Antimicrobial ingredients
The antimicrobial compositions, comprising quaternary ammonium compounds, polymers, and other components, address the challenges of toxicity and regulatory compliance, achieving effective and residual antimicrobial activity against a broad spectrum of microorganisms.
Patent Information
- Application Number
- JP2020173953
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2011-12-29
- Filing Date
- 2020-10-15
- Publication Date
- 2025-04-01
- Estimated Expiration
- 2032-10-31
AI Technical Summary
Existing antimicrobial compositions face challenges such as toxicity to humans and animals, environmental stability issues, and the development of resistant microorganism strains, while also needing to comply with regulations like the Biocidal Products Regulations (Directive 98/8/EC).
The development of antimicrobial compositions that include a combination of quaternary ammonium compounds, polymers, polar solvents, nonionic surfactants, and chelates, which provide effective antimicrobial activity on a wide range of organisms while minimizing toxicity and regulatory concerns.
These compositions exhibit residual antimicrobial effects, are resistant to washing and wiping with water, and achieve significant microbial reductions, thereby effectively controlling microorganism growth and preventing the formation of biofilms.
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Abstract
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. They can also cause damage and unpleasant odors in items such as clothing. When present on the surface of a substrate, microorganisms can rapidly replicate and form colonies.
[0003] A large 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 when they come into 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 to microorganisms. Therefore, handling these antimicrobial agents is dangerous and therefore requires specialized handling, processing and equipment to handle them safely. Therefore, there can be many problems in the manufacture 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 the 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 denoting "toxicity" should be construed accordingly.
[0007] When antimicrobials enter the environment, they can affect the health of forms of life that they were not intended to affect. Furthermore, antimicrobials are often extremely stable and can cause long-term environmental problems.
[0008] Other antimicrobial agents currently in use include antibiotic-type compounds that disrupt the biochemistry within microorganisms, and although antibiotics are effective, they are thought to be able to selectively allow the development of resistant strains of the species for which they are used.
[0009] 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 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 with antimicrobial properties for various applications and uses, such as cleaning applications, and that address one or more of the above problems. However, this is not a simple matter to achieve. 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. In addition, the potential reactivity of an antimicrobial agent when present in a composition is important, since some antimicrobial agents are rendered inactive by chemical reaction. Even if an antimicrobial agent is not inactivated by chemical reaction, its activity may be inhibited by other components of the composition. [Means for solving the problem]
[0014] Surprisingly, the inventors have found that the aforementioned shortcomings can be overcome by certain combinations of ingredients. It has also been found that compositions containing these combinations of ingredients can have 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 environments, offices, or public buildings such as hospitals, or on outdoor hard surfaces.
[0017] As used herein, cleaning refers to the removal of dirt, soap scum, limescale, and the like.
[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 term "comprising" or "comprises" is 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 term "consisting essentially of" or "consists essentially of" is 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 only contain the recited components. These terms can be applied to processes, methods and uses as well.
[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, more preferably 0.1% by weight or less. For example, a composition of the invention that is substantially free of alcohol contains less than 3% by weight of alcohol, preferably less than 1% by weight, 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 microbes (microorganisms). The term "microbicidal" is used to refer to a compound or composition that kills microbes. 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, yeasts, molds, 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, and 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, bactericidal refers to an agent that kills bacteria, and fungicidal refers to an agent that kills fungi. Examples of bactericidal agents include mycobactericidal and tuberculocidal agents. Preferably, the composition of the present invention comprises at least one agent selected from bactericides, fungicides, algicides, sporicides, virucides, yeasticides and moldicides, and mixtures thereof. More preferably, the composition of the present invention comprises at least one bactericide, virucide, fungicide and / or moldicide.
[0027] The compositions of the present invention are effective against a broad range of organisms, including gram-negative and gram-positive bacteria, fungi, yeasts, viruses and some spore formers.
[0028] The antimicrobial component (i) may comprise (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 linear, unsubstituted, uninterrupted C 8~12 is an alkyl group, and X - is a halide anion such as chloride, bromide, fluoride, iodide, or a sulfonate, saccharinate, carbonate, or bicarbonate, and a benzalkonium compound having the formula (B):
[0033] [ka]
[0034] [In the formula, m is 8 to 18; X -is a halide anion such as chloride, bromide, fluoride, iodide, sulfonate, saccharinate, carbonate or bicarbonate. Compounds of formula (B) are generally called benzalkonium compounds. Benzalkonium chloride is represented by the formula (B): 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 In one embodiment, R is an alkyl group, for example an alkyl group containing 8, 9, 10, 11 or 12 carbon atoms. 1 Groups and R 2 The groups may 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 a chloride anion.
[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 a mixture of compounds with different 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 can be used instead or in addition.
[0041] [Table 1]
[0042] It should be understood that one CAS number often refers to a blend or mixture. The CAS classification of a commercial preparation typically includes a blend that contains the specified compound in a defined range of amounts. The compositions with the CAS numbers cited above are only 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 ratio is about 2:1:1:2.7 by weight. 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, from 10:1 to 1:10, or from 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. They may further include 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 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, iodophores, phenolic compounds, amine antimicrobial agents, and nitrogen-based heterocyclic compounds, orthophenylphenol (OPP), as well as 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 (industrial 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 include compounds of formula (C)
[0056] [ka]
[0057] [Wherein, R is an unsubstituted C8-C 18 Preferably, R is an unsubstituted C 10 ~C 14 , for example 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 called 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 nitrobromopropanes, such as bronopol, and / or any hypochlorite.
[0059] In a particular embodiment, the composition of the present invention comprising a compound of formula (C), such as N,N-bis(3-aminopropyl)-dodecylamine, does not comprise PHMB, or does not comprise polymeric biguanidine or does not comprise biguanidine (e.g., does not comprise polymeric biguanidine and non-polymeric biguanidine).However, compositions comprising a compound of formula (C), such as N,N-bis(3-aminopropyl)-dodecylamine and a biguanidine, such as polymeric biguanidine or non-polymeric biguanidine, such as PHMB, are also contemplated.
[0060] Examples of 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, 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 component (b) may contain further 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-mentioned 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 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) does not contain isothiazole. In this embodiment, the composition of the present invention does not contain isothiazole.
[0064] The compositions of the invention may be provided in a concentrated form for dilution before use or in a ready-to-use form. The compositions of the invention are preferably provided in a ready-to-use form, and unless otherwise stated, the data on amounts (such as % by weight or ppm) given herein relate to the ready-to-use composition.
[0065] Typically, but not essential, 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.
[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 may 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 those comprising, consisting of, or consisting essentially of at least one monomer of type (1) and at least one monomer of type (3), those comprising at least one monomer of type (2) and at least one monomer of type (3), and those 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 the 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 documents describe water-soluble or water-dispersible copolymers that contain, 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 with ethylenic unsaturation. The copolymers include quaternized ammonium acrylamido acid copolymers.
[0069] Examples of cationic monomers (1) include, but are not limited to, the following:
[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 are C 2~12 , for example 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 the 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, the following:
[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 as 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 tradename Polyquat 7 or PQ7, or by Lubrizol under the tradename 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 acid 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 under the name PQ11 by BRB International.
[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 polymer has not been modified by reaction, such as, for example, grafting with a functionalizing agent or a hydrophobic material.
[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 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 to be used for the same or similar purpose as the given composition of the present invention.Formulations used for purposes such as cleaning kitchens or bathrooms can have a low pH, such as a pH of 3 or less, for example a pH of about 2, or a high pH, such as a pH of 10 or more, for example a pH of 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 higher, such as a pH of 2.5 or higher, such as 3.5 or higher or 4 or higher or 4.5 or higher.
[0099] The composition of the present invention comprises at least one suitable nonionic surfactant or a combination of surfactants including at least one nonionic surfactant (for example, at least one nonionic surfactant and at least one cationic surfactant and / or amphoteric surfactant, optionally in combination).The choice of surfactant depends on the nature of the composition and the intended purpose.The surfactants suitable for use in formulations for different purposes are within the knowledge of a person skilled in the art.Similarly, it is also within the knowledge of a person skilled in the art to select the appropriate amount of surfactant.
[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 or free of anionic surfactants, hi 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, mixture of propanol isomers, n-butanol, sec-butanol, tert-butanol, iso-butanol, mixture of butanol isomers, 2-methyl-1-butanol, n-pentanol, mixture of pentanol isomers, and amyl alcohol (mixture of isomers), and mixtures thereof.
[0104] Preferred polar solvents for use in the compositions 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 mentioned above.In such mixtures, water is preferably the main component.The polar solvent can be essentially 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 composition of the present invention is substantially free of alcohol.For example, the composition may contain 1% or less by weight of alcohol.For example, the composition 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 composition of the present invention may be completely free of isopropanol, or completely free of alcohol.
[0107] The composition may comprise water or a mixture of water and one or more alcohols selected from those mentioned above, in which water is preferably the major component.
[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); 10 C, such as those sold by Rhodia Novecare 10 Amine oxide; C 12Longer chain glucosides such as amine oxides, e.g., 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 Linear and branched primary and secondary alcohol ethoxylates, such as alcohol ethoxylates, are included. Preferred linear primary alcohol alkoxylates include C9-C10 alkoxylates having 5 to 12 EO units, such as 7 to 12 EO units. 11 Examples of suitable branched alcohol ethoxylates include alcohol ethoxylates. These surfactants are offered under the commercial name Neodol series (Shell Chemical Company). Examples of C12-15 secondary alcohol ethoxylates include those having about 3 to about 10 EO units, such as those offered as the Tergitol series (Dow), particularly those offered as 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 with mixtures of EO and PO 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 may also be used.
[0112] Another group of nonionic surfactants which 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 predominantly of alkylene oxides. Specific examples include those commercially available under the trade name Pluronic, particularly the Pluronic F series, Pluronic L series, Pluronic P series, and Pluronic R series.
[0113] Another group of suitable nonionic surfactants are alkyl polyglucosides or glucosides.Suitable examples include Surface APG, capryl glucoside from Surfachem and Glucopon series from BASF (Glucopon 425N / HH (C8-14), Glucopon 215 (C8-10) and Glucopon 600 (C12-14) alkyl polyglucosides).
[0114] In one embodiment of the present invention, the composition of the present invention may be free of alcohol alkoxylates. For example, the composition of the present invention containing a compound of formula (C) as defined herein, such as one containing N,N-bis(3-aminopropyl)-dodecylamine, may be free of alcohol alkoxylates.
[0115] Alternatively or additionally, the compositions of the invention may be free of alkyl polyglucosides. For example, compositions of the invention containing a compound of formula (C) as defined herein, such as those containing N,N-bis(3-aminopropyl)-dodecylamine, may be free of alkyl polyglucosides (APG).
[0116] Typically, component (iv) is present in the compositions of the present invention in an amount of about 500 ppm to 35000 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. The preferred range of the amount of surfactant (iv) in compositions having a pH of 8 to 10.5 is 2000 ppm to 13500 ppm.
[0117] Suitable amphoteric surfactants include C6-C 20 Alkyl amphoacetates or amphodiacetates (such as 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, coconut oil type 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 effect 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 circumstances.Furthermore, 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, such as free of propylene glycol n-butyl ether, and / or free of binary solvent combinations of glycols and linear primary alcohols.
[0121] The composition of the present invention comprises 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 diglycine acid), and mixtures thereof. When 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.
[0122] Preferred chelators 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 composition of the present invention may contain other components commonly used in the art. The nature of any other components used depends 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 buffer, citrate buffer, and their salts, and their mixtures.
[0126] Complexing agents can be used.For example, complexing agents can be used to help the composition of the present invention form clear compositions even when used with hard water.Suitable complexing agents include, but are 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 the sodium salt of nitrilotriacetic acid (NTA), citrate and gluconate, or the 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 or substantially free of acid or base.For example, some compositions of the present invention are free of citrate or citric acid or lactic acid.Other compositions may contain acid or base appropriate for their intended use.In one embodiment of the present invention, the composition contains 0.5% or less by weight of formic acid or is free of formic acid.
[0129] Siloxanes suitable for use in the present invention include those having 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 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.
[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 polydimethylsiloxane.
[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%, 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 the 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, for example 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) non-ionic 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.
[0137] Preferably the polymer comprises DMAEMA, MAPTA and methylacrylic acid, a commercial 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 first applied to a surface (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 (so-called "dry kill").
[0140] The compositions of the present invention also exhibit resistance to washing and wiping with water, 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 effects, and provide antimicrobial effects even after undergoing the residual effectiveness test described herein.That is, these compositions achieve a reduction in microorganisms when undergoing three abrasion cycles on non-porous stainless steel, glass or plastic substrates, and typically achieve a reduction of 3 logs or more over 24 hours.This means that 24 hours after applying the compositions of the present invention to the surface, when 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 forming biofilms. The formation of large and 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 do not need to contain components that are highly toxic to mammals. The antimicrobial agents used in the antimicrobial compositions are typically well-known, widely understood and tested antimicrobial agents. The effectiveness of known antimicrobial agents is amplified in the formulations of the present invention. Thus, antimicrobial agents with low toxicity can be used in the antimicrobial compositions. Conversely, in the known art of sanitization, many "new" antimicrobial agents use "stronger", more toxic and / or less tested materials.
[0144] The antimicrobial compositions of the present invention do not contain materials that produce highly persistent residues or rinses, or products that contain heavy metals and their salts, therefore 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 resistance development and the emergence of resistant strains.
[0146] The antimicrobial compositions of the present invention can be dual-effective in that they not only provide an antimicrobial effect 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 a 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 the step of 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 the step of applying the composition to the surface.
[0150] It should be understood that wiping or scrubbing the surface may also be necessary to achieve cleaning. Thus, 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 the ready-to-use form or can be diluted with water before use. The invention therefore also provides a method, such as defined above, in which the compositions of the invention are diluted before use.
[0152] The compositions of the present invention comprising a compound of formula (C), such as N,N-bis(3-aminopropyl)-dodecylamine, are particularly useful in controlling or reducing or preventing the formation of fungi.
[0153] The antimicrobial compositions of the present invention typically degrade when immersed in water, allowing for rinse / leachate with low toxicity and short residence time in the environment.
[0154] The mobility of the product allows materials that are washed or rinsed frequently 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. The antimicrobial composition is drawn to the surface of the product to be "refueled" due to the presence of hydrophobic elements. Thus, the sanitizing properties of the formulation are restored without the need for remanufacturing or difficult processing methods.
[0156] Any such refill solutions and any waste wash or rinse liquors containing the antimicrobial composition or formulation diluted with water will rapidly separate into the biodegradable components previously described.
[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 the formation of microbial colonies 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 homogenous. 3. Optionally, if a polar solvent is used in addition to water, add it and stir until the mixture is homogenous. 4. In a separate container, prepare a combination of nonionic and amphoteric surfactants (if used) and fragrance (if used) and then add to the mixture from step 3 and stir the mixture until homogenous. 5. If any cationic surfactants are used, add them and stir the mixture until homogenous. 6. Add the quaternary ammonium compound and stir until the mixture is homogenous. 7. Add the polymer and stir until the mixture is homogenous. 8. Add water until 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 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 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 an additional antimicrobial agent, such as PHMB, is desired to be included in the composition, it is added between steps 6 and 7.
[0162] The compositions 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 description of the drawings]
[0164] [Figure 1] FIG. 1 shows the results of the cleaning test reported in Example 6. [Diagram 2] FIG. 1 shows the results of the cleaning test reported in Example 7. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[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 sanitization efficacy of an antimicrobial product against certain microorganisms on a non-porous stainless steel surface 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 Effectiveness 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 approx. 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 stated in en1276:2009) Incubator capable of maintaining temperature at 37℃±1℃
[0168] method Preparation of steel coupons Steel coupons (stainless steel disks) were rinsed thoroughly with clean, hot water (tap water) to remove contaminating mud from the surface, then rinsed for a few 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 a sterile Petri dish and allowed to evaporate dry under laminar airflow with the lid slightly ajar. Five replicates were used for each time point taken plus a control set.
[0169] Abrasive Cycle A 50 ml centrifuge tube was weighed to weigh approximately 200 g (± 20 g). A professional care wipe was folded twice (4 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 Wipe 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 (2 sprays, approximately 50 cm distance 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 exerted on 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 wipe Similar mechanism to the wet wipe cycle, but the wipe was not moistened.
[0172] c) Bacterial challenge The required concentration of bacterial suspension containing the interfering substance was then determined. 6 CFU / ml (midpoint / wear point) or concentration 10 8 The CFU / ml (0 and final wear cycle) was used to subject the discs to a bacterial challenge (see below for bacterial challenge preparation).
[0173] Bacterial challenge preparation Bacterial suspensions were freshly prepared from second subcultures in TSA (subcultures prepared as specified in EN13697:2001). Tryptone saline was used to dilute the bacterial suspensions as necessary to obtain a cell concentration of approximately 10 8A suspension of CFU / ml was obtained. 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 obtain a final concentration of 0.3% bovine albumin solution in the bacterial suspension. A concentration of 10 8 Bacterial suspensions of CFU / ml were used for the initial and final bacterial challenges of the study.
[0174] For reinoculation (included in the ablation step), tryptone saline solution was used to 8 CFU / ml suspension was further increased to 10 6 CFU / ml was diluted to 10 6 The CFU / ml suspension was mixed 1:1 with bovine albumin solution (0.6%) prior to 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 1000 CFU / ml was added to the 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 effect mixing, then allowed to sit 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 onto the plate, left 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 a first abrasive wear cycle. 6 The tests consisted of a dry wipe followed by bacterial challenge and a wet wipe followed by bacterial challenge using a bacterial suspension of 10 CFU / ml (0.3% bovine albumin concentration). 6 10 μl 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 a 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 reinoculation, the disks were given a final wet wipe and then rinsed for 10 min 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 dropped using sterile forceps into another vial containing 10 ml of neutralizer solution. The vial was briefly shaken to effect mixing, then allowed to sit for 5 minutes, after which the vial was vortexed for 30 seconds. -4 Serial dilutions (up to 100 µL) 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 give 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 sit for 5 minutes. After neutralization, 10 8 10 μl of CFU / ml of antimicrobial test suspension was inoculated, transferred to a vial, mixed thoroughly, 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 the plates, left 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 log 10 bacterial reduction / was calculated from the disks treated with hard water as a control.
[0182] A tested composition was considered to have passed the test and provided residual antimicrobial efficacy if it demonstrated a log 3 or greater bacterial reduction at the end of the test. EXAMPLES
[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 suitably sized container was added deionized water (760.00 g) followed by DDQ (Acticide DDQ40) (200.00 g) and the mixture was allowed to stir with a magnetic stirrer for 10 minutes, then BAC (Acticide BAC50M) (40.00 g) was added and allowed to stir 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 allowed to stir with a magnetic stirrer for 15 minutes. 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. 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 was 100 g (4.61 g) and then stirred for an additional 15 minutes. EXAMPLES
[0188] Low pH mixed surfactant formulation Residual performance against Pseudomonas spp.
[0189] [Table 3]
[0190] These results show that compositions without polymer do not achieve the desired level of residual antimicrobial performance. It is known that the addition of 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 show 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, deionized water (approximately 78.35 g) was added, followed by Dissolvine GL-47 (Brenntag) (0.2 g), and the mixture was then allowed to stir with a magnetic stirrer 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, 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) (4.14 g). Deionized water was then added to 100 g, and then stirred for an additional 15 minutes.
[0192] Samples Sharp 3A, Sharp 3C and Sharp 3E were prepared using the same procedure as for Sharp 3B, except that the components specified in the table were omitted. EXAMPLES
[0193] Low pH mixed surfactant formulations containing different 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), then C10 amine oxide (Euroxide D40-EOC) (1.0 g) and the mixture was allowed to stir for 15 minutes. After this, Quat blend (4:1 blend of DDAC and BAC) (14.0 g) was added and the mixture was allowed to stir for a further 10 minutes. Mirapol Surf S110 (Rhodia) (0.95 g) was then added and the mixture was allowed to stir for a further 10 minutes. Tetrasodium EDTA (Surfac Na4EDTA Liquor) (0.4 g) was then added and the mixture was allowed to stir for a further 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 a further 15 minutes.
[0196] All other formulations were prepared in the same manner as Sharp 4A using alternative chelates. EXAMPLES
[0197] High pH formulations - 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 amounts of these components can improve the clarity of the composition.
[0201] Project Sharp 2: Sharp 2A (RSH008 / 96A) Experimental Section 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) 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. Quat blend (4:1 blend of DDAC:BAC) (14.00 g) was then added and allowed to stir for an additional 10 minutes. Mirapol Surf S110 (Rhodia) (0.95 g) was then added and allowed to stir for an additional 10 minutes. The solution becomes cloudy at this point. Tetrasodium Chelate-EDTA (Surfac Na4 EDTA Liquor- Surfachem) (0.4 g) was then added and allowed to stir 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 there may be stability and clarity issues. The use of a chelate may help improve the clarity and subsequent stability of the composition. Absence of a chelate (EDTA) may have an adverse effect on microbiological performance.
[0203] [Table 6]
[0204] 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 fragrance. The inclusion of such solvents does not have a detrimental effect on the 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 made in the manner described for Composition Sharp 2A with the addition of solvent added after the surfactant. EXAMPLES
[0206] High pH formulations with or without polymers (Mirapol), with or without chelates, residual performance against Pseudomonas spp.
[0207] [Table 7]
[0208] These results show that the absence of chelate and / or polymer may reduce residual antimicrobial effectiveness. It also shows that compositions containing both polymer and chelate pass the test for residual antimicrobial efficacy. Formulation Sharp 11B did not contain any surfactant, resulting in an opaque solution, which is undesirable. While desirable residual performance was achieved, the sample that did not contain surfactant had 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 ability (see Example 6).
[0209] Experimental section The compositions were prepared as described above for the Sharp 2 series. EXAMPLES
[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 - High pH formulation without surfactants Line 3 - Sharp 3A - Surfactant-free low pH formulation Line 4 - Sharp 3B - Low pH formulations containing surfactants
[0211] The results show that surfactants are essential for cleaning, and that high pH compositions can achieve slightly better cleaning than low pH compositions. Mixed surfactants can improve cleaning performance, especially on a broad range of soils.
[0212] Cleanliness test procedure (using wet abrasive scrub tester Re 903PG) A white acrylic panel with a simulated bathtub stain composition (a combination of calcium carbonate, soap, and grease) applied to it was placed on the Wet Abrasive Scrub Tester with the applied side facing up. Four sponges, labeled 1-4, were immersed in cold water and then squeezed between two tiles. For each product, 2 grams were added to the sponge and it was noted which product was added to which sponge. The sponges were placed in sponge holders 1-4 on 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. Once the run was complete, the panel was removed from the tester and the level of stain removal was evaluated on tracks 1-4. The tracks were then scored between 0 and 10, with 0 corresponding to no stain removal and 10 corresponding to complete stain removal.
[0213] Series 6: High pH and the presence or absence of surfactants
[0214] [Table 8]
[0215] Series 6: Low pH with or without surfactant
[0216] [Table 9] EXAMPLES
[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, deionized water (85 g) was added, followed by Quat blend (RSH008 / 100A-Byotrol) (7.0 g), and the mixture was then 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 allowed to stir for an additional 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 min.
[0222] Compositions Sharp 8A, Sharp 8B and Sharp 8C were made using the same procedure except for omitting the indicated components.
Claims
1. (i) (I) Formula (A): 【Chemistry 1】 [In the formula, R 1 and R 2 are each independently 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) Formula (B): 【Chemistry 2】 [In the formula, m is 8 to 18; X - is chloride, bromide, fluoride, or iodide] or benzalkonium chloride. an antimicrobial component comprising a quaternary ammonium component (a) comprising (ii) a hydrophilic polymer; (iii) a polar solvent, (iv) nonionic surfactants that are combinations of 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 is an acidic monomer. Including, An antimicrobial composition having a pH of 4 or greater.
2. (i) The benzalkonium compound of formula (B) is 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 2. The composition of claim 1, wherein the compound of formula (A) is di-n-decyldimethylammonium chloride, octyldecyldimethylammonium chloride, or dioctyldimethylammonium chloride.
3. 3. The composition of claim 1 or 2, 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 acid), and mixtures thereof.
4. 4. The composition of claim 1 having a pH of 4.5 or greater.
5. 5. The composition of claim 1, comprising from 2000 ppm to 10000 ppm of component (i).
6. 6. The composition according to claim 1, comprising from 500 ppm to 3000 ppm of the hydrophilic polymer.
7. 7. The composition of claim 1, comprising from 400 ppm to 3000 ppm of a chelating agent.
8. 8. The composition of claim 1, comprising from 2000 ppm to 13500 ppm of a nonionic surfactant.
9. 9. A composition according to any one of the preceding claims, comprising less than 3% by weight of alcohol.
10. 10. The composition of claim 1, which does not contain alkyl polyglucosides.
11. 11. The composition of any one of claims 1 to 10, comprising an additional antimicrobial component (b).
12. 12. The composition of claim 11, wherein the additional antimicrobial agent (b) is selected from polymeric and non-polymeric biguanidines, silver, octenidine HCl, amphoteric compounds, iodophores, phenolic compounds, isothiazalones, nitrobromopropanes, nitrogen-based heterocyclic compounds, alkyl betaines, alkyl amine oxides, arginine-based cationic surfactants, anionic amino acid-based surfactants, and amine antimicrobial agents, and mixtures thereof.
13. 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 12, wherein:
14. 14. The composition of claim 13, wherein the compound of formula (C) is N,N-bis(3-aminopropyl)-dodecylamine.
15. 15. The composition of claim 1, comprising no more than 0.5% by weight of formic acid.
16. 16. The composition according to any one of claims 1 to 15, which is also a cleaning composition.
17. (i) (C 10 H 21 ) 2 (CH 3 ) 2 N + Cl - and benzalkonium chloride; (ii) a polymer comprising DADMAC and acrylic acid; (iii) water; (iv) nonionic surfactants which are alcohol ethoxylates and amine oxides; and (v) a chelating agent that is EDTA or GLDA 2. The composition of claim 1, comprising:
18. 18. The composition according to claim 1, for use on hard surfaces.
19. 20. A method of cleaning a hard surface and providing a residual antimicrobial benefit to said hard surface, comprising applying to said hard surface a composition according to any one of claims 1 to 18.
20. 20. Use of a composition according to any one of claims 1 to 18 to reduce or control the formation of microbial colonies on or near hard surfaces.
21. 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 18.
22. 20. A method for disrupting, preventing or reducing the adhesion and / or attachment of microorganisms to a hard surface, the method comprising the step of applying to said surface a composition according to any one of claims 1 to 18.
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