _{- C20} alkylamphoacetates or amphodiacetates (such as cocoamphoacetate), _C10 - _C18 alkyldimethylbetaines, _C10 - _C18 alkylamidopropyldimethylbetaines. include, but are not limited to. Examples include cocoamidopropyl betaine (CAPB) (Surfac B4, CAS 61789-40-9), a coconut oil type amphoteric surfactant, cocoimidazoline betaine, oleamidopropyl betaine, and tall oil imidazoline, but It is not limited to these.

Without wishing to be bound by theory, it has been found that the surfactant component can have several effects on the properties of the compositions of the present invention. The presence of nonionic surfactants can improve the cleaning ability of the composition, ie, improve dirt and mud removal. It has been found that the use of alcohol alkoxylates in combination with amine oxides can improve cleaning performance in some circumstances. Additionally, the inclusion of nonionic surfactants may improve the stability of the compositions of the present invention.

Surprisingly, the inventors have found that using the combinations described herein results in stable compositions that achieve residual antimicrobial performance.

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

Compositions of the invention include chelates. Any suitable chelate can be used. Suitable chelates include EDTA (ethylenediaminetetraacetic acid), gluconate, GLDA (glutamic diacetic acid) - tradename Dissolvine GL, EDDS (ethylenediamine-N,N'-disuccinic acid), DPTA (diethylenetriaminepentaacetic acid), HEDTA (hydroxy ethylethylenediaminetriacetic acid), MGDA (methylglycinediacetic acid)-trade name Trilon M, PDTA (1,3-propylenediaminetetraacetic acid), and EDG (ethanoldiglycinic acid), and mixtures thereof. is not limited to If the chelate contains a counterion, it is preferred that the counterion is metallic. Suitable metal counterions include, but are not limited to Na, Ca, Fe, K, Zn, Mg and Mn.

Preferred chelates are GLDA (Dissolvine) and EDTA.

Chelates are typically present in an amount of about 100 ppm to 10,000 ppm, preferably about 400 ppm to 3,000 ppm, such as about 500 ppm to 2000 ppm.

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

Additional components that can be used in compositions of the invention include, but are not limited to, buffering agents. Buffers include hydrophobic substances such as siloxane, hydrogen carbonates such as sodium hydrogen carbonate, sodium chloride, potassium chloride, triethylamine, triethylenetetramine, tetraethylethylenediamine, tetramethylenediamine, piperazine, histidine, imidazole, morpholine, 2-amino ethanol, aminoalcohols such as 2-amino-2-methyl-1-propanol (AMP) and triethanolamine, phosphate buffers, citrate buffers, salts thereof, and mixtures thereof; is not limited to

A complexing agent may be used. For example, complexing agents can be used to help form clear compositions even when the compositions of the present invention are used with hard water. Suitable complexing agents include methanediphosphonic acid, hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, amino-trimethylenephosphonic acid, ethylenediamine-tetra(methylenephosphonic acid), Sodium salts, citrates and gluconates of diethylenetriamine-penta(methylenephosphonic acid), 2-phosphonobutanebutane-1,2,4-tricarboxylic acid, and nitrilotriacetic acid (NTA), or of glutaric, adipic and succinic acids Salts, and mixtures thereof include, but are not limited to.

A pH adjuster may be used. Suitable pH adjusters include acids such as citric, sulfamic, hydrochloric, phosphoric, nitric, lactic, formic, acetic, glycolic, or gluconic acids, or other inorganic or organic acids, or sodium hydroxide or Bases such as potassium and sodium or potassium carbonate, and mixtures thereof, include, but are not limited to. The compositions of the invention may 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.

Some compositions of the present invention are free or substantially free of acids or bases. For example, some compositions of the present invention do not contain citrate or citric acid or lactic acid. Other compositions may contain acids or bases as appropriate for their intended use. In one aspect of the invention, the composition contains no more than 0.5% by weight or no formic acid.

Suitable siloxanes for use in the present invention include those of the formula ( _H3C )[SiO( _CH3 ) ₂ ] _nSi ( _CH3 ) ₃ and ( _H3C )[SiO( _CH3 )H] _n. Si(CH3) ₃ , and mixtures thereof, wherein n is an integer from 1 to 10, more preferably from 1 to 6, most preferably from 1 to 4, for example n is ₁ , It can be 2, 3, 4, 5, 6, 7, 8, 9, 10, especially 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 ), 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.

In certain embodiments of the invention, the compositions of the invention are free or substantially free of hydrophobic materials. For example, free or substantially free of siloxanes, silicones, polysiloxanes such as polydimethylsiloxane.

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

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

The weight ratio of component (a) to additional antimicrobial agent (b) is typically about 1:10 or about 1:2 or about 1:1 to about 50:1 or about 30:1, such as about 1 about 0.4:1 to about 4:1, such as: 1 or about 2:1 or about 3:1 to about 20:1 or about 10:1 or about 6:1, or 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.

Typically, the polar solvent component (iii) is present in the composition of the 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, such as about 80% by weight. to about 99.99 wt%, preferably about 90 wt% to about 99.9 wt%, more preferably about 95 wt% to about 99.8 wt% (e.g., 97 wt% to 99.7 wt% or 97.5 wt% to 99.6 wt%) present in quantity.

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

Examples of compositions of the invention are compositions comprising:
(i) ( _C10H21 ) ₂ ( _CH3 ) _2N ^{+ Cl-} and benzalkonium chloride, which may be present in a weight ratio of about 1:10 to 10:1, such as _about 4:1;
(ii) 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 polymers as defined above such as those containing DMAEMA and acrylamide;
(iii) water;
(iv) nonionic surfactants such as alcohol ethoxylates or amine oxides or mixtures 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.

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

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

In use, it has been found that the compositions of the invention exhibit advantageous antimicrobial effects. For example, such compositions exhibit antimicrobial efficacy when first applied to a surface (so-called "wet kill") and control, reduce or prevent the formation of new microbial colonies on the surface (so-called "dry kill"). A residual antimicrobial effect can also be demonstrated in terms of "killing").

Also, the compositions of the present invention resist washing with water and wiping. This allows the compositions of the present invention to provide residual antimicrobial benefit even when the treated surface is subsequently wiped and/or washed or rinsed with water.

The compositions of the present invention provide residual antimicrobial efficacy and provide antimicrobial efficacy even after undergoing residual efficacy testing as described herein. That is, these compositions provide microbial reduction when subjected to 3 abrasion cycles on non-porous stainless steel, glass or plastic substrates, typically achieving a 3 log or greater reduction over 24 hours. do. This is because 24 hours after applying the composition of the invention to a surface, if microorganisms were applied to the surface (without further addition of the composition of the invention or another antimicrobial agent), the microorganisms means that a reduction of at least 3 logs of is achieved.

An 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 from forming biofilms. Formation of large numbers of colonies is also substantially prevented. Accordingly, the colony's ability to grow is substantially reduced or even prevented. The present invention is therefore general in the control of microorganisms.

Typically, the compositions of the present invention need not contain components that are highly toxic to mammals. Antimicrobial agents used in antimicrobial compositions are typically well known, widely understood and tested antimicrobial agents. The efficacy of known antimicrobial agents is amplified in the formulations of the present invention. Therefore, antimicrobial agents with low toxicity can be used in antimicrobial compositions. Conversely, known techniques for sanitization use "more potent", more toxic and/or less tested substances for many "new" antimicrobial agents.

The antimicrobial compositions of the present invention do not contain materials that produce a highly persistent residue or rinse, or products containing heavy metals and their salts. Therefore, the risk of long-term hazards is greatly reduced.

The antimicrobial compositions of the present invention do not interfere with the biochemical reproductive pathways of the microorganisms being controlled. Therefore, the risk of resistance build-up and the emergence of resistant strains is low.

The antimicrobial composition of the present invention can exhibit a dual benefit as it not only provides an antimicrobial effect during use, but also exhibits a preservative effect on the composition. This typically eliminates the need to include additional preservatives in the formulations of the present invention.

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

According to another aspect of the invention there is provided the use of the composition of the invention for controlling, reducing or preventing the formation of microbial colonies on surfaces to which the composition of the invention has been applied.

The present invention provides a method of providing a residual antimicrobial effect to a surface, such as a hard surface or skin, comprising applying to the surface a composition as defined herein. 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 invention, the method need not involve any steps other than simply applying the composition to the surface. Accordingly, there is provided a method consisting essentially of, or consisting of, the step of applying the composition to a surface.

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 a surface when applying the composition of the present invention to the surface.

The compositions of the invention can be used in ready-to-use form or can be diluted with water before use. The invention therefore also provides a method, such as the method defined above, wherein the composition of the invention is diluted prior to use.

Compositions of the invention comprising compounds of formula (C) such as N,N-bis(3-aminopropyl)-dodecylamine are particularly useful for controlling or reducing or preventing fungal formation.

The antimicrobial compositions of the present invention can typically degrade upon immersion in water to provide a rinse/leaf solution with low toxicity and short residence time in the environment.

The mobility of the product allows materials that are frequently washed or rinsed to be "recharged" with the antimicrobial composition during routine cleaning or maintenance actions.

Typically, antimicrobial compositions are incorporated into simple regular detergent solutions or added to the "final rinse" when cleaning. The antimicrobial composition is drawn to the surface of the product to be "recharged" due to the presence of the hydrophobic element. Thus, the sanitary processing properties of the formulation are restored without the need for remanufacturing or difficult processing methods.

Both such replenishing solutions and wash effluents or rinses containing water-diluted antimicrobial compositions or formulations rapidly separate into the biodegradable components previously described.

According to another aspect of the invention there is provided the use of the antimicrobial composition of the invention to reduce or prevent the formation of microbial colonies on a surface to which the antimicrobial composition of the invention is applied.

The antimicrobial compositions of the invention are typically made by the methods described below.

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

A person skilled in the art knows how to adjust the pH of the composition. For example, sodium carbonate and/or sodium bicarbonate and/or other suitable pH adjusting agents can be added in step 2 if the process is to produce a high pH composition. If this method is used to produce a low pH composition, the pH can be adjusted by adding acid to the composition between steps 7 and 8.

If you want to include an additional antimicrobial agent such as PHMB in the composition, add it between steps 6 and 7.

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

The present invention provides a composition obtained by the above method.

FIG. 10 shows the results of cleaning tests reported in Example 6. FIG. FIG. 10 shows the results of cleaning tests reported in Example 7. FIG.

The invention will now be illustrated with the following non-limiting examples.

Experimental Residual Effectiveness Test Goal: Test to determine the residual sanitary treatment effectiveness of antimicrobial products against certain microorganisms on nonporous stainless steel surfaces using an ablation process and microbial challenge over a 24 hour period. carried out.

Instrument stainless steel coupon, 2 cm diameter, grade 304/1.4301, grade 2B finish (confirmed by EN13697:2001)
Trypton Soy Agar (TSA), Malt Extract Agar (MEA) for Antibacterial Efficacy Test, Tryptone-Saline Diluent for Antifungal Efficacy Test (confirmed by EN1276-2009)
Bovine albumin (Fraction V)
Vortex-validated neutralization solution sterile plastic container, >3 cm and <5 cm diameter
forceps
50 ml centrifuge tube, sterile Petri dish inoculation loop up to approx. 200 g weight
70% (v/v) isopropanol Balance to at least two decimal places
LAF Class 2 Biological Safety Cabinet Deionized Water Hard Surface Polypropylene Wipes Standard Hard Water (described in en1276:2009)
Incubator capable of 37℃±1℃

Methods Steel coupon preparation Steel coupons (stainless steel discs) were rinsed thoroughly with clean, hot water (tap water) to remove contaminant mud from the surface, and then rinsed with fresh deionized water for a few seconds. Sanitization was performed by immersing the cleaned coupons in 70% (v/v) isopropanol for 15 minutes. Using sterile forceps, the coupon was transferred to a sterile petri dish and allowed to evaporate to dryness under a laminar air stream with the lid slightly open. Five replicates were used for each time point collected plus a control set.

abrasive cycle
A 50 ml centrifuge tube was weighed to a weight of approximately 200 g (±20 g). A professional care wipe was folded twice (4 layers) and wrapped around the lid of the centrifuge tube to provide a smooth covering. Abrasive cycles consisted of a dry wipe followed by a bacterial challenge and a wet wipe followed by a bacterial challenge (detailed below).

a) Wet Wipe This consisted of ablation by wrapping a polypropylene hard surface wipe over the lid of a 50 ml centrifuge tube. The wipes were moistened by spraying a mist of standard sterile hard water using a trigger spray (2 sprays, approximately 50 cm distance from the wipe). The centrifuge tube was wiped over the stainless steel coupon in a back and forth motion for 2-3 seconds, allowing all of the downward pressure to be exerted on the coupon surface by the weight of the centrifuge tube. A dry wipe was then performed after the wiped disc was dried.

b) Dry Wipe Mechanism similar to the wet wipe cycle, but the wipe was not wetted.

c) Bacterial challenge Then use the required bacterial suspension with a concentration of 10 ⁶ CFU/ml (intermediate time point/wear time) or a concentration of 10 ⁸ CFU/ml (0 and final wear cycle) containing interfering substances. The discs were then subjected to a bacterial challenge (see below for bacterial challenge preparation).

Bacterial Challenge Preparation Bacterial suspensions were freshly prepared from secondary subcultures (subcultures prepared as identified in EN 13697:2001) on TSA. Tryptone saline was used to dilute the bacterial suspension as necessary to obtain a suspension with a cell concentration of approximately 10 ⁸ CFU/ml. A colorimeter was used to determine the concentration of the bacterial suspension. The suspension was mixed 1:1 with bovine albumin solution (0.6%) before use to give a final concentration of 0.3% bovine albumin solution in the bacterial suspension. A bacterial suspension with a concentration of 10 ⁸ CFU/ml was used for the initial and final bacterial challenge of the study.

For re-inoculation (included in the ablation step), tryptone saline solution was used to further dilute the 10 ⁸ CFU/ml suspension to 10 ⁶ CFU/ml. The 10 ⁶ CFU/ml suspension was mixed 1:1 with bovine albumin solution (0.6%) before use to give a final concentration of 0.3% bovine albumin solution in the bacterial suspension.

Test method (all tests were performed using 5 replicates)
1. Time 0 hours: Pipet 100 μl of the product to be tested or sterile hard water (for control coupons) onto the sterile coupon and spread the product with the inoculation loop so that the entire surface is covered. bottom. The coupons were left to dry on a level surface in a biosafety cabinet at ambient temperature (21-23°C) until completely dry.

2. (0 wear) Control steel discs were evaluated for initial antibacterial efficacy - 10 μL of a bacterial suspension (10 ⁸ CFU/ml) containing 0.3% bovine albumin was added to the steel discs for a contact time of 5. Minutes later, using sterile forceps, the disc was placed in a vial containing 10 ml of neutralizer solution. The vial was shaken briefly to mix, then allowed to sit for 5 minutes and then the vial was vortexed for 30 seconds. Serial dilutions (10 ⁻⁴ ) were then prepared in neutralizing solution and incubated. The molten TSA was poured onto the plate, left to solidify, and then incubated at 37°C for 48 hours.

3. Ablation Samples 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. This consisted of a dry wipe followed by a bacterial challenge and a wet wipe followed by a bacterial challenge using a bacterial suspension with a concentration of 10 ⁶ CFU/ml (0.3% bovine albumin concentration). 10 μl of the 10 ⁶ CFU/ml bacteria/bovine albumin suspension was applied to the center of the disc and spread gently using a sterile disposable loop. The discs were left to dry in a Petri dish in a safety cabinet. Once dry, the lid was replaced and the disc was allowed to sit until the next abrasive cycle was required.

2nd Abrasive Wear Cycle - Exactly as above 3rd Abrasive Wear Cycle (24 hours). After dry wiping followed by re-inoculation, discs were subjected to a final wet wipe, similar to initial activity (0 wear) using 10 ⁸ CFU/ml bovine albumin bacterial suspension as follows: Antibacterial efficacy was determined.

10 μl of the 10 ⁸ CFU/ml bacteria/bovine albumin suspension was added to the discs and after a contact time of 5 minutes, the discs were dispensed into another vial containing 10 ml of neutralizer solution using sterile forceps. . The vial was shaken briefly to mix, then allowed to sit for 5 minutes and then the vial was vortexed for 30 seconds. Serial dilutions (up to 10 ⁻⁴ ) were then prepared in neutralizing solution and incubated. The molten TSA was poured onto the plate, left to solidify, and then incubated at 37°C for 48 hours.

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 give a final concentration of 0.3% bovine albumin solution in the bacterial suspension.

For each product under test, 100 μl of product was pipetted into a sterile container containing 10 ml of neutralizer, mixed gently and left for 5 minutes. After neutralization, the discs were inoculated with 10 μl of the 10 ⁸ CFU/ml antimicrobial test suspension, transferred to vials, mixed well, and the vials allowed to sit for 5 minutes and vortexed for 30 seconds. Serial dilutions up to 10 ⁻⁴ were prepared in neutralizing solution and incubated. Morten TSA (trypton soy agar) was poured onto the plates and left to solidify before incubating at 37° C. for 48 hours. The TVC (total viable count of bacteria grown in agar) was obtained from the products and the log 10 bacterial reduction/ was calculated from discs treated with hard water as a control.

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

Simple Formulations, Quats/Chelates/Surfactants with or without Polymers (Mirapol)

These results show that formulations without the polymer (Mirapol Surf S110) do not achieve residual antimicrobial performance against Pseudomonas or E. coli. These results also show that formulations containing all the essential constituents of the compositions of the present invention achieve residual antimicrobial performance.

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

Preparation of 12E In an appropriately sized container, deionized water (90.00 g) is added followed by Surfac Na4 EDTA Liquor-Surfachem (0.2 g) and the mixture is stirred for 15 minutes with a magnetic stirrer. allowed to stir. C9-11 alcohol ethoxylate (Surfac UN9090-Surfachem) (0.11 g) was then added and the mixture was allowed to stir for an additional 15 minutes. The Quat blend (RSH008/100A-Byotrol) (7.00 g) was then added and allowed to stir 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 then stirred for an additional 15 minutes.

Low pH Mixed Surfactant Formulation Residual Performance against Pseudomonas

These results show that compositions without polymers 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 the composition. However, the Sharp 3E results show the following effects. Addition of the polymer of component (ii) and chelate (v) produces formulations that exhibit desirable levels of residual antimicrobial performance (>3 logs).

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

Sample Sharp 3A, Sample Sharp 3C and Sample Sharp 3E were made following the same procedure as for Sharp 3B except that the components specified in the table were omitted.

Low pH Mixed Surfactant Formulations Containing Various Chelates - Residual Performance Against Pseudomonas

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

All other formulations were prepared in the same manner as Sharp 4A using alternate chelates.

High pH Formulations - Residual Performance Against Pseudomonas

These results show that chelates can improve formulation clarity as well as improve residual antimicrobial performance at high pH. This is particularly important in achieving an aesthetically pleasing product.

We have found that the monomer chemistry can also cause clarity problems at higher pH (>4.5) when formulated with polymers of the type described herein. I found what I can do. Selection of surfactants, chelates and amounts of these components can improve the clarity of the composition.

Project Sharp 2: Experimental Section of Sharp 2A (RSH008/96A) To an appropriately sized vessel, add deionized water (75g) followed by sodium carbonate (Fisher) (0.36g) and sodium bicarbonate (Fisher). (0.10 g) was added and the mixture was allowed to stir 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 allowed to stir for an additional 30 minutes. The Quat blend (4:1 blend of DDAC:BAC) (14.00 g) was then added and stirred for an additional 10 minutes. Mirapol Surf S110 (Rhodia) (0.95 g) was then added and stirred for an additional 10 minutes. The solution becomes cloudy at this point. 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 stirred for an additional 15 minutes. A Sharp 2F was made in the same fashion, omitting the chelate.

At high pH there can be stability and clarity issues. The use of chelates can help improve the clarity and subsequent stability of the composition. Absence of chelate (EDTA) may have adverse effects on microbiological performance.

These results show that the use of polar solvents in addition to water can help improve the stability of the composition, especially when the composition contains perfume. Inclusion of such solvents does not have a detrimental effect on residual antimicrobial performance. All of the compositions tested in this example passed the residual antimicrobial efficacy test.

Experimental Part Composition Sharp 2E, Composition Sharp 2G and Composition Sharp 2H were made in the manner described for composition Sharp 2A with the addition of solvent added after the surfactant.

High pH formulations with or without polymers (Mirapol), with or without chelates, residual performance against Pseudomonas

These results indicate that the absence of chelate and/or polymer may result in reduced residual antimicrobial efficacy. It can also be seen that compositions containing both polymer and chelate pass the test for residual antimicrobial efficacy. Formulation Sharp 11B did not contain any surfactant and resulted in an opaque solution. This is undesirable. Desirable retention performance was achieved, but samples that did not contain surfactant showed 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 capacity (see Example 6). ).

Experimental part
Compositions were prepared as described above for the Sharp 2 series.

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

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.

Cleaning Test Procedure (Using Wet Abrasion Scrub Tester Re 903PG)
A white acrylic panel to which a simulated bathtub soil composition (combination of calcium carbonate, soap and grease) was applied was placed on the wet abrasion scrub tester with the applied side facing up. Four sponges labeled 1-4 were soaked in cold water and then squeezed between two tiles. For each product, 2 grams were added to the sponge and recorded which product was added to which sponge. The sponges were placed in sponge holders 1-4 of the wet ablation scrub tester. An extra weight of 300 grams was added to each sponge holder. The tester was set to 100 wear cycles and then started. Once the run was complete, the panels were removed from the tester and the level of soil removal was evaluated on Tracks 1-4. Tracks were then scored between 0 and 10. 0 corresponds to no soil removal and 10 corresponds to complete soil removal.

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

Series 6: Low pH with or without surfactant

Cleaning performance

The results of this experiment are shown in FIG.
Line 1 - Sharp 8A - Low pH composition with polymer, no surfactant, no chelate Line 2 - Sharp 8B - Low pH composition with polymer and chelate, no surfactant Line 3 - Sharp 8C - Low pH Composition, No Surfactant, No Polymer, No Chelate Line 4-Sharp 8D- Low pH Composition with Surfactant, Chelate and Polymer

The results show that the surfactant facilitates cleaning.

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

Composition Sharp 8A, Composition Sharp 8B and Composition Sharp 8C were made using the same procedure except that the indicated components were omitted.

Claims (32)

(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) an antimicrobial composition comprising a chelate, wherein said polymer is a monomer of the type:
(1) a monomer that has a permanent cationic charge or a monomer that can form a cationic charge upon protonation;
(2) an acidic monomer that has an anionic charge or is capable of forming an anionic charge; and
(3) A composition comprising at least two of the neutral monomers. 2. The composition of claim 1, wherein antimicrobial component (i) comprises at least two antimicrobial quaternary ammonium compounds. the cationic monomer (1) is diallyldimethylammonium halide or N,N,N-trimethyl-3-((2-methyl-1-oxo-2-propenyl)amino)-1-propanaminium halide or a mixture thereof 3. The composition of claim 1 or 2, wherein 4. The composition according to any one of claims 1 to 3, wherein the acidic monomer (2) is acrylic acid and/or methylacrylic acid. 4. The neutral monomer (3) is 2-(dimethylamino)ethyl methacrylate (DMAEMA), N-vinylpyrrolidone (NVP), N-vinylimidazole, acrylamide, or methacrylamide, or mixtures thereof. A composition according to any one of 1 to 4. 6. The hydrophilic polymer of claims 1-5, wherein the hydrophilic polymer comprises monomeric units selected from dimethylaminomethacrylate (DMAMA), methacrylamidopropyltrimethylammonium chloride (MAPTAC), and methylacrylic acid, and mixtures thereof. A composition according to any one of the preceding claims. Composition according to any one of claims 1 to 6, wherein the hydrophilic polymer is a copolymer containing 2 or 3 of the monomer units defined in claims 1, 3, 4 and 5. thing. Antimicrobial component (i) is at least one quaternary ammonium compound of formula (A)

[wherein R ¹ and R ² are each independently a linear unsubstituted uninterrupted C _8-12 alkyl group, and X ^- is a halogen such as chloride, bromide, fluoride, iodide, etc.] or a sulfonate, saccharinate, carbonate, or bicarbonate] and/or at least one benzalkonium compound of formula (B)

wherein m is 8 to 18 and X ⁻ is a halide anion such as chloride, bromide, fluoride, iodide, or a sulfonate, saccharinate, carbonate, or bicarbonate. A composition according to any one of 1 to 7. 9. The composition of claim 8, comprising a compound of formula (A) and a compound of formula (B). The benzalkonium compound of formula (B) is benzethonium chloride, benzyldimethyl-n-tetradecyl-ammonium chloride, benzyldimethyl-n-dodecyl-ammonium chloride, benzyl-C ₁₂ -C ₁₆ -alkyl-dimethyl-ammonium chloride, or 9. Benzyl-cocoalkyl-dimethyl-ammonium chloride and/or the compound of formula (A) is di-n-decyldimethylammonium chloride, octyldecyldimethylammonium chloride, or dioctyldimethylammonium chloride, or 9. The composition according to 9. Chelates are EDTA (ethylenediaminetetraacetic acid), gluconate, GLDA (glutamic diacetic acid), EDDS (ethylenediamine-N,N'-disuccinic acid), DPTA (diethylenetriaminepentaacetic acid), HEDTA (hydroxyethyl-ethylenediaminetriacetic acid), MGDA (methylglycinediacetic acid), PDTA (1,3-propylenediaminetetraacetic acid) and EDG (ethanoldiglycinic acid), and mixtures thereof. Composition. 12. A composition according to any one of claims 1 to 11, wherein the nonionic surfactant is an alcohol alkyl oxylate or amine oxide, or mixtures thereof. 13. The composition of any one of claims 1-12, having a pH of 2.5 or higher, or a pH of 3.5 or higher, or a pH of 4.5 or higher. 14. A composition according to any preceding claim, comprising from 2000 ppm to 10000 ppm of component (i). 15. A composition according to any preceding claim, comprising from 500 ppm to 3000 ppm of hydrophilic polymer. 16. The composition of any one of claims 1-15, comprising 400 ppm to 3000 ppm of chelate. 17. A composition according to any preceding claim, comprising from 2000 ppm to 13500 ppm of nonionic surfactant. 18. The composition of any one of claims 1-17, which is substantially free of alcohol. 19. A composition according to any one of claims 1 to 18, comprising an additional antimicrobial component (b). Additional antimicrobial agents (b) are polymeric and non-polymeric biguanidines, silver, octenidine HCl, amphoteric compounds, iodophors, phenolic compounds, isothiazalones, nitrobromopropanes, nitrogen-based heterocyclic compounds, alkylbetaines. , alkylamine oxides, arginine-based cationic surfactants, anionic amino acid-based surfactants, and amine antimicrobial agents, and mixtures thereof. . the additional antimicrobial agent is polyhexamethylene biguanidine or a compound of formula (C)

21. The composition of claim 20, wherein R is unsubstituted _C8 - _C18 alkyl, such as N,N-bis(3-aminopropyl)-dodecylamine. 22. A composition according to any preceding claim which is also a cleaning composition. 23. A composition according to any one of claims 1 to 22, which in use provides a residual antimicrobial effect. 24. A composition according to any preceding claim for use on hard surfaces. 25. A composition according to any one of claims 1 to 24 which, when applied to a surface, acts to substantially reduce or control the formation of microbial colonies on or near the surface. 26. A method of cleaning a hard surface and providing a residual antimicrobial effect to the hard surface, the method comprising applying a composition according to any one of claims 1 to 25 to the hard surface. 26. Use of a composition according to any one of claims 1 to 25 for substantially reducing or controlling microbial colonization on or near a surface. 26. A method of substantially reducing or controlling the formation of microbial colonies on or near a surface comprising applying a composition according to any one of claims 1 to 25 to the surface. 26. A method of interfering with, preventing or reducing adhesion and/or adherence of microorganisms to a surface, comprising applying a composition according to any one of claims 1 to 25 to the surface. The use of claim 27 or claims 26, 28 or 26, 28 or 28, which achieves a 3 log or greater reduction in microorganisms after 24 hours when subjected to 3 abrasion cycles on a non-porous stainless steel, glass or plastic substrate. 30. The method of any one of clauses 29. Any composition, use or method as generally described herein. Any composition, use or method as generally described herein with reference to the Examples.

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