Solid effervescent compositions comprising antimicrobial agents

By developing a solid effervescent cleaning composition containing acid, gas generator and antimicrobial compounds, the problem of the lack of effective antimicrobial activity of higher acidic compositions in the prior art on Gram (-) microorganisms is solved, and the problem of the high acidic compositions in the prior art lack of effective antimicrobial activity on Gram (-) microorganisms is achieved. Effective killing of Gram-positive and negative bacteria under lower acidic conditions.

CN119506008APending Publication Date: 2025-02-253M INNOVATIVE PROPERTIES CO
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Patent Information

Application Number
CN202411071420.9
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Priority Date
2023-08-23
Filing Date
2024-08-06
Publication Date
2025-02-25

AI Technical Summary

Technical Problem

The existing cleaning compositions with higher acidity lack effective antimicrobial activity on Gram (-) microorganisms such as E. coli, and the lower acidity compositions have high corrosiveness and are difficult to use in industry.

Method used

A solid effervescent cleaning composition has been developed, comprising one or more acids, gas generators and at least one antimicrobial compound, with a pH range of between 4 and 9, which can effectively reduce Gram-positive and negative bacterial quantity.

Benefits of technology

The composition is able to provide effective antimicrobial activity against Gram (-) microorganisms under lower acidic conditions while reducing corrosiveness, achieving a reduction of at least 3 logarithms for Gram-positive and negative bacteria.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention relates to a solid effervescent composition comprising an antimicrobial agent. A solid effervescent cleansing composition is described, the solid effervescent cleansing composition comprising one or more acids and a gas generating agent; wherein the 1% by weight aqueous solution of the solid cleaning composition has a pH in the range of from 4 to 9; and at least one antimicrobial compound. In some embodiments, a 1% by weight aqueous solution of the solid effervescent cleansing composition provides a reduction of at least 3 logarithms of gram-positive bacteria and gram-negative bacteria. In some embodiments, the antimicrobial compound is selected from aromatic alcohols; an aliphatic alcohol, the aliphatic alcohol optionally further comprising an ester moiety; and combinations thereof. Also described is a (e.g., dry) wipe comprising a woven or non-woven substrate, the woven or non-woven substrate further comprising the solid effervescent cleaning composition described herein; and a cleaning tool having a handle.
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Description

Summary of the invention

[0001] Although various acid-based (e.g., solid effervescent) cleaning compositions are known, only highly acidic compositions have been found to provide effective antimicrobial activity against Gram (-) (e.g., E. coli) and Gram (+) (e.g., Staphylococcus aureus (S. aureus)) bacteria. Less acidic compositions in the pH range of 4 to 6 do not provide effective antimicrobial activity against Gram (-) microorganisms (e.g., E. coli). Less acidic cleaning compositions may be desirable because such compositions are less corrosive. Therefore, it would be advantageous for the industry to find less acidic cleaning compositions that provide effective antimicrobial activity against both Gram-negative and Gram-positive bacteria.

[0002] In one embodiment, a solid effervescent cleaning composition is described, the solid effervescent cleaning composition comprising:

[0003] One or more acids and gas generating agents; wherein 1% by weight of the solid cleaning composition

[0004] The aqueous solution has a pH in the range of 4 to 9; and at least one antimicrobial compound. In some embodiments, a 1 wt % aqueous solution of the solid effervescent cleaning composition provides at least a 3 log reduction in Gram-positive and Gram-negative bacteria. In some embodiments, the antimicrobial compound is selected from an aromatic alcohol; an aliphatic alcohol, optionally further comprising an ester moiety; and combinations thereof.

[0005] The solid effervescent cleaning composition may be a powder, optionally provided in a water-soluble sachet or pod; or a solid block, such as a tablet.

[0006] Also described are (eg, dry) wipes comprising a woven or nonwoven substrate further comprising the solid effervescent cleaning composition described herein.

[0007] A solid effervescent cleaning composition or a (eg, woven or nonwoven) substrate comprising such a solid effervescent cleaning composition may be attached to the handle. DETAILED DESCRIPTION

[0008] The present invention is a solid effervescent cleaning composition including a powder or tablet. In some embodiments, the solid effervescent cleaning composition can be compressed (e.g., molded under pressure) into a solid article (e.g., tablet) at room temperature and low temperature. In other embodiments, the powder can be provided in a pre-measured pouch or pod of a water-soluble (e.g., polyvinyl alcohol) film. The composition, when dissolved in water, produces effervescence, foaming, and acidity.

[0009] acid

[0010] The solid effervescent cleaning composition comprises one or more acids. The acid acts as an effervescent agent and a cleaning agent. The reaction of the acid with the gas generating agent provides foaming. In some embodiments, the acid may also provide antimicrobial activity against Gram (+) (e.g., Staphylococcus aureus) bacteria.

[0011] Cleaning compositions typically comprise a weak acid, optionally in combination with a strong acid.

[0012] A weak acid is defined as an acid having a pKa between about 2.5 and about 5. Weak acids can help increase tablet strength. In one embodiment, the weak acid is a carboxylic acid. Examples of suitable weak acids include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, sorbic acid, fumaric acid, malic acid, tartaric acid, citric acid, benzoic acid, adipic acid, ascorbic acid, and glycolic acid.

[0013] Strong acids are defined as acids with a pKa between about -3 and about 2. Strong acids serve to provide rapid foaming and are generally less hygroscopic. In one embodiment, the strong acid may also perform a disinfecting function. In one embodiment, the strong acid is one of an alkyl sulfonic acid, an aryl sulfonic acid, and an oxalic acid. Examples of suitable alkyl sulfonic acids and aryl sulfonic acids include, but are not limited to, aminosulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid.

[0014] The solid effervescent cleaning composition typically comprises at least 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, or 45% by weight of one or more weak acids, such as citric acid. In some embodiments, such as when the solid effervescent cleaning composition comprises a small amount of strong acid or does not comprise a strong acid, the amount of weak acid may be at least 50%, 55%, or 60% by weight. In some embodiments, the solid effervescent cleaning composition may comprise no more than 60%, 59%, 59%, 57%, 56%, 55%, 54%, 53%, 52%, 51%, or 50% by weight of one or more weak acids, such as citric acid.

[0015] In some embodiments, the solid effervescent cleaning composition further comprises a strong acid, such as aminosulfonic acid, in an amount of at least 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt % or 15 wt % of the total solid effervescent cleaning composition. In some embodiments, the amount of a strong acid, such as aminosulfonic acid, is no greater than 20 wt %, 19 wt %, 18 wt %, 17 wt %, 16 wt %, 15 wt %, 14 wt %, 13 wt %, 12 wt %, 11 wt % or 10 wt % of the total weight of the total solid effervescent cleaning composition. In some embodiments, the amount of a strong acid, such as aminosulfonic acid, is less than 10 wt %, 9 wt %, 8 wt %, 7 wt %, 6 wt %, 5 wt %, 4 wt %, 3 wt %, 2 wt % or 1 wt % of the total solid effervescent cleaning composition.

[0016] When a strong acid such as sulfamic acid is present, the amount of weak acid is greater than the amount of strong acid. In some embodiments, the weight ratio of weak acid to strong acid is in the range of at least 1.75:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1.

[0017] The composition has an acidic pH, making it useful for cleaning surfaces, such as toilet bowls. Hard water stains and scale can be dissolved under acidic conditions. In typical embodiments, the composition has a pH of at least 4 and typically no greater than 6 or 5.5.

[0018] The pH of the cleaning composition is a function of the choice of acid, the concentration of the acid, the choice and amount of gas generating agent, and the concentration of the water to which the solid cleaning agent is added (eg, dissolved).

[0019] A 1 wt % aqueous solution of the solid effervescent cleaning composition has a pH of at least 4 and typically no greater than 9, 8.5, 8, 7.5, 7, or 6.5. In some embodiments, a 1 wt % aqueous solution of the solid effervescent cleaning composition has a pH of no greater than 6 or 5.5.

[0020] In one embodiment, the solid effervescent cleaning composition can remove at least about 25%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95% of hard water stains when added to water. In one embodiment, the composition can remove at least about 25%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95% of scale.

[0021] Gas generating agent

[0022] Solid effervescent cleaning composition comprises gas generating agent. Gas generating agent is used as effervescent agent for producing foam / bubbles. Gas generating agent is the basic component that interacts with the acid in composition to provide effervescence. Examples of suitable gas generating agent include, for example, carbon dioxide generating agent and oxygen generating agent. Examples of suitable carbon dioxide generating agent include, but are not limited to: bicarbonate of Group I metal, Group II metal and other cations (including ammonium, alkyl (mono-, di- or tri-) ammonium), or bicarbonate of transition metal; carbonate of Group I metal, Group II metal and other cations (including ammonium, alkyl (mono-, di- or tri-) ammonium), or carbonate of transition metal; and percarbonate of Group I metal, Group II metal and other cations (including ammonium, alkyl (mono-, di- or tri-) ammonium), or percarbonate of transition metal. Examples of carbon dioxide generating agent include, for example, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and calcium bicarbonate.

[0023] In order to generate maximum foam in the effervescent system of the composition, the normality ratio of the acid to the base in the composition is generally about 1. The normality ratio is defined as the equal number of moles of acidic functional groups to the equal number of moles of basic functional groups in the formulation. When this ratio deviates from 1, the total amount of foam in the system will be reduced accordingly. In one embodiment, the ratio of the acid to the base of the composition is between about 10:1 and about 1:10, specifically between about 5:1 and about 1:5, and more specifically between about 3:1 and about 1:3.

[0024] Examples of suitable oxygen generators include, but are not limited to, hydrogen peroxide; peracetic acid produced from sodium percarbonate / TAED (tetraacetylethylenediamine); percarbonates of Group I metals, Group II metals and other cations (including ammonium, alkyl (mono-, di- or tri-) ammonium), or percarbonates of transition metals; chlorates and perchlorates of Group I metals, Group II metals and other cations (including ammonium, alkyl (mono-, di- or tri-) ammonium), or chlorates and perchlorates of transition metals; superoxide salts of Group I metals, Group II metals and other cations (including ammonium, alkyl (mono-, di- or tri-) ammonium), or superoxide salts of transition metals; and peroxide salts of Group I metals, Group II metals and other cations (including ammonium, alkyl (mono-, di- or tri-) ammonium), or peroxide salts of transition metals.

[0025] Foaming enables compositions to contact hard-to-reach surfaces, such as the downside of the inner surface of a toilet bowl. In one embodiment, utilizing 40g samples in 2 liters of water, after the sample tablet is immersed in the water for one to five minutes, a sufficient amount of foam is produced to have at least about 0.1cm, at least about 0.5cm, at least about 0.75cm, at least about 1cm, at least about 1.25cm, at least about 1.5cm, at least about 1.75cm, at least about 2cm, at least about 3.0cm and at least about 3.5cm of foam height. Foam height can be measured by adding 2000 grams of room temperature deionized water to 4 liters of beakers, followed by adding 40 grams of solid effervescent cleaning compositions (i.e. 2 % by weight solution). The foam height of an effervescent tablet can be measured and recorded when it dissolves after different durations such as 15 seconds, 30 seconds, 1 minute, two minutes, three minutes and five minutes.

[0026] Antimicrobial compounds

[0027] The solid effervescent cleaning composition comprises a gas generating agent, at least one antimicrobial compound, and the at least one antimicrobial compound provides at least partial antimicrobial activity. In a typical embodiment, a 1 wt % aqueous solution of the solid effervescent cleaning composition provides at least 3 log reductions of Gram-positive bacteria and Gram-negative bacteria. Acids can provide at least partial antimicrobial activity. When the cleaning composition has sufficient acidity, a separate acid can provide sufficient antimicrobial activity to Gram-positive bacteria. However, in the absence of an antimicrobial compound, a 1 wt % aqueous solution of the solid effervescent cleaning composition does not provide at least 3 log reductions of Gram-negative bacteria. When the solid effervescent cleaning composition is weakly acidic, neutral or alkaline, a separate antimicrobial compound can provide at least 3 log reductions of Gram-positive bacteria and Gram-negative bacteria for a 1 wt % aqueous solution.

[0028] In some embodiments, the antimicrobial compound is an aromatic alcohol, including phenolic compounds such as thymol, carvacrol, eugenol, and natural oils containing phenolic compounds such as thyme oil and clove oil.

[0029] In some embodiments, the antimicrobial compound is an aliphatic alcohol, such as (C5-C12) 1,2-saturated alkanediol and / or (C12-C18) 1,2-unsaturated alkanediol. Examples include 1,2 hexanediol, 1,2 octanediol, 1,2 decanediol, 1,2 oleyl glycol, and mixtures thereof.

[0030] In another embodiment, the aliphatic alcohol may also contain a continuous ester moiety. In this embodiment, the aliphatic alcohol may be characterized as a fatty acid ester of a polyol. Such an aliphatic alcohol may have the formula (R 1 -C(O)-O) n -R2 , where R 1 is a residue of a (C8-C12) saturated fatty acid or a (C12-C22) unsaturated fatty acid (including a polyunsaturated fatty acid), R 2 is the residue of a polyol (usually and preferably glycerol, propylene glycol and sucrose, but others may be used, including pentaerythritol, sorbitol, mannitol, xylitol, etc.), and n=1 or 2. R 2 The group contains at least one free hydroxyl group (preferably a residue of glycerol, propylene glycol or sucrose). Preferred polyol fatty acid esters are esters derived from (C8-C12) saturated fatty acids. For embodiments in which the polyol is glycerol or propylene glycol, n=1, but when it is sucrose, n=1 or 2.

[0031] Exemplary fatty acid monoesters include, but are not limited to, glycerol monoesters of lauric acid (monolaurin), caprylic acid (monocaprylic acid) and capric acid (monocapric acid); and propylene glycol monoesters of lauric acid, caprylic acid and capric acid; and sucrose monoesters of lauric acid, caprylic acid, and capric acid. Other fatty acid monoesters include glycerol and propylene glycol monoesters of unsaturated (including polyunsaturated) fatty acids of oleic acid (18:1), linoleic acid (18:2), linolenic acid (18:3) and arachidonic acid (20:4). As is generally known, for example, 18:1 means that the compound contains 18 carbon atoms and 1 carbon-carbon double bond.

[0032] In some embodiments, the desired antimicrobial lipid is a liquid when in pure form (ie, not mixed with a solvent) at room temperature (23°C).

[0033] In some embodiments, the total amount of antimicrobial compounds is at least 1 wt%, 2 wt%, 3 wt%, 4 wt% or 5 wt% based on the total solid effervescent cleaning composition. In some embodiments, the total amount of antimicrobial compounds is no more than 20 wt%, 15 wt% or 10 wt% based on the total solid effervescent cleaning composition. Solid effervescent cleaning compositions typically include a minimum amount of one or more antimicrobial compounds to provide the desired antimicrobial activity when the composition is diluted in water. In some embodiments, the solid effervescent cleaning composition includes at least 2 wt%, 3 wt%, 4 wt% or 5 wt% of a single phenolic compound (e.g., thymol) or a single fatty acid monoester.

[0034] In other embodiments, the solid effervescent cleaning composition comprises at least 2%, 3%, 4%, or 5% by weight of a phenolic compound (e.g., thymol) in combination with at least 0.25%, 0.5%, 1%, 2%, 3%, 4%, or 5% by weight of an aliphatic alcohol and / or a fatty acid monoester.

[0035] In some embodiments, the antimicrobial compound has a low solubility in water (i.e., no more than 10 g / 1000 g (1.0 L) of deionized water). The solubility in water of various compounds, including antimicrobial compounds, is generally known (e.g., reported by the supplier). Solubility can also be estimated using the "Conventional Solubility Estimations" as in Henrik Vorum et al., "Solubility of Long-Chain Fatty Acids in Phosphate Buffer at pH 7.4" (Acta Biochimica et Biophysica Sinica, 1996). Biochimica et Biophysica Acta .), 1126, 135-142 (1992)).

[0036] It has been found that the presence of an antimicrobial compound with low solubility in water (e.g. an insoluble oil) does not hinder the effervescence and foam formation of the cleaning composition. This is surprising since insoluble oils are known defoamers.

[0037] In typical embodiments, the acids and antimicrobial compounds described herein are the only biocides in the composition. In such embodiments, the composition does not include other biocides, such as benzalkonium chloride, sodium dichloroisocyanurate, benzisothiazolinone chlorhexidine, quaternary ammonium derivatives, and combinations thereof.

[0038] Solid effervescent cleaning compositions in combination with water can be used to provide effective antimicrobial activity to (e.g., hard) surfaces. The compositions can be used in methods under conditions that effectively kill or inactivate one or more microorganisms, such as bacteria, fungi, and viruses. In certain embodiments, the compositions provide antimicrobial killing of Gram-positive and Gram-negative bacteria according to the Antimicrobial Efficacy Test (illustrated in the Examples section).

[0039] In certain embodiments, the solid effervescent cleaning composition in combination with water provides at least a 3, 4, 5, or 6 log reduction in test bacteria of Gram-positive and Gram-negative bacteria when evaluated by the Antimicrobial Efficacy Test illustrated in the Examples section. This antimicrobial activity can be achieved within 1, 2, 5, or 10 minutes.

[0040] Gram-positive and Gram-negative bacteria include, for example, Escherichia coli, Staphylococcus spp., Streptococcus spp., Pseudomonas spp., Enterococcus spp., and Escherichia spp., Aspergillus spp., Fusarium spp., Candida spp., food pathogens such as Listeria sp., Listeria monocytogenes, Campylobacter sp., Clostridium sp., Salmonella sp., and combinations thereof. Other relevant organisms include viruses, such as herpes viruses, rhinoviruses, human coronaviruses, and influenza viruses, and particularly virulent organisms include Staphylococcus aureus (including resistant strains, such as Methicillin Resistant Staphylococcus Aureus (MRSA), Staphylococcus epidermidis, Streptococcus pneumoniae, Enterococcus faecalis, Vancomycin Resistant Enterococcus (VRE), Pseudomonas aeruginosa, Escherichia coli, Aspergillus niger, Aspergillus fumigatus, Aspergillus clavatus, Fusarium solani, Fusarium oxysporum, and the like. oxysporum), Fusarium chlamydosporum, Candida albicans, Candida glabrata, Candida krusei, and combinations thereof. Solid effervescent cleaning compositions combined with water are particularly effective for killing or inactivating bacteria such as Staphylococcus aureus and Escherichia coli.

[0041] Optional water-soluble acrylic polymer

[0042] In some embodiments, the solid effervescent cleaning composition also comprises (e.g., water-soluble) acrylic polymers. Acrylic polymers are preferably hydrophilic, and have been found to provide significant antifouling properties for surfaces with effervescent compositions described herein. This property can prevent microorganisms from reattaching to the surface just cleaned. In a preferred embodiment, the acrylic polymer is a copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate. In some embodiments, the acrylic copolymer comprises a hydrophilic acrylic copolymer, such as polyacrylamide acrylic acid.

[0043] Acrylic copolymers that can be used in the provided cleaning compositions are available from Solvay, SA, Neder-Over-Heembeek, Brussels, Belgium, under the trade name MIRAPOL, from Miwon Specialty Chemical Co., Ltd., under the trade name MIHAPOL, and from Ashland Global Specialty Chemicals Inc., Wilmington, DE, U.S.A., as SOREZ.

[0044] When present, the solid effervescent cleaning composition typically comprises a water-soluble copolymer of acrylic acid and acrylamide in an amount of at least 0.5%, 1%, 2%, 3%, 4%, or 5% solids by weight. In some embodiments, the amount of the water-soluble copolymer of acrylic acid and acrylamide is no greater than 20%, 15%, 10%, 9%, 8%, 7%, 6%, or 5% solids by weight.

[0045] Binder

[0046] Solid effervescent cleaning compositions typically contain an inorganic binder, an organic binder, or a combination thereof. Inorganic and organic binders function to chemically and / or physically hold the components of the composition together.

[0047] In some embodiments, the inorganic binder reacts with water to cause the composition to harden. The hardened inorganic binder provides structural support to the composition and makes it resistant to degradation caused by water.

[0048] Examples of suitable reactive inorganic binders include, but are not limited to, calcium sulfate hemihydrate (e.g., gypsum), anhydrous calcium sulfate, sodium silicate, sodium metasilicate, potassium silicate, potassium metasilicate, lithium metasilicate, lithium silicate, cement, and combinations thereof. Examples of particularly suitable reactive inorganic binders include, but are not limited to, formulated binder compositions based on calcium sulfate hemihydrate, such as DURABOND 20, DURABOND 45, and DURABOND 90 available from USG, located in Chicago, IL.

[0049] The solid effervescent cleaning composition generally comprises at least 0.1 wt%, 0.5 wt% or 1 wt% of an inorganic binder based on the total solid cleaning composition. The amount of the inorganic binder is generally not greater than 30 wt%, 25 wt%, 20 wt%, 15 wt%, 10 wt% or 5 wt%.

[0050] The composition may include an organic binder. An organic binder may improve the overall strength of a compressed powder such as a tablet.

[0051] Examples of suitable organic binders include, but are not limited to, sugars (such as glucose, fructose, galactose, sucrose, lactose, maltose, and liquid glucose), organic acid salts (such as sodium acetate, calcium acetate, sodium propionate, sodium glycolate, and sodium citrate), polymers (such as hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, gelatin, gum arabic, chitosan, alginic acid, starch (e.g., corn starch), polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, acrylate polymers, polyurethanes, styrene-butadiene rubber, polyesters, polyamides, polyethylene imines, vinyl polymers, and combinations thereof. Examples of particularly suitable organic binders include polyethylene glycols, particularly low molecular weight polyethylene glycols. Examples of particularly suitable polyethylene glycols include polyethylene glycols having an average molecular weight range of less than about 20,000 g / mol, specifically between about 400 g / mol and about 10,000 g / mol, and more specifically between about 4,000 g / mol and about 6,000 g / mol. The average molecular weight of the solid polyethylene glycol allows the polyethylene glycol to dissolve rapidly in water.As used herein, "molecular weight" refers to the weight average molecular weight measured using standard gel permeation chromatography methods known in the art.

[0052] The solid effervescent cleaning composition may contain at least 0.1 wt%, 0.5 wt%, or 1 wt% of an organic binder based on the total solid effervescent cleaning composition. In a typical embodiment, the amount of the organic binder is at least 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt% of the total solid cleaning composition. The amount of the organic binder is typically no greater than 30 wt%, 25 wt%, or 20 wt%.

[0053] Surfactants

[0054] Solid effervescent cleaning compositions typically comprise one or more surfactants.

[0055] The term "surfactant" as used herein describes a molecule having hydrophilic (polar) and hydrophobic (non-polar) segments on the same molecule that are capable of reducing the surface tension of a composition. Surfactants can be classified according to the effective charged groups present in their head. The head of an ionic (e.g., anionic or cationic) surfactant carries a net charge. Nonionic surfactants do not have a charged group in their head.

[0056] The molecular weight of the surfactant is typically at least 150 g / mole, and typically no greater than 500 g / mole or 600 g / mole. In some embodiments, the molecular weight of the surfactant is at least 200 g / mole, 250 g / mole, or 300 g / mole.

[0057] Anionic surfactants contain anionic (ie, negatively charged) functional groups in their head groups, such as sulfate, sulfonate, phosphate, and carboxylate ions in combination with positively charged counter ions.

[0058] Suitable anionic surfactants are preferably C 6 -C 18 -Alkylbenzene sulfonate, C 6 -C 20 -Alkyl sulfonate, C 6 -C 18 -monoalkyl sulfate, C having 2 to 6 ethylene oxide units (EO) in the ether part 6 -C 18 -alkyl polyglycol ether sulfates, and mono- and di-C 6 -C 18 -alkyl sulfosuccinates. In addition, C 6 -C 18 -α-olefin sulfonates (also described as α-sulfoesters), sulfonated C 6 -C 18 Fatty acids, specifically dodecylbenzene sulfonate, C 6 -C22 Formamide ether sulfate, C 6 -C 18 -Alkyl polyglycol ether carboxylate, C 6 -C 18 N-Acyltaurine, C 8 -C 18 N-sarcosinate and C 6 -C 18 -Alkyl isethionates and mixtures thereof. Specific examples include dodecylbenzene sulfonate, dioctyl ester of sodium sulfosuccinate and polyethoxylated alkyl (C 12 ) ether sulfate.

[0059] The anionic surfactants are usually in the form of sodium salts, but may also be present in the form of other alkali metal salts or alkaline earth metal salts, such as magnesium salts, and in the form of ammonium or monoalkylammonium salts, dialkylammonium salts, trialkylammonium salts or tetraalkylammonium salts. In the case of sulfonates, the anionic surfactants may also be present in the form of their corresponding acids, such as dodecylbenzenesulfonic acid.

[0060] In some embodiments, the anionic surfactant has the general formula R 1 OSO 3 - X + , where R 1 C 8 -C 20 An alkyl or alkenyl group, and X is an alkali metal or alkaline earth metal, such as sodium or potassium. A common aliphatic sulfate is shown below:

[0061]

[0062] In some embodiments, the concentration of anionic surfactant is at least 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt% or 1 wt%. In some embodiments, the concentration of anionic surfactant is no more than 15 wt%, 14 wt%, 13 wt%, 12 wt%, 11 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt% or 4 wt%. In some embodiments, the concentration of anionic surfactant is no more than 3 wt% or 2 wt%.

[0063] The composition may optionally include at least one nonionic surfactant. Nonionic surfactants do not have ions and therefore do not have an electric charge. Nonionic surfactants typically obtain their polarity by having a (e.g., oxygen-rich) polar portion of the molecule at one end and a large organic molecule (e.g., an alkyl or alkenyl group containing 6 to 30 carbon atoms) at the other end. The oxygen component is typically derived from a short polymer of ethylene oxide or propylene oxide. Nonionic surfactants include, for example, alkyl polysaccharides, amine oxides, fatty alcohol ethoxylates, alkylphenol ethoxylates, and ethylene oxide / propylene oxide block copolymers. Some nonionic surfactants such as alkyl pyrrolidones and ethylene glycol monohexyl ethers can also reduce smears on surfaces such as glass. Various nonionic surfactants are commercially available, such as from Huntsman under the trade name "Surfonic".

[0064] additive

[0065] Other additives may be included in the composition to perform various functions. Examples include, but are not limited to: chelating agents, surfactants, oxidizing agents, anti-caking agents, hydrophilic agents, dispersants, co-binders, processing aids, fillers / tougheners, softeners, abrasive particles, desiccants, mold release agents, lubricants, disintegrants, detergents, coupling agents, photoinitiators, thermal initiators, viscosity modifiers, tackifiers, grinding aids, wetting agents, dispersants, light stabilizers, antioxidants, colorants, dyes, pigments and fragrances, anti-caking agents, dispersants.

[0066] In some embodiments, the solid effervescent cleaning composition is a powder. In some embodiments, the powder can be provided in a pre-measured pouch or pod of a water-soluble (e.g., polyvinyl alcohol) film. When the powder is a pre-measured pouch or pod, the pouch or pod may include more than one compartment to separate a portion of the cleaning composition components from other components.

[0067] In other embodiments, powder can be compressed (e.g., molded under pressure) into solid products (e.g., tablets) at room temperature and low temperatures. After being molded into concentrated solid forms, the composition provides enough mechanical integrity, hardness, toughness, and durability for use on hard surfaces. In one embodiment, the solid composition is a form of powder, tablet, or pod that can be dripped into, for example, a flush toilet to provide cleaning. In one embodiment, the composition can be molded into a cleaning head and used in combination with a handheld tool. This provides a soluble head for use as a scrubbing tool, and provides the required chemical for cleaning. Therefore, the solid composition has the dual function of being used as a tablet and / or being used on the handle. The solid composition can also be first used on the handle to clean with mechanical force, and then released into water to perform static cleaning.

[0068] In some embodiments, the solid compressed composition has a hardness and durability such that it does not immediately dissolve or decompose upon contact with water and remains in solid form long enough to contact and clean a surface.

[0069] In one embodiment, when the solid compressed composition has a mass of 40 grams and a diameter of 48 mm (± 1.0 mm) and a height of 21.0 mm (± 1.0 mm) and a concave diameter of 29.8 mm (± 1.0 mm) and a concave height of 12.8 mm (± 1.0 mm) and is a rectangular shape with curved corners, the tablet crushing force is at least about 10 lbf, about 15 lbf, about 20 lbf, and in particular at least about 25 lbf. In one embodiment, the aged Shore A hardness of the solid compressed composition is at least about 30, specifically at least about 30, more specifically at least about 50 and about 100, even more specifically at least about 80. In one embodiment, the aged Shore D hardness of the solid compressed composition is between about 10 and about 100, specifically between about 20 and about 70. The amount of time that the composition remains in solid form can be measured as the dissolution time, which is defined as the time it takes for 40 grams of the solid compressed composition to disintegrate and dissolve when immersed in 2 liters of water without stirring after the 40 grams of solid compressed composition has been aged in air under ambient conditions for two weeks. The solid compressed composition has an optimal dissolution time for scrubbing the surface to be cleaned. In one embodiment, the dissolution time of the solid compressed composition is between about 1 minute and about 60 minutes, specifically between about 5 minutes and about 40 minutes, and specifically between about 10 minutes and about 30 minutes.

[0070] In order to prepare the solid composition, the components are mixed together. If there is a fragrance, the fragrance is mixed with sodium carbonate. First, sodium carbonate and fragrance are mixed, then mixed with any surfactant to form a premix, and then the premix is ​​mixed with the mixture of the remaining components. The final mixture of the composition is added to a cavity or a mold, wherein, for example, a mechanical force is applied by a hydraulic press or a mechanical press to compress the mixture into a compressed product. The solid compressed product can adopt any geometric shape without departing from the expected scope of the present invention. After releasing from the cavity or the mold, the compressed product is aged in the air or in a sealed environment under ambient conditions to allow it to harden over time. In one embodiment, the solid composition obtained is pressed into tablets. In one embodiment, the solid composition is wrapped by a water-soluble polymer film to form a pod.

[0071] The solid effervescent cleaning composition is combined with water or an aqueous liquid (such as toilet water) during use. When combined with water or an aqueous liquid, an aqueous cleaning composition is formed.

[0072] The solid weight percent of the solid effervescent cleaning composition in water is typically at least 0.5 weight percent, 0.75 weight percent, or 1 weight percent. In some embodiments, the solid weight percent of the solid effervescent cleaning composition in water is no greater than 10 weight percent, 9 weight percent, 8 weight percent, 7 weight percent, 6 weight percent, 5 weight percent, 4 weight percent, 3 weight percent, 2 weight percent. As described in the examples below, good cleaning performance and antimicrobial efficacy against Gram-positive and Gram-negative bacteria were obtained with a 1 weight percent aqueous solution of the solid effervescent cleaning composition. However, other concentrations may also be effective.

[0073] In some embodiments, the solid effervescent cleaning composition can be dissolved to form an aqueous cleaning composition. The aqueous composition can be delivered using a variety of techniques. This can be done by spraying, dipping, smearing, dripping, pouring, wiping with a towel, etc. on the surface area to be treated.

[0074] In some embodiments, the aqueous or dry solid cleaning compositions can be delivered from a substrate (eg, woven or knitted cloth, nonwovens, sponges, foams, paper products such as paper towels, towelettes, laminates of one or more of these substrates).

[0075] The nonwoven substrate can be made of synthetic, natural or chemically modified natural materials or their mixtures. Suitable synthetic materials include, but are not limited to, synthetic organic polymers, such as polyolefins (including polyethylene (LDPE, LLDPE, metallocene polyethylene, etc.), polypropylene, ethylene / propylene copolymers, polybutene, ethylene copolymers such as ethylene vinyl acetate and ethylene acrylate copolymers), aliphatic and aromatic polyesters, including but not limited to PET, PETG, polylactic acid, polyhydroxybutyrate, polyhydroxyvalerate, poly (ethylene succinate) etc.; polyamides, polyurethanes, block copolymers such as Kraton polymers, thermoplastic starches, and copolymers and polymer blends. Non-synthetic materials include natural or chemically modified natural materials. Man-made materials include materials made of cellulose (derived or regenerated). Typical examples of man-made fibers are regenerated viscose rayon and cellulose acetate. Natural fibers include, but are not limited to, wood pulp, cotton, rayon, bamboo, jute and hemp. The substrate can be prepared by any method known in the art. Suitable manufacturing methods for preparing nonwoven substrates that can be used in conjunction with the present invention include, but are not limited to, combing, meltblowing, wet-laid, air-laid, spunbonded, spunlaced, needle-punched, thermal bonding, etc. and combinations thereof. The fiber used for nonwoven substrates may include fibers (e.g., filaments) of uncertain length, fibers (e.g., staple fibers) and multifilaments with discrete lengths. The fiber used may also be multicomponent fibers, including skin / core type, side-by-side type and split-off type fibers. The substrate may be a single-layer structure or a multilayer structure. The nonwoven substrate may also be an abrasive wipe, such as a nonwoven having a cured resin or a binder printed in a certain pattern on its surface.

[0076] In some embodiments, the solid effervescent cleaning composition is provided as a dry wipe that is not wetted until use. A roll of perforated wipes may be provided in a container, and the user removes one or more wipes and submerges the wipes in water or contacts the wipes with a wet surface before use.

[0077] In some embodiments, the handle may be attached to a solid effervescent cleaning composition as previously described or a (e.g., woven or nonwoven) substrate comprising the solid effervescent cleaning composition. The handle typically releases the composition or substrate after use. Various cleaning tools are known. (See, e.g., US 7,530,138).

[0078] The present invention is illustrated by the following examples. Unless otherwise indicated or readily apparent from the context, all parts, percentages, ratios, etc. in the examples and the remainder of the specification are by weight.

[0079] Components of the Examples

[0080]

[0081]

[0082]

[0083] Test Method

[0084] Method 1. Solution preparation

[0085] Prior to antimicrobial testing, 20 g of powder was dissolved in 2 liters of water for 10 minutes.

[0086] Method 2. Antimicrobial Assay Protocol

[0087] The in vitro time kill assay is used to determine the effectiveness of an antimicrobial solution. This test shows the ability of an antimicrobial agent to reduce the number of viable cells of a selected microorganism during a selected contact time.

[0088] The microorganisms tested in these experiments were Escherichia coli (ATCC 8739) and Staphylococcus aureus (ATCC 6538). The microorganisms were grown on appropriate agars and inoculum was prepared in Butterfield phosphate buffered saline with an optical cell density of approximately 3.0 McFarland.

[0089] The antimicrobial solution (test sample, 2.7 ml) was mixed with inoculum (300 μl) and vortexed to achieve good mixing. After a determined time point, the solution was neutralized with DE (Dey-Engley) liquid culture medium to terminate the antimicrobial activity. The neutralized sample was further diluted serially and applied to a 3M Aerobic test piece. After cultivation, the test piece was counted and the number of surviving microorganisms expressed in colony forming units (CFU) was estimated. The test control was prepared by mixing Butterfield phosphate buffer with inoculum, and carried out in the same manner as the test sample.

[0090] Test Results

[0091] The compositions of tablets (Comparative Example-01) and powders (Example-02 and Example-03) are listed in Table 1. Tablets (Comparative Example-01) (40 g) were dissolved in 4 liters of water for 10 or 20 minutes.

[0092] Table 1: Solid effervescent cleaning compositions

[0093] Comparative Example-01 Example-02 Example-03 Components % % % Sodium carbonate 23 24 23.4 PEG400 0.3 0 0 Blue dye (opyrite disodium salt) 0.01 0 0 Lemon Fragrance 0.3 0 0 Sodium metabisulfite 0.06 0 0 Sodium lauryl sulfate 1.5 1.4 1.4 Sodium lauryl sulfoacetate 2.5 2.3 2.3 Chemically prepared silicon dioxide 0.5 0.4 0.4 Calcium sulfate hemihydrate 5 4.6 4.5 Sodium Benzoate 0 4.4 4.4 Thymol 0 0 2 Caprylyl glycol 0 4 4 Citric Acid 12 425 416 Sulfamic acid 49.83 164 16 PEG 6000 5.0 0 0 pH 2.20 4.09 4.18

[0094] Table 2: Composition of effervescent powder

[0095]

[0096]

[0097] Table 3: Antimicrobial activity (log reduction)

[0098]

[0099] As shown in Table 3, Comparative Example-01, which has a sufficiently low pH, demonstrated very effective antimicrobial killing (1 minute contact time) for both Gram (+) and Gram (-) bacteria. However, at higher pH, in the absence of an antimicrobial agent, Gram (-) bacteria such as E. coli were not effectively killed.

[0100] Table 4A: Examples containing acrylic polymers

[0101]

[0102]

[0103] Table 4B: Examples containing acrylic polymers

[0104] Comparative Example 10 Embodiment 11 Components % % Citric Acid 44.5 43.5 Sodium bicarbonate 40 39 Stepan Me-Dry 4 4 Corn starch 1.5 0.5 Sipernat 50S 0.5 0.5 Sodium Benzoate 4.5 4 Thymol 0 3 Caprylyl glycol 0 0.5 Mirapol Surf-S 900(solid) 5 5 pH 5.37 5.2

[0105] Table 5: Antimicrobial Activity (Log Reduction) - Weight of Solid Cleaning Composition = 20 g, 2000 g Water, Contact Time 5min .

[0106]

[0107] For the compositions of Table 6A, the bottles with the dry formulation components were shaken for 30 min to ensure mixing of the solid powders. The powders (40 g) were mixed with 160 g DI water to prepare a mother solution. The mother solution was stirred for 45 min before antimicrobial assay.

[0108] Table 6A: Composition of effervescent powder

[0109]

[0110] Solutions for antimicrobial efficacy testing were prepared by diluting 10 mL of the stock solution with 18 mL of water. The amount of antimicrobial agent in the diluted solution is reported in Table 6B below.

[0111] Table 6B: Dilution compositions of effervescent tablets and powders

[0112]

[0113] Table 7: Antibacterial activity (log reduction)

[0114]

[0115]

Claims

1. A solid effervescent cleaning composition, comprising: one or more acids; Gas generating agent; wherein a 1 wt % aqueous solution of the solid cleaning composition has a pH in the range of 4 to 9; and At least one antimicrobial compound.

2. The solid effervescent cleaning composition of claim 1, wherein a 1 wt% aqueous solution of the solid effervescent cleaning composition provides at least a 3 log reduction of Gram-positive and Gram-negative bacteria.

3. The solid effervescent cleaning composition of claims 1 to 2, wherein a 1 wt% aqueous solution of the solid effervescent cleaning composition does not provide at least a 3 log reduction in Gram-negative bacteria in the absence of the antimicrobial compound.

4. A solid effervescent cleaning composition according to claims 1 to 3, wherein the antimicrobial compound is selected from aromatic alcohols; aliphatic alcohols, optionally further comprising an ester moiety; and their combinations.

5. The solid effervescent cleaning composition of claims 1 to 4, wherein the acid comprises a weak acid.

6. The solid effervescent cleaning composition according to claims 1 to 5, wherein the weak acid is citric acid.

7. The solid effervescent cleaning composition of claims 1 to 6, wherein the acid comprises a strong acid.

8. The solid effervescent cleaning composition of claim 7, wherein the strong acid is aminosulfonic acid.

9. The solid effervescent cleaning composition of claims 1 to 8, wherein the at least one antimicrobial compound has a solubility in water at 25°C of less than 10 g / L.

10. A solid effervescent cleaning composition according to claims 1 to 9, wherein the solid effervescent cleaning composition is a powder optionally provided in a water soluble sachet or pod.

11. The solid effervescent cleaning composition according to claims 1 to 10, wherein the solid effervescent cleaning composition is a tablet.

12. The solid effervescent cleaning composition according to claims 1 to 11, wherein the solid effervescent cleaning composition further comprises a water-soluble acrylic polymer.

13. The solid effervescent cleaning composition according to claims 1 to 12, wherein the solid effervescent cleaning composition further comprises: an organic binder including polyethylene glycol, an inorganic binder, or a combination thereof.

14. The solid effervescent cleaning composition according to claims 1 to 13, wherein the solid effervescent cleaning composition further comprises an additive, the additive comprising a fragrance, a colorant, a surfactant.

15. A woven or nonwoven substrate further comprising a solid effervescent cleaning composition according to claims 1 to 14.

16. A handle comprising the solid effervescent cleaning composition of claims 1 to 14 or the woven or nonwoven substrate comprising the solid effervescent cleaning composition of claim 15.

Citation Information

Patent Citations

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