WO2024133116A1

WO2024133116A1 - A foamable hard surface cleaning composition

Info

Publication number: WO2024133116A1
Application number: PCT/EP2023/086413
Authority: WO
Inventors: Uma Madhavan; Maheshwara Shiva NAIK; Ramasubramaniam Rajagopal
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Priority date: 2022-12-19
Filing date: 2023-12-18
Publication date: 2024-06-27
Anticipated expiration: 2025-06-19
Also published as: CN120359286A; EP4638676A1

Abstract

The present invention is in the field of hard surface cleaning compositions. In particular, it provides a foamable aqueous hard surface cleaning composition delivering long-lasting cleaning and hygiene benefit. The composition comprising 0.1 to 10% by weight of quaternary ammonium compound; 0.1 to 10% by weight of amphoteric surfactant comprising amine oxide and/or cocamidopropyl betaine; 0.1 to 20% by weight of acid; and a copolymer comprising: a cationic monomer selected from 2-(acryloyloxy) ethyl trimethylammonium chloride, [2- (acryloylamino) ethyl] trimethylammonium chloride, [2-(acryloyloxy) ethyl] trimethylammonium methosulfate, [2-(methacryloyloxy) ethyl] trimethylammonium chloride or methosulfate, [3- (acryloylamino) propyl] trimethylammonium chloride, [3-(methacryloylamino) propyl] trimethylammonium chloride (MAPTAC), diallyl dimethylammonium chloride (DADMAC); an acrylamide monomer; and at least one monomer selected from polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane-sulphonic acid and/or its salt, wherein the pH of the composition is in the range 1 to 4 at 20° C, wherein the composition provides a foam volume of at least 140 millilitre as measured by Bartsch method. It further provides a cleaning product comprising the composition contained in a container with a foam trigger that dispenses a cleaning foam in use.

Description

A FOAMABLE HARD SURFACE CLEANING COMPOSITION

Field of the Invention

The present invention is in the field of hard surface cleaning compositions. In particular, it relates to a foamble hard surface cleaning composition providing long-lasting cleaning and hydrophobicity to a surface.

Background of the Invention

Cleaning hard surfaces like, kitchen tops, tiles, table-top, cupboards, wash basin and toilet bowls are part of house-hold chores. Often consumers spend considerable amount of time and effort in such cleaning activities. They prefer to use various cleaning products for the same. Such products differ in their constituents, such as detersive actives, acids, builder, colourants; as well, they are available in different formats, such as powder, liquid, tablet block, spray, foam and wipe.

Generally, hard surface cleaning involves steps like, dosing an aliquot of a cleaning product on a surface, applying it with an implement, such as sponge, brush, wipe, scrub and rinsing with water. Hard surfaces, particularly like, toilet bowls, bathroom tiles or wash basin are continuously in contact with water, they are prone to scaling, microbial growth and deposition of dirt. Thus, consumers may require frequent cleaning of those surfaces adding to their efforts. It is desired that a cleaning product provides a cleaning performance, which sustains for a longer period, thereby reduces requirement of frequent cleaning and subsequently reduces consumer efforts.

One of the ways to deliver long-lasting cleaning benefit is by depositing a layer of a hydrophobic material on a surface while cleaning. It reduces water retention on the surface and thus reduces the accumulation of scaling, dirt deposition and microbial growth.

In this regards, US 2019/0375871 A1 describes copolymers obtainable form free-radical copolymerisation at least of the following components: (a)cationic monomers selected from the group consisting of cationic (meth)acrylamide monomers and diallyl dimethyl ammonium chloride, (b)polyethylene glycol macromonomers, and (c)uncharged acrylamide monomers. The copolymers are suitable for using in detergent compositions providing advantageous shine results. EP 1 767 554 A1 describes a water-soluble amphoteric terpolymers containing acrylic or methacrylic acid, alkyl acrylamides, and N-isopropylacrylamide as monomer building blocks. The polymers are suitable for using in hard surface cleaners.

Despite the prior art documents, there is still need for an improved foamable hard surface cleaning composition, which provides an enhanced cleaning efficacy which sustains for a longer time, thereby reduces the requirement of frequent cleaning. It also provides improved hygiene benefit.

Further, it is observed that a cleaning product in foam format gaining popularity among consumers. Foam is an air-liquid mix, it covers a significantly larger surface area compared to similar dosage of liquid product. Foam clings to a surface and prevents run off, thus reducing the dosage of a product. Further, it retains on the surface leading to increase contact time, thus provides improve cleaning. Further, a product in foam format may be dispensed directly on the surface, thus easing out cleaning process. It is desired that the composition is applied on a hard surface in foam format or as cleaning foam. It is also desired that the cleaning foam stays on or clings to the surface for a longer period providing sufficient contact time and thereby improves cleaning efficacy.

Surprisingly, it has been found that a hard surface cleaning composition having select amphoteric surfactant and a copolymer with select monomeric group at a select pH range generates copious foam in use. It delivers hydrophobicity to a hard surface, that inhibits soil deposition/accumulation, that delays the requirement of frequent cleaning. of the Invention

In a first aspect, the present invention provides a foambale aqueous hard surface cleaning composition comprising:

(a) 0.1 to 10% by weight of quaternary ammonium compound;

(b) 0.1 to 10% by weight of amphoteric surfactant comprising amine oxide and/or cocamidopropyl betaine;

(c) 0.1 to 20% by weight of acid; and

(d) a copolymer comprising:

(i) a cationic monomer selected from 2-(acryloyloxy) ethyl trimethylammonium chloride, [2-(acryloylamino) ethyl] trimethylammonium chloride, [2-(acryloyloxy) ethyl] trimethylammonium methosulfate, [2-(methacryloyloxy) ethyl] trimethylammonium chloride or methosulfate, [3-(acryloylamino) propyl] trimethylammonium chloride, [3-(methacryloylamino) propyl] trimethylammonium chloride (MAPTAC), diallyl dimethylammonium chloride (DADMAC);

(ii) acrylamide monomer; and

(iii) at least one monomer selected from polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2- acrylamido-2-methylpropane-sulphonic acid and/or its salt. wherein the pH of the composition is in the range 0.5 to 4 at 20°C, wherein the composition provides a foam volume of at least 140 millilitre as measured by Bartsch method.

In another aspect, the present invention provides a cleaning product comprising a cleaning composition according to the first aspect contained in a container equipped with a foam trigger, wherein the product dispenses a cleaning foam in use.

In another aspect, there is provided a method for providing long-lasting cleaning to a surface comprising steps of:

(a) applying a composition according to the first aspect as foam to the surface; and

(b) leaving the composition on the surface for at least 30 seconds; and

(c) rinsing the surface with water.

The term “foamable composition” herein refers to a liquid composition capable of generating copious amount of foam in use. Preferably the composition generates foam without a pressurised gas or a propellant.

These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from reading of the following detailed description. For the avoidance of doubt, 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. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. 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 "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.

Detailed Description of the Invention

According to the present invention there is provided an aqueous hard surface cleaning composition. The composition comprises 0.1 to 10% by weight of quaternary ammonium compound, 0.1 to 10 % by weight of amphoteric surfactant, 0.1 to 20% by weight of acid and a copolymer. The pH of the composition is in the range 0.5 to 4 at 20° C.

The copolymer comprises a cationic monomer selected from 2-(acryloyloxy) ethyl trimethylammonium chloride, [2-(acryloylamino) ethyl] trimethylammonium chloride, [2- (acryloyloxy) ethyl] trimethylammonium methosulfate, [2-(methacryloyloxy) ethyl] trimethylammonium chloride or methosulfate, [3-(acryloylamino) propyl] trimethylammonium chloride, [3-(methacryloylamino) propyl] trimethylammonium chloride (MAPTAC), diallyl dimethylammonium chloride (DADMAC); an acrylamide monomer and at least one monomer selected from polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane-sulphonic acid and/or its salt.

Quaternary ammonium compound

The composition comprises a quaternary ammonium compound. The quaternary ammonium compound is present in the composition in an amount 0.1 to 10% by weight. Preferably the quaternary ammonium compound is present in an amount 0.1 to 8% by weight, more preferably 0.1 to 6% by weight and most preferably 0.1 to 5% by weight of the composition.

Examples of quaternary ammonium compounds suitable for the present invention include 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 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 includes 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 (BKC), octyl decyl dimethyl ammonium chloride; didecyl dimethyl ammonium chloride, 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 chloride, didecyl 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 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. Most preferred quaternary ammonium compound is benzalkonium chloride. Amphoteric surfactant

The composition comprises 0.1 to 10% by weight of amphoteric surfactant. Preferably the composition comprises 0.2 to 9% by weight, more preferably 0.3 to 8% by weight, even more preferably 0.4 to 7% by weight and most preferably 0.5 to 6% by weight of the amphoteric surfactant.

Examples of the amphoteric surfactant suitable for the present invention include alkyl amine oxides, alkyl betaines, alkyl amido propyl betaines and alkyl sulpho-betaines. Examples of suitable amphoteric surfactant include lauryl amine oxide, decyl dimethyl amine oxide, myristyl dimethyl amine oxide, lauryl/myristyl amido amine oxide, octyl amine oxide, decyl amine oxide, cocamidopropyl amine oxide, lauramido propyl dimethyl N oxide, cocodimethyl sulphopropyl betaine, lauryl betaine, sodium cocamphopropionate, lauryl dimethylamine oxide, coco amido propyl dimethyl amine oxide, cocamidopropyl betaine (CAPB), coco amido propyl amine oxide (CAPAO), cocodiethanol amide (CDEA) and cocomonoethanol amide (CMEA).

The amphoteric surfactant comprises amine oxide and/or cocamidopropyl betaine. Preferably the composition comprises more than one amphoteric surfactant. It is observed that such combinations provide improved foaming in use, preferably when the composition is dispensed through a foam dispenser. Most preferred amphoteric surfactant is a combination of cocamidopropyl betaine (CAPB) and amine oxide.

Acid

The composition comprises 0.1 to 20 % by weight of acid. Preferably composition comprises 0.2 to 16% by weight, more preferably 0.5 to 12% by weight and most preferably 1 to 10% by weight of the acid.

Preferably the acid is an organic acid. More preferably the organic acid may be selected from organic acids having a pKa value in the range from 2 to 5.5. Examples to such organic acids 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), 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), 4- methoxy benzoic acid (pKa = 4.37). Preferably the organic acid is selected from citric acid, lactic acid, acetic acid, malonic acid, adipic acid, glutaric acid, glycolic acid and maleic acid, succinic acid, malic acid, tartaric acid, hexanoic acid, cyclohexanoic acid, heptanoic acid, octanoic acid, 4-methyl octanoic acid, nonanoic acid, decanoic acid, benzoic acid, 4-methoxy benzoic acid, methane sulphonic acid and combinations thereof. Most preferred organic acid is citric acid.

The composition may comprise an inorganic acid. Examples of inorganic acid suitable for the present invention include hydrochloric acid, hydroiodic acid, hydrobromic acid, perchloric acid, nitric acid, sulphuric acid and sulphamic acid.

The composition comprises a copolymer. The copolymer comprises three or more monomers. The copolymer comprises a cationic monomer selected form 2-(acryloyloxy) ethyl trimethylammonium chloride, [2-(acryloylamino) ethyl] trimethylammonium chloride, [2- (acryloyloxy) ethyl] trimethylammonium methosulfate, [2-(methacryloyloxy) ethyl] trimethylammonium chloride or methosulfate, [3-(acryloylamino) propyl] trimethylammonium chloride, [3-(methacryloylamino) propyl] trimethylammonium chloride (MAPTAC), diallyl dimethylammonium chloride (DADMAC). Preferably the cationic monomer is selected from [3- (methacryloylamino)propyl] trimethylammonium chloride (MAPTAC) and diallyl dimethylammonium chloride (DADMAC).

The copolymer comprises an acrylamide monomer. The acrylamide monomer may be selected from acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N- ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N- isopropylacrylamide (NIPAM) and N-tert-butylacrylamide. Most preferred acrylamide monomer is N-isopropylacrylamide (NIPAM).

The copolymer comprises at least one monomer selected from polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether, polyethylene glycol-co- polypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2-acrylamido-2- methylpropane-sulphonic acid and/or its salt.

One of the preferred copolymers is that which comprises a cationic monomer selected from [3- (methacryloylamino)propyl] trimethylammonium chloride (MAPTAC) or diallyl dimethylammonium chloride (DADMAC), N-isopropylacrylamide (NIPAM) monomer and a monomer selected from polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co- polypropylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol (meth)acrylate. Detail of obtaining such copolymer could be found in WO 2018/095920 A1 or WO 2018/095918 A1.

Another suitable copolymer is that which comprises four monomers, namely, a cationic monomer selected from [3-(methacryloylamino) propyl] trimethylammonium chloride (MAPTAC) or diallyl dimethylammonium chloride (DADMAC), N-isopropylacrylamide (NIPAM) monomer, acrylic acid and/or methacrylic acid monomer and 2-acrylamido-2-methylpropane-sulphonic acid or its salt monomer. Such copolymers are commercially available from BASF under the trade name Polyquart® Pro A.

The copolymer may be present in the composition in an amount from 0.005 to 1% by weight, more preferably 0.01 to 1% by weight, even more preferably 0.02 to 1% by weight and most preferably 0.05 to 1% by weight of the composition. pH

The composition according to the present invention has a pH in the range 0.5 to 4 at 20° C. It is observed that the copolymer in said pH range work efficiently and provides improved hydrophobicity to a surface, which remains on the surface even after multiple wash cycle.

Preferably the pH of the composition is in the range 0.5 to 3.5, more preferably 1 to 3.5, even more preferably 1 to 3 and most preferably 1 to 2.5 at 20° C.

Water

The composition is an aqueous composition. The term ‘aqueous’ herein refers to water, and the composition contain significant amount of water. More particularly water acts as balance in the composition.

Water may present in the composition at an amount from 60 to 99% by weight, more preferably 60 to 95% by weight and most preferably 60 to 90% by weight of the composition. Preferably the composition when formulated as concentrate, may contain 60 to 80% by weight, more preferably 65 to 80% by weight and most preferably 70 to 80% by weight of water.

Further ingredients The composition may comprise further ingredients for boosting the performance of the composition. Such ingredients include additional surfactant, sequestrant, builder, perfume, and colourant.

The composition may further comprise a non-ionic surfactant. Example of suitable non-ionic surfactant include alcohol ethoxylate having C8 to C18 alkyl chain and 1 to 10 ethoxylate (EO) per mole.

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 1 to 10 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 10 EO per mole of alcohol. Preferably the alcohol ethoxylate has from 3 to 9 EO, more preferably 5 to 8 EO and even more preferably 7 EO. 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.

The non-ionic surfactant may be selected such that it comprises a mixture of fatty alcohols e.g., a mixture of C12, C13, C14 and C15 in varying proportions along with 1 to 10 ethoxylate groups. Such non-ionic surfactants are commercially available under NEODOLTM series from Shell. For example, NEODOLTM 91-51 which is a mixture of 09, C10 and C11 with 5 EO; NEODOLTM 91-61 which is a mixture of 09, C10 and C11 with 6 EO; NEODOLTM 91-8 which is a mixture of 09, C10, and C11 with 8 EO; NEODOLTM 23-2 which is a mixture of C12 and C13 with 2 EO; NEODOLTM 25-3 which is a mixture of C12, C13, C14 and C15 with 3 EO; NEODOLTM 25-7 which is a mixture of C12, C13, C14 and C15 with 7 EO; and NEODOLTM 45-7 which is a mixture of C14 and C15 with 7 EO. Particularly preferred non-ionic surfactant is a mixture of C12, C13, 014 and 015 with 7 EO

Another suitable non-ionic surfactant is alkyl polyglycoside having formula I: R1O(R2O)b(Z)a, wherein R1 is a alkyl radical, having from about 1 to about 30 carbon atoms; R2 is an alkylene radical having from 2 to 4 carbon atoms; Z is a saccharide residue having 5 or 6 carbon atoms; b is a number having a value from 0 to about 12; and a is a number having a value from 1 to about 6 (the degree of polymerization). Preferred alkyl polyglycosides suitable for use in the disclosed cleaning formulation include those having the formula I wherein Z is a glucose residue, b is zero, R1 is an alkyl group that contains 4 to 22 carbon atoms, and the average value of a is about 1-2. Preferably R1 is an alkyl group that contains 8 to 16 carbon atoms, and the average value of a is about 1-2. Such alkyl polyglucosides are commercially available, for example, Glucopon® branded alkyl polyglucoside compositions from BASF (formerly Cognis Corporation), including Glucopon® 215CS UP and 225 DK.

The composition may comprise 0.1 to 5% by weight, more preferably 0.2 to 4% by weight and most preferably 0.5 to 3% by weight non-ionic surfactant.

The composition may further comprise a sequestrant. Preferably the composition comprises 0.05 to 5% by weight of sequestrant, more preferably 0.1 to 5 % by weight and most preferably 0.2 to 5% by weight.

Suitable sequestrants are those based on organophosphonates, aminopolycarboxylates and carboxylic acids. It will be understood that suitable sequestrants include both the acid form and salts thereof.

Examples of sequestrants based on organophosphonates include diethylenetriamine penta(methylene phosphonic acid) (DTPMP), hydroxyethylidenediphosphonic acid (HEDP), and nitrilotrimethylenephosphonic acid (NTMP).

Examples of sequestrants based on aminopolycarboxylates include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA), and L-Glutamic acid N, N diacetic acid (GLDA).

Examples of sequestrants based on carboxylic acids include gluconic acid and itaconic acid.

Preferably the sequestrant is biodegradable. Preferred biodegradable sequestrants are nitrilotriacetic acid (NTA), ethylenediaminedisuccinic acid, (EDDS), iminodisuccinic acid, (IDS), methylglycine diacetic acid (MGDA), L-Glutamic acid N,N diacetic acid (GLDA), 2- hydroxyethyliminodiacetic acid (HEIDA), ethylenediamine-N,N'-dimalonic acid (EDDM), ethylenediamine-N,N'-diglutaric acid (EDDG), 3-hydroxy-2,2-iminodisuccinic acid (HIDS), and 2,6-pyridine dicarboxylic acid (PDA), gluconic acid and itaconic acid. Most preferred sequestrant are methylglycine diacetic acid (MGDA) and L-Glutamic acid N, N diacetic acid (GLDA) and combinations thereof.

Product format

The composition is a liquid composition that provides copious foam in use. The composition provides a foam volume of at least 140 millilitre as measured by Bartsch method. Preferably the composition provides a foam volume of at least 160 millilitre, more preferably at least 180 millilitre and most preferably at least 200 millilitre as measured by Bartsch method. Bartsch method is one of the foam testing methods and it is known in the art. Broadly, it measures the volume of foam generated by a liquid in a predetermined condition. For example, 100 millilitre of a liquid is taken in 300 millilitre measuring cylinder and foam volume is measured after 10 shakes. Details regarding the Bartsch method can be found in literatures and textbooks, such as, “Mechanisms of Foam Destruction by Oil-Based Antifoams”, by Nikolai D. Denkov, Langmuir 2004, 20, 9463-9505; “Bubble and foam chemistry”, edited by Robert J. Pugh, Cambridge University Press, 2016.

Based on application, the composition may be formulated as neat or concentrated format. The term ‘neat’ herein refers to the composition is used as is without further dilution. Whereas in ‘concentrated’ format, preferably the composition is diluted in water to form a working solution and use it. Particular advantage of the concentrated format is that the composition in such form may be packed in significantly small pack and consumes much less packaging material.

The composition in neat format may be provided in a container, which is equipped with a foam trigger, and the composition is dispensed as foam on the desired surface. It may also be possible to pack such composition in a refill pouch or pack, which may be used to fill the container once it is empty.

The composition may also be provided in concentrated format. Consumer dilutes the concentrated composition by adding sufficient water, thereby forms a working solution and use it. The composition in concentrated format may be provided in a container with sufficient empty space and the container is equipped with a foam trigger. In use consumer add water in the container to a pre-set label making a working solution. Alternatively, the composition may also be available in a smaller refill pouch and consumer prepare the working solution by adding water separately and subsequently fill a container equipped with a foam trigger. The composition is dispensed as foam on the desired surface. Preferably the composition when diluted in water, the ratio of the composition to water is in the range 1 : 1 to 1 : 20 by weight, more preferably 1 :2 to 1:16, even more preferably 1:3 to 1 :12 and most preferably 1: 4 to 1:10 by weight.

There is provided a cleaning product comprising a cleaning composition according to the present invention contained in a container equipped with a foam trigger or foam head or foam engine. The foam dispenser herein may be a pressurised gas-based or foam trigger-based dispenser.

Preferably the foam dispenser comprises a container to hold the composition and a foam trigger, which includes a trigger lever, a pump, a mixing chamber and a nozzle. The pump comprises a piston moving in a cavity against a spring. The cavity is in fluid communication with the container and the mixing chamber, wherein it has one-way valves which allow the composition to flow from the container to the mixing chamber. Typically, the foam trigger is actuated by pressing the trigger lever, which in turn pressed the piston against the spring thereby pushing the composition stored in the cavity to the mixing chamber. In the mixing chamber the composition mixed with air and pass through a mesh before dispensing out of the nozzle as foam. On subsequent release of the trigger lever, the spring push back the piston, thereby the empty cavity fills with the composition flowing from the container. Foam dispensers equipped with foam trigger rely on the pump action, hence do not require a pressurised gas. Preferably the product is free of pressurises gas or a propellant.

In another scenario, it may also possible that the foam dispenser comprises a pressurised gas, stored along with the composition in the container. Such dispenser is activated by opening a one-way valve, thereby releases the gas along with composition through a nozzle and dispenses a foam.

The composition preferably is dispensed as foam using a foam dispenser. Foam dispensers are known in the arts, often comprises a container to house a liquid composition and a foam trigger or foam head or foam engine, that dispense the liquid as foam in use. Preferably, the composition provides a thick, creamy foam that cling to a vertical surface for considerably long time. The foam according to the present invention may cling to a vertical surface, such as a ceramic tile, for at least 15 seconds. Preferably, the foam clint to the vertical surface for at least 30 seconds, more preferably for at least 1 minute, even more preferably for at least 2 minutes and most preferably for at least 5 minutes. The foam preferably clings to the vertical surface for at most 60 minutes.

Application

There is provided a method for providing long lasting cleaning to a surface comprising steps of applying the composition as foam on the surface, leaving the composition on the surface for at least 30 seconds, and rinsing the surface with water. Preferably the composition is left on the surface for at least 1 minutes, more preferably at least for 5 minutes, even more preferably at least for 10 minutes, yet more preferably at least for 20 minutes and most preferably at least 0 minutes. Preferably the composition is left on the surface not more than 120 minutes and most preferably not more than 60 minutes. Preferably, the surface is rinsed more than once. The composition may be applied with the help of an implement, such as, a mop, wipes, paper, cloth or scrubbed using a brush.

Examples

Examples were prepared following the recipe provided in table 1.

Table 1

*Aristocare Smart from Clariant.

Ex-A is a control example, it does not contain the copolymer. Ex-1X was prepared first containing the copolymer. Subsequently, Ex-10 to 12 and Ex-1 B to Ex-1 C were prepared from Ex-1X by adjusting the pH using citric acid or sodium hydroxide solution. Ex-10 to 12 are within the scope of the present invention, whereas Ex-1 B to 1C are comparative examples. Ex 10 to 12 generated a foam volume in the range 170 to 200 millilitre measure by Bartsch method. Evaluation

Each example was evaluated for delivering hydrophobicity to a surface. It was measured in terms of the amount of water retained post wash on a ceramic tile. Ceramic tiles (10 cm x 15 cm) were procured and pre-treated with 20% by weight citric acid solution for 2 hours. Followed by the tiles were washed with water, rubbed with calcite powder using the scotch bright scrubber and finally cleaned with water. The tiles were allowed to dry. Often new tiles contain a surface coating provided by the manufacturers for improved shine. Such coating may interfere in the evaluation; hence they were pre-treated in said manner to remove such coating (if present).

Each tile was treated with one of the examples, by applying and brushing with a toilet brush and allowed to dry for 30 min. Followed by the tile was washed with water to remove product residue.

For evaluating water retention, each tile was left under running tap water for 2 minutes to wash off dust or any residue. Each tile was then placed onto a platform resting at 45° angle mimicking surface of a toilet bowl. 50 ml of tap water was poured on the tile. Water was allowed to drain from the tile for 30 seconds. Post this, the water retained on the tile was wiped using a preweighed tissue paper. The difference in weight of the tissue paper before and after wiping each tile was recorded and summarised below.

Table 3

From table 3, it is evident that Ex-10 to 12 show significantly low water retention compared to Ex- A, Ex-1B and Ex-1C. Lower the value of water retention suggests better hydrophobicity is obtained, therefore provides long lasting cleaning benefit.

Claims

1. A foamable aqueous hard surface cleaning composition comprising:

(a) 0.1 to 10% by weight of quaternary ammonium compound;

(c) 0.1 to 20% by weight of acid; and

(d) a copolymer comprising:

(ii) an acrylamide monomer; and

(iii) at least one monomer selected from polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2- acrylamido-2-methylpropane-sulphonic acid and/or its salt, wherein the pH of the composition is in the range 0.5 to 4 at 20° C, wherein the composition provides a foam volume of at least 140 millilitre as measured by Bartsch method.

2. A composition as claimed in claim 1 wherein the quaternary ammonium compound is selected from didecyl dimethylammonium chloride, dioctyl dimethylammonium 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.

3. A composition as claimed in 2 wherein the quaternary ammonium compound is benzalkonium chloride.

4. A composition as claimed in claims 1 or 3 wherein the amphoteric surfactant is selected from alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulpho-betaines, and combinations thereof.

5. A composition as claimed in any one of claims 1 to 4 wherein the pH of the composition is in the range 0.5 to 3.5 at 20° C.

6. A composition as claimed in any one of claims 1 to 5 wherein the acid comprises an organic acid.

7. A composition as claimed in 6 wherein the organic acid is selected from citric acid, lactic acid, acetic acid, malonic acid, adipic acid, glutaric acid, glycolic acid and maleic acid, succinic acid, malic acid, tartaric acid, hexanoic acid, cyclohexanoic acid, heptanoic acid, octanoic acid, 4-methyl octanoic acid, nonanoic acid, decanoic acid, benzoic acid, 4- methoxy benzoic acid and combinations thereof.

8. A composition as claimed in any one of claims 1 to 7 comprising 0.005 to 1% by weight of the copolymer.

9. A composition as claimed in any one of claims 1 to 8 wherein the cationic monomer is selected from [3-(methacryloylamino)propyl] trimethylammonium chloride (MAPTAC) and diallyl dimethylammonium chloride (DADMAC).

10. A composition as claimed in any one of claims 1 to 9 the acrylamide monomer selected from acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N- ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N- isopropylacrylamide and N-tert-butylacrylamide.

11. A composition as claimed in any one of claims 1 to 10 wherein the copolymer comprises:

(i) a cationic monomer selected from [3-(methacryloylamino)propyl] trimethylammonium chloride (MAPTAC) or diallyl dimethylammonium chloride (DADMAC);

(ii) N-isopropylacrylamide (NIPAM) monomer; and (iii) a monomer selected from polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether, polyethylene glycol-co- polypropylene glycol (meth)acrylate and combinations thereof.

12. A composition as claimed in any one of claims 1 to 10 wherein the copolymer comprises:

(ii) N-isopropylacrylamide (NIPAM) monomer; and

(iii) acrylic acid and/or methacrylic acid monomer; and

(iv) 2-acrylamido-2-methylpropane-sulphonic acid or its salt monomer.

13. A cleaning product comprising a cleaning composition as claimed in any one of claims 1 to 11 contained in a container equipped with a foam trigger, wherein the product dispenses a cleaning foam in use.

14. A method for providing long-lasting cleaning to a surface comprising steps of:

(a) applying a composition as claimed in any one of claims 1 to 12 as foam on the surface;

(b) leaving the composition on the surface for at least 30 seconds; and

(c) rinsing the surface with water.