Foamable hard surface cleaning composition

Abstract

The present invention is in the field of hard surface cleaning compositions. In particular, foamable aqueous hard surface cleaning compositions that deliver long-lasting cleaning and hygiene benefits are provided. The composition comprises from 0.1 to 10% by weight of a quaternary ammonium compound; 0.1 to 10% by weight of an amphoteric surfactant comprising amine oxide and / or cocamidopropyl betaine; 0.1 to 20% by weight of an acid; and a copolymer, the present invention relates to a composition comprising: a composition selected from the group consisting of 2-(acryloyloxy) ethyltrimethyl ammonium chloride, [2-(acrylamido) ethyl] trimethyl ammonium chloride, methyl sulfuric acid [2-(acryloyloxy) ethyl] trimethyl ammonium chloride, [2-(methacryloyloxy) ethyl] trimethyl ammonium chloride, or methyl sulfuric acid [2-(methacryloyloxy) ethyl] trimethyl ammonium chloride, [3-(acrylamido) propyl] trimethyl ammonium chloride, [3-(acrylamido) propyl] trimethyl ammonium chloride, and [3-(methacryloyloxy) ethyl] trimethyl ammonium chloride. The cationic monomers comprise N-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2- An acrylamide monomer; and at least one monomer selected from the group consisting of polyethylene glycol ethylene oxybutyl ethers, polyethylene glycol-co-polypropylene glycol ethylene oxybutyl ethers, polyethylene glycol-co-polypropylene glycol (meth) acrylates, acrylic acid, methacrylic acid, 2-acrylamide-2-methylpropane-sulfonic acid and / or salts thereof, the pH of the composition being in the range of from 1 to 4 at 20 DEG C, and at least one monomer selected from the group consisting of polyethylene glycol ethylene oxybutyl ethers, polyethylene glycol-co-polypropylene glycol ethylene oxybutyl ethers, polyethylene glycol-co-polypropylene glycol (meth) acrylates, acrylic acid, methacrylic acid, 2-acrylamide-2-methylpropane-sulfonic acid and / or salts thereof, wherein the composition provides a foam volume of at least 140 ml as measured by the Bartsch method. Also provided is a cleaning product comprising a composition contained in a container having a foam trigger that dispenses a cleaning foam in use.

Description

Technical Field

[0001] The present invention belongs to the field of hard surface cleaning compositions. In particular, the present invention relates to a foamable hard surface cleaning composition that provides durable cleaning and hydrophobicity to surfaces. Background Art

[0002] Cleaning hard surfaces such as kitchen countertops, tiles, tabletops, cabinets, washbasins, and flush toilets is part of household chores. Typically, consumers spend a significant amount of time and effort on these cleaning activities. They prefer to use a variety of cleaning products for these cleaning activities. Such products differ in their composition, such as detergency actives, acids, builders, colorants; and they can also be obtained in different forms, such as powders, liquids, tablet blocks, sprays, foams, and wipes.

[0003] Typically, hard surface cleaning involves steps such as metering an equal portion of the cleaning product onto the surface, applying it with a tool (such as a sponge, brush, wipe, scrubber), and rinsing with water. Hard surfaces, especially like flush toilets, bathroom tiles, or washbasins, are constantly in contact with water and are prone to scaling, microbial growth, and dirt deposition. Therefore, consumers may need to clean these surfaces frequently, which increases their workload. It is desirable for cleaning products to provide cleaning performance that lasts for a longer period, thereby reducing the need for frequent cleaning and subsequently reducing the consumer's workload.

[0004] One way to deliver durable cleaning benefits is by depositing a layer of hydrophobic material on the surface while cleaning. It reduces water retention on the surface, thereby reducing the accumulation of scaling, dirt deposition, and microbial growth.

[0005] In this regard, US2019 / 0375871 A1 describes a copolymer obtainable by free radical copolymerization of at least the following components: (a) a cationic monomer selected from cationic (meth)acrylamide monomers and diallyldimethylammonium chloride, (b) a polyethylene glycol macromonomer, and (c) an uncharged acrylamide monomer. The copolymer is suitable for use in detergent compositions that provide favorable brightening results.

[0006] EP 1 767 554 A1 describes a water-soluble amphoteric terpolymer containing acrylic acid or methacrylic acid, alkylacrylamide, and N-isopropylacrylamide as monomer building blocks. The polymer is suitable for use in hard surface cleaners.

[0007] Despite the prior art literature, there is still a need for improved foamable hard surface cleaning compositions that provide enhanced cleaning efficacy for a longer period, thereby reducing the need for frequent cleaning. It also provides improved hygienic benefits.

[0008] In addition, it has been observed that cleaning products in the form of foam are becoming increasingly popular among consumers. Foam is an air-liquid mixture that covers a significantly larger surface area compared to a liquid product of similar dosage. The foam adheres to the surface and prevents runoff, thereby reducing the dosage of the product. In addition, it remains on the surface, resulting in an increased contact time and thus providing improved cleaning. Further, the product in the form of foam can be directly dispensed onto the surface, thereby simplifying the cleaning process. It is desirable to apply the composition in the form of foam or as a cleaning foam onto a hard surface. It is also desirable that the cleaning foam remains on or adheres to the surface for a longer time to provide sufficient contact time, thereby improving the cleaning efficacy.

[0009] Surprisingly, it has been found that a hard surface cleaning composition containing a selected zwitterionic surfactant and a copolymer having selected monomer groups produces a large amount of foam during use in a selected pH range. It provides hydrophobicity to the hard surface, which inhibits dirt deposition / accumulation and delays the need for frequent cleaning. Summary of the Invention

[0010] In a first aspect, the present invention provides a foamable aqueous hard surface cleaning composition comprising:

[0011] (a) 0.1 to 10% by weight of a quaternary ammonium compound;

[0012] (b) 0.1 to 10% by weight of a zwitterionic surfactant comprising amine oxide and / or cocamidopropyl betaine;

[0013] (c) 0.1 to 20% by weight of an acid; and

[0014] (d) a copolymer comprising:

[0015] (i) a cationic monomer selected from 2-(acryloyloxy)ethyltrimethylammonium chloride, [2-(acrylamido)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methyl sulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride or [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate, [3-(acrylamido)propyl]trimethylammonium chloride, [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC), diallyldimethylammonium chloride (DADMAC);

[0016] (ii) an acrylamide monomer; and

[0017] (iii) at least one monomer selected from polyethylene glycol vinyl oxybutyl ether, polyethylene glycol - co - polypropylene glycol vinyl oxybutyl ether, polyethylene glycol - co - polypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2 - acrylamido - 2 - methylpropane - sulfonic acid and / or its salts.

[0018] The pH of the composition is in the range of 0.5 to 4 at 20 °C, and the composition provides a foam volume of at least 140 ml, as measured by the Bartsch method.

[0019] 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.

[0020] In another aspect, a method for providing durable cleaning to a surface is provided, the method comprising the steps of:

[0021] (a) applying the composition according to the first aspect as a foam to the surface; and

[0022] (b) leaving the composition on the surface for at least 30 seconds; and

[0023] (c) rinsing the surface with water.

[0024] The term "foamable composition" as used herein refers to a liquid composition capable of generating a large amount of foam in use. Preferably, the composition generates foam without a pressurized gas or propellant.

[0025] By reading the following detailed description, these and other aspects, features and advantages will become apparent to those of ordinary skill in the art. For the avoidance of doubt, any feature of one aspect of the invention can be used in any other aspect of the invention. The word "comprising" is intended to mean "including" but not necessarily "consisting of" or "constituted by". In other words, the listed steps or options need not be exhaustive. It should be noted that the examples given in the following description are intended to illustrate the invention and are not intended to limit the invention to those examples themselves. Similarly, unless otherwise stated, all percentages are weight / weight percentages. Except in the operating and comparative examples, or where otherwise expressly indicated, all numbers in this specification representing amounts of materials or reaction conditions, physical properties of materials and / or uses should be understood to be modified by the word "about". Numerical ranges expressed in the format "x to y" should be understood to include x and y. When multiple preferred ranges for a particular feature are described in the form "x to y", it should be understood that all ranges combining different endpoints are also contemplated. Detailed Description

[0026] According to the present invention, an aqueous hard surface cleaning composition is provided. The composition comprises 0.1 to 10% by weight of a quaternary ammonium compound, 0.1 to 10% by weight of an amphoteric surfactant, 0.1 to 20% by weight of an acid and a copolymer. The pH of the composition is in the range of 0.5 to 4 at 20 °C.

[0027] The copolymer comprises a cationic monomer selected from 2-(acryloyloxy)ethyltrimethylammonium chloride, [2-(acrylamido)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methyl sulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride or [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate, [3-(acrylamido)propyl]trimethylammonium chloride, [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC), diallyldimethylammonium chloride (DADMAC); an acrylamide monomer and at least one monomer selected from polyethylene glycol ethylene oxide butyl ether, polyethylene glycol - co - polypropylene glycol ethylene oxide butyl ether, polyethylene glycol - co - polypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2 - acrylamido - 2 - methylpropane - sulfonic acid and / or its salts.

[0028] Quaternary ammonium compound

[0029] The composition comprises a quaternary ammonium compound. The quaternary ammonium compound is present in the composition in an amount of 0.1 to 10% by weight. Preferably, the quaternary ammonium compound is present in the composition in an amount of 0.1 to 8% by weight, more preferably 0.1 to 6% by weight, and most preferably 0.1 to 5% by weight.

[0030] Examples of quaternary ammonium compounds suitable for the present invention include alkylammonium halides such as cetyltrimethylammonium bromide, alkylarylammonium halides such as octadecyldimethylammonium bromide, N - alkylpyridinium halides such as N - hexadecylpyridinium bromide, etc. A suitable type of quaternary ammonium compound includes those in which the molecule contains amine, ether or ester bonds, such as octylphenoxyethoxyethyl dimethylbenzylammonium chloride, N - (laurylcocamidomethyl) - pyridinium chloride, etc. Another effective type of quaternary ammonium compound includes those in which the hydrophobic group is characterized by a substituted aromatic nucleus, as in the case of lauryloxyphenyltrimethylammonium chloride, cetylaminophenyltrimethylammonium methyl sulfate, dodecylphenyltrimethylammonium methyl sulfate, dodecylbenzyltrimethylammonium chloride, dodecylbenzyltrimethylammonium chloride, etc. Preferably, the quaternary ammonium compound used in the practice of the present technology exhibits biocidal activity or is biocidal in nature.

[0031] Particularly useful quaternary ammonium compound bactericides include compositions comprising a single quaternary compound, as well as mixtures of two or more different quaternary compounds. Such useful quaternary compounds are available under the trademarks EMPIGEN, BARDAC, BARQUAT, HYAMINE, LONZABAC and ONYXIDE, which are more fully described in, for example, McCutcheon's Functional Materials (Volume 2), North American Edition, 1998, and in the corresponding product literature from the following designated suppliers.

[0032] For example, BARDAC 205M is described as containing the following liquids: alkyldimethylbenzylammonium chloride (BKC), octyldecyldimethylammonium chloride; dicetyldimethylammonium chloride, and dioctyldimethylammonium chloride (50% active) (also available at 80% active (BARDAC 208M)); generally described in McCutcheon’s as a combination of alkyldimethylbenzylammonium chloride and dialkyldimethylammonium chloride); BARDAC 2050 is described as a combination of octyldecyldimethylammonium chloride, dicetyldimethylammonium chloride and dioctyldimethylammonium chloride (50% active) (also available at 80% active (BARDAC 2080)); BARDAC 2250 is described as dicetyldimethylammonium chloride (50% active); BARDAC LF (or BARDAC LF-80), is described as based on dioctyldimethylammonium chloride (BARQUAT MB-50, MX-50, OJ-50 (each 50% liquid) and MB-80 or MX-80 (each 80% liquid) are each described as alkyldimethylbenzylammonium chloride; BARDAC 4250 and BARQUAT 4250Z (each 50% active) or BARQUAT 4280 and BARQUAT 4280Z (each 80% active) are each described as alkyldimethylbenzylammonium chloride / alkyldimethylethylbenzylammonium chloride. Also, HYAMINE 1622, is described as diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride (50% solution); HYAMINE 3500 (50% active), is described as alkyldimethylbenzylammonium chloride (also available at 80% active (HYAMINE 3500-80)); and HYMAINE 2389, is described as based on methyldodecylbenzylammonium chloride and / or methyldodecyldimethylxylene-bis-trimethylammonium chloride.

[0033] BARDAC, BARQUAT, and HYAMINE are currently commercially available from Lonza, Inc., Fairlawn, N.J. BTC 50NF (or BTC 65NF) is described as alkyldimethylbenzylammonium chloride (50% active); BTC 99 is described as dicocodimethylammonium chloride (50% active); BTC 776 is described as myrisalkonium chloride (50% active); BTC 818 is described as octyldecyldimethylammonium chloride, dicocodimethylammonium chloride, and dioctyldimethylammonium chloride (50% active) (also available at 80% active (BTC 818 - 80%)); BTC 824 and BTC 835 are each described as alkyldimethylbenzylammonium chloride (each 50% active); BTC 885 is described as a combination of BTC 835 and BTC 818 (50% active) (also available at 80% active (BTC 888)); BTC 1010 is described as dicocodimethylammonium chloride (50% active) (also available at 80% active (BTC 1010 - 80)); BTC 2125 (or BTC 2125M) is described as alkyldimethylbenzylammonium chloride and alkyldimethylethylbenzylammonium chloride (each 50% active) (also available at 80% active (BTC 2125 80 or BTC 2125M)); BTC 2565 is described as alkyldimethylbenzylammonium chloride (50% active) (also available at 80% active (BTC 2568)); BTC 8248 (or BTC 8358) is described as alkyldimethylbenzylammonium chloride (80% active) (also available at 90% active (BTC 8249)); ONYXIDE 3300 is described as n-alkyldimethylbenzylammonium saccharinate (95% active). (BTC and ONYXIDE are currently commercially available from Stepan Company, Northfield, III.)

[0034] Benzyl-C12-14-alkyldimethylammonium chloride, benzyl C12-C16-alkyldimethyl chloride, is also available as EMPIGEN BAC 50 and EMPIGEN BAC 80. These are aqueous solutions of benzalkonium chloride at approximately 50% or 80% respectively. EMPIGEN BAC 50 and EMPIGEN 80 are readily biodegradable and EMPIGEN is commercially available from Innospec Performance Chemicals.

[0035] Polymeric quaternary ammonium salts based on these monomeric structures may also be considered desirable for the present invention. An example is POLYQUAT, which is described as a polymer of 2-butenyldimethylammonium chloride.

[0036] Preferably, the quaternary ammonium compound is selected from didecyldimethylammonium chloride, dioctyldimethylammonium chloride, alkyldimethylbenzylammonium chloride, diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride, alkyldimethylbenzylammonium saccharinate, octyldecyldimethylammonium chloride, alkyldimethylethylbenzylammonium chloride, methyldodecylbenzylammonium chloride, methyldodecyldimethylxylene-bis-trimethylammonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, cetrimide and combinations thereof. The most preferred quaternary ammonium compound is benzalkonium chloride.

[0037] Amphoteric surfactant

[0038] The composition comprises 0.1 to 10% by weight of an 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.

[0039] Examples of amphoteric surfactants suitable for use in the present invention include alkylamine oxides, alkylbetaines, alkylamidopropylbetaines and alkylsulfobetaines. Examples of suitable amphoteric surfactants include lauryldimethylamine oxide, decyldimethylamine oxide, myristyldimethylamine oxide, lauryl / myristylamidamine oxide, octyldimethylamine oxide, decyldimethylamine oxide, cocamidopropylamine oxide, lauramidopropyldimethyl N-oxide, cocodimethylsulfopropylbetaine, laurylbetaine, sodium cocamphopropionate, lauryldimethylamine oxide, cocamidopropyldimethylamine oxide, cocamidopropylbetaine (CAPB), cocamidopropylamine oxide (CAPAO), cocodiethanolamide (CDEA) and cocoethanolamide (CMEA).

[0040] The amphoteric surfactant comprises amine oxide and / or cocamidopropylbetaine. Preferably, the composition comprises more than one amphoteric surfactant. It has been observed that such combinations provide improved foaming in use, preferably when the composition is dispensed through a foam dispenser. The most preferred amphoteric surfactants are a combination of cocamidopropylbetaine (CAPB) and amine oxide.

[0041] Acid

[0042] The composition comprises 0.1 to 20% by weight of an acid. Preferably, the 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.

[0043] 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 of 2 to 5.5. Examples of 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), caproic acid (pKa = 4.88), cyclohexanoic acid (pKa = 4.82), enanthic acid (pKa = 4.8), caprylic acid (pKa = 4.89), 4-methyloctanoic acid (pKa = 5.23), pelargonic acid (pKa = 4.95), capric acid (pKa = 4.9), benzoic acid (pKa = 4.2), 4-methoxybenzoic acid (pKa = 4.37).

[0044] Preferably, the organic acid is selected from citric acid, lactic acid, acetic acid, malonic acid, adipic acid, glutaric acid, glycolic acid, maleic acid, succinic acid, malic acid, tartaric acid, caproic acid, cyclohexanoic acid, enanthic acid, caprylic acid, 4-methyloctanoic acid, pelargonic acid, capric acid, benzoic acid, 4-methoxybenzoic acid, methanesulfonic acid, and combinations thereof. The most preferred organic acid is citric acid.

[0045] The composition may contain an inorganic acid. Examples of inorganic acids suitable for the present invention include hydrochloric acid, hydroiodic acid, hydrobromic acid, perchloric acid, nitric acid, sulfuric acid, and sulfamic acid.

[0046] Copolymer

[0047] The composition contains a copolymer. The copolymer contains three or more kinds of monomers. The copolymer contains cationic monomers selected from the following: 2-(acryloyloxy)ethyltrimethylammonium chloride, [2-(acrylamido)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methyl sulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride, or [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate, [3-(acrylamido)propyl]trimethylammonium chloride, [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC), diallyldimethylammonium chloride (DADMAC). Preferably, the cationic monomer is selected from [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC) and diallyldimethylammonium chloride (DADMAC).

[0048] The copolymer contains acrylamide monomers. The acrylamide monomers can be selected from acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-hydroxymethylacrylamide, N-isopropylacrylamide (NIPAM), and N-tert-butylacrylamide. The most preferred acrylamide monomer is N-isopropylacrylamide (NIPAM).

[0049] The copolymer contains at least one monomer selected from polyethylene glycol ethylene oxide butyl ether, polyethylene glycol-co-polypropylene glycol ethylene oxide butyl ether, polyethylene glycol-co-polypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane-sulfonic acid, and / or its salts.

[0050] One of the preferred copolymers is a copolymer containing a cationic monomer selected from [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC)) or diallyldimethylammonium chloride (DADMAC), an N-isopropylacrylamide (NIPAM) monomer, and a monomer selected from polyethylene glycol ethylene oxide butyl ether, polyethylene glycol-co-polypropylene glycol ethylene oxide butyl ether, polyethylene glycol-co-polypropylene glycol (meth)acrylate. Details for obtaining such a copolymer can be found in WO 2018 / 095920 A1 or WO 2018 / 095918A1.

[0051] Another suitable copolymer is a copolymer containing four monomers, namely a cationic monomer selected from [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC) or diallyldimethylammonium chloride (DADMAC), an N-isopropylacrylamide (NIPAM) monomer, an acrylic acid and / or methacrylic acid monomer, and a 2-acrylamido-2-methylpropane sulfonic acid or its salt monomer. Such a copolymer can be commercially obtained under the trade name Pro A from BASF.

[0052] The copolymer can be present in the composition in an amount of 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.

[0053] pH

[0054] The composition according to the invention is in the pH range of 0.5 to 4 at 20°C. It can be observed that the copolymer functions effectively within the said pH range and provides improved hydrophobicity to the surface and remains on the surface even after multiple washing cycles.

[0055] Preferably, the composition has a pH at 20 °C in the range of 0.5 to 3.5, more preferably 1 to 3.5, even more preferably 1 to 3, and most preferably 1 to 2.5.

[0056] Water

[0057] The composition is an aqueous composition. The term "aqueous" herein refers to water, and the composition contains a significant amount of water. More particularly, water is the balance in the composition.

[0058] Water may be present in the composition in an amount of 60 to 99% by weight, more preferably 60 to 95% by weight, and most preferably 60 to 90% by weight of the composition. Preferably, when formulated as a concentrate, the composition may contain 60 to 80% by weight, more preferably 65 to 80% by weight, and most preferably 70 to 80% by weight of water.

[0059] Further components

[0060] The composition may contain further ingredients for enhancing the performance of the composition. Such ingredients include additional surfactants, chelating agents, builders, fragrances, and colorants.

[0061] The composition may also contain a nonionic surfactant. Examples of suitable nonionic surfactants include alcohol ethoxylates having a C8 to C18 alkyl chain and 1 to 10 ethylene oxides (EO) per mole.

[0062] Suitable alcohol ethoxylate surfactants include condensation products of higher alcohols (e.g., alkanols having a chain of about 8 to 18 carbon atoms in a straight-chain or branched-chain configuration) condensed with about 1 to 10 moles of ethylene oxide, e.g., lauryl alcohol 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, a condensation product of EO with a coconut fatty alcohol fraction (a mixture of fatty alcohols having alkyl chains with lengths of 10 to about 14 carbon atoms), and wherein the condensate contains about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol, as well as tallow alcohol ethoxylates containing 6 to 10 EO per mole of alcohol. Preferably, the alcohol ethoxylate has 3 to 9 EO, more preferably 5 to 8 EO, and even more preferably 7 EO. Particularly preferred are 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 a mixture thereof.

[0063] A nonionic surfactant can be selected such that it comprises a mixture of fatty alcohols, e.g., a mixture of C12, C13, C14, and C15 in different proportions having from 1 to 10 ethoxide groups. Such nonionic surfactants are commercially available from Shell under the NEODOLTM series. For example, NEODOLTM 91-51, which is a mixture of C9, C10, and C11 having 5 EO; NEODOLTM 91-61, which is a mixture of C9, C10, and C11 having 6 EO; NEODOLTM 91-8, which is a mixture of C9, C10, and C11 having 8 EO; NEODOLTM 23-2, which is a mixture of C12 and C13 having 2 EO; NEODOLTM 25-3, which is a mixture of C12, C13, C14, and C15 having 3 EO; NEODOLTM 25-7, which is a mixture of C12, C13, C14, and C15 having 7 EO; and NEODOLTM 45-7, which is a mixture of C14 and C15 having 7 EO. A particularly preferred nonionic surfactant is a mixture of C12, C13, C14, and C15 having 7 EO.

[0064] Another suitable nonionic surfactant is an alkyl polyglycoside of formula I: R1O(R2O) b (Z) a , where R1 is an alkyl group having from about 1 to about 30 carbon atoms; R2 is an alkylene group having 2 to 4 carbon atoms; Z is a sugar 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 (degree of polymerization). Preferred alkyl polyglycosides for use in the disclosed cleaning formulations include those of formula I where Z is a glucose residue, b is 0, R1 is an alkyl group containing 4 to 22 carbon atoms, and the average value of a is about 1-2. Preferably, R1 is an alkyl group containing 8 to 16 carbon atoms and the average value of a is about 1-2. Such alkyl polyglucosides are commercially available, e.g., alkyl polyglycoside compositions of the brand from BASF (formerly Cognis Corporation), including 215CS UP and 225DK.

[0065] The composition may comprise from 0.1 to 5% by weight, more preferably from 0.2 to 4% by weight, and most preferably from 0.5 to 3% by weight of the nonionic surfactant.

[0066] Chelating agent

[0067] The composition may further comprise a chelating agent. Preferably, the composition comprises from 0.05 to 5% by weight, more preferably from 0.1 to 5% by weight, and most preferably from 0.2 to 5% by weight of the chelating agent.

[0068] Suitable chelating agents are those based on organic phosphonates, aminopolycarboxylates and carboxylic acids. It should be understood that suitable chelating agents include the acid form and its salts.

[0069] Examples of chelating agents based on organic phosphonates include diethylenetriamine penta(methylenephosphonic acid) (DTPMP), hydroxyethane diphosphonic acid (HEDP) and nitrilotri(methylenephosphonic acid) (NTMP).

[0070] Examples of chelating agents based on aminopolycarboxylates include ethylenediaminetetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA), nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA) and L-glutamic acid N,N-diacetic acid (GLDA).

[0071] Examples of chelating agents based on carboxylic acids include gluconic acid and itaconic acid.

[0072] Preferably, the chelating agent is biodegradable. Preferred biodegradable chelating agents are nitrilotriacetic acid (NTA), ethylenediamine disuccinic 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'-divaleric acid (EDDG), 3-hydroxy-2,2-iminodisuccinic acid (HIDS) and 2,6-pyridinedicarboxylic acid (PDA), gluconic acid and itaconic acid. The most preferred chelating agents are methylglycine diacetic acid (MGDA) and L-glutamic acid N,N-diacetic acid (GLDA) and combinations thereof.

[0073] Product form

[0074] The composition is a liquid composition that provides a large amount of foam in use. The composition provides a foam volume of at least 140 milliliters as measured by the Bartsch method. Preferably, the composition provides a foam volume of at least 160 milliliters, more preferably at least 180 milliliters, and most preferably at least 200 milliliters as measured by the Bartsch method. The Bartsch method is one of the foam test methods and is known in the art. Generally, it measures the volume of foam produced by a liquid under predetermined conditions. For example, 100 milliliters of the liquid is placed in a 300-milliliter graduated cylinder, and the foam volume is measured after 10 shakes. Details about the Bartsch method can be found in the literature and textbooks, such as "Mechanisms of Foam Destruction by Oil-Based Antifoams", Nikolai D. Denkov, Langmuir 2004, 20, 9463 - 9505; "Bubble and foam chemistry", edited by Robert J. Pugh, Cambridge University Press, 2016.

[0075] Based on the application, the composition can be formulated in a neat or concentrated form. The term "neat" herein means that the composition is used as it is without further dilution. In the "concentrated" form, preferably the composition is diluted in water to form a working solution and then used. A particular advantage of the concentrated form is that the composition in this form can be packaged in a significantly smaller package and consumes much less packaging material.

[0076] The neat form of the composition can be provided in a container equipped with a foam trigger, and the composition is dispensed as a foam onto the desired surface. It is also possible to package such a composition in a refill sachet or package, which can be used to refill the container once the container becomes empty.

[0077] The composition can also be provided in a concentrated form. The consumer dilutes the concentrated composition by adding sufficient water to form a working solution and then uses it. The concentrated form of the composition can be provided in a container having sufficient empty space, and the container is equipped with a foam trigger. In use, the consumer adds water to the container up to a preset label to make a working solution. Alternatively, the composition can also be obtained in a smaller refill sachet, and the consumer prepares the working solution by adding water separately and then filling a container equipped with a foam trigger. The composition is dispensed as a foam onto the desired surface. Preferably, when diluted in water, the ratio of the composition to water is in the range of 1:1 to 1:20, 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.

[0078] 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 a foam head or a foam engine. The foam dispenser herein can be a pressurized gas-based or foam trigger-based dispenser.

[0079] Preferably, the foam dispenser comprises a container containing the composition and a foam trigger, which includes a trigger rod, a pump, a mixing chamber, and a nozzle. The pump includes a piston that moves against a spring in a cavity. The cavity is in fluid communication with the container and the mixing chamber, where it has a one-way valve that allows the composition to flow from the container to the mixing chamber. Generally, the foam trigger is actuated by pressing the trigger rod, which in turn presses the piston against the spring, thereby pushing the composition stored in the cavity into the mixing chamber. In the mixing chamber, the composition is mixed with air and passes through a screen, and then is dispensed as foam from the nozzle. When the trigger rod is subsequently released, the spring pushes the piston back, so that the empty cavity is filled with the composition flowing out of the container. The foam dispenser equipped with a foam trigger relies on pump action and thus does not require pressurized gas. Preferably, the product does not contain pressurized gas or propellant.

[0080] In another case, the foam dispenser may further include a pressurized gas stored in the container together with the composition. This dispenser is activated by opening a one-way valve, thereby releasing the gas together with the composition through the nozzle and dispensing the foam.

[0081] The composition is preferably dispensed as foam using a foam dispenser. Foam dispensers are known in the art and generally include a container containing a liquid composition and a foam trigger or a foam head or a foam engine that dispenses the liquid as foam in use. Preferably, the composition provides a thick, creamy foam that adheres to a vertical surface for a relatively long time. The foam according to the present invention can adhere to a vertical surface, such as a tile, for at least 15 seconds. Preferably, the foam adheres to a vertical surface for at least 30 seconds, more preferably at least 1 minute, even more preferably at least 2 minutes, and most preferably at least 5 minutes. The foam preferably adheres to a vertical surface for at most 60 minutes.

[0082] Application

[0083] The present invention provides a method for providing durable cleaning to a surface, the method comprising the steps of: applying the composition as foam onto the surface, the composition remaining on the surface for at least 30 seconds, and rinsing the surface with water. Preferably, the composition remains on the surface for at least 1 minute, more preferably at least 5 minutes, even more preferably at least 10 minutes, still more preferably at least 20 minutes, and most preferably at least 0 minutes. Preferably, the composition remains on the surface for no more than 120 minutes, and most preferably no more than 60 minutes. Preferably, the surface is rinsed more than once. The composition can be applied by means of tools, such as a mop, a wipe, paper, a cloth, or scrubbing using a brush.

[0084] Example

[0085] Prepare the examples according to the formulations provided in Table 1.

[0086] Table 1

[0087] Materials (% w / w) Ex-A Ex-1X Benzalkonium chloride (BKC) 0.75 0.75 Cocamidopropyl betaine (CAPB) 0.85 0.85 N,N-Dimethyldecylamine N-oxide 0.2 0.2 Citric acid 3 3 Sodium hydroxide 0.08 0.08 Fragrance 0.15 0.15 Copolymer * - 0.075 Water Up to 100 Up to 100

[0088] *Aristocare Smart, from Clariant.

[0089] Ex-A is a control example that does not contain a copolymer. First, prepare Ex-1X that contains the copolymer. Subsequently, adjust the pH by using citric acid or sodium hydroxide solution to prepare Ex-10 to 12 and EX-1B to Ex-1C from Ex-1X. Ex-10 to 12 are within the scope of the present invention, while Ex-1B to 1C are comparative examples. Ex10 to 12 produced a foam volume in the range of 170 to 200 ml measured by the Bartsch method.

[0090] Evaluation

[0091] Evaluate the hydrophobic delivery to the surface for each example. It is measured according to the amount of water retained on the tile after washing. Obtain tiles (10 cm × 15 cm) and pretreat them with 20 wt% citric acid solution for 2 hours. Then wash the tiles with water, rub them with calcite powder using a scotch bright scrubber, and finally clean them with water. Let the tiles dry. New tiles usually contain a surface coating provided by the manufacturer to obtain improved gloss. This coating may interfere with the evaluation; therefore, pretreat them in the described manner to remove this coating (if present).

[0092] By applying and scrubbing with a toilet brush, each tile is treated with one of the examples and allowed to dry for 30 minutes. Then wash the tiles with water to remove the product residue.

[0093] To evaluate the water retention, place each tile under running tap water for 2 minutes to wash away dust or any residue. Then place each tile on a platform that is placed at a 45° angle to simulate the surface of a flush toilet. Pour 50 ml of tap water onto the tile. Let the water drain from the tile for 30 seconds. After that, wipe the water retained on the tile with a pre-weighed paper towel. Record the weight difference of the paper towel before and after wiping each tile and summarize as follows.

[0094] Table 3

[0095] Observation Ex-A Ex-10 Ex-11 Ex-12 Ex-1B Ex-1C pH → 2.5 2.5 1.1 4 5.5 7.0 Water retention (mg) → 335 61 44 99 144 246

[0096] As can be seen from Table 3, Ex-10 to 12 showed significantly lower water retention compared to EX-A, Ex-1B, and Ex-1C. The lower the water retention value, the better the hydrophobicity obtained, thus providing a lasting cleaning benefit.

Claims

1. A foamable aqueous hard surface cleaning composition comprising: (a) 0.1 to 10% by weight of a quaternary ammonium compound; (b) 0.1 to 10% by weight of an amphoteric surfactant comprising amine oxide and / or cocamidopropyl betaine; (c) 0.1 to 20% by weight of an acid; and (d) a copolymer comprising: (i) a cationic monomer selected from 2-(acryloyloxy)ethyltrimethylammonium chloride, [2-(acrylamido)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methyl sulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride or [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate, [3-(acrylamido)propyl]trimethylammonium chloride, [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC), diallyldimethylammonium chloride (DADMAC); (ii) an acrylamide monomer; and (iii) at least one monomer selected from polyethylene glycol ethylene oxide butyl ether, polyethylene glycol - co - polypropylene glycol ethylene oxide butyl ether, polyethylene glycol - co - polypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2 - acrylamido - 2 - methylpropane - sulfonic acid and / or its salts, wherein the pH of the composition is in the range of 0.5 to 4 at 20°C, and wherein the composition provides a foam volume of at least 140 ml as measured by the Bartsch method.

2. The composition according to claim 1, wherein the quaternary ammonium compound is selected from didecyldimethylammonium chloride, dioctyldimethylammonium chloride, alkyldimethylbenzylammonium chloride, diisobutylphenoxyethoxyethyl dimethylbenzylammonium chloride, alkyldimethylbenzyl saccharin ammonium, octyldecyldimethylammonium chloride, alkyldimethylethylbenzylammonium chloride, methyldodecylbenzylammonium chloride, methyldodecyldimethylxylene - bis - trimethylammonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, cetrimide and combinations thereof.

3. The composition according to claim 2, wherein the quaternary ammonium compound is benzalkonium chloride.

4. The composition according to claim 1 or 3, wherein the amphoteric surfactant is selected from alkylamine oxides, alkyl betaines, alkylamidopropyl betaines, alkylsulfobetaines and combinations thereof.

5. The composition according to any one of claims 1 to 4, wherein the pH of the composition is in the range of 0.5 to 3.5 at 20°C.

6. The composition according to any one of claims 1 to 5, wherein the acid comprises an organic acid.

7. The composition according to claim 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 - methyloctanoic acid, nonanoic acid, decanoic acid, benzoic acid, 4 - methoxybenzoic acid and combinations thereof.

8. The composition according to any one of claims 1 to 7, which comprises 0.005 to 1% by weight of the copolymer.

9. The composition according to any one of claims 1 to 8, wherein the cationic monomer is selected from [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC) and diallyldimethylammonium chloride (DADMAC).

10. The composition according to any one of claims 1 to 9, wherein the acrylamide monomer is selected from acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-hydroxymethylacrylamide, N-isopropylacrylamide, and N-tert-butylacrylamide.

11. The composition according to any one of claims 1 to 10, wherein the copolymer comprises: (i) a cationic monomer selected from [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC) or diallyldimethylammonium chloride (DADMAC); (ii) N-isopropylacrylamide (NIPAM) monomer; and (iii) a monomer selected from polyethylene glycol ethylene oxide butyl ether, polyethylene glycol-co-polypropylene glycol ethylene oxide butyl ether, polyethylene glycol-co-polypropylene glycol (meth)acrylate, and combinations thereof.

12. The composition according to any one of claims 1 to 10, wherein the copolymer comprises: (i) a cationic monomer selected from [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC) or diallyldimethylammonium chloride (DADMAC); (ii) N-isopropylacrylamide (NIPAM) monomer; and (iii) acrylic acid and / or methacrylic acid monomer; and (iv) 2-acrylamido-2-methylpropanesulfonic acid or its salt monomer.

13. A cleaning product comprising the cleaning composition according to 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 the steps of: (a) applying the composition according to any one of claims 1 to 12 as a foam onto the surface; (b) leaving the composition on the surface for at least 30 seconds; and (c) rinsing the surface with water.