WO2012123721A1 - Substrats de nettoyage contenant du peroxyde d'hydrogène ayant une stabilité améliorée au stockage - Google Patents

Substrats de nettoyage contenant du peroxyde d'hydrogène ayant une stabilité améliorée au stockage Download PDF

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Publication number
WO2012123721A1
WO2012123721A1 PCT/GB2012/050527 GB2012050527W WO2012123721A1 WO 2012123721 A1 WO2012123721 A1 WO 2012123721A1 GB 2012050527 W GB2012050527 W GB 2012050527W WO 2012123721 A1 WO2012123721 A1 WO 2012123721A1
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Prior art keywords
cleaning substrate
cleaning
composition
compound
acid
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PCT/GB2012/050527
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English (en)
Inventor
Matthew Kaser
Original Assignee
Reckitt Benckiser Llc
Reckitt & Colman (Overseas) Limited
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Application filed by Reckitt Benckiser Llc, Reckitt & Colman (Overseas) Limited filed Critical Reckitt Benckiser Llc
Priority to EP12710312.5A priority Critical patent/EP2683809A1/fr
Priority to MX2013010413A priority patent/MX2013010413A/es
Priority to AU2012228066A priority patent/AU2012228066B2/en
Priority to US14/001,308 priority patent/US20140020711A1/en
Priority to JP2013557176A priority patent/JP5963061B2/ja
Priority to CA2829311A priority patent/CA2829311A1/fr
Publication of WO2012123721A1 publication Critical patent/WO2012123721A1/fr
Priority to ZA2013/06329A priority patent/ZA201306329B/en

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Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/16—Cloths; Pads; Sponges
    • A47L13/17—Cloths; Pads; Sponges containing cleaning agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/049—Cleaning or scouring pads; Wipes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • a particularly popular class cleaning products are so-called wipes which are typically a flexible cleaning substrate, such as a substantially planar thin flexible wipe article which is preimpregnated with the quantity of a surface treatment composition, as well as somewhat thicker, three-dimensional sponge type articles which are also preimpregnated with a quantity of a surface treatment composition.
  • wipes are typically packaged either individually in a sealed, but breachable container or as a plurality of such wipes in an openable container but typically resealable or closable container. Subsequent to their manufacture and prior to their use such manufactured wipes are typically stored for a period of time, which can be weeks or months prior to their being used.
  • wipe articles include a reactive constituents such as an oxidizing agent in particular a peroxygen compound, e.g., hydrogen peroxide.
  • Hydrogen peroxide provides many advantages in treatment compositions which are supplied to a surface by the application (contact) of a wipe or other cleaning substrate especially in the reduction or eradication of undesired microorganisms, such as pathogens (bacteria, viruses, etc.) which may be present on services being treated with such wipe articles.
  • oxidizing agents, and especially peroxygen compounds such as hydrogen peroxide is known to undergo degradation when stored for extended periods of time and/or when stored at elevated temperatures, e.g., 25°C or more, and especially at even higher temperatures of 30°C, 35 °C, and 40°C.
  • elevated temperatures e.g. 25°C or more, and especially at even higher temperatures of 30°C, 35 °C, and 40°C.
  • the degradation of hydroperoxide present withi such a wipe article which is been packaged, and marketed for use in the treatment of hard surfaces in order to provide a cleaning benefit and especially a anti -pathogenic benefits to treated hard surfaces is particularly problematic.
  • the maximum retention of hydroperoxide or other oxidizing agent present within such a wipe article for an extended period of time is essential.
  • the present invention provides peroxygen compound containing cleaning substrates, e.g, wipes, sponges, which cleaning substrates exhibit improved storage stability, and in preferred embodiments also exhibit an anti-pathogentic benefit to hard surfaces which are treated with the said peroxygen compound containing cleaning substrates.
  • the present invention provides a method for improving the stability of peroxygen compounds, and especially hydrogen peroxide contained within cleaning substrates, e.g, wipes, sponges, over extended periods of time and/or when the cleaning substrates are stored at elevated temperatures, e.g., 25°C or more, and especially at even higher temperatures of 30°C, 35°C, and 40°C.
  • the present invention provides a method for the manufacture of peroxygen compound containing, cleaning substrates, e.g, wipes, sponges, which cleaning substrates exhibit improved storage stability, and in preferred embodiments also exhibit an anti-pathogentic benefit to hard surfaces which are treated with the said hydrogen peroxide containing cleaning substrates.
  • the peroxygen compound containing cleaning substrates of the invention comprise a largely aqueous treatment composition which is impregnated within, or applied onto a cleaning substrate.
  • the largely aqueous treatment composition comprises at least water, and also comprises at least one or more peroxygen compounds, and especially preferably wherein the peroxygen compound comprises, or consists of, hydrogen peroxide.
  • the peroxygen compound may be essentially any compound containing a dioxygen (O— O) bond. Dioxygen bonds, particularly bivalent 0--0 bonds, are readily cleavable, thereby allowing compounds containing them to act as powerful oxidizers.
  • Non-limiting examples of classes ofperoxygen compounds include peracids, peracid salts, and peroxides such as hydrogen peroxide.
  • the peroxygen can be any aliphatic or aromatic peracid (orperoxyacid) that is functional for disinfectant pmposes in accordance with embodiments of the present invention. While any functional peroxyacid can be used, peroxyacids containing from 1 to 7 carbons are the most practical for use. These peroxyacids can include, but not be limited to, peroxyformic acid, peroxyacetic acid, peroxyoxalic acid, peroxypropanoic acid, perlactic acid,
  • peroxybutanoic acid peroxypentanoic acid, peroxyhexanoic acid, peroxyadipic acid, peroxycitric, and/or peroxybenzoic acid.
  • exemplary peracid salts include permanganates, perborates, perchlorates, peracetates, ercarbonates, persulphates, and the like.
  • Exemplary peroxide compounds include hydrogen peroxide, metal peroxides and peroxyhydrates.
  • the metal peroxides that can be used include, but are not limited to, sodium peroxide, magnesium peroxide, calcium peroxide, barium peroxide, and/or strontium peroxide.
  • Other salts for example sodium percarbonate
  • hydrogen peroxide associated therewith are also considered to be a source of hydrogen peroxide, thereby producing hydrogen peroxide in situ.
  • the peroxygen compound constituent of the invention comprises, or consists of, hydrogen peroxide.
  • hydroperoxide or precursor or source thereof comprise at least 50% by weight of the peroxygen compound constituent, but more advantageously comprises at least 75%w , and especially preferably comprises at least 80%wt., 85%wt., 90%wt perennial 95%wt., 97%wt., 98%wt, 99%wt. of the largely aqueous treatment composition which is impregnated within, or applied onto a cleaning substrate.
  • the compositions applied to the cleaning substrates are largely aqueous in nature.
  • Water is added to order to provide to 100% by weight of the largely aqueous treatment compositions.
  • the water may be tap water, but is preferably distilled and is most preferably deionized water. If the water is tap water, it is preferably substantially free of any undesirable impurities such as organics or inorganics, especially minerals salts which are present in hard water which may thus undesirably interfere with the operation of the constituents present in the treatment compositions applied to the wipe articles according to the invention.
  • water provides at least 90%wt, and in order of increasing preference at least 91 %wt., 92%w , 93%wt., 94%w , 95%w , 96%wt, 97%wt. 98%wt., and 99%wt. of the aqueous treatment compositions which is impregnated within, or applied onto a cleaning substrate.
  • the treatment compositions of the invention comprises (preferably consists essentially of, or consists of) a peroxygen compound, especially preferably wherein the peroxygen compound is hydrogen peroxide, and water, according to further inventive aspects one or more further constituents are also necessarily present as well.
  • the aqueous treatment compositions further necessarily include an acid constituent.
  • One or more organic or inorganic acids which may be used to adjust the pH of the composition to a target range or level, and/or to impart an antimicrobial benefit.
  • the acids may be one or more of a water soluble inorganic acids, mineral acids, or organic acids, with virtually all such known materials contemplated as being useful in the aqueous treatment compositions.
  • useful inorganic acids include mineral acids, hydrochloric acid, phosphoric acid, sulfuric acid, and the like.
  • the aqueous treatment compositions may comprise or necessarily comprise one or more organic acids which may be used to adjust the pH of the treatment composition, and which optionally may also provide an antimicrobial benefit.
  • organic acids are those which generally include at least one carbon atom, and include at least one carboxyl group (-COOH) in its structure. Derivatives of said organic acids are also contemplated to be useful.
  • Exemplary organic acid include linear aliphatic acids such as acetic acid; dicarboxylic acids, acidic amino acids, and hydroxy acids such as glycolic acid, lactic acid, hydroxyacrylic acid, alpha- hydroxybutyric acid, glyceric acid, malic acid, tartaric acid and citric acid, as well as acid salts of these organic acids.
  • salicylic acid derivatives such as esters of salicylic acid, such as ethylhexyl salicylate, dipropylene glycol salicylate, TEA salicylate, salicylic acid 2-ethylhexylester, salicylic acid 4-isopropyl benzylester, salicylic acid homomenthylester are preferred.
  • such one or more acids may be present in any effective amount in order to impart a desired pH range or level to the largely aqueous treatment composition impregnated within the cleaning substrate.
  • the one or more acids comprise at least about 0.05%wt., yet more preferably at least about 0.1%wt., 0.2%wt.,
  • the one or more acids comprise not more than about 2.5%wt, and preferably not more than about 2%wt., 1.9%wt.,
  • such one or more acids are selected from organic acids, and especially preferably why the acids demonstrated in one or more of the following Examples.
  • organic acids may be present to the exclusion of inorganic acids.
  • Citric acid is one such particularly preferred acid, and is demonstrated amongst the following Examples.
  • the aqueous treatment compositions may comprise or necessarily comprise, one or more surfactants.
  • surfactants may be one or more anionic, no ionic, cationic, amphoteric or zwitterionic surfactants.
  • anionic, no ionic, cationic, amphoteric or zwitterionic surfactants The presence of one or more such surfactants which are advantageously included to typically provide for the loosening of soils or other hydrophobic matter which may be present on a surface being treated with the device of the invention.
  • Such surfactants may be selected from one or more of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants. Such are per se, known to the art.
  • Non-limiting examples of useful anionic surfactants include one or more of:
  • alcohol sulfates and sulfonates alcohol phosphates and phosphonates, alkyl ester sulfates, alkyl diphenyl ether sulfonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates, alkyl sulfonates, alkyl ether sulfates, alpha-olefin sulfonates, beta-alkoxy alkane sulfonates, alkyl ether sulfonates, ethoxylated alkyl sulfonates, alkylaryl sulfonates, alkylaryl sulfates, alkyl monoglyceride sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl alkoxy carboxylates having 1 to 5 moles of
  • sulfosuccinates (containing up to 10 moles of ethylene oxide), sulfosuccinates, octoxynol or nonoxynol phosphates, taurates, fatty taurides, fatty acid amide polyoxyethylene sulfates, acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, alkylpolysaccharide sulfates, alkyl olyglucoside sulfates, alkyl polyethoxy carboxylates, and sarcosinates or mixtures thereof.
  • Anionic soaps may also be used in the inventive compositions.
  • anionic surfactants are available under the following tradenames: Rhodapon®, Stepanol®, Hostapur®, Surfine®, Sandopan®, and Biosoft® tradenames.
  • anionic surfactants include water soluble salts or acids of the formula (ROS0 3 ) x M or (RS0 3 ) x M wherein R is preferably a C 6 -C 2 4 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C 18 alkyi or hydroxyalkyl, and M is H or a mono-, di- or tri-valent cation, e. g., an alkali metal cation (e. g., sodium, potassium, lithium), or aimnonium or substituted ammonium (e.
  • R is preferably a C 6 -C 2 4 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C 18 alkyi or hydroxyalkyl
  • M is H or a mono-, di- or tri-valent cation, e. g.
  • metl yl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl- ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethyl amine, and mixtures thereof, and the like) and x is an integer, preferably 1 to 3, most preferably 1.
  • Materials sold under the Hostapur® and Biosoft® trademarks are examples of such preferred anionic surfactants.
  • Exemplary useful nonionic surfactants are those which include a hydrophobic base portion, such as a long chain alkyi group or an alkylated aryl group, and a hydrophilic chain portion comprising a sufficient number of ethoxy and/or propoxy moieties to render the nonionic surfactant at least partially soluble or dispersible in water.
  • nonionic surfactants include ethoxylated alkylphenols, alkoxylated fatty alcohols, polyethylene glycol ethers of methyl glucose, polyethylene glycol ethers of sorbitol, ethylene oxidepropylene oxide block copolymers, ethoxylated esters of fatty (C 6 -C 24 ) acids, condensation products of ethylene oxide with long chain amines or amides, condensates of alkylene oxides, particularly ethylene oxide with sorbitan fatty acid esters, e.g., polyoxyethylene sorbitan monolaurate,
  • polyoxyethylene sorbitan monopalmitate polyoxyethylene sorbitan trioleates
  • alkoxylated alkanol amides e.g. C 8 -C 2 4 alkyi di(C 2 -C 3 alkanol amide) as well as mixtures thereof.
  • useful nonionic surfactants include materials are available under the Tomadol®, Neodol®, Rhodasurf®, Genapol®, Pluronic®, Lutensol®, Emulgen® and Alfonic® tradenames. Further useful nonionic surfactants include
  • alkylmonoglycosides and alkylpolyglycosides are prepared generally by reacting a monosaccharide, or a compound hydrolyzable to a monosaccharide with an alcohol such as a fatty alcohol in an acid medium; examples include D-glucopyranoside, available as Glucopon® 625 CS which is described as being a 50% C 10 -Ci 6 alkyi polyglycoside.
  • One class of preferred nonionic surfactants include amine oxides.
  • Exemplary amine oxides include:
  • Alkyi di (lower alkyi) amine oxides in which the alkyi group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated.
  • the lower alkyl groups include between 1 and 7 carbon atoms. Examples include lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and those in which the alkyl group is a mixture of different amine oxide, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl palmityl dimethyl amine oxide;
  • Alkylamidopropyl di(lower alkyl) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples are cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl amine oxide; and
  • Alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated.
  • the amine oxide constituent is an alkyl di (lower alkyl) amine oxide as denoted above and which may be represented by the following structure:
  • Rj is a straight chained C1-C4 alkyl group, preferably both Ri are methyl groups; and,
  • R 2 is a straight chained C 8 -Cig alkyl group, preferably is C I 0 -CH alkyl group, most preferably is a C
  • Each of the alkyl groups may be linear or branched, but most preferably are linear. Most preferably the amine oxide constituent is lauryl dimethyl amine oxide.
  • the amine oxides used in the present invention include R 2 groups which comprise at least 50%wt, preferably at least 60%wt. of Cj 2 alkyl groups and at least 25%wt. of C 14 alkyl groups, with not more than 15%wt. of Ci6, Cig or higher alkyl groups as the R 2 group.
  • the treatment compositions may include one or more amphoteric surfactants, non-limiting examples of which are: derivatives of secondary and tertiary amines having aliphatic radicals that are straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one of the aliphatic substituents contains an anionic water-so lubilizing group, e.g., a carboxy, sulfonate, or a sulfate group, such as sodium 3-(dodecylamino)propionate, and sodium 3- (dodecylamino)propane-l -sulfonate, sarcosinates, taurates, amide sulfosuccinates, and betaines including phosphobetaines.
  • amphoteric surfactants non-limiting examples of which are: derivatives of secondary and tertiary amines having aliphatic radicals that are straight chain or
  • the treatment composition may also comprise one or more cationic surfactant constituents, especially preferably one cationic surfactants which provide an appreciable germicidal benefit.
  • cationic surfactant constituents especially preferably one cationic surfactants which provide an appreciable germicidal benefit.
  • prefened cationic surfactant compositions which may be included in the treatment compositions are those which provide an appreciable germicidal benefit, and especially preferred are quaternary ammonium compounds and salts thereof, which may be characterized by the general structural formula:
  • Rt, R 2 , R 3 and R 4 is a alkyl, aryl or alkylaryl substituent of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular weight of at least 165.
  • the alkyl substituents may be long-chain alkyl, long-chain alkoxyaryl, long- chain alkylaryl, halogen-substituted long-chain alkylaryl, long-chain alkylphenoxyalkyl, arylalkyl, etc.
  • the remaining substituents on the nitrogen atoms other than the abovementioned alkyl substituents are hydrocarbons usually containing no more than 12 carbon atoms.
  • the substituents Rj, R 2 , R 3 and R4 may be straight-chained or may be branched, but are preferably straight-chained, and may include one or more amide, ether or ester linkages.
  • the counterion X may be any salt-forming anion which permits water solubility or water miscibility of the quaternary ammonium complex.
  • Preferred quaternary ammonium compounds which act as germicides according to the foregoing formula are those in which R 2 and R 3 are the same or different Cs-C ⁇ alkyl, or R 2 is C
  • alkyl, Cs-igalkylethoxy, Cs-isalkylphenolethoxy and R 3 is benzyl
  • X is a halide, for example chloride, bromide or iodide, or is a methosulfate anion.
  • the alkyl groups recited in R 2 and R 3 may be straight-chained or branched, but are preferably substantially linear.
  • Particularly useful quaternary germicides include compositions which include a single quaternary compound, as well as mixtures of two or more different quaternary compounds. Such useful quaternary compounds are available under the Bardac®, Barquat®, Hyamine®, Lonzabac®, and Onyxide® trademarks.
  • cationic surfactants which provide an appreciable germicidal benefit may be present as a co-antimicrobial agent, with a further antimicrobial agent described hereinafter.
  • cationic surfactants which provide an appreciable germicidal benefit are present, preferably anionic surfactants and further optionally, amphoteric surfactants are omitted from the treatment compositions of the invention.
  • Other surfactants although not specifically disclosed herein but known to the art may also be used within the treatment compositions of the present invention.
  • such one or more surfactants may be present in any effective amount in order to impart a desired technical advantage, e.g. cleaning, and in the case of certain cationic surfactants, an ancillary antimicrobial benefit to the largely aqueous treatment composition impregnated within the cleaning substrate.
  • the one or more surfactants comprise at least about 0.05%wt., yet more preferably at least about 0.1%wt, 0.2%wt, 0.25%wt perennial 0.3%wt., 0.35%wt., 0.4%wt. ? and 0.5%wt. of the largely aqueous treatment compositions.
  • the one or more surfactants comprise not more than about 5%wt., and preferably not more than about 2.3 %wt., 2.25%wt, 2.2%wt, 2.1%wt. t 2%wt, 1.9%wt.,
  • aqueous treatment compositions may comprise or necessarily comprise, one or more organic solvents.
  • exemplary useful organic solvents which may be included in the treatment compositions include those which are at least partially water-miscible such as alcohols (e.g., low molecular weight alcohols, such as, for example, ethanol, propanol, isopropanol, and the like), glycols (such as, for example, ethylene glycol, propylene glycol, hexylene glycol, and the like), water-miscible ethers (e.g. diethylene glycol diethylether, diethylene glycol dimethylether, propylene glycol dimethylether), water-miscible glycol ether (e.g. propylene glycol monomethylether, propylene glycol mono ethylether, propylene glycol
  • alcohols e.g., low molecular weight alcohols, such as, for example, ethanol, propanol, isopropanol, and the like
  • glycols such as, for example, ethylene glycol, propylene glycol, hex
  • such one or more organic solvents may be present in any effective amount in order to impart a technical benefit, e.g., cleaning benefit and/or ancillary antip thogentic benefit the largely aqueous treatment composition impregnated within the cleaning substrate.
  • the one or more organic solvents comprise at least about 0.05%wt., yet more preferably at least about 0.1 %w , 0.2%wt, 0.25%w , 0.3%wt, 0.35%wt., 0.4%wt., 0.5%wt. ofthe largely aqueous treatment compositions.
  • such one or more organic solvents include those demonstrated in one or more ofthe following Examples.
  • the organic solvent constituent comprises, or consists (solely) of a single C1-C4 monohydric alcohol or a plurality of C1 -C4 monohydric alcohols. In certain preferred embodiments the organic solvent constituent comprises, or consists (solely) of at least one monohydric alcohol with at least one glycol ether. In further preferred embodiments the organic solvent constituent comprises, or consists (solely) of at least two different monohydric alcohols which are preferably selected from C1-C4 monohydric alcohols concurrently with at least one glycol ether solvent constituent. Preferred combinations of organic solvents, including the respective amounts of each organic solvents present, are demonstrated in one or more of the following Examples.
  • the largely aqueous peroxygen compound containing treatment compositions present in the cleaning substrates exhibit a pH in the range of about 1 to about 3.5, preferably in the range of about 2 to about 3.
  • the pH may be adjusted by the inclusion of an appropriate amount of one or more acids as described previously.
  • the pH of the said largely aqueous peroxygen compound containing treatment compositions present in the cleaning substrates may also be adjusted by the addition of other constituents, such bases, inorganic salts, as well as one or more amine compounds such as one or more alkanolamines which in addition to providing an improved cleaning benefit may also be used to concurrently adjust the pH of the treatment composition.
  • amine compounds such as one or more alkanolamines which in addition to providing an improved cleaning benefit may also be used to concurrently adjust the pH of the treatment composition.
  • alkanol and alkyl groups are generally short to medium chain length, that is, from 1 to 7 carbons in length.
  • the largely aqueous peroxygen compound containing treatment compositions may include one or more further optional constituents which may be included to provide an improved aesthetic and/or technical benefit to the treatment compositions, and or the cleaning substrates impregnated with the said treatment compositions.
  • further optional constituents are generally present in a cumulative amount of less than about 25%wt. based on the total weight of the largely aqueous peroxygen compound containing treatment compositions wherein one or more such fuither optional constituents may be present.
  • such further optional constituents include one or more of: coloring agents, fragrances and fragrance solubilizers, viscosity modifying agents, further oxidizing agents, germicidal agents, further pH adjusting agents and pH buffers including organic and inorganic salts as well as organic and inorganic acids, chelating agents, and preservatives, as well as other optional constituents known to the skilled artisan.
  • coloring agents i.e., fragrance
  • fragrance solubilizers i.e., viscosity modifying agents
  • further oxidizing agents oxidizing agents
  • germicidal agents germicidal agents
  • further pH adjusting agents and pH buffers including organic and inorganic salts as well as organic and inorganic acids, chelating agents, and preservatives, as well as other optional constituents known to the skilled artisan.
  • the inventive compositions may comprise a germicide constituent (other than the cationic germicidally active quaternary ammonium halide surfactants noted above) which has germicidal or antimicrobial efficacy against at least one of gram- positive or gram-negative pathogens, e.g., bacteria or other microorganisms.
  • a germicide constituent other than the cationic germicidally active quaternary ammonium halide surfactants noted above
  • Such may be based, for example, on one or more non-cationic antimicrobial compounds or constituents, e.g., halophenols such 3-trifluoiOmethyl-4,4'-dichlorocarbanilide, 3,3', 4- trichlorocarbanilide, as well as 2,4-dichloro-3,5-m-xylenol ("DCMX").
  • the phenol based non-cationic antimicrobials are preferred, of which parachloiOmetacresol
  • PCMC parachlorometaxylenol
  • PCMX parachlorometaxylenol
  • the optional germicide constituent may also be based on one or more acids, including organic acids such as salicylic and citric acid, and/or inorganic acid such as hydrochloric acid when present in effective amounts in order to sufficiently acidify the treatment composition formed from the inventive compositions.
  • organic acids such as salicylic and citric acid
  • inorganic acid such as hydrochloric acid
  • chelating agents or mixtures to deactivate trace catalytic impurities may have a beneficial effecting improving the storage stability of the peroxygen compound(s).
  • exemplary suitable phosphonate chelating agents for use herein may include alkali metal ethane 1 -hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino amino tri (methylene phosphonic acid) (AT P), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
  • the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred
  • phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1 -hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.
  • compositions may also include a small amount of an antifoaming agent; typically silicone antifoaming agents comprising silicone and siloxane polymers often provided as emulsions in water.
  • an antifoaming agent typically silicone antifoaming agents comprising silicone and siloxane polymers often provided as emulsions in water.
  • a particularly suitable antifoam agent is a
  • silicone antifoaming agents comprising silicone and siloxane polymers in aqueous emulsions are widely commercially available.
  • the total amount of the largely aqueous peroxygen compound containing treatment compositions applied to a cleaning substrate may vary, but typically the treatment composition is applied to the cleaning substrate on a wt:wt ratio basis of the former to the latter of about 40-0.5:1, preferably about 15-1 :1. It is preferred, especially wherein the cleaning substrate is a wipe formed of substantially polymeric fibers that the amount of the largely aqueous peroxygen compound containing treatment composition be at least equal to, per preferably in excess of the weight of the wipe. Particularly advantageously, the respective weight ratios of the treatment composition: wipe falls in the range of about 10-2: 1. In such manner the retention of the treatment composition within the wipe prior to use in the treatment of a hard surface, as well as for the effective delivery of the treatment composition from the wipe onto the hard surface being released by the cleaning substrate can be provided.
  • the cleaning substrates can be of a woven or non-woven nature.
  • cleaning substrates to which the foregoing compositions may be applied include woven or nonwoven wipe articles, nonwoven or woven pouches, sponges, any of which may also include a later or part thereof which includes an abrasive material or abrasive layer.
  • the cleaning substrates can be resin bonded, hydro entanged, thermally bonded, meltblown, needlepunched or any combination of the former.
  • the cleaning substrates may also be open celled or closed celled polymers especially foams, e.g.
  • the cleaning substrates may also be in the form of sponges which are formed from regenerated cellulose, or formed from other foamed materials such as foamed hydrophobic or hydrophilic synthetic polymers.
  • Nonlimiting examples of wipes useful as the cleaning substrate may also be nonwoven fabrics formed from a combination of wood pulp fibers and textile length synthetic fibers formed by well known dry-form or wet-lay processes. Synthetic fibers such as rayon, nylon, orlon and polyester as well as blends thereof can be employed.
  • the wood pulp fibers should comprise about 30 to about 60 percent by weight of the nonwoven fabric, preferably about 55 to about 60 percent by weight, the remainder being synthetic fibers.
  • the wood pulp fibers provide for absorbency, abrasion and soil retention whereas the synthetic fibers provide for substrate strength and resiliency.
  • preferred wipes are those which are substantially formed of, meaning at least 75%wt, and in order of increasing preference, at least;
  • aqueous insoluble polymer fibers preferably wherein the polymer used to form the fibers are based on polyolefin or polyester polymers, such as polyalkylene terephthalate polymers. Copolymers containing polyolefin or polyester groups may also be used, preferably wherein at least about 50%wt, of the polymer is based on polyolefin or polyester polymers. Blends of different fibers formed of different polymers are also useful, preferably at least 50%wt. of fibers used to form a wipe are based on polyolefin or polyester polymers.
  • the substrate of such a wipe may also be a film forming material such as a water soluble polymer.
  • a film forming material such as a water soluble polymer.
  • Such self-supporting film substrates may be sandwiched between layers of fabric substrates and heat sealed to form a useful substrate.
  • the free standing films can be extruded utilizing standard equipment to devolatilize the blend. Casting technology can be used to form and diy films, or a liquid blend can be saturated into a carrier and then dried in a variety of known methods.
  • the cleaning substrate preferably a wipe or sponge, or a part or element thereof has been pretreated with a finishing composition which comprises at least one diamidoamine quaternary ammonium compound.
  • exemplary amidoamine quaternary ammonium compounds that can be used according to the invention are methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, methyl bis(oleylamidoethyl)-2-hydroxyethyl ammonium methyl sulfate, and methyl
  • the finishing composition which comprises at least one diamidoamine quaternary ammonium compound is applied to the fibers used form a wipe, and/or to a sponge, and/or to a cleaning substrate which is formed from fibers and/or a polymeric foam.
  • the said finishing composition may be applied in a
  • the cleaning substrate is formed, and thereafter a largely aqueous composition comprising the finishing composition, or alternately a largely aqueous composition comprising at least the diamidoamine quaternary ammonium compound is contacted with the cleaning substrate or any material part thereof, and thereafter the bulk of the water is withdrawn.
  • the diamidoamine quaternary ammonium compound is retained upon the cleaning substrate or component part thereof, and advantageously between 0.001 - l%w , preferably between 0.001 - 0.35%wt. of the cleaning substrate or component part thereof is the diamidoamine quaternary ammonium compound.
  • the largely aqueous peroxygen compound containing compositions of the present invention are absorbed onto the cleaning substrate, e.g., sponge or wipe to impregnate the cleaning substrate.
  • the cleaning wipe can then be sealed individually in a pouch which can then be opened when needed or a multitude of wipes can be placed in a container for use on an as-needed basis.
  • the container when closed, is sufficiently sealed to prevent evaporation of any components from the compositions.
  • hard surfaces include surfaces composed of re fractory materials such as: glazed and unglazed tile, brick, porcelain, ceramics as well as stone including marble, granite, and other stones surfaces; glass; metals; plastics e.g. polyester, vinyl; fiberglass, Foimica®, Coiian® and other hard surfaces known to the industry, as well as flooring surfaces, e.g., wood, tile, glass, ceramic, cement surfaces, grout, linoleum, and the like.
  • Further hard surfaces include nonporous surfaces which may be found in areas or spaces found in domestic or industrial or institutional environments, especially areas used for the preparation of food, in nurseries, in child daycare centers, in nursing homes, in clinics, in hospitals and in other locations wherein healthcare services or are provided.
  • the cleaning articles of the invention may be used in virtually any environment or in any application wherein the treatment of hard surfaces in order to provide a cleaning and/or anti-pathogenic or antimicrobial treatment benefit is desired.
  • a method for the treatment of hard surfaces comprises the step of applying a cleaning substrate which is impregnated or which otherwise contains a quantity of the largely aqueous treatment composition as described above onto a hard surface wherein the largely aqueous treatment composition contacts the hard surface and provides a cleaning benefit, and optionally but preferably, also provides an anti-pathogenic or antimicrobial benefit thereto.
  • Illustrative example compositions which were produced include those set forth below.
  • the illustrative example compositions demonstrate particularly preferred embodiment of the invention as well as preferred weight percentages as well as preferred relative weight percentages/weight ratios with regard to the respective individual constituents present within the composition. Examples:
  • the order of addition is not critical, but good results are obtained where the surfactants (which may be also the premixture of the fragrance and surfactants) are produced prior to the addition of the remaining constituents to the water.
  • the peroxygen compound viz., hydrogen peroxide constituent is added last.
  • the amounts of the named constituents are indicated in %w/w based on a total weight of the peroxygen containing hard surface treatment composition of which they form a part.
  • compositions of Table 1 were applied at a respective weight ratio of an example composition:pretreated wipe (cleaning substrate) of 4:1.
  • the cleaning substrate used was a nonwoven wipe (having mass of 50 grams/m 2 ) formed of spun polyethylene terephalate fiber, which fibers had been heated with a finishing composition to coat the fibers prior to the foimation of the wipe.
  • the spin finish was an aqueous composition, namely Accosoft® 501 (ex. Stepan) which is described to contain 3%wt. of methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, and 2%wt. of an alkoxylated oleic acid.
  • the spin finish was applied to the fibers, which are then formed into a wipe article, wherein the methyl-bis (tallow amidoethyl)-2- hydroxyethyl ammonium methyl sulfate and alkoxylated oleic acid comprised about 0.03%wt. of the wipe, prior to the application of the example composition at the respective weight ratios identified above.
  • a further wipe articles formed from spun finished PET fibers as used in the articles according to the invention wherein the a different spin finish was applied as the finishing composition.
  • This comparative example applied a spin finish which was largely aqueous, but included 1.4%wt. of polyethylene glycol, l%wt. terephtalate ethylene glycol esters and 0.1 %wt. of an amphoteric surfactant.
  • methyl- bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate was not applied present in the wi e.
  • composition according to T ble 3 was applied at a respective weight ratio of an example composition:pretreated wipe (cleaning substrate) of 4:1.
  • the constituents of the following formula were produced in a manner similar to that used in the production of examples El - E4. The constituents were used "as supplied", and the identity of these constituents and their respective active weights are described with reference to Table 2.
  • the example composition "E5" when applied to a clean substrate formed of fibers treated with a finishing composition which excluded methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate exhibited poor storage stability of the hydrogen peroxide. It is hypothesized, believed by the inventors, that the E5 composition would exhibit improved store stability when applied to fibrous substrates which had been pretreated with a finishing composition which comprises methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate.
  • the wipe articles were tested and evaluated according to one or more of the following test protocols.
  • Samples of the compositions from Table 1 and Table 2 as well as wipe articles formed using these compositions were tested for their retention of hydrogen peroxide under storage conditions at a range of temperatures.
  • Plural aliquots of each of the liquid compositions were stored in white HDPE sample jars and during the duration of the test a small quantity of the aliquot was removed and then analyzed to determine the %wt. of hydrogen peroxide present.
  • a single sample jar of each of the compositions was used and maintained at each of the temperatures of the test, which are indicated in the following Table 4.
  • each of the compositions of Table 1 were applied to a plurality of rolls of pretreated wipe articles formed of 28 contiguous sheets of 7 inch by 8 inch individual wipes which were joined at opposite edges by a perforation, which perforations facilitated the separation of each wipe from the roll.
  • Each of the roll of pretreated wipe articles were formed from 100% polyethylene terephalate fibers, having a mass of 50 gram per square meter of area, and one of the individual compositions of El - E5 was loaded at a mass ratio of 4:1 of composition:wipe.
  • the El - E4 compositions had been applied to wipe articles which had been pretreated with had been pretreated with a finishing composition which comprises methyl-bis(tallow amidoetiryl)-2-hydroxyethyl ammonium methyl sulfate, and which wipe article had a loading of approx. 0.03%wt. of the wipe, prior to the application of the example composition, whereas the "comparative" wipe article was formed by the application of the E5 composition at a mass ratio of 4:1 of composition:wipe, which wipe substrate had been pretreated with a finishing composition which was largely aqueous, but included 1.4%wt. of polyethylene glycol, l%wt.
  • Sample jars containing aliquots of the compositions as well as a plurality of sealed canisters congaing the preimpregnated wipe articles as formed above were stored at one of several temperature conditions for various time intervals, during which they were withdrawn from their storage conditions, allowed to equilibrate to room temperature (approx. 20°C) and then tested for their hydrogen peroxide content which was expressed as %wt. Tests of the liquid compositions of El - E5 used small samples withdrawn from a sample jar.
  • Tests of the El - E5 compositions applied to a wipe were based on the liquid "expressed" (manually squeezed) out of a roll of wipes which had been stored at a specific temperature for a requisite time period; an individual roll was used for each test, and rolls were not retested at a later date or later test but were discarded.
  • the hydrogen peroxide content of a test sample was evaluated by a standard quantitative laboratory titration method. The test results of this evaluation are set forth in the following Table 4.
  • the wipe articles which had been preheated with the finishing composition which comprises methyl-bis(tallow amidoethyl)-2- hydroxyethyl ammonium methyl sulfate (viz., Accosoft® 501) and to which were thereafter applied the El or E2 compositions retained a significant proportion of the hydrogen peroxide even following 6 weeks, and particularly following 12 weeks of storage at elevated temperatures.
  • the E5 composition while demonstrating good retention of its original concentration of hydrogen peroxide when in its liquid form, the same composition which was applied to the wipe article exhibited a drastic loss of hydrogen peroxide content even at short storage times at higher temperature, particularly when compared to the wipe which comprised the El or E2 compositions.
  • the percentage of the hydrogen peroxide "lost" (reduction of hydrogen peroxide as compared to initial levels in wipe, or of initial liquid) from the various wipes of Table 4 is quantified in the following Table 5.
  • Certain of the largely aqueous peroxygen compound containing treatment compositions similar to those described above were also subjected to testing in order to evaluate their anti-pathogenic benefits (antimicrobial efficacy) against Rhinovirus and against Staphylococcus aureus.
  • compositions, E6 and E7 were produced and which were substantially similar to composition El except that the amount of hydrogen peroxide was slightly reduced relative thereto; in the following Table 6 the content of hydrogen peroxide is expressed on the basis of "100 %wt. active", while all other constituents are as described as on Table 2.
  • compositions according to E6 exhibited excellent activity, ('complete inactivation') against sample of Rhinovims when tested according to an accepted protocol.
  • compositions according to E7 were applied at a respective weight ratio of an example composition:pretreated wipe (cleaning substrate) of 4:1.
  • the cleaning substrate used was a nonwoven wipe (having mass of 50 grams/m 2 ) formed of spun polyethylene terephalate fiber, which fibers had been treated with a finishing composition to coat the fibers prior to the formation of the wipe.
  • the spin finish was an aqueous composition, namely Accosoft® 50 ' . (ex. Stepan) which is described to contain 3%wt. of methyl- bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, and 2%wt. of an alkoxylated oleic acid.
  • Such wipe articles impregnated with the E7 composition were tested according to a protocol generally in conformance with the "Standard Operating Procedure for Disinfectant Towelette Test Against Staphylococcus aureus, Pseudomonas aueruginosa, and Salmonella enterica", SOP Number: MB-09-04, Date Revised: 02-26- 10, issued by the US Environmental Protection Agency, Office of Pesticide Programs.
  • the said wipe article containing the E7 composition demonstrated a result of "1/60" positive samples, which coi esponded to excellent antimicrobial efficacy pursuant that test protocol.

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Abstract

L'invention concerne des substrats de nettoyage contenant du peroxyde d'hydrogène, tels que des lingettes et des éponges qui présentent une stabilité améliorée au stockage, et dans des modes de réalisation préférés, présentent également un bénéfice antimicrobien pour des surfaces dures traitées par les substrats de nettoyage contenant du peroxyde d'hydrogène.
PCT/GB2012/050527 2011-03-11 2012-03-09 Substrats de nettoyage contenant du peroxyde d'hydrogène ayant une stabilité améliorée au stockage WO2012123721A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP12710312.5A EP2683809A1 (fr) 2011-03-11 2012-03-09 Substrats de nettoyage contenant du peroxyde d'hydrogène ayant une stabilité améliorée au stockage
MX2013010413A MX2013010413A (es) 2011-03-11 2012-03-09 Sustratos de limpieza que contienen peroxigeno con estabilidad de almacenamiento mejorada.
AU2012228066A AU2012228066B2 (en) 2011-03-11 2012-03-09 Peroxygen containing cleaning substrates with improved storage stability
US14/001,308 US20140020711A1 (en) 2011-03-11 2012-03-09 Peroxygen Containing Cleaning Substrates with Improved Storage Stability
JP2013557176A JP5963061B2 (ja) 2011-03-11 2012-03-09 改良された貯蔵安定性を有する過酸素物含有クリーニング用基材
CA2829311A CA2829311A1 (fr) 2011-03-11 2012-03-09 Substrats de nettoyage contenant du peroxyde d'hydrogene ayant une stabilite amelioree au stockage
ZA2013/06329A ZA201306329B (en) 2011-03-11 2013-08-22 Peroxygen containing cleaning substrates with improved storage stability

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US201161451707P 2011-03-11 2011-03-11
US61/451,707 2011-03-11

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CA (1) CA2829311A1 (fr)
MX (1) MX2013010413A (fr)
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WO2016197147A1 (fr) * 2015-06-05 2016-12-08 Kielbania Andrew J Agents nettoyants à usages multiples ne comportant pas de composés organiques volatils
US10849929B2 (en) 2016-08-30 2020-12-01 Chuch & Dwight Co., Inc. Composition and method for allergen deactivation
EP3417709A1 (fr) * 2017-06-21 2018-12-26 The Procter & Gamble Company Solvant contenant des compositions de nettoyage de surface dure antimicrobiennes
EP3418368A1 (fr) * 2017-06-21 2018-12-26 The Procter & Gamble Company Compositions de nettoyage de surfaces dures contenant un solvant
EP3418363A1 (fr) 2017-06-21 2018-12-26 The Procter & Gamble Company Polymère contenant des compositions de nettoyage de surface dure antimicrobiennes
IT201800004475A1 (it) * 2018-04-13 2019-10-13 Composizione detergente
CA3074199A1 (fr) * 2020-02-28 2021-08-28 Fluid Energy Group Ltd. Acide sulfurique modifie et utilisations connexes

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US20140020711A1 (en) 2014-01-23
AU2012228066B2 (en) 2015-12-17
AU2012228066A1 (en) 2013-09-12
JP2014507544A (ja) 2014-03-27
JP5963061B2 (ja) 2016-08-03
EP2683809A1 (fr) 2014-01-15
ZA201306329B (en) 2014-10-29
CA2829311A1 (fr) 2012-09-20
MX2013010413A (es) 2013-10-17

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