Germ-reducing aqueous composition comprising hydrogen peroxide and efficacy-enhancing components

Abstract

Containing aqueous composition 0.5 wt.% to 6.5 wt.%, in particular 1 wt.% to 3 wt.%, hydrogen peroxide; 0.1 wt.% to 4 wt.%, in particular 0.5 wt.% to 3 wt.%, phenoxyethanol; 0.01 wt.% to 2 wt.%, in particular 0.05 wt.% to 1.5 wt.%, etidronic acid; 0.01 wt.% to 2 wt.%, in particular 0.05 wt.% to 1.0 wt.%, of at least one amino compound, wherein at least one amino compound is a non-cyclic organic amino compound with at least one amino group and with a molar mass of at most 500 g / mol, where which contains the amino compound: a) at least one hydroxy group (-OH); and / or b) at least one carboxy group (-COOH), wherein the carboxy group(s) may also be present as salt(s), wherein a) the oxygen atom of the hydroxy group is separated from the nitrogen atom of the amino group by at least one carbon atom, b) the carbonyl carbon atom of the carboxyl group is removed from the nitrogen atom of the amino group by at least one carbon atom, wherein the longest continuous carbon chain in the molecule of the amino compound consists of up to three connected carbon atoms; and wherein - the weight ratio of etidronic acid to the sum of the amino compounds is 10:1 to 1:1, preferably 5:1 to 2:1; - the proportion of water is more than 70% by weight; and - the aqueous composition has a pH value of 1 to 4, preferably 2 to 3.

Description

[0001] The present invention relates to an aqueous composition comprising, besides water, hydrogen peroxide, phenoxyethanol, etidronic acid and an amino compound with a carboxylic acid and / or alcohol group, and the use of the aqueous composition for disinfection, in particular of hard surfaces.

[0002] Clostridioides difficile is an anaerobic, spore-forming bacterium and is frequently responsible for causing diarrheal diseases. A new strain, ribotype 027, is particularly virulent. This is one reason why the demand for spore-effective disinfectants, for example in healthcare or the food processing industry, remains high.

[0003] Spores are very difficult to kill. Spore-effective disinfectants such as chlorine bleach or peracetic acid are often described by users as having a pungent odor and being irritating. Hydrogen peroxide, as an oxygen-releasing agent, is generally effective against bacterial spores. However, its effectiveness in practical applications is either linked to very high concentrations of 7% by weight or more of hydrogen peroxide in disinfectant solutions, or the disinfection process is not fast enough for practical use. Disinfectants are now subject to strict regulation in Europe. They fall under the regulatory category of biocides and must not have contact times exceeding one hour for surface disinfection. The basis for testing spore efficacy is the European standard EN 17126, which sets high testing requirements. It was published in 2019.

[0004] Etidronic acid is used, among other substances, as a stabilizer for hydrogen peroxide. Alternatively, other chelating agents, such as ethylenediaminetetraacetic acid (EDTA), can also be used as stabilizers for hydrogen peroxide.

[0005] There are many approaches to increasing the effectiveness of hydrogen peroxide in disinfectants. EP 1987121 B1 discloses the combination of hydrogen peroxide with a long-chain phosphorus compound. EP 2329002 B1 teaches the combination of several substances with hydrogen peroxide, including a cyclic carboxylic acid and a block copolymer surfactant. WO 2018150359 A1 discloses the use of hydrogen peroxide together with amphoteric amine oxide surfactants. EP 2023733 B1 discloses the combination of hydrogen peroxide and ethoxylated carboxylic acids. US 8304378 B2 discloses the combination of hydrogen peroxide with long-chain carboxylic acids, while EP 1139762 B1 and EP 1473998 B1 address the combination with anionic surfactants. WO 2009 / 021336 A1 discloses the combination of hydrogen peroxide and glycolic acid with benzyl alcohol and / or phenoxyethanol.Of particular interest is example 25 in Table 9, which, in addition to hydrogen peroxide, also contains 1-hydroxyethylidene bisphosphonic acid (Briquest ADPA-60W), phenoxyethanol, an anionic surfactant, a nonionic surfactant, and several other substances, has a pH of 2.7, and shows no efficacy whatsoever. Only the addition of glycolic acid instead of lactic acid (example 27) leads to efficacy against spores.

[0006] Although there are numerous approaches to improving the effectiveness of hydrogen peroxide against spores, it is striking that even newly introduced hydrogen peroxide-based products from market leaders do not advertise sporicidal efficacy at launch. One example is the recently launched product Incidin OxyWipe NG, based on hydrogen peroxide and phenoxyethanol, from Ecolab. Its product information refers to the aforementioned EP 1987121 B1, but it does not claim sporicidal efficacy that meets the requirements of the EN 17126-2019-02 standard.

[0007] There is therefore still a need to increase the effectiveness of hydrogen peroxide in aqueous compositions to such an extent that practical, standards-compliant sporicidal disinfectants become possible. This is the object of the present invention. A further object of the present invention is to provide a usable, aqueous disinfectant composition that is suitable for surface disinfection – especially of hard surfaces – is low in odor, and has a long shelf life. Summary of the invention

[0008] The problem is solved according to the invention with the aqueous composition according to claim 1. The aqueous composition is germ-reducing and can be used as a disinfectant composition. Preferred embodiments are explained below or are the subject of the dependent claims.

[0009] The invention comprises an aqueous composition comprising, in addition to water: hydrogen peroxide, phenoxyethanol, etidronic acid, and at least one of the amino compounds described in more detail below. The following applies to the composition with regard to the concentration of the above components, also independently with regard to the preferred ranges: - 0.5 wt.% to 6.5 wt.%, in particular 1 wt.% to 3 wt.%, hydrogen peroxide; - 0.1 wt.% to 4 wt.%, in particular 0.5 wt.% to 3 wt.%, phenoxyethanol; - 0.01 wt.% to 2 wt.%, in particular 0.05 wt.% to 1.5 wt.%, etidronic acid; - 0.01 wt.% to 2 wt.%, in particular 0.05 wt.% to 1.5 wt.%, of at least one amino compound.

[0010] The weight ratio of etidronic acid to the amino compound, and if there are several amino compounds (or several of the preferred amino compounds), to the sum of the amino compounds (or the sum of the preferred amino compounds), is 10:1 to 1:1, preferably 5:1 to 2:1.

[0011] The water content is greater than 70% by weight.

[0012] The pH value of the aqueous composition is 1 to 4, preferably 2 to 3 (measured at 25 °C).

[0013] The at least one amino compound is a non-cyclic organic amino compound with at least one amino group and a molar mass of at most 500 g / mol.

[0014] The amino compound exhibits a) at least one hydroxyl group (-OH); and / or b) at least one carboxyl group (-COOH), wherein the carboxyl group may also be present as a salt or the carboxyl groups may also be present as salts, wherein a) the oxygen atom of the hydroxy group is separated from the nitrogen atom of the amino group by at least one carbon atom; b) the carbonyl carbon atom of the carboxyl group is removed from the nitrogen atom of the amino group by at least one carbon atom.

[0015] The longest continuous carbon chain in the molecule of the amino compound consists of up to three connected carbon atoms.

[0016] The information refers to the concentration of the respective substance in the composition in wt.% and can be determined by weighing during mixing or, for example, by common methods such as titration, HPLC or GC analysis.

[0017] Surprisingly and unforeseen, the above aqueous compositions based on water, hydrogen peroxide, phenoxyethanol and etidronic acid exhibited a standard-compliant sporicidal efficacy when small amounts of the amino compound were added and the aqueous composition had the required pH value.

[0018] Another aspect of the invention is the non-therapeutic use of the aqueous composition for the non-therapeutic disinfection of hard surfaces. Hard surfaces include, for example, floors, walls, tables and shelves, containers or equipment, such as those used in the food and agricultural food industries or in the preparation, processing and packaging of food and beverages, in the bio-industry, the pharmaceutical industry, the cosmetics industry, in cleanrooms, in greenhouses and plant or animal breeding facilities, or also in the field of hygiene and health.

[0019] A particular area of ​​application for the compositions according to the invention is the disinfection of hospital rooms, medical practices, and nursing homes. "Non-therapeutic" means that it is not intended for use on the human or animal body.

[0020] The surfaces to be treated can vary, especially hard surfaces; examples include commercial or public facilities, floors, equipment, tools and utensils, containers such as tanks, preservative packaging, pipes and hoses.

[0021] The surface to be treated can be made of any material and in particular of glass, aluminium or stainless steel, ceramic or organic polymer, such as polyethylene, polypropylene, polycarbonate, polyamide, polyester, such as polyethylene terephthalate (PET), polyurethane, fluoropolymers, such as PTFE, PVDF and PFA, and polyvinyl chloride (PVC).

[0022] According to one embodiment of the present invention, the aqueous composition is absorbed by a porous material, such as a cloth, sponge, paper, brush fibers, or fabric, resulting in a ready-to-use formulation on a solid carrier, such as a nonwoven cloth, mop, or other textile material. The cloths can be made of, for example, cellulose, cellulose derivatives, viscose, PET, PE, and / or PP. The mops can also be multi-layered, with the layers consisting of different materials.

[0023] The mops and cloths are pre-assembled, meaning they are soaked with the aqueous solution and offered in this form, for example, in plastic bags or containers for use. These can also be intended for single use.

[0024] The aqueous composition can also be sprayed on or applied to the surface in any other way and then spread with a cloth or mop. Detailed description of the invention

[0025] The amino compound has one or more amino groups and a molar mass of at most 500 g / mol.

[0026] The amino compound contains one or more substructures of the formula NR 3-x H x , where covalent bonds exist between the nitrogen atom and a carbon atom of the R group. X is 0, 1, or 2.

[0027] In the pH range of the formulations according to the invention, the amino groups can also be all or partially protonated.

[0028] Preferably, the following compounds are not included in the definition of the amino compounds used according to the invention: - quaternary ammonium groups with a substructure NR4 + , and / or - N-oxide groups, and / or - Amide groups, and / or - Ester groups, and / or - Keto groups, and / or - Contains aldehyde groups and is further preferred - also not have any other functional groups, except those described in claim 1, such as phosphorus- or sulfur-based functional groups.

[0029] Preferably, the amino compounds contain only H, C, O, and N atoms. This definition does not extend to the counterion of the amino compounds in the case of a salt. The counterion can be, for example, Na. + , K + , Ca 2+ , Mg 2+ or NH4 + be.

[0030] The term that "the longest continuous carbon chain in the molecule consists of up to three connected carbon atoms" means that, for example, long-chain amines such as laurylamine derivatives do not fall under the definition of amino compounds.

[0031] Examples of amino compounds used according to the invention are, for example, monoethanolamine, glycine, tetrahydroxypropylethylenediamine or methylglycine diacetic acid trisodium salt.

[0032] The aqueous composition may also include: one or more anionic surfactants, in particular C10 to C22 fatty alcohol sulfates, C10 to C22 fatty alcohol ether sulfates, C10 to C22 fatty alcohol sulfonates and / or C10 to C22 olefin sulfonates, preferably sodium lauryl sulfate, sodium lauryl ether sulfate, sodium coco sulfate, alkyl sulfonates, branched and unbranched, and / or alpha-olefin sulfonates.

[0033] The aqueous composition may also include: one or more non-ionic surfactants such as alcohol alkoxylates and / or alcohol alkoxylate ethers with different chain lengths (C5- to C22-) and a degree of alkoxylation of, for example, x=3-25 (e.g., (-CH2-CH2-O-) x-units). In some cases, combinations of alcohol ethoxylates with a longer chain length (C ≥ 12, fatty alcohol alkoxylates) and alcohol ethoxylates or alcohol alkoxylate ethers with a shorter chain length (C < 12) are advantageous, with the weight fraction of the longer-chain fatty alcohol ethoxylates being lower in each case. Examples of alcohol alkoxylates with a longer chain length are, for example, C 16 -C 18 Alcohol ethoxylate, 25 EO (e.g. Lutensol AT 25, BASF), Iso C 13 Alcohol ethoxylate 8 EO (e.g., Lutensol TO89, BASF). An example of a short-chain alcohol alkoxylate is ethoxylated hexan-1-ol (e.g., Lutensol CS 6250, BASF). An example of an alcohol alkoxylate ether is the modified alcohol polyglycol ether, 22 EO, CAS 501019-90-5 (e.g., Dehypon wet, BASF).

[0034] The aqueous composition may further include: a solvent such as C2 / C3 alcohols, like ethanol, propan-1-ol, and propan-2-ol, and / or a further solubilizer, each with ether and / or alcohol and / or ester groups, in particular ether and / or alcohol groups, such as diols or polyols, each preferably with 3, 4, or 5 interconnected carbon atoms in at least one of the groups (optionally also only in one segment or also segments of, for example, 3 plus 3, 3 plus 4, or 4 plus 4 carbon atoms), and preferably a maximum of 8 carbon atoms per molecule. The solvents or solubilizers are preferably used in amounts of 1 to less than 20 wt.%, more preferably 2 to less than 15 wt.%, and particularly preferably 2 to less than 10 wt.%.

[0035] The aqueous composition may also contain: other substances that regulate the pH value, such as inorganic acids like phosphoric acid or sulfuric acid, inorganic bases like sodium hydroxide, potassium hydroxide, or potassium carbonate. Additionally, it may contain corrosion inhibitors like phosphate esters or benzotriazole, as well as odor-enhancing substances, dyes and / or fragrances, and / or, depending on the application, defoamers or foaming agents and / or cleaning boosters.

[0036] The aqueous composition preferably consists of the aforementioned components or compounds in a proportion greater than 97 wt.%, preferably greater than 99 wt.%, and particularly preferably greater than 99.9 wt.%.

[0037] The aqueous composition can also be used to impregnate wipes for cleaning or disinfecting smaller surfaces and to impregnate mops for cleaning or disinfecting larger surfaces such as floors. These wipes and mops are preferably pre-assembled and packaged ready for use, particularly preferably pre-assembled and packaged ready for use with viscose-based wipes or mops, such as those made from viscose produced using solvent processes (Lyocell) or from hydrophobic viscose variants.

[0038] It should be emphasized that the aqueous composition is also characterized by high storage stability in or on cloths or mops, e.g. on a viscose base. Experimental section

[0039] After 18 weeks of storage at 30 °C, the hydrogen peroxide and phenoxyethanol content remains within + / -5% of the original value, and the pH value remains essentially stable. The data were determined from the squeezed aqueous solution after storage of the pre-moistened wipes, packaged in a flow pack (a tubular pouch with a dispensing opening at the top).

[0040] Three formulations according to the invention are shown in Table 3. For better comparability, the concentrations of the biocidal active ingredients hydrogen peroxide and phenoxyethanol were identical at 2 wt% each, the content of etidronic acid was identical at 0.38 wt%, the content of all other ingredients such as surfactants and solvents was identical, only the content of the amine compounds according to the invention varied. The pH value was adjusted to an identical value of pH = 2.1 at 25 °C for all three formulations. Purified water was added to 100%. Table 1: Inventive formulations with results of the test according to EN 17126, C. difficile, 60 minutes, results shown in log reductions of an 80% concentration and a 97% concentration Concentration values ​​in wt.% Example 1 Example 2 Example 3 H2O2 2 2 2 Phenoxyethanol 2 2 2 Etidronic acid 0,38 0,38 0,38 Methylglycine diacetic acid trisodium salt 0,1 Tetrahydroxypropyl ethylenediamine 0,1 Glycine 0,06 The remainder consists of equal amounts of surfactants, solvents, and water to 100% by weight. PH value 2,1 2,1 2,1 Results EN 17126 80% solution, log reduction 4,74 5,4 4,7 97% solution, log reduction 4,24 5,0 4,2

[0041] The tests according to EN 17126 met the standard requirements and were carried out in an accredited laboratory. The concentrations of 80 wt% and 97 wt% were due to technical reasons.

[0042] Sufficient efficacy of the tested solution is achieved when a reduction of 4 log units is reached at 97% dilution. It can be seen that the required efficacy was also achieved at an 80% dilution. Thus, very good, standard-compliant efficacy against C. difficile according to EN 17126 was demonstrated. Table 2: Further examples according to the invention 4 to 11 and 14 to 17 and examples not according to the invention 12 and 13 Concentration values ​​in wt.% Example 4 Example 5 Example 6 Example 7 Example 8 H2O2 2,4 2 3 1 0,5 Phenoxyethanol 2,4 2 0,5 3 3 Etidronic acid 0,38 0,38 0,4 1,2 0,06 Monoethanolamine 0,05 Methylglycine diacetic acid trisodium salt 0,1 0,06 Tetrahydroxypropylethylenediamine 0,2 Glycine 0,06 0,15 Surfactant 1 0,2 0,2 Surfactant 2 0,2 0,1 0,2 Surfactant 3 0,4 0,5 Surfactant 4 0,2 0,2 Surfactant 5 0,2 Surfactant 6 0,045 0,045 0,02 0,02 0,02 Solvent 1 9 8 15 10 Solvent 2 12 Solvent3 Phosphoric acid / Potassium hydroxide to pH 2.2 to pH 2.2 to pH 2.2 PH value 2 2,1 2,2 2,2 2,2 Table 2 (continued) Concentration values ​​in wt.% Example 9 Example 10 Example 11 Example 12 Example 13 H2O2 2 2 2 2,4 2 Phenoxyethanol 2 2 2 2,4 2 Etidronic acid 0,4 0,4 0,4 0,15 0,5 Monoethanolamine 0,05 0,08 0,08 Methylglycine diacetic acid trisodium salt Tetrahydroxypropylethylenediamine Glycine Surfactant 1 0,2 0,2 0,2 0,2 Surfactant 2 0,2 0,2 0,2 0,2 Surfactant 3 0,4 Surfactant 4 0,2 0,2 0,2 Surfactant 5 Surfactant 6 0,02 0,02 0,02 0,045 0,045 Solvent 1 15 10 9 8 Solvent 2 8 Solvent3 Phosphoric acid / Potassium hydroxide to pH 2.2 to pH 2.2 to pH 2.2 to pH 2.2 PH value 2,2 2,2 2,2 2,1 2,2 Table 2 (continued) Concentration values ​​in wt.% Example 14 Example 15 Example 16 Example 17 H2O2 2 2 2 2 Phenoxyethanol 2 2 2 2 Etidronic acid 0,38 0,4 0,4 0,4 Monoethanolamine Methylglycine diacetic acid trisodium salt 0,1 0,1 0,1 0,1 Tetrahydroxypropylethylenediamine Glycine Surfactant 1 0,2 0,2 0,2 Surfactant 2 0,2 0,2 0,2 Surfactant 3 0,4 Surfactant 4 0,2 0,2 0,2 Surfactant 5 Surfactant 6 0,045 0,02 0,02 0,02 Solvent 1 15 8 Solvent 2 8 8 Solvent3 3 Phosphoric acid / Potassium hydroxide PH value 2,1 2,1 2,1 2,1

[0043] Surfactant 1: Sulfonic acids, C14-16-alkane hydroxy and C14-C16-alkene, sodium salts; Surfactant 2: Sodium dodecyl sulfate; Surfactant 3: Sulfonic acids, C14-17-sec-alkane, sodium salts; Surfactant 4: Hexan-1-ol, ethoxylated; Surfactant 5: Modified alcohol polyglycol ether, 22EO; Surfactant 6: Isotridecanol, ethoxylated; Solvent 1: Ethanol; Solvent 2: Propan-1-ol; Solvent 3: 3-Methoxy-3-methylbutan-1-ol. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] EP 1987121 B1 [0005, 0006] EP 2329002 B1

[0005] WO 2018150359 A1

[0005] EP 2023733 B1

[0005] US 8304378 B2

[0005] EP 1139762 B1

[0005] WO 2009 / 021336 A1

[0005]

Claims

[1] Containing aqueous composition 0.5 wt.% to 6.5 wt.%, in particular 1 wt.% to 3 wt.%, hydrogen peroxide; 0.1 wt.% to 4 wt.%, in particular 0.5 wt.% to 3 wt.%, phenoxyethanol; 0.01 wt.% to 2 wt.%, in particular 0.05 wt.% to 1.5 wt.%, etidronic acid; 0.01 wt.% to 2 wt.%, in particular 0.05 wt.% to 1.0 wt.%, of at least one amino compound, wherein at least one amino compound is a non-cyclic organic amino compound with at least one amino group and with a molar mass of at most 500 g / mol, where which contains the amino compound: a) at least one hydroxy group (-OH); and / or b) at least one carboxy group (-COOH), wherein the carboxy group(s) may also be present as salt(s), wherein a) the oxygen atom of the hydroxy group is separated from the nitrogen atom of the amino group by at least one carbon atom, b) the carbonyl carbon atom of the carboxyl group is removed from the nitrogen atom of the amino group by at least one carbon atom, wherein the longest continuous carbon chain in the molecule of the amino compound consists of up to three connected carbon atoms; and wherein - the weight ratio of etidronic acid to the sum of the amino compounds is 10:1 to 1:1, preferably 5:1 to 2:1; - the proportion of water is more than 70% by weight; and - the aqueous composition has a pH value of 1 to 4, preferably 2 to 3. [2] The aqueous composition according to at least one of the preceding claims further comprising one or more anionic surfactants, in particular C10 to C22 fatty alcohol sulfates, C10 to C22 fatty alcohol ether sulfates, C10 to C22 fatty alcohol sulfonates and / or C10 to C22 olefin sulfonates. [3] The aqueous composition according to at least one of the preceding claims further comprising one or more non-ionic surfactants, in particular C5 to C22 alcohol alkoxylates and / or alcohol alkoxylate ethers, preferably with a degree of alkoxylation of 3 to 25. [4] The aqueous composition according to at least one of the preceding claims further comprising ethanol and / or propan-1-ol and / or propan-2-ol, preferably in total from 1 to less than 20 wt.%, preferably 2 to less than 15 wt.%, particularly preferably 2 to less than 10 wt.%. [5] The aqueous composition according to at least one of the preceding claims further comprising at least one solubilizer, each comprising ether and / or alcohol and / or ester groups, in particular ether and / or alcohol groups, such as diols or polyols, each more preferably comprising 3 or 4 or 5 interconnected carbon atoms in at least one of the groups, and preferably a maximum of 8 carbon atoms per molecule, preferably in total from 1 to less than 20 wt.%, preferably 2 to less than 15 wt.%, particularly preferably 2 to less than 10 wt.%. [6] The aqueous composition according to at least one of the preceding claims, wherein the amino compound is methylglycine diacetic acid trisodium salt and / or tetrahydroxypropylethylenediamine and / or glycine. [7] The aqueous composition according to at least one of the preceding claims, wherein the amino compound is or comprises monoethanolamine. [8] The aqueous composition according to at least one of the preceding claims further comprising as pH regulators inorganic acids or bases and / or corrosion inhibitors and / or perfumes and / or defoamers or foaming agents and / or cleaning enhancers. [9] The aqueous composition according to at least one of the preceding claims consisting of the components or compounds mentioned in one or more of the preceding claims in greater than 97 wt.%, preferably greater than 99 wt.%, particularly preferably greater than 99.9 wt.%. [10] Cloths or mops soaked with the aqueous composition according to at least one of the preceding claims, preferably pre-assembled and packaged ready for use, wherein the cloths or mops are preferably viscose-based cloths or mops. [11] Non-therapeutic use of the aqueous composition according to at least one of claims 1 to 9 or of the wipes or mops according to claim 10 for disinfection, in particular against Clostridioides difficile spores, wherein the use preferably reduces Clostridioides difficile spores by at least 4 log steps in at least 1 hour according to EN 17126. [12] The non-therapeutic use according to claim 11 for disinfecting hard surfaces.