AU2012228066B2 - Peroxygen containing cleaning substrates with improved storage stability - Google Patents

Abstract

Peroxygen containing cleaning substrates, such as wipes and sponges which exhibit improved storage stability, and in preferred embodiments, also exhibit an antimicrobial benefit to hard surfaces treated with the peroxygen containing cleaning substrates.

Description

WO 20121123721 PCT/GB2012/050527 PEROXYGEN CONTAINING CLEANING SUBSTRATES WITH 5 IMPROVED STORAGE STABILITY The present invention relates peroxygen containing cleaning substrates, which cleaning substrates exhibit improved storage stability, and in preferred embodiments exhibit an antimicrobial benefit to hard surfaces which are treated with the peroxygen 10 containing cleaning substrates. 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 15 preimpregnated with a quantity of a surface treatment composition. Such 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 20 their being used. It is during this storage that the chemical constituents which are impregnated into the wipe article are subject to undesirable reactions, including the degradation of one or more of the constituents. This is a particularly notorious problem wherein such wipe articles include a reactive constituents such as an oxidizing agent in particular a peroxygen compound, e.g., hydrogen peroxide. Hydrogen peroxide provides 25 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. Many oxidizing agents, and especially peroxygen compounds such as hydrogen peroxide is known to 30 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 - 1 - 30'C, 35'C, and 40'C. The degradation of hydroperoxide present within 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. In order to ensure satisfactory 5 product performance, the maximum retention of hydroperoxide or other oxidizing agent present within such a wipe article for an extended period of time is essential. Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field. 10 Admittedly, while there are currently widely commercially available a number of so-called wipes impregnated with a hard surface treatment composition which comprise peroxygen compounds, and especially hydrogen peroxide which are marketed as providing a hard surface cleaning benefit an concurrently also a anti pathogenic benefits, there is nonetheless a real and urgent need in the relevant order in 15 order to provide improved so-called wipes impregnated with a hard surface treatment composition comprising an a peroxygen compound and particularly hydrogen peroxide, wherein such wipes exhibit improved storage stability. It is to this object, as well as to further objects, that the present invention is directed. A full understanding of the benefits of the present invention will be understood from the following 20 specification. It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative. According to a first aspect, the invention provides a cleaning product which comprises: 25 a cleaning substrate pretreated with a finishing composition which composition comprises: at least one diamidoamine quaternary ammonium compound; and an alkoxylated acid compound; and an aqueous composition disposed on said cleaning substrate after said cleaning 30 substrate has been pretreated with said finishing composition, said aqueous composition comprising: 0.01%wt. - 5%wt. hydrogen peroxide; and 90%wt. - 99%wt. water. -2- Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to". 5 In one aspect, 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. 10 A further aspect, 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. 15 According to further aspect, 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. 20 - 2a - WO 2012/123721 PCT/GB2012/050527 These and further aspects of the invention will become apparent from the following description of the invention and from the several examples of peroxygen compound containing cleaning substrates described hereinafter. The peroxygen compound containing cleaning substrates of the invention 5 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 10 containing a dioxygen (O--O) bond. Dioxygen bonds, particularly bivalent O-O bonds, are readily cleavable, thereby allowing compounds containing them to act as powerful oxidizers. Non-limiting examples of classes of peroxygen compounds include peracids, peracid salts, and peroxides such as hydrogen peroxide. The peroxygen can be any aliphatic or aromatic peracid (or peroxyacid) that is functional for disinfectant purposes 15 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, peroxyfonnic acid, peroxyacetic acid, peroxyoxalic acid, peroxypropanoic acid, perlactic acid, peroxybutanoic acid, peroxypentanoic acid, peroxyhexanoic acid, peroxyadipic acid, 20 peroxycitric, and/or peroxybenzoic acid. Exemplary peracid salts include pennanganates, perborates, perchlorates, peracetates, percarbonates, 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 25 strontium peroxide. Other salts (for example sodium percarbonate) have hydrogen peroxide associated therewith are also considered to be a source of hydrogen peroxide, thereby producing hydrogen peroxide in situ. Advantageously the peroxygen compound comprises up to about 5%wt., preferably up to about 3%wt., yet more preferably up to about 2%wt, still more 30 preferably up to about 1.5%wt., of the largely aqueous treatment compositions which is impregnated within, or applied onto a cleaning substrate. Advantageously also, the -3- WO 2012/123721 PCT/GB2012/050527 peroxygen compound comprises at least about 0.01%wt., yet more preferably at least about 0.1%wt, still more preferably an amount of at least about 0.2%wt., 0.3 %wt., 0.4%wt., 0.5%wt., 0.6%wt., 0.7%wt., 0.8%wt., 0.9%wt. and 1%wt. of the said largely aqueous treatment compositions. 5 As noted the peroxygen compound constituent of the invention comprises, or consists of, hydrogen peroxide. Advantageously when two or more different peroxygen compounds are present in the largely aqueous treatment composition, then it is preferred that hydroperoxide or precursor or source thereof comprise at least 50% by weight of the peroxygen compound constituent, but more advantageously comprises at least 75%wt., 10 and especially preferably comprises at least 80%wt., 85%wt., 90%wt., 95%wt., 97%wt., 98%wt., 99%wt. of the largely aqueous treatment composition which is impregnated within, or applied onto a cleaning substrate. As is noted above, 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 15 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 20 articles according to the invention. Advantageously, water provides at least 90%wt, and in order of increasing preference at least 91 %wt., 92%wt., 93%wt., 94%wt., 95%wt., 96%wt., 97%wt. 98%wt., and 99%wt. of the aqueous treatment compositions which is impregnated within, or applied onto a cleaning substrate. While, according to one aspect, the treatment compositions of the invention 25 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. In certain embodiments, the aqueous treatment compositions further necessarily 30 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 -4- WO 2012/123721 PCT/GB2012/050527 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. By way of non-limiting example useful inorganic acids include mineral acids, hydrochloric acid, phosphoric acid, sulfuric 5 acid, and the like. In certain embodiments, 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. Exemplary organic acids are those which generally include at least one carbon 10 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 15 salts of these organic acids. Of these, citric acid, sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, matonic acid, glycolic acid, salicylic acid and/or derivatives thereof e.g., 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 20 homomenthylester are preferred. Of course mixtures of one or more acids are contemplated as being useful. When present, 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. Advantageously, the one or more acids 25 comprise at least about 0.05%wt., yet more preferably at least about 0.1%wt., 0.2%wt., 0.25%wt., 0.

3 %wt., 0.3 5%wt., 0.4%wt., and 0.5%wt. of the largely aqueous treatment compositions. Similarly advantageously, the one or more acids comprise not more than about 2.5%wt, and preferably not more than about 2%wt., 1.9%wt., 1.8%wt.,1.7%wt.,1.6%wt.,1.5%wt., 1.4%wt,,1.3%wt., 1.2%wt., 1.1%wt., and 1%wt., of 30 the largely aqueous treatment compositions. Preferably, when present, such one or more acids are selected from organic acids, and especially preferably why the acids 5 - WO 2012/123721 PCT/GB2012/050527 demonstrated in one or more of the following Examples. Such 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. In certain embodiments the aqueous treatment compositions may comprise or 5 necessarily comprise, one or more surfactants. Such may be one or more anionic, nonionic, 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 ofthe invention. Such surfactants may be selected from one or more of 10 anionic, nonionic, cationic, amphoteric and zwitterionic surfactants. Such are per se, known to the art. Non-limiting examples ofuseful anionic surfactants include one or more of: alcohol sulfates and sulfonates, alcohol phosphates and phosphonates, alkyl ester sulfates, alkyl diphonyl ether sulfonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of an 15 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 I to 5 moles of ethylene oxide, alkylpolyglycolethersulfates 20 (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, alkylpolyglucoside 25 sulfates, alkyl polyethoxy carboxylates, and sarcosinates or mixtures thereof Anionic soaps may also be used in the inventive compositions. Examples of the foregoing anionic surfactants are available under the following tradenames: Rhodapon@, Stepanol@, Hostapmt@, Surfine@, Sandopan@, and Biosoft@ tradenames. Preferred examples of anionic surfactants include water soluble salts or acids of 30 the formula (ROS03)xM or (RS03).M wherein R is preferably a C 6

-C

24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a CIO-C20 alkyl component, more preferably a -6- WO 2012/123721 PCT/GB2012/050527

C

12 -Cis alkyl 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 ammonium or substituted ammonium (e. g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations 5 and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, 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 10 base portion, such as a long chain alkyl 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. By way of non-limiting example, such nonionic surfactants include ethoxylated alkylphenols, alkoxylated fatty alcohols, polyethylene glycol ethers of methyl glucose, 15 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, 20 alkoxylated alkanolamides, e.g. Cs-C 2 4 alkyl di(C 2

-C

3 alkanol amide) as well as mixtures thereof Examples of the 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 25 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

-C

16 alkyl polyglycoside. One class of preferred nonionic surfactants include amine oxides. Exemplary amine oxides include: 30 A) Alkyl 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 -7- WO 2012/123721 PCT/GB2012/050527 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 5 oxide; B) Alkyl di (hydroxy 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 bis(2-hydroxyethyl) cocoamine oxide, bis(2 hydroxyethyl) tallowamine oxide; and bis(2-hydroxyethyl) stearylamine oxide; 10 C) 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 D) Alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 15 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Preferably the amine oxide constituent is an alkyl di (lower alkyl) amine oxide as denoted above and which may be represented by the following structure: RI R2-N 0 1 wherein each: 20 Ri is a straight chained C 1

-C

4 alkyl group, preferably both R 1 are methyl groups; and,

R

2 is a straight chained C8-CI 8 alkyl group, preferably is CIO-C 14 alkyl group, most preferably is a C 1 2 alkyl group. Each of the alkyl groups may be linear or branched, but most preferably are 25 linear. Most preferably the amine oxide constituent is lauryl dimethyl amine oxide. Technical grade mixtures oftwo or more amine oxides may be used, wherein amine oxides of varying chains ofthe R 2 group are present. Preferably, the amine oxides used in the present invention include R 2 groups which comprise at least 50%wt., preferably at - 8- WO 2012/123721 PCT/GB2012/050527 least 60%wt. of C12 alkyl groups and at least 25%wt. of C14 alkyl groups, with not more than 15%wt. of C16, C s or higher ailkyl groups as the R2 group. The treatment compositions may include one or more amphoteric surfactants, non-limiting examples of which are: derivatives of secondary and tertiary amines having 5 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-solubilizing group, e.g., a carboxy, sulfonate, or a sulfate group, such as sodium 3-(dodecylamino)propionate, and sodium 3 (dodecylamino)propane-1-sulfonate, sarcosinates, taurates, amide sulfosuccinates, and 10 betaines including phosphobetaines. Exemplary betaines include dodecyl dimethyl betaine, cetyl dimethyl betaine, and dodecyl amidopropyldimethyl betaine. The treatment composition may also comprise one or more cationic surfactant constituents, especially preferably one cationic surfactants which provide an appreciable gennicidal benefit. Non-limiting examples ofpreferred cationic surfactant compositions 15 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: R1

R

2

-N*-R

3

X

20 where at least one of RI, R2, R3 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 25 abovementioned alkyl substituents are hydrocarbons usually containing no more than 12 carbon atoms. The substituents RI, R2, R3 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 pennits water -9- WO 2012/123721 PCT/GB2012/050527 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 R2 and R3 are the same or different Cs-Ci 2 alkyl, or R 2 is C12 1 6 alkyl, Csa isalkylethoxy, C_ 1 salkylphenotethoxy and R3 is benzyl, and X is a halide, for 5 example chloride, bromide or iodide, or is a methosulfate anion. The alkyl groups recited in R2 and R3 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@, 10 Barquat®, Hyamine@, Lonzabac®, and Onyxide@ trademarks. When one or more cationic surfactants which provide an appreciable germicidal benefit are present, they may be present as a co-antimicrobial agent, with a further antimicrobial agent described hereinafter. When one or more cationic surfactants which provide an appreciable germicidal benefit are present preferably anionic surfactants and further optionally, 15 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. When present, 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 20 certain cationic surfactants, an ancillary antimicrobial benefit to the largely aqueous treatment composition impregnated within the cleaning substrate. Advantageously, the one or more surfactants comprise at least about 0.05%wt., yet more preferably at least about 0.%wt., 0.2%wt., 0.25%wt., 0.3%wt., 0.35%wt., 0.4%wt., and 0.5%wt. of the largely aqueous treatment compositions. Similarly advantageously, the one or more 25 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., 2%wt., 1.9%wt., 1.8%wt.,1.7%wt.,1.6%wt.,1.5%wt., 1.4%wt.,1.3%wt., 1.2%wt., 1.1%wt., l%wt., 0.9%wt., 0.8%wt., 0.75%wt., 0.6%wt and 0.5%wt. of the largely aqueous treatment compositions. Preferably, when present, preferred surfactants arc demonstrated amongst 30 the following Examples. - 10- WO 2012/123721 PCT/GB2012/050527 In certain embodiments the aqueous treatment compositions may comprise or necessarily comprise, one or more organic solvents. By way ofnon-limiting example 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 5 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 10 monopropylether, propylene glycol monobutylether, ethylene glycol monobutylether, dipropylene glycol monomethylether, diethyleneglycol monobutylether), lower esters of monoalkylethers of ethylene glycol or propylene glycol (e.g. propylene glycol monomethyl ether acetate), and mixtures thereof, Of course, mixtures of two or more organic solvents may be used concurrently. 15 When present, 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 antipathogentic benefit the largely aqueous treatment composition impregnated within the cleaning substrate. Advantageously, the one or more organic solvents comprise at least about 0.05%wt., yet more preferably at least about 0.1 %wt., 0.2%wt., 0.25%wt., 20 0.3 %wt., 0.35%wt., 0.4%wt., 0.5 %wt. of the largely aqueous treatment compositions. Similarly advantageously, the one or more organic solvents comprise not more than about 5%wt, and preferably not more than about 4.5 %wt., 4

.

2 5%wt., 4%wt., 3.9%wt., 3.8%wt., 3.7%wt., 3.6%wt., 3.5%wt., 3.4%wt., 3.3%wt., 3.2%wt., 3.1%wt., 3.0%wt., 2.9%wt., 2 .8%wt., 2.7%wt., 2.6%wt., 2.5%wt., 2.4%wt., 2.3%wt., 2.2%wt., 2.1%wt., 2.0%wL, 25 1.9%wt., 1.

8 %wt.,1.7%wt.,.6%wt.,1.5%wt., l.4%wt.,l.3%wt., 1.

2 %wt., 1.1%wt., and 1 %wt., of the largely aqueous treatment compositions. Preferably, when present, such one or more organic solvents include those demonstrated in one or more of the following Examples. In certain preferred embodiments the organic solvent constituent comprises, or 30 consists (solely) of a single C-C 4 monohydric alcohol or a plurality of C -- C 4 monohydric alcohols. In certain preferred embodiments the organic solvent constituent comprises, or -11- WO 2012/123721 PCT/GB2012/050527 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

C-C

4 monohydric alcohols concurrently with at least one glycol ether solvent 5 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 I to about 3.5, 10 preferably in the range of about 2 to about 3. Preferably the pH may be adjusted by the inclusion of an appropriate amount of one or more acids as described previously. Specifically preferred pHs are demonstrated in the following Examples. 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 15 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. By way of nonlimiting examples such include monoalkanolamines, dialkanolamines, trialkanolamines, and alkylalkanolamines such as alkyl-dialkanolamines, and dialkyl 20 monoalkanolamines. The alkanol and alkyl groups are generally short to medium chain length, that is, from I to 7 carbons in length. For di- and trialkanolamines and dialkyl monoalkanolamines, these groups can be combined on the same amine to produce for example, methylethylhydroxypropylhydroxylamine. One of skill can readily ascertain other members of this group. 25 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. When present, such further optional constituents are generally present in a cumulative amount ofless 30 than about 2 5%wt. based on the total weight of the largely aqueous peroxygen compound containing treatment compositions wherein one or more such further optional constituents - 12 - WO 2012/123721 PCT/GB2012/050527 may be present. By way of non-limiting example 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 5 inorganic acids, chelating agents, and preservatives, as well as other optional constituents known to the skilled artisan. When one or more of the optional constituents is added, i.e., fragrance, the esthetic and consumer appeal of the product is often favorably improved. The use and selection of these optional constituents should be based on imparting a desired additional aesthetic or technical benefit, as well as to ensure compatibility with 10 the further constituents present in the inventive adhesive lavatory treatment compositions, especially such that the desirable properties, especially storage stability, of the cleaning substrate product impregnated with or containing the largely aqueous peroxygen compound containing treatment compositions are not deleteriously diminished. Optionally the inventive compositions may comprise a germicide constituent 15 (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. 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 20 trichlorocarbanilide, as well as 2,4-dichloro-3,5-m-xylenol ("DCMX"). The phenol based non-cationic antimicrobials are preferred, of which parachlorometacresol ("PCMC") and especially p arachlorometaxylenol ("PCMX"). Alternately such may be based, for example, on one or more phenol derivatives such as those based on 2-hydroxydiphenyl compounds, including Triclosan@ (ex. Ciba), 25 those based on 2,2'-hydroxy-5,5'-dibromo-diphenyl ethers, such as one or more of chlorophenols (o-, in-, p-), 2,4-dichlorophenol, p-nitrophenol, picric acid, xylenol, p chloro-m-xylenol, cresols (o-, in-, p-), p-chloro-m-cresol, pyrocatechol, resorcinol, 4-n hexylresorcinol, pyrogallol, phloroglucin, carvacrol, thymol, p-chlorothymol, o phenylphenol, o-benzylphenol, p-chloro-o-benzylphenol, phenol, 4-ethylphenol, and 4 30 phenolsulfonic acid, as well as further diphenol compounds such as hexachlorophene, tetrachlorophene, dichlorophene, 2,3-dihydroxy-5,5'-dichlorodiphenyl sulfide, 2,2' - 13 - WO 2012/123721 PCT/GB2012/050527 dihydroxy-3,3',5,5'-tetrachlorodiphenyl sulfide, 2,2'-dihydroxy-3,5',5,5', 6,6' hexachlorodiphenyl sulfide, and 3,3'-dibromo-5,5'-dichloro-2,2' dihydroxydiphenylamine, and especially "Triclocarban", 3,4,4'-trichlorocarbanilide as well as derivatives thererof 5 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. Optionally there may be included a small amount (preferably less than 1 %wt.) of 10 chelating agents or mixtures to deactivate trace catalytic impurities, thereof Such 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 aminotri(methylene phosphonic 15 acid) (ATMP), 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 20 phosphonate (DTPMP) and ethane 1 -hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST@. The compositions may also include a small amount of an antifoaming agent; typically silicone antifoaming agents comprising silicone and siloxane polymers often 25 provided as emulsions in water. A particularly suitable antifoam agent is a polydimethylsiloxane composition. Such 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 30 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 -14- WO 2012/123721 PCT/GB2012/050527 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 5 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 ofthe 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. Non-limiting 10 examples of 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, hydroentanged, thermally bonded, meltblown, needlepunched or any combination of the former. The cleaning 15 substrates may also be open celled or closed celled polymers especially foams, e.g. sponges. 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. 20 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-forn 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 25 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. Further nonlimiting examples of preferred wipes are those which are substantially formed of, meaning at least 75%wt., and in order of increasing preference, at least; 30 80%wt., 8 5%wt., 90%wt., 92%wt, 93%wt,, 94%wt., 95%wt., 96%wt., 97%wt., 98%wt., 99%wt. and 100%wt. of one or more aqueous insoluble polymer fibers, preferably - 15 - WO 2012/123721 PCT/GB2012/050527 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 5 fibers fonned 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. 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 10 can be extruded utilizing standard equipment to devolatilize the blend. Casting technology can be used to form and dry films, or a liquid blend can be saturated into a carrier and then dried in a variety of known methods. It is an essential and characterizing feature of the invention that, prior to the application of the largely aqueous peroxygen compound containing compositions 15 described above that 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 20 bis(oleylamidoethyl)-2-hydroxycthyl ammonium methyl sulfate, and methyl bis(hydr.tallowamidoethyl)-2-hydroxyethy ammonium methyl sulfate. Examples of such materials which are presently commercially available include those marketed under the name Accosoft@ (ex. Stepan), and Varisoft@ (ex. Evonik Industries). Particularly preferred is methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, 25 which is commercially available in a preparation marketed as 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 acid. In preferred embodiments of the invention an alkoxylated acid compound is also necessarily present within the finishing composition used to pretreat the cleaning substrate. 30 The inventors have unexpectedly and surprisingly found that when fibers, and or cleaning substrates formed from fibers are pretreated with such a finishing composition, - 16- WO 2012/123721 PCT/GB2012/050527 that an appreciable improvement in the storage stability of the cleaning substrate containing the largely aqueous peroxygen compound containing compositions described above is realized. At the same time, in preferred embodiments, the resultant articles provided by the invention, viz., the cleaning substrate the largely aqueous peroxygen 5 compound containing compositions described above also provide a useful anti pathogenic benefits to hard surfaces treated with the said articles. As noted above, 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 10 and/or a polymeric foam. The said finishing composition may be applied in a conventional manner to the cleaning substrate or to any materials, e.g. fibers, used to form the cleaning substrate. According to a preferred embodiment, 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 15 diamidoamine quaternary ammonium compound is contacted with the cleaning substrate or any material part thereof, and thereafter the bulk of the water is withdrawn. Concurrently, at least a part of the diamidoamine quaternary ammonium compound is retained upon the cleaning substrate or component part thereof, and advantageously between 0.001 - 1%wt., preferably between 0.001 - 0.35%wt. of the cleaning substrate or 20 component part thereof is the diamidoamine quaternary ammonium compound. Thereafter the largely aqueous peroxygen compound containing compositions described above may be applied. The largely aqueous peroxygen compound containing compositions of the present invention are absorbed onto the cleaning substrate, e.g., sponge or wipe to impregnate 25 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. The articles provided by the present invention are p articularly useful in the 30 treatment oflhard surfaces. By way of non-limiting example, hard surfaces include surfaces composed of refractory materials such as: glazed and unglazed tile, brick, - 17 - WO 2012/123721 PCT/GB2012/050527 porcelain, ceramics as well as stone including marble, granite, and other stones surfaces; glass; metals; plastics e.g. polyester, vinyl; fiberglass, Formica@, Corian@ 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 5 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 10 treatment of hard surfaces in order to provide a cleaning and/or anti-pathogenic or antimicrobial treatment benefit is desired. According to a further aspect of the invention, there is provided a method for the treatment of hard surfaces which method comprises the step of applying a cleaning substrate which is impregnated or which otherwise contains a quantity of the largely 15 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 20 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. 25 Examples: Examples of inventive peroxygen containing hard surface treatment compositions are described in the following Table 1; the constituents indicated on Table I used to produce the formulations were used on an "as supplied" basis; the identity of these constituents are disclosed in more detail on Table 2. The peroxygen containing treatment 30 compositions were produced by mixing the constituents into water as outlined in Table 1 in a beaker at room temperature which was stirred with a conventional magnetic string - 18 - WO 2012/123721 PCT/GB2012/050527 rod or paddle mixer; stirring continued until the formulation was homogenous in appearance. It is to be noted that the constituents might be added in any order, but it is preferred that a first premixture is made of any fragrance constituent with one or more surfactants in an aliquot of water used in the peroxygen containing hard surface treatment 5 compositions. 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. Preferably also 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 10 containing hard surface treatment composition of which they form a part. Table i El E2 E3 E4 hydrogen peroxide (5C/a) 2 2 2 2 sodium alkylbenzene sulfonate (38%) 1.2 1.2 1.2 lauryl dimethylamineoxide (30%) - - - 0.5 denatured ethanol (95%) 1 1 1 1 isopropanol 0.5 0.5 0.5 0.5 propylene glycol n-prooyl ether 0.5 0.5 0.5 0.5 anhydrous citric acid 0.5 0.5 0.5 1 silicone emulsion (10%) - 0.04 - tetrasodium iminodisuccinate - - - 0.5 fragrance#1 0.075 0.075 - fragrance#2 - - - 0.05 di water q.s. q.s. q.s. q.s. pH -2.5 -2.5 -2.5 -2.5 All of the constituents in the compositions on the foregoing Table 1 are indicated in weight percent, and each composition comprised 100%wt. The individual constituents 15 were used, "as-supplied" from their respective source and unless otherwise indicated, each of the constituents are to be understood as being "100%wt. actives". Deionized water was added in quantum sufficient, "q.s." to provide the balance to l00%wt. of each - 19 - WO 2012/123721 PCT/GB2012/050527 of the example and comparative example compositions. Further identity of, and the sources of the constituents used in the formulations of Tables 1 are described on the following Table 2. Table 2 hydrogen peroxide (50%) hydrogen peroxide, 50%wt. actives, supplied as Peroxal 50% Bio (ex. Arkema) sodium alkylbenzene sulfonate (38%) anionic surfactant, sodium alkylbenzene sulfonate, 38% wt. active, supplied as Biosoft D 40 (ex. Stepan Co.) lauryl dimethylamineoxide (30%) nonionic surfactant, lauryl dimethylamineoxide, 30%wt. active, supplied as Ammonyx LO (ex. Stepan Co.) denatured ethanol (95%) denatured ethanol, 95%wt. active, supplied as SDA 40B (ex. MGP) isopropanol anhydrous isopropanol, technical grade, 100%wt. active propylene glycol n-propyl ether propylene glycol n-propyl ether, 95-100%wt. active, supplied as Dowanol PnP (ex. Dow Chem. Co.) anhydrous citric acid anhydrous citric acid, 100%wt. active silicone emuIsion (10%) antifoam additive, silicone based emulsion (1 0%wt. solids), supplied as DSP Antifoam Emulsion (ex. Dow Corning) tetrasodium iminodisuccinate tetrasodium iminodisuccinate, 34%wt. actives, supplied as Baypure CX 00 (ex. Lanxess) fragrance#1 proprietary fragrance composition fragrance#2 proprietary fragrance composition di water deionized water, 1 00%wt. actives 5 Each of the foregoing compositions of Table I 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 of50 grams/m 2 ) formed of spun polyethylene terephalate fiber, which fibers had been treated with a finishing 10 composition to coat the fibers prior to the formation of the wipe. The spin finish was an aqueous composition, namely Accosofl@ 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 15 hydroxyethyl ammonium methyl sulfate and alkoxylated oleic acid comprised about -20- WO 2012/123721 PCT/GB2012/050527 0.03%wt. of the wipe, prior to the application of the example composition at the respective weight ratios identified above. Additionally for use as an "comparative" example of a wipe article, a further wipe articles formed from spun finished PET fibers as used in the articles according to the 5 invention, however 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, 1 %wt. terephtalate ethylene glycol esters and 0.l%wt. of an amphoteric surfactant. Notably, in this comparative example, methyl bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate was not applied present 10 in the wipe. Subsequently the composition according to Table 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 E l - E4. The constituents were used "as supplied", and the identity of these constituents and their respective active weights are described 15 with reference to Table 2. Table 3 E5 hydrogen peroxide (50%) 2 sodium alkylbenzene sulfonate (38%) 1.2 lauryl d methylamineoxide (30%) denatured ethanol (95%) 1 isopropanol 0.5 propylene glycol n-propyl ether 0.5 anhydrous citric acid 0.5 silicone emulsion (10%) 0.01 tetrasodium iminodisuccinate fragrance#1 fragrance#2 di water g q.s. pH -2.5 -21 - WO 2012/123721 PCT/GB2012/050527 As is discussed in more detail with reference to the following test, the example composition "E5" when applied to a clean substrate formed of fibers treated with a fishing composition which excluded methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate exhibited poor storage stability of the hydrogen peroxide. It is 5 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 10 following test protocols. Evaluation of Hydro gen Peroxide Storage Stability 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 15 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 20 following Table 4. Additionally a suitable quantity of each of the compositions of Table I 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 ofpretreated wipe articles were formed from 100% polyethylene terephalate 25 fibers, having a mass of 50 gram per square meter of area, and one of the individual compositions of E I - E5 was loaded at a mass ratio of 4:1 of composition:wipe. It is noted that 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 amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, and which 30 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 -22- WO 2012/123721 PCT/GB2012/050527 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, 1 %wt. terephtalate ethylene glycol esters and 0.1%wt. of an amphoteric surfactant. Thereafter each of the rolls of wipe articles 5 were supplied to individual polymeric canisters having a snap-fit polymeric cap which cap included a sealable opening through which the wipes could be withdrawn from the roll in a sequential manner. 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 10 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 thmn 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 15 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. 20 -23- WO 2012/123721 PCT/GB2012/050527 C) o > c N o 0 w E ON'~ CO Lo o o CO HO c w 0 c 2 I 10 :t C o 8 N C - N-V NCOo E 0O6r 6 to c' = w 0 a m 0) w C m CO C 0) CO (D 6' M1 1 M N D CLD O M C N m 0 N C! q N q Lq E = .~ o O co I- I- L O M m m Lo 0 CN I) 0 S O N L CO N) L ., N O a. NN I O O O CO N N HO CO O ) HO 0 o L o co I r O o Nj CAC N w .0 0 -- X O 0) CJ -0 N4 Vt LOO a~0 N1 OD 'It HO 0 t- O ~ O H EN CA c! 'l N C N 0)j ' ~NO N~~~ - Q~t In 0 oo 0 N O N o N~ V, CNO Lo N T L a) N) N ) N) CO a) a 0 0) 0) N 0) N' *NN I: N I : N : 3 N N .- C-4 o-C4 N N c q I It I r- C0 I- co Ic Ic - I - - - 2 WO 2012/123721 PCT/GB2012/050527 As is evident from the foregoing the wipe articles which had been pretreated 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 5 hydrogen peroxide even following 6 weeks, and particularly following 12 weeks of storage at elevated temperatures. In contrast 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, p articularly 10 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. Table 5 El E2 E5 wipe wipe (comparative) initial level of hydrogen peroxide (%wt.) 1.25 1.22 1.0 final level of hydrogen peroxide (%wt.) 1.14 1.19 0.37 % change in hydrogen peroxide level -9% -3% -63% 15 "-" indicates not tested The foregoing results reported on Table 5 confirm the earlier reported results of Table 4 wherein the wipe articles which had been treated with a diamidoamine quaternary ammonium compound and which had been produced with the compositions 20 E l and E2 exhibited superior storage stability than the wipe article produced using composition E5 which wipes had been pretreated with a finishing composition other than a diamidoamine quaternary ammonium compound. - 25 - WO 2012/123721 PCT/GB2012/050527 Evaluation of Antimicrobial Efficacy Certain of the largely aqueous peroxygen compound containing treatment compositions similar to those described above were also subjected to testing in order to 5 evaluate their anti-pathogenic benefits (antimicrobial efficacy) against Rhinovirus and against Staphylococcus aureus. The following 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 10 peroxide is expressed on the basis of " 100 %wt. active", while all other constituents are as described as on Table 2. Table 6 E6 E7 hydrogen peroxide (100%) 0.75 0.94 sodium alkylbenzene sulfonate (38%) 1.2 1.2 lauryl dimethylamineoxide (30%) -- denatured ethanol (95%) 1 1 isopropanol 0.5 0.5 propylene glycol n-propyl ether 0.5 0.5 anhydrous citric acid 0.5 0.5 silicone emulsion (10%) 0.01 0.01 tetrasodium iminodisuccinate fragrance#1 fragrance#2 di water q.s. q.s. pH ~-2.5 -2.5 15 -26- WO 2012/123721 PCT/GB2012/050527 The compositions according to E6 exhibited excellent activity, ('complete inactivation') against sample of Rhinovirus when tested according to an accepted protocol. The compositions according to E7 were applied at a respective weight ratio of an 5 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 10 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 15 10, issued by the US Environmental Protection Agency, Office ofPesticide Programs. The said wipe article containing the E7 composition demonstrated a result of "1/60" positive samples, which corresponded to excellent antimicrobial efficacy pursuant that test protocol. While the invention is susceptible of various modifications and alternative forms, 20 it is to be understood that specific embodiments thereof have been shown by way of example in the drawings which are not intended to limit the invention to the particular forms disclosed; on the contrary the intention is to cover all modifications, equivalents and alternatives falling within the scope and spirit of the invention as expressed in the appended claims. 25 -27-

Claims (6)

1. A cleaning product which comprises: a cleaning substrate pretreated with a finishing composition which composition comprises: at least one diamidoamine quaternary ammonium compound; and an alkoxylated acid compound; and an aqueous composition disposed on said cleaning substrate after said cleaning substrate has been pretreated with said finishing composition, said aqueous composition comprising: 0.01%wt. - 5%wt. hydrogen peroxide; and 90%wt. - 99%wt. water.

2. The cleaning product of claim 1, wherein said diamidoamine quaternary ammonium compound is selected from the group consisting of: methyl-bis(tallow amidoethyl)-2 hydroxyethyl ammonium methyl sulphate, methyl-bis(oleylamidoethyl)-2-hydroxyethyl ammonium methyl sulphate, and methyl-bis(hydr.tallowamidoethyl)-2-hydroxyethyl ammonium methyl sulphate

3. The cleaning product of claim 1 or 2. wherein said aqueous composition further comprises one or more surfactants.

4. The cleaning product of claim 3. wherein said one or more surfactants comprise about 0.05%wt. - 5%wt. of said aqueous composition.

5. The cleaning product of claims 1 - 4, wherein said aqueous composition further comprises one or more organic solvents.

6. The cleaning product of claim 5, wherein said one or more organic solvents comprise about 0.05%wt. - 5%wt. of said aqueous composition.