BR112017004645B1 - DISINFECTANT COMPOSITION, ITS USE, METHOD OF EXTERMINING OR INHIBITING THE GROWTH OF MICRO-ORGANISMS, METHOD OF DISINFECTING A SURFACE - Google Patents

Abstract

DISINFECTANT COMPOSITION CONTAINING QUATERNARY AMMONIUM COMPOUNDS. The disinfectant compositions disclosed herein comprise at least one biocidal quaternary ammonium compound, hydrogen peroxide and optionally an inorganic acid and/or an organic acid. Particularly, a composition comprising a compound of biocidal quaternary ammonium chloride, hydrogen peroxide and C1 to C8 carboxylic acid, mono, di and tricarboxylic acids significantly enhances the antimicrobial activities of hydrogen peroxide or quaternary ammonium chloride alone.

Description

[0001] This application claims priority from Application No. U.S. 62/047,806, filed on September 9, 2014, which is incorporated herein by reference, in its entirety.

BACKGROUND 1. FIELD

[0002] The present invention relates to a disinfecting composition comprising a biocidal quaternary ammonium compound and hydrogen peroxide. One embodiment of the composition comprises a biocidal quaternary ammonium chloride compound in a hydrogen peroxide/water solution. Furthermore, the composition may additionally comprise an acid. The disclosure also provides methods of using the same to kill or inhibit the growth of microorganisms such as bacteria, viruses, fungi, mildew and mold. The disclosure also provides methods of disinfecting surfaces, such as a hard surface, comprising applying a disinfecting composition of the invention to the surface.

2. DESCRIPTION OF RELATED TECHNIQUE

[0003] Pathogenic organisms such as bacteria, fungi, and viruses continue to cause infections in humans as well as domestic animals and pets. In recent years, there has been particular growing concern regarding foodborne pathogens and their potential to contaminate the food chain. Disinfectant formulations have been developed over the last few decades to reduce or destroy pathogenic organisms and consequently reduce the rate of infection. Literally any hard surface, including floors, walls, countertops, windows, window sills, sinks, faucets, waste receptacles, equipment and cabinet surfaces, can become contaminated. Disinfectants have been developed to treat hard surfaces for use in hospitals, nursing homes, schools and homes.

[0004] The use of quaternary ammonium compounds (quats) as biocides is well known (See, for example, Kirt-Othmer's Encyclopedia of Chemical technology, 3rd edition, volume 7, pages 793 to 832, in particular, pages 815 to 818 ).

[0005] However, quaternary ammonium compounds (ie, dialkyl quaternary ammonium compound (DDAC) and Dodecyl Dimethyl Benzyl Ammonium Chloride (ADBAC)), although inexpensive and effective biocides, have limitations. For example, when exposed to hard water, the effectiveness is severely reduced. For compensation, the use of chelants is often required to sequester water-insoluble cations.

[0006] The typical quaternary ammonium compound uses chloride as the anionic counterion which, when in the presence of metals such as steel, tin and aluminum, can cause corrosion. For compensation, the use of corrosion inhibitors is sometimes necessary.

[0007] The proposed quantified standardized methods that will be used to assess and sustain antimicrobial activity have demonstrated bias at various levels of quat-containing formulas.

[0008] The compound of didecyl dimethyl ammonium carbonate/bicarbonate (DDABC) helps to mitigate (but not totally eliminate) hard water and corrosion problems, as described above. However, there are still limiting factors even with this compound. Although most chlorine-containing quats are stable over most of the pH range, DDABC is limited to alkaline systems. If attempts are made to utilize the DDABC molecule in neutral or acidic systems, the carbonate/bicarbonate reacts, which undesirably releases carbon dioxide gas.

[0009] Accordingly, there is a need for compositions with improved efficacy against microorganisms.

[0010] A solution to this technical problem is provided by the embodiments distinguished in the claims.

BRIEF SUMMARY

[0011] In one aspect, the disclosure provides a disinfecting composition comprising a biocidal quaternary ammonium compound and hydrogen peroxide with improved antimicrobial efficacy. One embodiment of the composition comprises a biocidal quaternary ammonium chloride compound in a hydrogen peroxide/water solution. Furthermore, the composition may additionally comprise an acid.

[0012] In one aspect, the disclosure provides a biocidal quaternary ammonium chloride compound with improved antimicrobial efficacy.

[0013] In one aspect, the disclosure provides another disinfecting composition comprising a quaternary ammonium chloride compound, an acid and hydrogen peroxide with improved effectiveness against microorganisms.

[0014] In one aspect, the quaternary ammonium chloride compound comprises didecyl dimethyl ammonium chloride and/or C8 to C18 alkyldimethylbenzylammonium chloride.

[0015] In one aspect, the acid comprises phosphoric acid. In other aspects, the acid comprises one or more of C1 to C8 organic acid (or acids), mono, di and tricarboxylic acid, and hydroxylacid, such as acetic acid, phosphoric acid, tartaric acid, adipic acid, oxalic acid, sulfamic acid, succinic acid , lactic acid, glutaric acid, benzoic acid, polymeric acid such as poly(co-acrylic-maleic acid), formic acid, citric acid, glycolic acid and a mixture thereof.

[0016] In one aspect, the revelation also provides a method of using them.

[0017] The disclosure also provides a method of disinfecting surfaces, preferably a rigid surface, comprising applying a disinfecting composition of the invention to the surface.

[0018] In one aspect, the innovative disinfecting composition and the innovative disinfecting active have improved efficacy against Pseudomonas aeruginosa and Staphylococcus aureus and Mycobacterium terrae.

DETAILED DESCRIPTION

[0019] Before the disclosure is further described, it is to be understood that the disclosure is not limited to the particular embodiments of the disclosure described below, as variations of the particular embodiments can be made and are still within the scope of the appended claims. It should also be understood that the terminology employed is intended to describe particular modalities, and is not intended to be limiting. Rather, the scope of the present disclosure will be established by the appended claims.

[0020] In this specification and in the appended claims, the singular forms “a”, “an”, “the” and “the” include plural references, unless the context clearly indicates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art to which this disclosure belongs.

[0021] The disclosure features, in one aspect, a disinfecting composition comprising a compound of quaternary ammonium chloride and hydrogen peroxide with improved antimicrobial efficacy. One embodiment of the composition comprises a quaternary ammonium chloride compound in a hydrogen peroxide/water solution. Furthermore, the composition may additionally comprise an acid. In a further embodiment, the composition consists essentially of a quaternary ammonium chloride compound, hydrogen peroxide and an acid. In another embodiment, the composition consists of a quaternary ammonium chloride compound, hydrogen peroxide and an acid.

[0022] In one aspect, the disclosure provides a quaternary ammonium chloride compound with improved antimicrobial efficacy. In one aspect, the combination of quaternary ammonium chloride, hydrogen peroxide and optional acid act synergistically.

[0023] Quaternary ammonium compounds useful in the present invention include, but are not limited to, those having formula (I):

[0024] wherein R1 is a benzyl group, a C1 to C22 alkyl or an optionally aryl-substituted alkyl group;

[0025] R2 and R3 are independently optionally substituted C1 to C22 alkyl groups;

[0026] R4 is selected from the group consisting of a C1 to C22 alkyl group or aryl-substituted alkyl group, benzyl group and -[(CH2)2-O]n-R5, where n is an integer of 1 to 20 and R5 is selected from the group consisting of hydrogen, phenyl, alkyl and alkyl-substituted phenyl;

[0027] and X- is chlorine, bromine, and phosphate, and sulfate, and nitrate.

[0028] In one aspect, R1 is a substituted benzyl group or a C1-22 alkyl group or aryl-substituted alkyl group.

[0029] In one aspect, R4 is selected from the group consisting of a C1-20 alkyl group or aryl-substituted alkyl group, benzyl group, and -[(CH2)2-O]n-R5, wherein n is an integer from 1 to 20 and R5 is selected from the group consisting of hydrogen, phenyl, alkyl and alkyl-substituted phenyl.

[0030] In one aspect, R1 and R4 are the same benzyl groups or C1-22 alkyl or aryl-substituted alkyl groups.

[0031] In one aspect, R1 and R4 are C1-22 alkyl.

[0032] In one aspect, R1 and R4 are C10 alkyl, preferably n-decyl.

[0033] In one aspect, R2 and R3 are independently C1-22 alkyl.

[0034] In one aspect, R2 and R3 are the same C1-22 alkyl groups. In one aspect, R2 and R3 are C1 to C4 alkyl. In one aspect, R2 and R3 are methyl.

[0035] Here and below, the expression “C1-22 alkyl” shall be understood to include methyl, ethyl and all linear or branched alkyl groups having from 3 to 22 carbon atoms. Accordingly, the expression "C3-22 alkyl" is to be understood as comprising all linear or branched alkyl groups having from 3 to 22 carbon atoms.

[0036] The term "aryl-substituted alkyl group" refers to the hydrogen atom (or atoms) of an alkyl group substituted by one or more aromatic carbon rings. Similarly, the term "aryl-substituted C1 to C22 alkyl group" refers to the hydrogen atom (or atoms) of C1 to C22 alkyl group substituted by one or more aromatic carbon rings.

[0037] The expression "alkyl-substituted phenyl" is to be understood as comprising any phenyl group bearing from one to five alkyl groups, in particular C1-20 alkyl groups and preferably C1-8 alkyl groups as substituents.

[0038] In one embodiment of the invention, the composition is a concentrated solution that can be diluted with water to a ready-to-use solution.

[0039] In one embodiment, the concentrated composition comprises about 0.1% to about 25% by weight of one or more quaternary ammonium compounds. In another embodiment, the concentrated composition comprises about 0.5% to about 10% by weight of one or more quaternary ammonium compounds. In a particular embodiment, the concentrated composition comprises about 1% to about 8% by weight of one or more quaternary ammonium compounds. In a preferred embodiment, the concentrated composition comprises about 2% to about 5% by weight of one or more quaternary ammonium compounds.

[0040] In a further embodiment, the ready-to-use composition comprises about 0.01% to about 2.5% by weight of one or more quaternary ammonium compounds. In a further embodiment, the ready-to-use composition comprises about 0.03% to about 2% by weight of one or more quaternary ammonium compounds, preferably 0.1% to 1.5% by weight of one or more compounds. of quaternary ammonium.

[0041] In one aspect, the concentrated composition can include from about 0.5% by weight to about 25% by weight of hydrogen peroxide. In another aspect, the concentrated composition can include from about 1% by weight to about 10% by weight of hydrogen peroxide. In a preferred aspect, the concentrated composition can include about 3% by weight to about 8% by weight hydrogen peroxide.

[0042] In a further aspect, the ready-to-use composition can include from about 0.01% by weight to about 5% by weight of hydrogen peroxide. In a further embodiment, the ready-to-use composition can include from about 0.06% by weight to about 2% by weight of hydrogen peroxide. In a preferred aspect, the ready-to-use composition can include about 0.1% by weight to about 1.5% by weight of hydrogen peroxide.

[0043] In one embodiment of the invention, the compositions comprise at least one acid or salt thereof. The acid can be an inorganic acid or an organic acid. In a preferred embodiment, the acid is a C1 to C8 carboxylic acid. In a more preferred embodiment, the acid is a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid or a mixture thereof. In a further embodiment, the acid is a hydroxy acid, an aromatic acid or a mixture thereof. In another further embodiment, the acid is methanesulfonic acid, phosphoric acid, etidronic acid, phytic acid, phosphoacetic acid, N-(phosphonomethyl)iminodiacetic acid, diethylenetriaminepentakis(methylphosphonoic acid), S,S-ethylenediamine-N'N'-disuccinic acid , their alkaline salts or any mixture thereof.

[0044] In some embodiments, the acid is citric acid, phosphoric acid, succinic acid, lactic acid, S,S-ethylenediamine-N,N'-disuccinic acid, 1-hydroxyethane 1,1-diphosphonic acid (HEDP), dipicolinic acid (DPA), methanesulfonic acid (MSA), its alkaline salts or any mixture thereof.

[0045] In a preferred embodiment, the acid is a mixture of acids. In some embodiments, the acid comprises one or more of the following organic acids: citric acid, succinic acid, phosphoric acid, and lactic acid. In another embodiment, the acid comprises one or more of the following acids: citric acid, succinic acid, phosphoric acid, and lactic acid, in combination with another acid. For example, citric acid can be used in combination with ethylenediamine-N,N'-disuccinic acid or its alkaline salt, HEDP and/or MSA. As another example, succinic acid can be used in combination with ethylenediamine-N,N'-disuccinic acid or its alkaline salt, HEDP and/or MSA. As another example, phosphoric acid can be used in combination with ethylenediamine-N,N'-disuccinic acid or its alkaline salt, HEDP and/or MSA. As another example, lactic acid can be used in combination with ethylenediamine-N,N'-disuccinic acid or its alkaline salt, HEDP and/or MSA.

[0046] In one aspect, the concentrated composition can include from about 0.01% by weight to about 25% by weight of the acid or mixture of acids. In a particular concentrate composition, it can include from about 0.05% by weight to about 14% by weight of the acid or mixture of acids. In a preferred aspect, the concentrated composition can include from about 1% by weight to about 5% by weight of the acid or mixture of acids.

[0047] In a further aspect, the ready-to-use composition can include from about 0.01% by weight to about 10% by weight of the acid or mixture of acids. In another aspect, the ready-to-use composition can include from about 0.05% by weight to about 6% by weight of the acid or mixture of acids. More preferably, the ready-to-use composition can include from about 0.5 to about 4% by weight of the acid or acid mixture.

[0048] In another aspect, the ready-to-use composition can include from about 1% by weight to about 5% by weight of an organic acid such as citric acid, succinic acid, phosphoric acid, lactic acid or any mixture thereof . In a preferred aspect, the ready-to-use composition can include from about 2% by weight to about 4% by weight of an organic acid, such as citric acid, succinic acid, phosphoric acid, lactic acid or any mixture thereof.

[0049] In a further aspect, the ready-to-use composition can include from about 1% by weight to about 5% by weight of an organic acid such as citric acid, succinic acid, phosphoric acid, lactic acid or any mixture thereof themselves, in combination with another acid. In another aspect, the ready-to-use composition can include from about 1% by weight to about 5% by weight of an organic acid, such as citric acid, succinic acid, phosphoric acid, lactic acid or any mixture thereof, in combination with about 0.05% by weight to about 5% by weight of another acid. In a preferred aspect, the ready-to-use composition can include from about 2% by weight to about 4% by weight of an organic acid, such as citric acid, succinic acid, phosphoric acid, lactic acid or any mixture thereof, in combination with about 0.1% by weight to about 4% by weight of another acid, such as ethylenediamine-N,N'-disuccinic acid or its alkaline salt, HEDP and/or MSA.

[0050] The composition can be prepared in any desired manner. For example, ingredients can be mixed in any order. Without limitation, one of the methods for preparing the disinfecting composition comprises mixing a quaternary ammonium chloride with an acid (mineral or organic) before adding hydrogen peroxide. The hydrogen peroxide can optionally be supplied to the end user separate from the quaternary ammonium compound and the acid. That is, the composition can be provided as a two-part composition to the end user and the end user mixes the two parts together. In addition, the end user can also add additional water to the composition to adjust the composition to ready-to-use compositions.

[0051] In one aspect, the disclosure also provides a method of using the compositions to kill or inhibit the growth of microorganisms. In one aspect, the quaternary ammonium compound, hydrogen peroxide and optionally at least one acid of the composition are applied together. In one aspect, the quaternary ammonium compound, hydrogen peroxide and optionally at least one acid of the composition are applied separately.

[0052] In one aspect, the compositions have improved microbial efficacy against a variety of microorganisms that are potentially harmful or capable of causing disease, such as Gram-positive and Gram-negative bacteria, viruses, fungi, mildew, and mold. Such microorganisms include Staphylococcus, Pseudomonas, hepatitis, rotavirus, rhinovirus and Mycobacterium terrae. In one aspect, the compositions have improved microbial efficacy against S. aureus, E. coli, Candida albicans, Aspergillus niger and P. aeruginosa, especially Mycobacterium terrae.

[0053] Suitable methods of determining an increase in biocidal effectiveness are known in the art. Biocidal effectiveness can be measured as an increase in percent kill for a biocidal target after a specified time in contact with the composition (eg, percent effectiveness). The EPA has regulations regarding required contact times for different surfaces and has also accepted regulatory protocols for testing, which are known to a person skilled in the art. In another embodiment, increased biocidal effectiveness can be measured as a decrease in the kill time of a composition, e.g., the amount of time required to kill at least 99.9% of the biocidal target on a surface after a specified contact time. . The standard EPA and industry approved contact time for a bucket dilutable composition using a dilution test for major biocidal targets eg Staphylococcus aureus, Salmonella enterica and Pseudomonas aeruginosa etc. is 10 minutes.

[0054] There is a need for shorter contact times of disinfectant compositions with, for example, a work surface for approximate real-world use of these compositions. Thus, as determined by the quantitative method for assessing bacterial activity of microbiocides used on rigid non-porous OECD surfaces, compositions of the invention may have a microbial contact kill time of less than 10 minutes, preferably a microbial contact kill time less than 5 minutes. In a more preferred embodiment, the compositions of the invention have a microbial contact kill time of about 3 minutes or less, alternatively about 2 minutes or less, alternatively about 1 minute or less, alternatively about 30 seconds or less.

[0055] In a further embodiment, the compositions of the invention demonstrate a minimum 4 log reduction in the number of microorganisms within about 5 minutes of contact time. In a preferred embodiment, the compositions of the invention demonstrate a minimum 4 log reduction in the number of microorganisms within about 3 minutes of contact time, alternatively within about 2 minutes of contact time, alternatively within about 1 minute of contact time, alternatively within about 30 seconds of contact time.

[0056] In a further embodiment, the compositions of the invention demonstrate a minimum 5 log reduction in the number of microorganisms within about 5 minutes of contact time. In a preferred embodiment, the compositions of the invention demonstrate a minimum 5 log reduction in the number of microorganisms within about 3 minutes of contact time, alternatively within about 2 minutes of contact time, alternatively within about 1 minute of contact time, alternatively within about 30 seconds of contact time.

[0057] Unexpectedly, the compositions disclosed herein comprising a compound of quaternary ammonium chloride, hydrogen peroxide and an acid, such as a composition of Examples 5 to 7 described below, demonstrated log reduction of more than 5 in Staphylococcus aureus and Pseudomonas aeruginosa, two major biocidal targets, within 3 minutes of contact time. Additionally, the ready-to-use compositions disclosed herein comprising a quaternary ammonium chloride compound, hydrogen peroxide and an acid diluted in hard water, as a composition of Examples 8 to 11 described below, demonstrated log reduction of more than 5 in Staphylococcus aureus and Pseudomonas aeruginosa within 1 minute of contact time. Increasing the hydrogen peroxide concentration to 1% in the ready-to-use composition, such as the Example 11 composition described below, surprisingly resulted in a greater than 5 log reduction in Staphylococcus aureus and Pseudomonas aeruginosa within 30 seconds of time of contact.

[0058] The storage stable compositions of the invention also have a pH that maintains the shelf life stability of the compositions, and in particular maintains the stability of hydrogen peroxide so that oxygen is not readily released from solution. Compositions of the invention have been demonstrated to be stable for four weeks in a temperature controlled oven of 45°C, which is equivalent to a shelf life of one year under normal storage conditions. The concentrated compositions of the invention have a pH of about 1.6 to about 5. The ready-to-use compositions of the invention have a pH of about 1.8 to about 6.

[0059] In another embodiment, the concentrate and ready-to-use solution may additionally include a stabilizer to deactivate impurities that may cause decomposition of hydrogen peroxide. Stabilizer can be added to prevent components from prematurely shelf decomposing during storage of formulations. Stabilizers for use in stabilizing acidic hydrogen peroxide solutions include organic and inorganic sequestering agents, ie stannates and phosphates, and combinations of organic compounds, organometallic salts and metal chelators with or without stannates and phosphates. In one embodiment, the stabilizer can be phosphoric acid, a derivative of phosphoric acid, 1-hydroxyethylidenediphosphonic acid (HEDP), phytic acid, aminophosphate, sodium phosphonate and glutamate, NaH2PO4, Na tripolyphosphate, organophosphonic acid, aminophosphonate, di -hydrogen silver citrate, diphosphonic acid, ethylenediaminetetraacetic acid (EDTA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA), tri(methylene phosphoric acid), diethylenetriaminepenta(methylene phosphoric acid), 2-hydroxyethylimino bis(ethylene phosphoric acid) ), citric acid, dipicolinic acid, ethylenediamine-N,N'-disuccinic acid, methylglycinediacetic acid and the alkaline salts thereof, nitriotriacetic acid (NTA), 2-hydroxyethyliminodiacetic acid (HEIDA), and salts thereof, cyclohexane acid -1,2-Diaminetetrakimethylene phosphonic acid or water solution, diethylenetriamine penta(methylene phosphonic acid), colloidal stannate, diethylenetriamine pentaacetic acid (DTPA), citrate salts, gallate salts, malate salts, malonate salts, oxaloacetate, oxalate salts, pyruvate salts, succinate salts or mixtures thereof. The hydrogen peroxide stabilizer can be a single component or a mixture of the phosphoric acid derivatives and the chelators described above. The amount of concentrated optical stabilizer can be from about 0.01% to about 5% by weight, preferably from 0.05% to 2% by weight, and more preferably from 0.1% to 1.0% by weight. . In other embodiments, stabilizers are not present.

[0060] The disclosure also provides a method of disinfecting a surface comprising applying the quaternary ammonium chloride compositions or compound to the surface. In one aspect, the quaternary ammonium compound, hydrogen peroxide and optionally the acid of the composition are applied together. In one aspect, the quaternary ammonium compound, hydrogen peroxide and optionally the acid of the composition are applied separately.

[0061] In one embodiment, the disinfecting compositions further comprise a solvent. In one embodiment, the solvent can be water. In another embodiment, the solvent can be mixtures of ethanol, propanol, propylene glycol, isopropanol or other alcohols. In another embodiment, the solvent may be mixtures of ethanol, propanol, isopropanol, and/or ethylene glycol or propylene glycol alkyl and dialkyl glycol ethers, such as diethylene glycol propyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether monopropyl, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, DEG monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol n-butyl ether, dipropylene glycol n-propyl ether, tripropylene glycol methyl ether, dipropylene glycol methyl ether and dipropylene glycol butyl ether. In another embodiment, the solvent can be glycol ethers, nonionic and amphoteric surfactants and chelants. For example, the glycol ether can be DOWANOL™ DPnP glycol ether. The amount of solvent in the composition can be from about 0.5% to about 20% by weight, preferably from about 1% to about 5% by weight. In other embodiments, solvents are not present.

[0062] Optionally, a surfactant can be added, as well as disinfection compositions. Suitable surfactants include, but are not limited to, amphoteric surfactants, surfactants, zwitterionic surfactants, or nonionic surfactants, for example, amine oxides, linear alcohol ethoxylate, secondary alcohol ethoxylates, ethoxylate esters, betamines, and alkyl polyglycerides. For example, the surfactant could be STEPANETEX® DA-6. In other embodiments, surfactants are not present.

[0063] The compositions of the invention may also include additives such as chelating agents, build-up salts, dyes, fragrances, hydrogen peroxide stabilizers, corrosion inhibitors, antifoam agents, pH buffers, pH adjusting agents, non-ionic surfactants, wetting and perfluorosurfactant agents, such as those commonly used in the art of cleaning and disinfecting solutions. The compositions of the invention may also include additives, such as leveling agents, such as those commonly used in the coating or ink art. The compositions can also be free of chelators. The composition may also be free of one or more of build-up salts, colorants, fragrances, hydrogen peroxide stabilizers, corrosion inhibitors, anti-foaming agents, pH buffers, pH adjusting agents, non-ionic surfactants, wetting agents, perfluorosurfactants and leveling agents.

[0064] In some embodiments, the compositions of the invention additionally comprise a chelator and/or a corrosion inhibitor. Any chelators or corrosion inhibitors can be used. The compositions can also be free of chelating agents and/or corrosion inhibitors.

[0065] The disclosure also provides a disinfecting composition which does not comprise a cationic polymer. Cationic polymers preferably excluded from the composition may have the following structure:

[0066] Regarding this structure, R1 can be independently selected from H (hydrogen) or methyl (CH3); R2 may be independently selected from H (hydrogen), halide (fluoride, chloride, bromide, iodide), C1 to C6 alkyl or alkoxy, aryl, dimethyl siloxane oligomeric or polymeric and linear or branched; R3 may independently be selected from hydroxyl, alkyl amine, dialkyl amine or polyether; R4 may be independently selected from H (hydrogen), C1 to C6 alkyl or benzyl; Z can be independently selected from O (oxygen) or NH; W may be independently selected from C1 to C6 alkyl; and X may be independently selected from fluoride, chloride, bromide, iodide, methosulfate or ethosulphate. Alternatively, the monomer represented by the subscript "n" can be a vinyl pyrrolidinone. The values of m, n and p can be the same or they can be different. The m, n, and p values are integers and are selected to make the average molecular weight range from 1,000 to 100,000 g/mol.

[0067] In one aspect, examples of cationic polymers preferably excluded from the composition include cationic polymers that include a (3-acrylamidopropyl)trimethylammonium chloride monomer combined with another monomer selected from a group consisting of a polar water-soluble monomer , a monomer containing hydrophobic silicone and mixtures of such monomers. The polar water soluble monomer can be selected from vinyl pyrrolidinone, hydroxy ethyl acrylate, hydroxy ethyl methacrylate, N,N'-dimethyl acrylamide, acrylamide and N-isopropyl acrylamide. The hydrophobic silicone-containing monomer may be selected from unsubstituted or substituted vinyl or ethynyl group-terminated siloxy compounds comprising monomethacyloxypropyl-terminated polydimethylsiloxane, methacyloxypropyl tris(trimethylsiloxysilane) and methacyloxypropyl-terminated T-structure siloxane.

[0068] In another aspect, examples of cationic polymers preferably excluded from the composition include cationic polymers that include a [2-acryloyloxy)ethyl]trimethylammonium chloride monomer combined with another monomer selected from a group consisting of a water-soluble monomer polar water, a monomer containing hydrophobic silicone, and mixtures of such monomers. The polar water soluble monomer can be selected from vinyl pyrrolidinone, hydroxy ethyl acrylate, hydroxy ethyl methacrylate, N,N'-dimethyl acrylamide, acrylamide and N-isopropyl acrylamide. The hydrophobic silicone-containing monomer may be selected from unsubstituted or substituted vinyl or ethynyl group-terminated siloxy compounds comprising monomethacyloxypropyl-terminated polydimethylsiloxane, methacyloxypropyl tris(trimethylsiloxysilane) and methacyloxypropyl-terminated T-structure siloxane.

[0069] According to document No. WO 2012/090100, cationic polymers are indicated to provide a durable or persistent activity to exterminate and prevent the growth of potentially harmful microorganisms. The cationic polymers of WO 2012/090100 are preferably not present in the compositions of the present invention.

[0070] Suitable surfaces include, but are not limited to, hard surfaces or food containers. In one aspect, the surface is a rigid surface. In a further embodiment, the hard surface is any hard surface found in the home or in an industrial or institutional setting. In another embodiment, the rigid surface is a floor, wall, bench, equipment or fixture.

[0071] Surfaces, which can be disinfected with the compositions, include, but are not limited to, those located in dairies, homes, health care facilities, swimming pools, canneries, food processing units, restaurants, hospitals, institutions and industries, including secondary oil recovery. Rigid surfaces such as glass and polished aluminum are particularly suitable for application. Specific areas targeted for application include hard surfaces in the home such as kitchen countertops, cabinets, appliances, trash cans, laundry areas, trash cans, bathroom fixtures, toilets, water tanks, faucets, mirrors, vanities, bathtubs and showers . The compositions can also be used to sanitize floors, walls, furniture, mirrors, bathroom fixtures, windows and wooden surfaces such as wooden fences, porch fences, decks, roof, siding, window frames and door frames. The compositions, composed of quaternary ammonium chloride, and disinfecting active are particularly well suited for application on indirect food contact surfaces, such as cutting boards, utensils, containers, tableware, sinks, equipment and countertops. The quaternary ammonium chloride compositions or compound can be used to sanitize plant equipment, milking machines, milk pails, tank trucks and the like. Areas in hospitals would include beds, gurneys, tables, canisters, toilets, bins, booths, cabinets, shower stalls, floors, walls, or any other non-porous surface.

[0072] The amount of compositions used to treat a surface is a biocidal effective amount, i.e., that amount to sanitize or disinfect the surface. The biocidal effective amount will depend on the intended use and can be determined by a person of ordinary skill in the art in light of the present detailed disclosure.

[0073] Typically, the disinfectant compositions may be supplied in a dilutable concentrated form or in a ready-to-use form. A typical dilutable concentrate will comprise from about 2% by weight to about 5% by weight of quaternary ammonium compounds, about 3% to about 8% hydrogen peroxide and about 1% to about 5% by weight of the acid based on 100% by weight of the total composition. Dilutable concentrates of the invention may be dilutable with water. A typical ready-to-use formulation will comprise from about 10 ppm to about 10,000 ppm of quaternary ammonium compounds, about 0.1% to about 1.5% by weight of hydrogen peroxide and about 0.5% to about 4% by weight of the acid based on the total composition. Water is added to achieve the desired ppm of the components.

[0074] Surface treatment is by any means known to those of ordinary skill in the art, including, but not limited to, dipping, drying, brushing, spraying, scrubbing, washing or the like. The length of treatment required will vary according to treatment conditions, the selection of which is known to those skilled in the art.

[0075] A particularly useful application method is to impregnate the disinfecting composition comprising the compound of quaternary ammonium chloride, hydrogen peroxide and, optionally, an acid, onto a tissue substrate. In this embodiment, the wipe is a single-use wipe that is impregnated with the disinfecting composition and stored in a container that will deliver the wipe to a user. The wipes container can hold a single wipe or multiple wipes. Suitable containers include a pouch that contains a single wipe, such as a wet wipe that is tear open by the user, or it may be a pouch with a resealable opening that contains multiple wipes in a stacked manner, a rolled manner or other suitable formation that would allow a single handkerchief to be removed from the opening at a time. Pouches are generally prepared to form a fluid-impermeable material such as film, coated paper or foil, or other similar fluid-impermeable materials. Another way to dispense wipes of the present invention is to place the wipe in a fluid impermeable container that has an opening for accessing the wipes in the container. The containers may be a molded plastic container with lids that are impermeable to fluid. Generally, the lid will have an opening to access the wipes in the container. The tissue in the container may be in an interleaved stack such that one tissue is removed from the container and the next tissue is positioned in the opening of the container ready for the user to remove the next tissue. Alternatively, the web can be a continuous material which is perforated between individual webs of the continuous material. The continuous scarf material with perforations may be in a folded form or it may be in a rolled form. Generally, in rolled form, the scarf material is fed from the center of the rolled material. As with the interleaved stack, as one wipe is removed from the container, the next wipe is positioned in the opening for use to remove the next wipe when needed.

[0076] Disposable wipes provide advantages over other application vehicles, such as a reusable sponge, rag or the like. Unlike sponges, rags and the like, which are used repeatedly, the impregnated wipe is used only once and discarded. As mentioned above, the sponge or rag poses problems, as the sponge or rags can carry microbes that are not easily killed by the disinfecting composition. Additionally, the disinfecting composition is formulated to treat hard surface, not porous soft surfaces that are present on sponges or rags.

[0077] The disinfecting composition may be impregnated into the wipe so that the wipe is pre-moistened and expresses or releases the disinfecting composition onto the surface as the wipe travels across the surface to be treated. Generally, the disinfecting composition is saturated in the wipe, so that the wipe releases the disinfecting composition onto the surface through the wiping action. Depending on the wipe substrate, saturation is generally achieved using 3 parts by weight of the use disinfecting composition per 1 part by weight of the wipe substrate to be saturated. Generally, the disinfecting composition is used at about 4 parts to 6 parts by weight per 1 part by weight of the cleaning substrate. In these ranges, complete saturation of the substrates can be achieved. It is noted that the amount of disinfecting solution may increase or decrease to achieve complete saturation of the wipe substrate, depending on the particular wipe substrate.

[0078] Suitable scarf substrates include woven and non-woven materials. Essentially any non-woven batting material can be used. Exemplary nonwoven materials may include, but are not limited to, melt blown materials, coform, continuous spun materials, airlaid, hydroentangled, hydroentangled nonwovens, carded filament batts, and laminates thereof. Optionally, the nonwovens can also be laminated with a film material. The fibers used to prepare the scarf substrate can be cellulosic fiber, thermoplastic fibers and mixtures thereof. The fibers can also be continuous fibers, staple fibers, textile fibers and mixtures thereof. Nonwoven batt basis weights can vary from about 12 grams per square meter to 200 grams per square meter or more.

[0079] In one embodiment, the wipe is impregnated with a liquid component that contains both the active and inert ingredients within allowable tolerance levels and the disinfecting composition expressed from the wipe containing active ingredients within two allowable tolerance levels. Once applied to the surface, the antimicrobial disinfecting composition is allowed to remain on the surface for a period of time. The antimicrobial composition may be applied to the surface and subjected to drying or may alternatively be dried by wiping the surface with a dry tissue or cleaning device, which is preferably not used.

[0080] The following examples serve to illustrate certain aspects of the disclosure and are not intended to limit the disclosure.

EXAMPLES EXAMPLE 1: BIOCIDAL ACTIVITIES AGAINST STAPHYLOCOCCUS AUREUS AND PSEUDOMONAS AERUGINOSA.

[0081] The biocidal activities of the exemplified compositions were determined using the OECD quantitative method to assess bacterial activity of microbiocides used on rigid non-porous surfaces.

[0082] Raw materials, 50% hydrogen peroxide, citric acid (CA), 85% phosphoric acid, glutaric acid (GA), 50% 1-hydroxyethane 1,1-diphosphonic acid (HEDP), stannate Sodium salt, dipicolinic acid (DPA) and S,S-ethylenediamine-N,N'-disuccinic acid trisodium salt (EDDS) were purchased from Aldrich-Sigma. Bardac 2250, which contains 50% didecyldimethylammonium chloride and 10% ethanol from Lonza, was used for the formulations.

[0083] The results shown in Table 1 demonstrate the antimicrobial effectiveness of the compositions when exposed to Staphylococcus aureus (Sa) and Pseudomonas aeruginosa (Pa). The compositions listed in Table 1 were tested by diluting the samples with 375 ppm of hard water to test the calculated hydrogen peroxide level based on the amount of hydrogen peroxide used to make the compositions.

[0084] The results demonstrate that both hydrogen peroxide and Bardac 22 alone are ineffective against both Sa and Pa within 5 min of contact time. As shown in samples 1 and 2, treatment with 0.5% and 6% hydrogen peroxide alone achieved only log reduction less than 1.6 and less than 3.2 against Pa and Sa, respectively, after 5 min. of contact time. As sample 3 shows, treatment with 5,000 ppm of Bardac 22 alone resulted in less than 3.3 log reduction against Pa and Sa after 5 min of contact time.

[0085] However, the combination of 3000 hydrogen peroxide and 2000 ppm Bardac 22, as shown in sample 4, achieved log reduction of more than 4 against Pa and Sa within 5 min of contact time. TABLE 1 Bardac 22: didecyldimethylammonium chloride

[0086] The results shown in Table 2 further demonstrate that the disclosed compositions comprising didecyldimethylammonium chloride, hydrogen peroxide and phosphoric acid and/or organic phosphonic acid such as HEDP show significant synergy enhancement of antimicrobial activities against both Pa and against Sa. For example, Samples 5 and 6 demonstrate that both compositions at 0.5% H2O2 and 0.3% Bardac 22 level achieved greater than 5 log reduction against Pa and Sa within 3 min of contact time . Additionally, both compositions containing 0.1% H2O2 and 0.06% Bardac 22 achieved more than 5 log reduction within 10 min contact time against both Pa and Sa.

[0087] The results further demonstrate that compositions containing an additional organic acid provide further enhancement of antimicrobial activities, as shown in samples 7, 8, 9, 10 and 11. Particularly, the formulation comprising 0.5% H2O2 and 0.3% Bardac 22 and 1.5% citric acid in sample 8 achieved log reduction of more than 5 against both Pa and Sa within 1 min of contact time. More particularly, composition 11 comprising 1.0% hydrogen peroxide achieved log reduction of more than 5 against Pa and Sa within just 30 seconds of contact time. In comparison, the same formulation without citric acid, as shown in sample 5, achieved only less than 1.6 log reduction against Pa and Sa within one minute of contact time. TABLE 2 PA=phosphoric acid; HEDP=edidronic acid; CA=citric acid; SA=succinic acid; Bardac 22=Didecyldimethylammonium chloride; EDDS= trisodium salt of S,S-ethylenediamine-N,N'-disuccinic acid.

[0088] Additionally, the results demonstrate that the composition comprising 0.5% hydrogen peroxide, 2% citric acid, 0.3% Bardac 22 and 0.05% EDDS shows excellent activity with log reduction of 4,6 against Mycobacterium terrae ATCC 15755 within 5 minutes of contact time as determined by OECD quantitative methods for assessing bacterial activity of mycobactericides used on hard non-porous surfaces (draft October 30, 2012).

EXAMPLE 2: BIOCIDAL ACTIVITIES AGAINST BACILLUS SUBTILLIS.

[0089] The biocidal activities of the exemplified compositions were determined using the OECD quantitative suspension test for the evaluation of sporicidal activity of chemical disinfectants used in food, industrial and domestic areas. Neutralization was performed by membrane filtration using D/E broth with 1% catalase as the rinse fluid. The test was performed at 20 °C for 60 minutes, using 0.3 g/l of bovine albumin as the interfering substance.

[0090] The following raw materials were used: 50% hydrogen peroxide, citric acid (CA), lactic acid, 50% 1-hydroxyethane 1,1-diphosphonic acid (HEDP), sodium stannate, dipicolinic acid (DPA) STEPANETEX® DA-6, DOWANOL™ DPnP, sodium hydroxide (NaOH), methanesulfonic acid (MSA), NOVEL® 1012-6 ethoxylate, bovine albumin, isopropanol, D/E broth and catalase. Bardac 2250, which contains 50% didecyldimethylammonium chloride and 10% ethanol from Lonza, was used for the formulations.

[0091] The results shown in Table 3 demonstrate the antimicrobial effectiveness of the compositions when exposed to Bacillus subtillis. The compositions listed in Table 3 were tested by diluting the samples with deionized water to test the calculated hydrogen peroxide level based on the amount of hydrogen peroxide used to make the compositions. TABLE 3

[0092] These results demonstrate that compositions comprising an alcoholic solvent exhibited effective antimicrobial activity against Bacillus subtillis.

[0093] Additionally, the results demonstrate that the composition comprising 2.0% hydrogen peroxide, 4.0% lactic acid, 0.6% Bardac 22, 0.5% MSA, 1.6% 1012-6 ethoxylate, 2.0% isopropanol and 0.10% HEDP (pH about 1.76) shows excellent activity with 4.7 log reduction against Bacillus subtillis ATCC 6633 (Spores) within 60 seconds of contact time.

[0094] All references cited in this specification are incorporated herein by reference, although each reference had been specifically and individually indicated to be incorporated by reference. Citation of any reference is to its disclosure prior to the date of filing and is not to be construed as an admission that the present disclosure is not entitled to backdate such reference by virtue of the prior invention.

[0095] It will be understood that each of the elements described above, or two or more together, may also find useful application in other types of methods that differ from the type described above. Without further analysis, the foregoing will fully reveal the essence of the present disclosure which others can, applying current knowledge, readily adapt for various applications without omitting features which, from the point of view of the prior art, constitute relatively essential characteristics of the generic or specific aspects of that disclosure set forth in the appended claims. The modalities are presented by way of example only; the scope of the present disclosure is to be limited only by the appended claims.

Claims (29)

1. Disinfectant composition characterized by the fact that it comprises a biocidal quaternary ammonium compound, hydrogen peroxide and an acid, a salt or mixtures thereof, in which the quaternary ammonium compound is a compound having the formula (I): wherein R1 is an optionally substituted benzyl group or an optionally substituted alkyl or aryl-substituted alkyl group; R2 and R3 are independently optionally substituted alkyl groups; R4 is selected from the group consisting of an optionally substituted alkyl or aryl-substituted alkyl group, benzyl group and -[(CH2)2-O]n-R5, where n is an integer from 1 to 20 and R5 is selected from the group consisting of hydrogen, phenyl and alkyl-substituted phenyl; and X- is chlorine, bromine, phosphate, sulfate or nitrate; wherein the acid or salt thereof is selected from the group consisting of citric acid, phosphoric acid, glutaric acid, succinic acid, lactic acid, S,S-ethylenediamine-N,N'-disuccinic acid, 1-hydroxyethane acid 1,1-diphosphonic acid (HEDP), dipicolinic acid (DPA), methanesulfonic acid (MSA), acetic acid, tartaric acid, adipic acid, oxalic acid, sulfamic acid, benzoic acid, formic acid, glycolic acid, polymeric acid, phytic acid , phosphoacetic acid, diethylenetriaminepentakis(methylphosphonoic) acid and N-(phosphonomethyl)iminodiacetic acid, or salts thereof; and wherein the composition is a dilutable composition comprising from 0.5% to 10% by weight of the quaternary ammonium compound, from 0.5% to 10% by weight of hydrogen peroxide, and from 1% to 5% by weight of acid, salt or mixtures thereof, and wherein the composition is free of peracids, and wherein the concentrated dilutable composition has a pH of 1.6 to 5. 2. Disinfectant composition characterized in that it is prepared in two separate parts, wherein the first part of the composition comprises a biocidal quaternary ammonium compound and an acid, salt or mixtures thereof, and wherein the second part of the composition comprises peroxide hydrogen, where the quaternary ammonium compound is a compound having the formula (I): that R1 is an optionally substituted benzyl group or an optionally substituted alkyl or aryl-substituted alkyl group; and R3 are independently optionally substituted alkyl groups; is selected from the group consisting of an optionally substituted alkyl or aryl-substituted alkyl group, benzyl group, and -[(CH2)2-O]n-R5, where n is an integer from 1 to 20 and R5 is selected from the group consisting of hydrogen, phenyl and alkyl-substituted phenyl; and X- is chlorine, bromine, phosphate, sulfate or nitrate; and wherein the acid or salt thereof is selected from the group consisting of citric acid, phosphoric acid, glutaric acid, succinic acid, lactic acid, S,S-ethylenediamine-N,N'-disuccinic acid, 1- 1,1-diphosphonic hydroxyethane (HEDP), dipicolinic acid (DPA), methanesulfonic acid (MSA), acetic acid, tartaric acid, adipic acid, oxalic acid, sulfamic acid, benzoic acid, formic acid, glycolic acid, polymeric acid, acid phytic, phosphoacetic acid, diethylenetriaminepentakis(methylphosphonoic) acid and N-(phosphonomethyl)iminodiacetic acid, or salts thereof; and wherein the composition is a dilutable composition comprising from 0.5 to 10% by weight of the quaternary ammonium compound, from 0.5 to 10% by weight of hydrogen peroxide and from 1 to 5% by weight of the acid, salts or mixtures thereof, and wherein the composition is free of peracids, and wherein the concentrated dilutable composition has a pH of 1.6 to 5. 3. Composition according to claim 1 or 2, characterized in that R1 and R4 are the same benzyl groups or C1-22 alkyl or aryl-substituted alkyl groups. 4. Composition according to claim 1 or 2, characterized in that R1 and R4 are C1-22 alkyl. 5. Composition according to claim 1 or 2, characterized in that R1 and R4 are C10 alkyl. 6. Composition according to claim 1 or 2, characterized in that R2 and R3 are C1-C4 alkyl. 7. Composition according to claim 1 or 2, characterized in that R2 and R3 are methyl. 8. Composition according to claim 1 or 2, characterized in that R1 and R4 are C1-22 alkyl, and R2 and R3 are methyl. 9. Composition according to any one of claims 1 to 8, characterized in that the quaternary ammonium compound comprises didecyl dimethyl ammonium chloride and/or C8-C18 alkyldimethylbenzylammonium chloride. 10. Composition according to any one of claims 1 to 9, characterized in that the acid is a C1 to Cs carboxylic acid or salt thereof. 11. Composition according to any one of claims 1 to 10, characterized in that the acid is a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid or a mixture thereof. 12. Composition according to any one of claims 1 to 11, characterized in that the acid is in the form of an alkali metal salt of the acid. 13. Composition according to any one of claims 1 to 12, characterized in that it is a dilutable composition that has a concentration of the quaternary ammonium compound from 2% by weight to 5% by weight of the composition. 14. Composition according to any one of claims 1 to 13, characterized in that it is a dilutable composition that has a hydrogen peroxide concentration of 3% by weight to 8% by weight of the composition. 15. Composition according to any one of claims 1 to 14, characterized in that it is a dilutable composition that has an acid or salt concentration of 1% by weight to 5% by weight of the composition. 16. Composition according to any one of claims 1 to 15, characterized in that the combination of the quaternary ammonium compound, hydrogen peroxide and the acid or salt thereof improves the antimicrobial effectiveness compared to hydrogen peroxide or to the quaternary ammonium compound alone. 17. Composition according to any one of claims 1 to 16, characterized in that it additionally comprises a stabilizer, solvent or additive. 18. Composition according to claim 17, characterized in that the solvent is present and is selected from the group consisting of: water, ethanol, propanol, isopropanol, propylene glycol, dipropylene glycol n-propyl ether and dipropylene glycol methyl ether . 19. Composition according to any one of claims 1 to 18, characterized in that it additionally comprises a chelator and/or a corrosion inhibitor. 20. Method of exterminating or inhibiting the growth of microorganisms on a surface characterized in that it comprises applying a composition, as defined in any one of claims 1 to 19, to a surface. 21. Method according to claim 20, characterized in that the microorganisms comprise one or more of Gram-positive bacteria, Gram-negative bacteria, viruses, fungi, mildew or mold. 22. Method according to claim 20 or 21, characterized in that the microorganisms comprise one or more of Staphylococcus, Pseudomonas, hepatitis, rotavirus, rhinovirus or Mycobacterium terrae. 23. Method of disinfecting a surface characterized by the fact that it comprises applying a composition, as defined in any one of claims 1 to 19, to the surface. 24. Use of a composition, as defined in any one of claims 1 to 19, characterized in that it is to exterminate or inhibit the growth of microorganisms on a surface. 25. Use of a composition, as defined in any one of claims 1 to 19, characterized in that it is to disinfect a surface. 26. Composition according to any one of claims 1 to 19, characterized in that it comprises two acids or salts thereof selected from the group consisting of citric acid, phosphoric acid, glutaric acid, lactic acid, S,S- ethylenediamine-N,N'-disuccinic acid, 1-hydroxyethane 1,1-diphosphonic acid (HEDP), dipicolinic acid (DPA), methanesulfonic acid (MSA), acetic acid, tartaric acid, adipic acid, oxalic acid, sulfamic acid, benzoic acid, formic acid, glycolic acid, polymeric acid, phytic acid, phosphoacetic acid, diethylenetriaminepentakis(methylphosphonoic) acid, and N-(phosphonomethyl)iminodiacetic acid, or salts thereof. 27. Method according to claim 20, characterized in that the composition demonstrates a log reduction of at least 5 in the number of microorganisms within about 5 minutes of contact time with the microorganisms. 28. Composition according to claim 26, characterized in that the two acids or salts thereof comprise an acid selected from the group consisting of citric acid, succinic acid, phosphoric acid, glutaric acid, dipicolinic acid (DPA), and lactic acid in combination with an acid selected from the group consisting of S,S-ethylenediamine-N,N'-disuccinic acid or its alkali salt, 1-hydroxyethane 1,1-diphosphonic acid (HEDP), and methanesulfonic acid (MSA ). 29. Composition according to any one of claims 1 to 19, characterized in that an acid or salt thereof is selected from the group consisting of citric acid, phosphoric acid, glutaric acid, succinic acid, lactic acid, S acid ,S-ethylenediamine-N,N'-disuccinic acid, 1-hydroxyethane 1,1-diphosphonic acid (HEDP), dipicolinic acid (DPA), methanesulfonic acid (MSA), acetic acid, tartaric acid, adipic acid, oxalic acid, sulfamic acid, benzoic acid, formic acid, glycolic acid, polymeric acid, phytic acid, phosphoacetic acid, diethylenetriaminepentakis(methylphosphonoic) acid and N-(phosphonomethyl)iminodiacetic acid, or salt thereof.