EP4240820B1

EP4240820B1 - Liquid aqueous cleaning composition

Info

Publication number: EP4240820B1
Application number: EP21791408.4A
Authority: EP
Inventors: Pintu PAUL; Claudia CREMONESI; Uma Madhavan; Giovanni Taino
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Priority date: 2020-11-09
Filing date: 2021-10-19
Publication date: 2024-05-08
Anticipated expiration: 2041-10-19
Also published as: AR124032A1; WO2022096260A1; ZA202304138B; HUE067565T2; CN116391021A; PL4240820T3; EP4240820C0; EP4240820A1

Description

Field of the Invention

The present invention relates to liquid aqueous cleaning compositions. More specifically it relates to storage stable acidic liquid aqueous cleaning compositions comprising hydrogen peroxide.

Background of the Invention

Cleaning products are well-known and play an important role in everyday life. Cleaning products for cleaning sanitary hard surfaces like toilets and other bathroom surfaces like for example floors and tiles usually comprise a disinfection agent and if desired further cleaning agents like surfactants. A well-known disinfecting agent often used in such products is hypochlorite as hypochlorite is a recognized disinfecting agent against bacteria and viruses. However, some consumers prefer a milder disinfecting agent, as hypochlorite has the risk of damaging delicate surfaces as it is a strong oxidizer and has a distinctive smell that is not always appreciated.
An alternative disinfecting agent that is sometimes used in cleaning products for sanitary hard surfaces is hydrogen peroxide. Hydrogen peroxide has a less distinctive smell and is generally considered to be a milder disinfecting agent. To provide adequate disinfection a certain amount of hydrogen peroxide needs to be present. Hydrogen peroxide is not always storage stable and may (at least in part) decompose over time upon storage thereby potentially diminishing its disinfection efficacy. To overcome this problem formulators sometimes overdose the amount of hydrogen peroxide to compensate for loss of hydrogen peroxide over time. In addition, other measures may be taken to stabilize the hydrogen peroxide and minimize loss by decomposition thereof. A common understanding is that hydrogen peroxide stability in acidic aqueous compositions increases as the pH goes down.
Hydrogen peroxide on its own may not provide the required broad spectrum disinfection and it may be desired to add further disinfecting agents to improve overall disinfecting efficacy of the cleaning product. Quaternary ammonium compounds are known for such use in said compositions. Organic acids, like for example citric acid, are also known for use as a disinfecting agent.
Cleaning products that are meant for cleaning sanitary hard surfaces must be able to address hard water stains. For this purpose, such cleaning products may have an acidic pH. Organic acids may be utilized to achieve the desired acidic pH
To increase contact time with a hard surface, cleaning products may be formulated to have a certain viscosity such that the product is easier to apply and clings to the surface. For a good user experience, it is important that the cleaning product maintains its initial viscosity over time, like for example upon storage.
WO99/27066 discloses compositions formulated using an alkylaryl detergent composition in combination with an alcohol and/or cationic surfactant, together with a hydrotropic solvent, in an acidic system further optionally comprising a peroxide. Research Disclosure 30115 having the title "Thickened cleaning composition" (XP000052468) discloses an aqueous liquid thickened cleaning composition comprising quaternary ammonium compound, citric acid and hydrogen peroxide.
WO 2008/127803 A1 discloses a cleaning composition comprising hydrogen peroxide, lactic acid and a betaine.
Storage stability of a cleaning product is an important attribute. That is to say, the product should maintain its product properties over its entire lifespan. For example, some ingredients may be less stable over time and/or under elevated temperatures and formulators may address this by including higher amounts of such ingredients to compensate for this loss. Another example is the aforementioned product viscosity.
In view of the above, there remains a need for milder cleaning compositions providing disinfection without compromising consumer satisfaction in terms of performance and/or storage stability.

Summary of the Invention

We have found that an acidic liquid aqueous cleaning composition comprising hydrogen peroxide and organic acid must meet specific requirements to provide for a mild disinfecting cleaning composition that is stable over time upon storage.
Accordingly, in a first aspect the invention relates to a liquid aqueous cleaning composition comprising:

0.05 to 1.5 wt% one or more quaternary ammonium compound;
0.5 to 4 wt% hydrogen peroxide;
0.25 to 2.5 wt% organic acid having a pKa of from 1 to 5.5;

^-1

The invention further relates to a method of cleaning a toilet comprising the step of:

a. contacting at least part of the toilet surface with the composition according to the present invention; and
b. optionally rinsing the surface with water.

The invention also relates to the use of a composition of the present invention as a toilet cleaner or bathroom cleaner.

Detailed Description of the Invention

Any feature of one aspect of the present invention may be utilized in any other aspect of the invention. The word "comprising" is intended to mean "including" but not necessarily "consisting of" or "composed of." In other words, the listed steps or options need not be exhaustive. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about". Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "x to y", it is understood that all ranges combining the different endpoints are also contemplated. Unless specified otherwise, amounts as used herein are expressed in percentage by weight based on total weight of the composition and is abbreviated as "wt%". The use of any and all examples or exemplary language e.g. "such as" provided herein is intended merely to better illuminate the invention and does not in any way limit the scope of the invention otherwise claimed. Room temperature is defined as a temperature of about 25 degrees Celsius.

Aqueous cleaning composition

The cleaning composition of the present invention is an aqueous cleaning composition, that is to say, the composition comprises water. The amount of water will depend on the desired concentration of the other ingredients but will at least be 80 wt%, like for example at least 85 wt% or at least 90 wt%, but typically not more than 99 wt%. The amount of water preferably is from 80 to 99 wt%, more preferably 80 to 95 wt% and even more preferably 85 to 95 wt%.
The composition is liquid, that is, it can be poured, and has viscosity at 25°C of 1 to 1000 mPa.s @ 20 s^-1. The viscosity is measured using an AR 1000 Rheometer (TA instruments) using a 4 cm, 2° cone-plate geometry @ 20 s^-1 and 25°C. Depending on the required use characteristics the composition may be more or less viscous. For example, a more water thin viscosity is desired if the composition is to be used in a trigger spray bottle. If dispensed from a squeeze bottle, a more viscous consistency may be desired. A more viscous viscosity may also be desired if the cleaning product is a toilet cleaning product. Preferably the composition has a viscosity of 100 to 700 mPa.s @ 20 s^-1 and more preferably of 200 to 600 mPa.s @ 20 s^-1. The desired viscosity can suitably be obtained by known methods like for example the use of a viscosity modifying agent.

Quaternary ammonium compound

The aqueous cleaning composition of the present invention comprises 0.05 to 1.5 wt% quaternary ammonium compound as a disinfecting agent. Preferably the composition comprises 0.1 to 1 wt% and more preferably 0.2 to 0.8 wt% of said quaternary ammonium compound.
The combination of a quaternary ammonium compound with hydrogen peroxide provides a broader disinfectant efficacy, which is further augmented if used in combination with an organic acid.
Any quaternary ammonium compound can be used in the presently described technology. Examples of quaternary ammonium compounds include, for example, alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. One suitable type of quaternary ammonium compound includes, for example, those in which the molecules contain amine, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like. Another effective type of quaternary ammonium compound include, for example, those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as the case of lauryloxyphenyltrimehyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethylammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like. Preferably, the quaternary ammonium compound utilized in the practice of the present technology exhibit biocidal activity or are biocidal in nature.
Particularly useful quaternary ammonium compound 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 EMPIGEN, BARDAC, BARQUAT, HYAMINE, LONZABAC, and ONYXIDE trademarks, which are more fully described in, for example, McCutcheon's Functional Materials (Vol. 2), North American Edition, 1998, as well as the respective product literature from the suppliers identified below.
For example, BARDAC 205M is described to be a liquid containing alkyl dimethyl benzyl ammonium chloride (Benzalkonium chloride, BKC), octyl decyl dimethyl ammonium chloride; didecyl dimethyl ammonium chloride (DDAC), and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC 208M)); described generally in McCutcheon's as a combination of alkyl dimethyl benzyl ammonium chloride and dialkyl dimethyl ammonium chloride); BARDAC 2050 is described to be a combination of octyl decyl dimethyl ammonium chloridedidecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC 2080)); BARDAC 2250 is described to be didecyl dimethyl ammonium chloride (50% active); BARDAC LF (or BARDAC LF-80), described as being based on dioctyl dimethyl ammonium chloride (BARQUAT MB-50, MX-50, OJ-50 (each 50% liquid) and MB-80 or MX-80 (each 80% liquid) are each described as an alkyl dimethyl benzyl ammonium chloride; BARDAC 4250 and BARQUAT 4250 Z (each 50% active) or BARQUAT 4280 and BARQUAT 4280Z (each 80% active) are each described as alkyl dimethyl benzyl ammonium chloride/alkyl dimethyl ethyl benzyl ammonium chloride. Also, HYAMINE 1622, described as diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (50% solution); HYAMINE 3500 (50% actives), described as alkyl dimethyl benzyl ammonium chloride (also available as 80% active (HYAMINE 3500-80)); and HYMAINE 2389 described as being based on methyldodecylbenzyl ammonium chloride and/or methyldodecylxylene-bis-trimethyl ammonium chloride.
(BARDAC, BARQUAT and HYAMINE are presently commercially available from Lonza, Inc., Fairlawn, N. J.). BTC 50 NF (or BTC 65 NF) is described to be alkyl dimethyl benzyl ammonium chloride (50% active); BTC 99 is described as didecyl dimethyl ammonium chloride (50% active); BTC 776 is described to be myrisalkonium chloride (50% active); BTC 818 is described as being octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (available also as 80% active (BTC 818-80%)); BTC 824 and BTC 835 are each described as being of alkyl dimethyl benzyl ammonium chloride (each 50% active); BTC 885 is described as a combination of BTC 835 and BTC 818 (50% active) (available also as 80% active (BTC 888)); BTC 1010 is described as didecyl dimethyl ammonium chloride (50% active) (also available as 80% active (BTC 1010-80)); BTC 2125 (or BTC 2125 M) is described as alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethylbenzyl ammonium chloride (each 50% active) (also available as 80% active (BTC 2125 80 or BTC 2125 M)); BTC 2565 is described as alkyl dimethyl benzyl ammonium chlorides (50% active) (also available as 80% active (BTC 2568)); BTC 8248 (or BTC 8358) is described as alkyl dimethyl benzyl ammonium chloride (80% active) (also available as 90% active (BTC 8249)); ONYXIDE 3300 is described as n-alkyl dimethyl benzyl ammonium saccharinate (95% active). (BTC and ONYXIDE are presently commercially available from Stepan Company, Northfield, III). Benzyl-C12-14-alkyldimethylammonium chlorides benzyl C12-C16- alkyl dimethyl chlorides also available as EMPIGEN BAC 50 and EMPIGEN BAC 80. It is an aqueous solution of benzalkonium chloride at ca. 50% or 80% in water respectively. EMPIGEN BAC 50 and EMPIGEN 80 are readily biodegradable, EMPIGEN is commercially available from Innospec Performance Chemicals.
Polymeric quaternary ammonium salts based on these monomeric structures are also considered desirable for the present invention. One example is POLYQUAT, described as being a 2-butenyldimethyl ammonium chloride polymer.
Preferably the quaternary ammonium compound is selected from alkyl dimethyl benzyl ammonium chloride (BKC), didecyl dimethyl ammonium chloride (DDAC) and combinations thereof.

Hydrogen peroxide

The cleaning composition of the present invention comprises 0.5 to 4 wt% hydrogen peroxide. The amount of hydrogen peroxide is chosen such that it provides adequate disinfection in combination with the other disinfecting agents present. The cleaning composition of the present invention provides for improved stability of the hydrogen peroxide in the composition. There is thus less or no need for formulating an excess of hydrogen peroxide to compensate for decomposition over time upon storage. Preferably the composition comprising 0.9 to 3 wt% hydrogen peroxide and more preferably 1.5 to 2.5 wt%.

Organic acid

The cleaning composition comprises 0.25 to 2.5 wt% organic acid having a pKa of from 1 to 5.5. The organic acid is one of the disinfecting agents and may also contribute to obtaining the desired acidic pH. It was surprisingly found that the combination of organic acid with hydrogen peroxide and a quaternary ammonium compound provides for good disinfection efficacy, but the amount of organic acid should be within certain limits to ensure hydrogen peroxide stability over time upon storage. Preferably the amount of organic acid is from 0.5 to 2 wt% and more preferably from 1 to 2 wt%.
Examples of suitable organic acids that may be used in the present invention include citric acid (pKa = 3.1), lactic acid (pKa = 3.86), acetic acid (pKa = 4.76), malonic acid (pKa = 2.85), adipic acid (pKa = 4.43), glutaric acid (pKa = 3.76), glycolic acid (pKa = 3.83) and maleic acid (pKa = 1.9), succinic acid (pKa = 4.2), malic acid (pKa = 3.4), tartaric acid (for L+ pKa = 2.89; and for meso pKa = 3.22), hexanoic acid (pKa = 4.88), cyclohexanoic acid (pKa = 4.82), heptanoic acid (pKa = 4.8), octanoic acid (pKa = 4.89), 4-methyl octanoic acid (pKa = 5.23), nonanoic acid (pKa = 4.95), decanoic acid (pKa = 4.9), benzoic acid (pKa = 4.2) and 4-methoxy benzoic acid (pKa = 4.37).
Preferably the organic acid has a pKa of 2 to 4.8 and more preferably 3 to 4.
Preferred organic acids are citric acid, lactic acid, acetic acid, malonic acid, adipic acid, glutaric acid, glycolic acid, maleic acid and combinations thereof. More preferably the organic acid is selected from citric acid, lactic acid, glycolic acid and combinations thereof. A preferred organic acid is citric acid.

pH

The aqueous cleaning composition of the present invention is an acidic cleaning composition having a pH from 2 to 5. The acidic pH helps to address hard water stains. It was found that the pH of the composition should not be low as otherwise this may negatively influence the hydrogen peroxide stability. Preferably the pH is from 2 to 4 and more preferably from 2 to 3. In addition to the present organic acid the desired pH of the composition may be obtained using suitable pH adjusting agents like e.g. hydrochloric acid and sodium hydroxide.

Water soluble rheology modifying polymer

To achieve the desired viscosity, the cleaning composition may comprise 0.01 to 1 wt% water soluble rheology modifying polymer. Rheology modifying polymers are known and their ability to impart viscosity to a composition may, in part, depend on the presence or absence of other ingredients.
Water soluble polymers can be used to thicken the composition which includes non-ionic, cationic and amphoteric polymers. Suitable polymers include hydroxy ethyl cellulose, modified hydroxy ethyl cellulose, guar gum, gum tragacanth, gum arbic, gum acacia, Jaguar^® C13S, Jaguar^® C14S, Jaguar^® C17, Jaguar^® HP 105 (hydroxy propyl guar), Jaguar^® HP 60 (hydroxylated propylated guar), Jaguar^® S (Native guar gum), Carbopol^® Aqua CC ,Merquat^™ 100, Merquat^™ 280, Merquat^™ 281 and Merquat^™ 550 from Lubrizol and poly ethylene glycols such as Polyox^™ WSR- 205 (PEG 14), Polyox^™ WSR N-60K (PEG 45), and Polyox^™ WSR-301 (PEG 90).
The cleaning composition of the present invention comprises a quaternary ammonium compound having a cationic nature, therefore the polymer preferably is a non-ionic watersoluble polymer, more preferably a hydroxy cellulose based polymer. Preferred polymers are hydrophobically modified hydroxyethyl celluloses. An example of a suitable polymer is PolySurf^™ 67 CS, i.e. cetyl hydroxyethylcellulose.

Surfactants

The cleaning composition may further comprise surfactant to act as a cleaning agent in addition to the disinfecting agents.

Amphoteric surfactant

Preferably the composition comprises 0.1 to 5 wt% amphoteric surfactant, like for example 0.2 to 4 wt%. More preferably the amount of amphoteric surfactant is 0.3 to 3 wt% and even more preferably 0.5 to 2 wt%. Suitable amphoteric surfactants include amine oxide and betaine.

Amine oxide

Preferred amine oxides are alkyl dimethyl amine oxide and alkyl amido propyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide. Especially preferred are lauryl dimethylamine oxide, coco dimethyl amine oxide and coco amido propyl dimethyl amine oxide.

Betaine

Preferably the amphoteric surfactant is a betaine. Suitable betaines include alkyl betaine, alkyl amido betaine, alkyl amidopropyl betaine, alkyl sulphobetaine and alkyl phosphobetaine, wherein the alkyl groups preferably have from 8 to 19 carbon atoms.
Examples include cocodimethyl sulphopropyl betaine, cetyl betaine, laurylamidopropyl betaine, caprylate/caprate betaine, capryl/capramidopropyl betaine, cocamidopropyl hydroxysultaine, cocobutyramido hydroxysultaine, and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate. Preferably the betaine is cocamidopropyl betaine (CAPB).

Non-ionic surfactant

Preferably the composition comprises 0.01 to 3 wt% non-ionic surfactant. More preferably the amount of non-ionic surfactant is 0.2 to 2 wt% and even more preferably 0.3 to 1.5 wt%.

Alcohol ethoxylate

Preferably the non-ionic surfactant is an alcohol ethoxylate. Suitable alcohol ethoxylate surfactants include the condensation products of a higher alcohol (e.g. an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol. Particularly preferred is Lauryl alcohol condensed with 5, 7 and 9 moles of ethylene oxide (Laureth 5, Laureth 7 and Laureth 9). Preferably, the alcohol ethoxylate surfactant is selected from Laureth 5, Laureth 7 and Laureth 9, or mixtures thereof.
Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C10-C20 alkanoic acid esters having a HLB of 10 to 15 also may be employed as the nonionic surfactant.

These surfactants are well known and are available from Imperial Chemical

Industries under the Tween trade name. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.

Ethoxylated amine

Preferably the cleaning composition is free from ethoxylated amine non-ionic surfactant. Ethoxylated amine surfactants are for example available under the brand name Ethomeen^® from Nouryon.

Anionic surfactants

The cleaning composition is free from anionic surfactant as these may interfere with the biocidal action of the quaternary ammonium compound.
Preferably 'free of anionic surfactant' herein refers to the composition comprising less than 0.2 wt%, more preferably less than 0.1 wt%, even more preferably less than 0.05 %wt and most preferably less than 0.01 wt% of anionic surfactant.
Most preferably the composition does not contain anionic surfactant.

Further ingredients

The cleaning composition may comprise further ingredients like fragrance and colorants. To enhance the environmental profile of the cleaning composition it is preferred that the composition is free from organic solvents like alcohol-based solvents, ether-based solvents and ester-based solvents.

Hydrotrope

The composition may further comprise one or more hydrotrope. Hydrotrope is a class of low molecular weight compounds which help in solubilizing hydrophobic ingredients in an aqueous solution. Typically, hydrotrope comprises a hydrophilic part and a hydrophobic part, similar to surfactants, however the hydrophobic part is much smaller compared to surfactants. Thus, they may not lead to spontaneous self-aggregation or micellar solubilization. It is also observed that hydrotrope does not have a critical micellar concentration (CMC) or a critical vesicle concentration (CVC) like surfactants. It may possible that hydrotrope aggregates in a step-wise self-aggregation process, gradually increasing aggregation size. Examples of hydrotrope suitable for the present invention include urea, tosylate, adenosine triphosphate (ATP), cumenesulfonate and xylenesulfonate.

Product format

The composition may be packaged in the form of any commercially available bottle for storing the liquid. The bottle containing the liquid can be of different sizes and shapes to accommodate different volumes of the liquid; preferably between 0.25 and 5 L, more preferably between 0.25 and 1.5 L or even between 0.25 and 1 L. The bottle is preferably provided with a dispenser, which enables the consumer an easier mode of dispersion of the liquid. Foam, spray or pump-dispensers may also be used.

Method

The invention also relates to a method of cleaning a toilet comprising the step of:

a. contacting at least part of the toilet surface with the composition according to the invention; and
b. optionally rinsing the surface with water.

In a further aspect, the invention relates to the use of the composition of the invention as a toilet cleaner or bathroom cleaner.
The composition of the invention is applied onto a hard surface in neat or diluted form. The composition may be applied by any known ways such as by using a cleaning implement, such as scrub, sponge paper, cloth, wipes or any other direct or indirect application. The applied composition may be cleaned using a cleaning implement such as a scrub, sponge, paper, cloth or wipes with or without water, or rinsed off with water, optionally running water.
The invention will now be illustrated by means of the following non-limiting examples.

Examples

The viscosity of the liquid compositions was determined using an AR 1000 Rheometer (TA instruments) using a 4 cm, 2° cone-plate geometry @ 20 s^-1 and 25°C. pH of the liquid compositions was measured using Orion Versa star (Thermo scientific) pH meter. Hydrogen peroxide level was measured by titration with potassium permanganate. Oxalic acid was used as primary standard.

Effect of organic acid on product stability

Formulations according to Table 1 were prepared and subjected to a storage test at 25°C and 37°C. The viscosity (mPa.s) @ 20 s^-1 at 25°C was measured at given intervals (days) and shown in Table 2.

TABLE 1 (wt% calculated on total product)

Ingredient	1	2	3	3A
Benzalkonium chloride (BKC)	0.6	0.6	0.6	0.6
Cetyl Hydroxyethylcellulose (Polysurf^™ 67 cs)	0.7	0.7	0.7	0.7
Cocamidopropyl betaine (CAPB)	0.85	0.85	0.85	0.85
Sodium cumene sulfonate (SCS)	0.13	0.13	0.13	0.13
Citric acid	0.5	1.5	3	4.5
Hydrogen peroxide	2	2	2	2
Water	To 100
pH (adjusted using HCl and NaOH)	2.2	2.2	2.2	2.2
Initial viscosity @ 20 s^-1(m.Pa.s)	814	491	435	180

Polysurf^™ 67 cs ex Ashland

TABLE 2 - viscosity (mPa.s) @ 20 s^-1 at 25°C measured at specific intervals (days)

Example	Storage Temperature	Storage Interval (days)
Example	Storage Temperature	0	15	28	42	60	91
1	25°C	814	765	744	725	680	670
1	37°C	-	650	605	566	445	337
2	25°C	491	-	444	432	416	400
2	37°C	-	340	263	226	183	118
3	25°C	435	290	209	-	-	-
3	37°C	-	105	<10	-	-	-

Level of hydrogen peroxide was estimated after 30 and 60 days of storage and data is shown in Table 3.

TABLE 3 -data on hydrogen peroxide stability

Example	Hydrogen peroxide level (wt%)			Drop in hydrogen peroxide level (%)
Example	Initial	30 days	60 days	30 days	60 days
1	1.99	1.93	1.89	3.3	5.1
2	1.99	1,.89	1.79	5.1	9.8
3	1.99	1.80	1.67	9.3	15.9
3A	1.99	1.74	1.53	12.6	22.9

Effect of pH on product stability

Formulations according to Table 4 were prepared and subjected to a storage test at 37°C. The pH, viscosity (mPA.s) @ 20 s^-1 at 25°C and level of hydrogen peroxide were measured after 6 weeks. The results are shown in Table 5.

TABLE 4 (wt% calculated on total product)

Ingredient	4	5	6	7	8	9
Benzalkonium chloride (BKC)	0.6	0.6	0.6	0.6	0.6	0.6
Cocamidopropyl betaine (CAPB)	0.85	0.85	0.85	0.85	0.85	0.85
Citric acid	1.5	1.5	1.5	1.5	1.5	1.5
Cetyl Hydroxyethylcellulose (Polysurf^™ 67 cs)	0.7	0.7	0.7	0.7	0.7	0.7
Hydrogen peroxide	2	2	2	2	2	2
Dequest^® 2010 (antiscalant phosphonate)	0.15	0.15	0.15	0.15	0.15	0.15
Sodium cumene sulfonate (SCS)	0.093	0.093	0.093	0.13	0.093	0.13
Water	To 100
Initial pH (adjusted using HCl and NaOH)	5.22	4.1	2.3	2.3	1	1
Initial viscosity @ 20 s^-1(mPa.s)	503	438	215	488	240	529

Dequest^® 2010 ex Thermphos

TABLE 5 - Storage stability results (storage for 6 weeks at 37°C)

Ingredient	4	5	6	7	8	9
Initial pH	5.22	4.1	2.3	2.3	1	1
pH after 6 weeks	4.95	4.04	2.09	2.1	0.94	1.04
Initial viscosity	503	438	215	488	240	529
Viscosity after 6 weeks	120	115	54	208	7	21
Drop in viscosity (%)	76	74	75	57	97	96
Initial hydrogen peroxide level (%)	2.06	2.06	2.06	2.06	2.06	2.06
Hydrogen peroxide level after 6 weeks	2.02	1.97	2	1.98	1.15	1.19
Drop in hydrogen peroxide level (%)	2	4	3	4	44	42

Effect of formulation ingredients on hydrogen peroxide stability

Formulations according to Table 6 were prepared to show the effect of different ingredients on hydrogen peroxide stability at pH 1 and pH 2.15 upon storage at 37°C. The level of hydrogen peroxide was measured after 2.5 months. The results for formulations having pH 2.15 are shown in Table 7 and for formulations having pH 1 in Table 8.

TABLE 6 (wt% calculated on total product)

Ingredient	10	11	12	13	14	15	16	17	18	19
Benzalkonium chloride	-	-	0.6	0.6	-	-	-	-	-	-
Cocamidopropyl betaine	0.85	0.85	-	-	-	-	-	-	-	-
Citric acid	-	-	-	-	1.5	1.5	-	-	-	-
Cetyl Hydroxyethylcellulose	-	-	-	-	-	-	0.7	0.7	-	-
Hydrogen peroxide	2	2	2	2	2	2	2	2	2	2
Dequest^® 2010	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15
Water	To 100
Initial pH (adjusted using HCl and NaOH)	2.15	1	2.15	1	2.15	1	2.15	1	2.15	1

TABLE 7 - Hydrogen peroxide stability at pH 2.15

Example	Hydrogen peroxide level (wt%)		Drop in hydrogen peroxide level (%)
Example	Initial	2.5 months	Drop in hydrogen peroxide level (%)
10	2.2	2.15	7
12	2.2	2.19	5
14	2.2	1.92	17
16	2.2	1.64	29
18	2.2	2.14	7

TABLE 8 - Hydrogen peroxide stability at pH 1

Example	Hydrogen peroxide level (wt%)		Drop in hydrogen peroxide level (%)
Example	Initial	2.5 months	Drop in hydrogen peroxide level (%)
11	2.2	1.5	35
13	2.2	1.74	24
15	2.2	1.67	27
17	2.2	0.18	92
19	2.2	1.9	17

Claims

Liquid aqueous cleaning composition comprising:
• 0.05 to 1.5 wt% one or more quaternary ammonium compound;

• 0.5 to 4 wt% hydrogen peroxide;

• 0.25 to 2.5 wt% organic acid having a pK _a of from 1 to 5.5;
wherein the composition has a pH of 2 to 5 and a viscosity at 25°C of 1 to 1000 mPa.s @ 20 s^-1; wherein the composition is free of anionic surfactant; and
wherein the composition optionally comprises:
• 0.1 to 5 wt% amphoteric surfactant;

• 0.01 to 3 wt% non-ionic surfactant; and

• 0.01 to 1 wt% water soluble rheology modifying polymer.
Composition according to claim 1 wherein the organic acid has a pK_a of 2 to 4.8 and preferably 3 to 4.
Composition according to claim 1 or 2 wherein the organic acid is selected from citric acid, lactic acid, acetic acid, malonic acid, adipic acid, glutaric acid, glycolic acid, maleic acid and combinations thereof, preferably citric acid, lactic acid, glycolic acid and combinations thereof.
Composition according to any one of claims 1 to 3 wherein the quaternary ammonium compound is selected from didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium saccharinate, octyl decyl dimethyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, methyldodecylbenzyl ammonium chloride, methyldodecylxylene-bis-trimethyl ammonium chloride, methyl benzethonium chloride, cetyl pyrinidinium chloride, cetrimonium bromide and combinations thereof.
Composition according to claim 4 wherein the quaternary ammonium compound is alkyl dimethyl benzyl ammonium chloride (BKC), didecyl dimethyl ammonium chloride (DDAC) and combinations thereof.
Composition according to any one of claims 1 to 5 comprising 0.1 to 5 wt% amphoteric surfactant, preferably betaine and more preferably cocamidopropyl betaine (CAPB).
Composition according to any one of claims 1 to 6 comprising 0.01 to 3 wt% non-ionic surfactant, preferably alcohol ethoxylate.
Composition according to any one of claims 1 to 7 comprising 0.01 to 1 wt% water soluble rheology modifying polymer.
Composition according to any one of claims 1 to 8 wherein the polymer is a non-ionic watersoluble polymer, preferably a hydrophobically modified hydroxyethyl cellulose.
Composition according to any one of claims 1 to 9 wherein the composition is free of organic solvent.
Composition according to any one of claims 1 to 10 wherein the composition has a pH of 2 to 4, preferably 2 to 3.
Composition according to any one of claims 1 to 11 wherein the composition has a viscosity of 100 to 700 mPa.s @ 20 s^-1, preferably 200 to 600 mPa.s @ 20 s^-1.
Method of cleaning a toilet comprising the step of:
a. contacting at least part of the toilet surface with the composition according to any one of claims 1 to 12; and

b. optionally rinsing the surface with water.
Use of a composition according to any one of claims 1 to 12 as a toilet cleaner or bathroom cleaner.