WO2025212774A1

WO2025212774A1 - Highly acidic cleaning compositions for hard surfaces

Info

Publication number: WO2025212774A1
Application number: PCT/US2025/022750
Authority: WO
Inventors: Mandar Pravin Lone; Nirav Paresh KOTHARI
Original assignee: Lubrizol Advanced Materials Inc
Current assignee: Lubrizol Advanced Materials Inc
Priority date: 2024-04-03
Filing date: 2025-04-02
Publication date: 2025-10-09
Anticipated expiration: 2026-10-03

Abstract

The present invention relates to acidic cleaning compositions for hard surfaces and particularly for acidic cleaning compositions comprising an inorganic acid, a nonionic surfactant and an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C10 to C30-alkyl esters of (meth)acrylic acid. The compositions have a pH of 1 or lower. Process for preparing said compositions and methods for cleaning hard surfaces are also contemplated in the disclosed invention.

Description

HIGHLY ACIDIC CLEANING COMPOSITIONS FOR HARD SURFACES

FIELD OF THE INVENTION

[0001] The present invention relates to acidic cleaning compositions for hard surfaces and particularly for acidic cleaning compositions comprising inorganic acids, nonionic surfactants and anionic polymers.

BACKGROUND OF THE INVENTION

[0002] Hard surface cleaning compositions are commercially important products. Acid cleaners are widely used in home care and institutional applications for removing of dirt and grim from hard surfaces. Many acid cleaners employ organic acids, strong inorganic acids or a combination of both. For household applications, organic acids may be preferred as they are less corrosive than strong inorganic acids and can also be less harmful for the person applying the cleanser. Nevertheless, in some applications, where high cleaning efficacy is necessary, such as institutional and industrial cleaning, compositions with very low pH are preferred and strong inorganic acids are necessary.

[0003] While most compositions of the prior art focus on providing enhanced cleaning efficacy, it is also desirable in some applications that the cleaning compositions show high viscosity. For example, cleaning compositions with high viscosity can be desirable to apply the compositions in non-horizontal surfaces such as toilet bowls, bathtubs, shower stall, walls with ceramic tiling, etc. The higher the viscosity, the higher the retention time of the cleaner on the surface, and thus the higher efficacy. A higher viscosity also allows a safer manipulation of strongly acidic cleaners.

[0004] However, increasing the viscosity of high acidic compositions comprising inorganic acids is a difficult challenge. Many of the rheology modifiers commonly used in cleaning compositions are incompatible with hard acids. High acidity levels in inorganic acid cleaners may degrade the backbones of conventional thickeners and/or reduce the anionic driven swelling created by anionionic polymers used as rheology modifiers.

[0005] Therefore, there is the need to provide cleaning compositions for hard surfaces with very low pH, comprising strong inorganic acids and offering suitable cleaning efficacy and viscosity. SUMMARY OF THE INVENTION

[0006] The present invention relates to high cleaning compositions showing suitable viscosity and stability.

[0007] In a first aspect the invention provides a hard surface cleaning composition comprising: a) water; b) from about 1 to about 20 wt.% of an inorganic acid; c) from about 10 to about 40 wt.% of a nonionic surfactant; and d) from about 1 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

[0008] The invention also provides a process for preparing a composition according to the first aspect comprising the steps of: i) mixing a dispersion of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C to C30 alkyl esters of (meth)acrylic acid with a nonionic surfactant; ii) optionally, adding an amphoteric surfactant; and iii) adding an inorganic acid to obtain a pH of 1 or lower in the composition.

[0009] The cleaning composition of the invention is particularly useful for cleaning hard surfaces.

[0010] Thus, in another aspect the invention relates to method for cleaning a hard surface comprising the step of applying a cleaning composition according to the first aspect onto said hard surface.

[0011] Use of a cleaning composition according to the first aspect for cleaning a hard surface is also contemplated herein.

DETAILED DESCRIPTION OF THE INVENTION

[0012] Various preferred features and embodiments will be described below by way of non-limiting illustration.

[0013] The articles "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article unless the context clearly indicates otherwise. By way of example, "an element" means one element or more than one element.

[0014] Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about". The term “about” as used herein, e.g. when referring to a measurable value (such as an amount or weight of a particular component or temperature), refers to variations of ±20%, ±10%, ±5%, ±1 %, ±0.5%, or, particularly, ±0.1% of the specified amount. Except where otherwise indicated, all numerical quantities in the description specifying amounts or ratios of materials are on a weight basis.

[0015] As used herein, the term “comprising”, which is inclusive or open-ended and does not exclude additional unrecited elements or method steps, is intended to encompass as alternative embodiments, the phrases “consisting essentially of” and “consisting of” where “consisting of’ excludes any element or step not specified and “consisting essentially of” permits the inclusion of additional unrecited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

[0016] The term "home care" as used herein includes, without being limited thereto, products employed in a domestic household for surface cleaning or maintaining sanitary conditions, such as in the kitchen and bathroom (e.g., hard surface cleaners, manual and automatic dish care, toilet bowl cleaners and disinfectants), and laundry products for fabric care and cleaning (e.g., detergents, fabric conditioners, pre-spotter stain removers), and the like.

[0017] The term “institutional and industrial care” (“I & I”) as used herein includes, without being limited thereto, products employed for surface cleaning or maintaining sanitary conditions in institutional and industrial environments, textile treatments (e.g., textile conditioners, carpet and upholstery cleaners), automobile care (e.g., hand and automatic car wash detergents, degreasers, tire shines, leather conditioners, liquid car polishes, plastic polishes and conditioners), paints and coatings, paint removers, carriers for active ingredients (e.g., pesticides, herbicides, antimicrobials, growth regulators), and the like. [0018] The term “hard surface”, as used in the context of the present invention, refers to any surface in household or institutional and industrial environments including the window, kitchen, lavatories, bathroom, furniture, or floor including windows, mirrors, sinks, basins, toilet bowls, baths/shower trays, bidet, wall tiles, floor tiles, cooker tops, oven interiors, cookware, washing machine drums, cooker hoods, extractor fans. These surfaces, for example, may be made of glass, glazed ceramics, metal, stone, plastics, lacquer, wood, or combination thereof.

[0019] The prefix "(meth)acryl" includes "acryl" as well as "methacryl". For example, the term "(meth)acrylic acid" includes both acrylic acid and methacrylic acid.

Inorganic acid

[0020] The cleaning composition of the present invention necessarily comprises an inorganic acid. The inorganic acid is in an amount of from about 1 to about 20 wt.%, particularly from about 5 to about 15 wt.%, more particularly from about 10 to about 14 wt.% based on the total weight of the composition.

[0021] The inorganic acid for use in the present invention may be any known to those skilled in the art of specialty chemicals and detergents. Suitable inorganic acids include peracetic acid, hydrochloric acid (HCI), nitric acid (HNO3), phosphoric acid (H3PO4), sulfuric acid (H2SO4), boric acid (H3BO3), hydrofluoric acid (HF), hydrobromic acid (HBr), perchloric acid (HCIO4), and hydroiodic acid (HI).

[0022] In particular, the inorganic acid can be selected from the group consisting of hydrochloric acid (HCI) and phosphoric acid (H3PO4). More particularly, the inorganic acid can be hydrochloric acid (HCI).

Anionic polymer

[0023] The cleaning composition of the presentation invention comprises an anionic polymer for thickening the composition. The anionic polymer comprises a crosslinked copolymer built up from (meth)acrylic acid and non-ethoxylated esters of (meth)acrylic acid with linear C10-C30 monoalcohols as monomers. The anionic polymer is in an amount of about 1 to about 10 wt.% based on the total weight of the composition.

[0024] In one embodiment, the anionic polymer can be in an amount of from 1.25 to 10 wt.%, particularly, from 1.25 to 5 wt.% based on the weight of the composition. [0025] In particular, the anionic polymer anionic polymer comprises a crosslinked copolymer of acrylic acid and C to C30 alkyl esters of acrylic acid (also referred herein as “Acrylates/C 10-30 Alkyl Acrylate crosspolymer”).

[0026] Non-limiting examples of C10 to C30 alkyl esters of (meth)acrylic acid include for example, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate and melissyl (meth)acrylate, and mixtures thereof.

[0027] The copolymer can be crosslinked with conventional crosslinking monomers. Non-limiting examples of crosslinking monomers include di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1 ,3-butylene glycol di(meth)acrylate, 1 ,6-butylene glycol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,9- nonanediol di(meth)acrylate, 2,2'-bis(4-(acryloxy-propyloxyphenyl)propane, and 2,2'- bis(4-(acryloxydiethoxy-phenyl)propane; tri(meth)acrylate compounds such as, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and tetramethylolmethane tri(meth)acrylate; tetra(meth)acrylate compounds such as ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate; hexa(meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate; allyl compounds such as allyl (meth)acrylate, diallylphthalate, diallyl itaconate, diallyl fumarate, and diallyl maleate; polyallyl ethers of sucrose having from 2 to 8 allyl groups per molecule, polyallyl ethers of pentaerythritol such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether, and combinations thereof; polyallyl ethers of trimethylolpropane such as trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, and combinations thereof. Other suitable polyunsaturated compounds include divinyl glycol, divinyl benzene, and methylenebisacrylamide.

[0028] Typically, the amount of carboxylic group containing monomer present in the polymerizable monomer mixture can range from about 60 to about 99 wt.%, and the amount of C10-C30 alkyl ester of (meth)acrylic acid monomer can range from about 1 to about 40 wt.%, and the amount of crosslinking monomer can range from about 0.01 to about 5 wt.% based on the total weight of monomers in the polymerizable monomer mixture, with the proviso that the total amount does not exceed 100%. [0029] The commercial product Carbopol™ SC-200 from Lubrizol Advanced Materials with the INCI designation Acrylates/C 10-30 Alkyl Acrylates Crosspolymer is a preferred crosslinked copolymer as contemplated herein.

Nonionic surfactants

[0030] It is essential that the cleaning composition comprises a nonionic surfactant. The nonionic surfactant can be in an amount of from about 10 to about 40 wt.% based on the weight of the total composition.

[0031] Nonionic surfactants can be broadly defined as compounds produced by the condensation of alkyl oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound, which may be aliphatic or aromatic in nature. The most widely used class of nonionic surfactants include those which are formed by condensing ethylene oxide and/or propylene oxide with a hydrophobic base. Thus, in particular, the alkylene oxide groups can be ethylene oxide and/or propylene oxide.

[0032] Of particular interest in the context of the present technology are fatty alcohol ethoxylates and alkyl phenols ethoxylates.

[0033] Examples of primary and secondary fatty alcohol ethoxylates include condensation products of aliphatic (Cs-Cis) primary or secondary linear or branched chain alcohols with alkylene oxides, usually ethylene oxide, and generally having from 3 to 30 ethylene oxide groups. Non-limiting examples of commercially available nonionic fatty alcohol ethoxylate surfactants are available under the Tomadol™ trade names from Evonik Industries AG, and Neodol™ and Dobanol™ trade names from Shell Chemicals, or the Plurafact™ trade names from BASF corporation.

[0034] The primary and secondary fatty alcohol ethoxylates can be represented by the formula: where R is a residue of a primary or secondary alcohol having an alkyl chain length of 12 to 18 carbon atoms, and n is from 3 to 18, or from 3 to 12, or from 5 to 9.

[0035] The alkylphenol ethoxylates are represented by the formula: wherein R¹ is a branched alkyl group containing 8 to 10 carbon atoms, and n is from 3 to 17. In particular, n can be from 4 to 12 or from 13 to 17. In particular, the alkylphenol ethoxylate can be selected from a nonylphenol or an octylphenol ethoxylate which are commercially available, for example, from the Dow Chemical Company under the Tergitol™ NP, Triton™ N-57 and Triton™ X-100 tradenames and from Stepan Company under the Makon™ tradename (product designations 4, 6 and 14). More particularly, the alkylphenol ethoxylate can be a nonylphenol ethoxylate. In a preferred embodiment, the alkylphenol ethoxylate can be a nonylphenol ethoxylate with 13 to 17 alkylene oxide groups, preferably 13 alkylene oxide groups.

[0036] In one embodiment, the nonionic surfactant can comprise 12 or less alkylene oxide groups, particularly 3 to 12 alkylene oxide groups, more particularly 5 to 9 alkylene oxide groups.

[0037] The hard cleaning composition of the present invention can comprise: a) water; b) from about 1 to about 20 wt.% of an inorganic acid; and i) c) from about 10 to about 40 wt.%, or from about 12 to about 40 wt.% of a nonionic surfactant comprising 12 or less alkylene oxide groups, and d) from about 1.25 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C to Cso-alkyl esters of (meth)acrylic acid, or ii) c) from about 10 to about 40 wt.%, or from about 10 to about 20 wt.% of a nonionic surfactant comprising 13 or more alkylene oxide groups, and d) from about 1 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C to Cso-alkyl esters of (meth)acrylic acid; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

[0038] In one embodiment, the cleaning composition of the present invention can comprise: c) from about 10 to about 40 wt.%, from about 12 to about 40 wt.%, or from about 12 to 20 wt.% of a nonionic surfactant comprising 12 or less alkylene oxide groups; and d) from about 1.25 to about 10 wt.%, or from 1.25 to 5 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid.

[0039] In particular, the cleaning composition of the present invention can comprise: c) from about 12 to 20 wt.% of a nonionic surfactant comprising from 3 to 12 alkylene oxide groups; and d) from about 1.25 to about 10 wt.%, or from about 1.25 to about 5 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C to Cso-alkyl esters of (meth)acrylic acid.

More particularly, the nonionic surfactant can be a fatty alcohol ethoxylate.

[0040] In particular, the cleaning composition of the present invention can comprise: c) from about 12 to 20 wt.% of a nonionic surfactant comprising from 5 to 9 alkylene oxide groups; and d) from about 1.25 to about 10 wt.%, or from about 1.25 to about 5 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid.

More particularly, the nonionic surfactant can be a fatty alcohol ethoxylate.

[0041] In one embodiment, the nonionic surfactant can comprise 13 or more alkylene oxide groups, or from 13 to 17 alkylene oxide groups. wherein all percentages are based on the weight of the total composition.

[0042] In particular, the cleaning composition of the invention can comprise: c) from about 10 to about 40 wt.%, or from about 10 to about 20 wt.% of a nonionic surfactant comprising from 13 to 17 alkylene oxide groups; and d) from about 1 to 10 wt.%, or from about 1 to about 5 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid.

More particularly, the nonionic surfactant can be an alkylphenol ethoxylate, preferably nonylphenol ethoxylate.

[0043] The cleaning composition of the invention can comprise: c) from about 10 to about 20 wt.% of a nonionic surfactant comprising from 13 to 17 alkylene oxide groups; and d) from about 1 to about 5 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C to Cso-alkyl esters of (meth)acrylic acid.

Amphoteric surfactants

[0044] The composition of the present invention can optionally comprise amphoteric (zwitterionic) surfactants.

[0045] Amphoteric surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. In all of these compounds, there is at least one aliphatic group, straight chain or branched, containing from 3 to 18 carbon atoms and at least one aliphatic substituent containing an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[0046] Suitable amphoteric surfactants include, but are not limited to, amino acids (e.g., N-alkyl amino acids and N-acyl amino acids), betaines, sultaines, and alkyl amphocarboxylates. The betaines and sultaines useful in the context of the present invention can be selected from alkyl betaines, alkylamino betaines, and alkylamido betaines, as well as the corresponding sulfobetaines (sultaines) represented by the following formulas:

wherein R³⁷ is a C7-C22 alkyl or alkenyl group, each R³⁸, independently, is a C1-C4 alkyl group, R³⁹ is a C1-C5 alkylene group or a hydroxy substituted C1-C5 alkylene group, n is an integer from 2 to 6, A is a carboxylate group (betaine) or sulfonate group (sultaine), and M is a salt forming cation. In one embodiment, R³⁷ is a C11-C18 alkyl group or a C11- C18 alkenyl group. In one embodiment, R³⁸ is methyl. In one embodiment, R³⁹ is methylene, ethylene or hydroxy propylene. In one embodiment, m is 3. M can be selected from sodium, potassium, magnesium, ammonium, and mono-, di- and triethanolamine cations.

[0047] Examples of suitable betaines and sultaines include, but are not limited to, lauryl betaine, coco betaine, oleyl betaine, coco hexadecyl dimethylbetaine, coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl amidopropyl betaine, cocoamidopropyl betaine (CAPB), coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, and cocam idopropyl hydroxysultaine. [0048] The alkylamphocarboxylates such as the alkylamphoacetates and alkylamphopropionates (mono- and disubstituted carboxylates) can be represented by the formula: wherein R⁴⁰ is a C7-C22 alkyl or alkenyl group, R⁴¹ is -CH2C(O)O' M⁺, -CH₂CH₂C(O)O- M⁺, or -CH₂CH(OH)CH₂SO₃- M⁺, R⁴² is hydrogen or -CH2C(O)O' M⁺, and M is a cation selected from sodium, potassium, magnesium, ammonium, and the ammonium salt of mono-, di- and triethanolamine.

[0049] Exemplary alkylamphocarboxylates include, but are not limited to, sodium cocoamphoacetate, sodium lauroamphoacetate, sodium capryloamphoacetate, disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, and disodium capryloamphodipropionate.

[0050] In one embodiment, the amphoteric surfactant is selected from the group consisting of betaine-based surfactants, amine oxides, and mixtures thereof. More particularly, the betaine-based surfactant can be cocam idopropyl betaine. In another particular embodiment, the amino oxide is myristamine oxide.

[0051] The amphoteric surfactants can be used in amounts ranging from about 0 to about 50 wt.%, or from about 0.5 to about 15 wt.%, or from about 1 to about 10 wt.%, or from about 2 to about 5 wt.% (based on the total weight of the composition). In one embodiment the amphoteric surfactant is in an amount of from about 1 to about 10 wt.%, particularly from about 2 to about 5 wt.% based on the total weight of the composition.

[0052] Exemplary embodiments of hard surface cleaning compositions of the invention include:

I. A hard surface cleaning composition comprising: a) water; b) from about 1 to about 20 wt.% of an inorganic acid; c) from about 10 to about 40 wt.% of a nonionic surfactant; d) from about 1 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid; and e) from about 1 to 10 wt.% of an amphoteric surfactant; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

II. A hard surface cleaning composition comprising: a) water; b) from about 1 to about 20 wt.% of an inorganic acid; and i) c) from about 10 to about 40 wt.%, or from about 12 to about 40 wt.% of a nonionic surfactant comprising 12 or less alkylene oxide groups, and d) from about 1.25 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C to Cso-alkyl esters of (meth)acrylic acid, or ii) c) from about 10 to about 40 wt.%, or from about 10 to about 20 wt.% of a nonionic surfactant comprising 13 or more alkylene oxide groups, and d) from about 1 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid; and e) from about 1 to about 10 wt.% of an amphoteric surfactant; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

III. A hard surface cleaning composition comprising: a) water; b) from about 1 to about 20 wt.% of an inorganic acid; c) from about 10 to about 40 wt.%, or from about12 to about 40 wt.%, or from about 12 to about 20 wt.% of a nonionic surfactant comprising from 12 or less alkylene oxide groups; d) from about 1 .25 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid; e) from about 1 to 10 wt.% of an amphoteric surfactant; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

IV. A hard surface cleaning composition comprising: a) water; b) from about 5 to about 15 wt.% of an inorganic acid; c) from about 12 to about 20 wt.% of a nonionic surfactant comprising from 3 to 9 alkylene oxide groups; d) from about 1.25 to about 5 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid; and e) from about 2 to about 5 wt.% of an amphoteric surfactant; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

V. A hard surface cleaning composition comprising: a) water; b) from about 5 to about 15 wt.% of an inorganic acid; c) from about 12 to about 20 wt.% of a nonionic surfactant comprising a fatty alcohol ethoxylate comprising from 3 to 9 alkylene oxide groups; d) from about 1.25 to about 5 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C to Cso-alkyl esters of (meth)acrylic acid; and e) from about 2 to about 5 wt.% of an amphoteric surfactant; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

VI. A hard surface cleaning composition comprising: a) water; b) from about 1 to about 20 wt.% of an inorganic acid; c) from about 10 to about 40 wt.%, or from about 10 to 20 wt.% of a nonionic surfactant comprising from 13 or more alkylene oxide groups; d) from about 1 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid; and e) from about 1 to about 10 wt.% of an amphoteric surfactant; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

VII. A hard surface cleaning composition comprising: a) water; b) from about 5 to about 15 wt.% of an inorganic acid; c) from about 10 to about 20 wt.% of a nonionic surfactant comprising from 13 to 17 alkylene oxide groups; d) from about 1 to about 5 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C to Cso-alkyl esters of (meth)acrylic acid; e) from about 2 to about 5 wt.% of an amphoteric surfactant; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

VIII. A hard surface cleaning composition comprising: a) water; b) from about 5 to about 15 wt.% of an inorganic acid; c) from about 10 to about 20 wt.% of a nonionic surfactant comprising an alkylphenol ethoxylate comprising from 13 to 17 alkylene oxide groups; d) from about 1 to about 5 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid; e) from about 2 to about 5 wt.% of an amphoteric surfactant; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition. Aqueous Diluent

[0053] Water is the primary constituent of the compositions disclosed herein as the compositions are largely aqueous in nature. The aqueous diluent or carrier comprises deionized water, although water from natural, municipal or commercial sources can be utilized if any mineral cations that may be present in such water do not deleteriously affect the intended function of any of the components contained in the cleaning composition.

[0054] The amount of water (depending on the delivery form) can range from about 0.5 to about 88 wt.%.

[0055] In addition to water, the aqueous carrier can comprise water miscible cosolvents. Cosolvents can aid in the dissolution of various nonionic laundry detergent adjuvants that require dissolution in the liquid phase. Suitable cosolvents include the lower alcohols such as ethanol and isopropanol but can be any lower monohydric alcohol containing up to 5 carbon atoms. Some or all of the alcohol may be replaced with dihydric or trihydric lower alcohols or glycol ethers which in addition to providing solubilizing properties and reducing the flash point of the product, also can provide anti-freezing attributes as well as to improve the compatibility of the solvent system with particular laundry detergent adjuvants. Exemplary dihydric and trihydric lower alcohols and glycol ethers are glycol, propanediol (e.g., propylene glycol, 1 ,3-propane diol ), butanediol, glycerol, diethylene glycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n- butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl ether monoethyl ether, diisopropylene glycol monomethyl ether, diisopropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, isobutoxyethoxy-2-propanol, 3-methyl- 3-methoxybutanol, propylene glycol t-butyl ether, and mixtures of these solvents.

[0056] The amount of cosolvent(s) if utilized can range from about 0 to about 15 wt.%, from about 0.5 to about 10 wt.%, and from about 1 to about 5 wt.% based on the weight of the total composition.

[0057] In one aspect, the invention also relates to a process for preparing a cleaning composition according to the present invention comprising the steps of: i) mixing a dispersion of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to C30 alkyl esters of (meth)acrylic acid with a nonionic surfactant; ii) optionally, adding an amphoteric surfactant; and iii) adding an inorganic acid in an amount to obtain a pH of 1 or lower in the composition.

[0058] The necessary amount of inorganic acid to obtain a pH of 1 or lower can be readily determined by the skilled person in chemistry. In particular, the inorganic acid is added in a necessary amount to obtain a final concentration of from about 1 to about 20 wt.%, or from about 5 to about 15 wt.%, or from about 10 to about 14 wt.% based on the total weight of the composition.

[0059] In particular, the dispersion of an anionic polymer is a dispersion of the anionic polymer in water.

[0060] The process can further comprise the step of iv) adding fragrances and other benefit agents, which typically takes place after step iii).

Other ingredients

[0061] The composition of the present technology may include, in addition, one or more other components that are known by those of ordinary skill in the art to be useful in formulating soaps, cleaning compositions, hard surface cleaners, and the like.

[0062] The composition of the invention can include other detersive surfactants such as anionic or cationic surfactants.

[0063] Anionic surfactants suitable in the context of the present technology are surface active compounds which contain a long chain hydrocarbon hydrophobic group in their molecular structure and a hydrophile group, i.e., water solubilizing group such as carboxylate, sulfonate or sulfate group or their corresponding acid forms. Suitable anionic surfactants include, but are not limited to, alkyl sulfates, alkyl ether sulfates, alkali metal alkyl polyether sulfates, alkyl sulfonates, alkaryl sulfonates, a-olefin-sulfonates, alkylamide sulfonates, alkarylpolyether sulphates, alkylamidoether sulfates, alkyl monoglyceryl ether sulfates, alkyl monoglyceride sulfates, alkyl monoglyceride sulfonates, alkyl succinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl sulfosuccinamates, alkyl amidosulfosuccinates; alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alkyl amidoethercarboxylates, acyl lactylates, alkyl isethionates, acyl isethionates, carboxylate salts and amino acid derived surfactants such as N-alkyl amino acids, N-acyl amino acids (such as taurates, glutamates, alanine, alaninates, sacosinates, aspartates, glycinates, and mixtures thereof), as well as alkyl peptides. Mixtures of these anionic surfactants are also useful. [0064] The amount of optional anionic surfactant can range from about 0.1 to about 10 wt.%, or from about 0.5 to about 5 wt.%, or from about 1 to about 3 wt.%, based on the weight of the total composition.

[0065] Cationic surfactants are known in the art, and almost any cationic surfactant having at least one long chain alkyl group of about 10 to 24 carbon atoms is suitable in the present technology. Specific cationic surfactants which can be used as surfactants in the present technology are described in detail in U.S. Patent No. 4,497,718, which is hereby incorporated by reference. Suitable cationic surfactants include, but are not limited to, monoalkyl quaternary ammonium surfactants, dialkyl quaternary ammonium compounds, and asymmetric dialkyl quaternary ammonium compound. Non-limiting examples of dialkyl quaternized ammonium compounds include dicocodimonium chloride; dicocodimonium bromide; dimyristyldimonium chloride; dimyristyldimonium bromide; dicetyldimonium chloride; dicetyldimonium bromide; dicetylmethylbenzylmonium chloride; distearyldimonium chloride; distearyldimonium bromide; dimetyldi(hydrogenated tallow)monium chloride; hydroxypropylbisstearylmonium chloride; distearylmethylbenzylmonium chloride; dibehenyl/diarachidyldimonium chloride; dibehenyl/diarachidyldimonium bromide; dibehenyldimonium chloride; dibehenyldimonium bromide; dibehenyldimonium methosulfate; dibehenylmethylbenzylmonium chloride; dihydrogenated tallow benzylmonium chloride; dihydrogenated tallowethyl hydroxyethylmonium methosulfate; dihydrogenated tallow hydroxyethylmonium methosulfate; di-Ci2-Cis alkyldimonium chloride; di-Ci2-Cis alkyldimonium chloride; di-Ci4-Cis alkyldimonium chloride; dicocoylethyl hydroxyethylmonium methosulfate; disoyoylethyl hydroxyethylmonium methosulfate; dipalmitoylethyldimonium chloride; dihydrogenated palmoylethyl hydroxyethylmonium methosulfate; dihydrogenated tallowamidoethyl hydroxyethylmonium chloride; dihydrogenated tallowamidoethyl hydroxyethylmonium methosulfate; dihydrogenated tallowoylethyl hydroxyethylmonium methosulfate; distearoylethyl hydroxyethylmonium methosulfate; and Quaternium-82.

[0066] Non-limiting examples of asymmetric dialkyl quaternized ammonium salt compounds include: stearylethylhexyldimonium chloride, stearylethylhexyldimonium bromide; stearyl ethylhexyl dimonium methosulfate; cetearyl ethylhexyldimonium methosulfate.

[0067] When present the cationic surfactant can be used in the composition of the present invention in an amount ranging from about 0.05 to about 20 wt.%, or from about 0.1 to about 15 wt.%, or from about 0.5 to about 10 wt.%, or from about 1 to about 5 wt.% (based on the weight of the total composition).

[0068] The composition of the present technology can comprise one or more optional benefit agents. By "benefit agent" is meant any compound, material or active ingredient that confers an aesthetic feature in a product in which it is contained to be more attractive for the consumer or provide a specific effect to the surface of a substrate to which it is delivered. Exemplary benefit agents include, but are not limited to, fragrances, fragrance solubilizers, botanicals, antimicrobials, humectants, emollients, enzymes, odor control agents, acidic and alkaline pH adjusting agents, preservatives, buffering agents, coloring agents, hydrotropes, chelating agents, and mixtures thereof.

[0069] The composition of the present technology may optionally comprise builders and electrolytes. The builder can be any material that can reduce the level of alkaline earth metal ions, particularly, magnesium and calcium in the wash water. Builders also can provide other beneficial properties such as generation of an alkaline pH and aiding in the suspension of soil removed from the fabric. The electrolyte that may be utilized can be any water-soluble salt. The electrolyte may also be a detergency builder, e.g., sodium tripolyphosphate, or it may be a non-functional electrolyte to promote the solubility of other electrolytes, for example, potassium salts can be used to promote the solubility of sodium salts enabling the amount of dissolved electrolyte to be increased considerably. Suitable builders include those which are commonly used in detergents, e.g., zeolites (aluminosilicate), crystalline and amorphous silicates, carbonates, phosphorous containing compositions, borates, as well as organic based builders.

[0070] A suitable zeolite or aluminosilicate which is useful in the composition of the present technology is an amorphous water insoluble hydrated compound of the formula (NaAIO2)x(SiC>2)y, wherein x is a number from 1.0 to 1 .2 and y is 1 , the amorphous material can be further characterized by a Mg⁺² exchange capacity of from about 50 mg eq. CaCOs/g. and a particle diameter of from about 0.01 to about 5 pm (volume distribution; measurement method: Coulter counter). In particular, a water insoluble synthetic aluminosilicate ion exchange material useful herein is crystalline and conforms to the formula Na_z[(AIO2)_y.(SiO2)]xH2O, wherein z and y are integers of at least 6; the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264, the aluminosilicate ion exchange material can be further characterized as having a particle size diameter from about 0.1 to about 100 pm (volume distribution; measurement method: Coulter counter); a calcium ion exchange capacity on an anhydrous basis of at least about 200 mg equivalent of CaCCh hardness per gram; and a calcium exchange rate on an anhydrous basis of at least about 2 grains/gallon/minute/gram.

[0071] Suitable silicates include crystalline, sheet like sodium silicates having the general formula MSixChx+i.tW, where M denotes sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20. Crystalline silicates or phyllosilicates of this kind are described, for example, in European Patent Application EP-A-0 164 514. In one aspect, M is sodium and x represent a value of 2 or 3.

[0072] In particular, suitable silicates can include amorphous sodium silicates having a Na2O:SiC>2 modulus of from 1 :2 to 1 :3.3, and which are dissolution-retarded and have secondary detergency properties. The retardation of dissolution relative to conventional amorphous sodium silicates may have been brought about in a variety of ways, for example, by surface treatment, compounding, compacting or over drying.

[0073] Representative carbonates include alkali metal carbonates and bicarbonates, such as, for example, sodium carbonate, potassium carbonate, sodium sesquicarbonate, sodium bicarbonate and potassium bicarbonate.

[0074] Exemplary phosphorous containing compositions include the alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates, specific examples of which are the sodium and potassium pyrophosphates, tripolyphosphates, phosphates, and hexametaphosphates.

[0075] Representative borates include the alkali metal borates such as sodium tetraborate. [0076] Examples of organic based builders are (1) water-soluble amino polycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2 hydroxyethyl)-nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates as set forth in U.S. Patent No. 2,379,942; (3) water-soluble polyphosphonates, including the sodium, potassium and lithium salts of ethane-1-hydroxy-1 ,1-diphosphonic acid; the sodium, potassium and lithium salts of methylene diphosphonic acid; the sodium, potassium and lithium salts of ethylene diphosphonic acid; and the sodium, potassium and lithium salts of ethane-1 ,1 ,2- triphosphonic acid. Other examples include the alkali metal salts of ethane-2-carboxy- 1 ,1 -diphosphonic acid, hydroxymethanediphosphonic acid, carboxyldiphosphonic acid, ethane-1-hydroxy-1 ,1 ,2-triphosphonic acid, ethane-2-hydroxy-1 ,1 ,2-triphosphonic acid, propane-1 ,1 , 3, 3-tetraphosphonic acid, propane-1 ,1 , 2, 3-tetraphosphonic acid, and propane-1 , 2, 2, 3-tetraphosphonic acid; (4) the water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Patent No. 3,308,067; and (5) polymers and copolymers containing structural units derived from itaconic acid, or an anhydride, ester or salt thereof alone or in combination with at least one of (meth)acrylic acid, and their anhydrides, esters and salts, AMPS and salts thereof) as described in International Patent Application Publication Nos. WO 2014/143773 and WO 2015/138872, incorporated herein by reference. The organic builders can be used alone or in admixture with other organic and/or inorganic builders.

[0077] In addition, mono- and polycarboxylate salts are also suitable, including the water-soluble salts of mellitic acid, citric acid, and carboxymethyloxysuccinic acid, imino disuccinate, salts of polymers and copolymers of itaconic acid and maleic acid, tartrate monosuccinate, tartrate disuccinate and mixtures thereof. Exemplary polycarboxylate salts are the sodium and potassium salts of citric acid and tartaric acid. In particular, the polycarboxylate salt is sodium citric acid, e.g., monosodium, disodium and trisodium citrate, or sodium tartaric acid, e.g., monosodium and disodium tartrate. An example of a monocarboxylate salt is sodium formate.

[0078] Other organic builders are polymers and copolymers of (meth)acrylic acid and maleic anhydride and the alkali metal salts thereof. More specifically such builder salts can consist of a copolymer which is the reaction product of about equal moles of methacrylic acid and maleic anhydride which has been completely neutralized to form the sodium salt thereof.

[0079] Suitable electrolytes for incorporation in the present compositions include inorganic salts. Non-limiting examples of suitable inorganic salts include: Mgl2, MgBr2, MgCh, Mg(NC>3)2, Mg3(PC>4)2, Mg2P2O?, MgSCU, magnesium silicate, Nal, NaBr, NaCI, NaF, Na₃(PC>4), NaSOs, Na₂SO4, Na₂SO3, NaNCh, NalCh, Na₃(PC>4), Na₄P2O ?, sodium zirconate, CaF₂, CaCI₂, CaBr₂, Cal₂, CaSO₄, Ca(NO₃)₂, KI, KBr, KCI, KF, KNO₃, KIO₃, K2SO4, K2SO3, KS(PO4), K4 (P2O7), potassium pyrosulfate, potassium pyrosulfite, Lil, LiBr, LiCI, LiF, LiNO₃, AIF₃, AICI3, AIBr 3, AIBr₃, AII₃Al2(SO₄)3, AI(PO₄), AI(NO₃)₃, and including combinations of these salts or salts with mixed cations e.g. potassium alum AIK(SC>4)2 and salts with mixed anions, e.g. potassium tetrachloroaluminate and sodium tetrafluoroaluminate.

[0080] The builders/electrolytes can be used in an amount ranging from about 0 to about 20 wt.%, or from about 0.1 to about 10 wt.%, or from about 1 to about 8 wt.%, or from about 2 to about 5 wt.% (based on the total weight of the composition).

[0081] Chelation agents (chelators) can be employed to stabilize the compositions against the deleterious effects of metal ions. When utilized, suitable chelating agents include amino carboxylates, ethylene diamine-N,N’-disuccinate, amino phosphonates (where low levels of phosphorus are permitted), citric acid and salts thereof (e.g., sodium), and cyclodextrins.

[0082] Amino carboxylates useful as chelating agents include ethylenediaminetetraacetates (EDTA), N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates (NTA), ethylenediamine tetraproprionates, ethylenediamine-N,N'- diglutamates, 2-hyroxypropylenediamine-N,N-disuccinates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates (DETPA), and ethanoldiglycines, including their water-soluble salts such as the alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof. Suitable amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in laundry compositions, and include ethylenediaminetetrakis(methylenephosphonates), diethylenetriamine-N,N,N',N",N"- pentakis(methanephosphonate) (DETMP) and l-hydroxyethane-1 ,1 -diphosphonate (HEDP). [0083] The composition of the present invention can also optionally comprise other acidifying agents such as organic acidifying agents. The organic acidifying agent can include organic acids which contain from 1 to 6 carbon atoms, and at least one carboxyl group. Exemplary useful organic acids include: linear aliphatic acids such as acetic acid, propionic acid, butyric acid and valeric acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid and maleic acid; acidic amino acids such as glutamic acid and aspartic acid; and hydroxy acids such as glycolic acid, lactic acid, hydroxyacrylic acid, alpha-hydroxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid and citric acid, as well as acid salts of these organic acids.

[0084] The composition of the invention optionally comprises one or more perfume or fragrance ingredients. If present, the perfume or fragrance is typically incorporated in an amount of from about 0.001 to about 10 wt.%, or from about 0.01 to about 5 wt.%, and from about 0.1 to about 3 wt.%, based on the total weight of the composition.

[0085] The cleaning composition of the invention is particularly suited for cleaning dirt and removing grim, soap deposits (“soap scum”), hard water stains, lime scale, rust, and the like.

[0086] Thus, in particular, the cleaning composition of the invention can be a toiler cleaner, a bathroom spry or an industrial and institutional cleaner.

[0087] Therefore, the present invention also provides a method for cleaning a hard surface comprising the step of applying a cleaning composition according to the invention onto the surface of said hard surface. Typically, hard surfaces are treated by the cleaning composition of the present invention and then rinsed with water. The cleaning composition can be applied “as is” or be diluted in water.

[0088] The present invention also relates to the use of a cleaning composition according to the present invention for cleaning a hard surface.

[0089] The compositions according to the invention are desirably provided as a ready to use product which may be directly applied to a hard surface. Hard surfaces which are to be particularly denoted are lavatory fixtures, lavatory appliances (toilets, bidets, shower stalls, bathtubs and bathing appliances), wall and flooring surfaces especially those which include refractory materials and the like. Further hard surfaces which are particularly denoted are those associated with dishwashers, kitchen environments and other environments associated with food preparation. Hard surfaces which are those associated with hospital environments, medical laboratories and medical treatment environments. Such hard surfaces described above are to be understood as being recited by way of illustration and not be way of limitation.

[0090] The composition of the present invention can also be applied to a hard surface by the use of a carrier substrate. One example of a useful carrier substrate is a fabric. Fabric substrates can include nonwoven or woven pouches, sponges including both closed cell and open celled sponges, including sponges formed from celluloses as well as other polymeric material, as well as in the form of abrasive or non-abrasive cleaning pads. Such fabrics are known commercially in this field and are often referred to as wipes. Such substrates can be resin bonded, hydroentangled, thermally bonded, meltblown, needle-punched, or any combination of the former.

[0091] The present technology is exemplified by the following examples that are merely for the purpose of illustration and are not to be regarded as limiting the scope of the technology or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight and are based on 100 percent active material.

EXAMPLES

Test Methodology

[0092] Viscosity was measured with a Brookfield viscosimeter at 25°C at 20 rpms. A Teflon spindle was used to avoid corrosion. The spindle size was selected depending on the viscosity of the composition: Spindle 2 for about 2000 cps, Spindle 3 for about 5000 cps, Spindle 4 for about 10000 cps, Spindle 5 for about 20 Kcps, Spindle for about 6 for 50 Kcps, Spindle 7 for 200Kcps) EXAMPLE 1

[0093] A cleaning composition was prepared as set out in TABLE 1. First, a dispersion of Acrylates/C10-30 Alkyl Acrylate Crosspolymer was prepared in water under constant stirring. A nonionic surfactant was added slowly under stirring. An increase of viscosity was observed. Subsequently, an amphoteric surfactant was added under stirring. Hydrocloric acid was added slowly under stirring. The composition was allowed to mix well from about 5 to 10 minutes to obtain a uniform formulation. TABLE 1

¹Carbopol® SC-200 polymer from Lubrizol Advanced Materials, Inc.

²Chemoxide™ MO surfactant from Lubrizol Advanced Materials, Inc. [0094] The composition was translucent and had a viscosity of 3040 cps. The formulation was stable for 1 month when stored at 50 °C, i.e. no phase separation was observed.

EXAMPLE 2 [0095] The following cleaning composition was prepared:

TABLE 2

¹Carbopol® SC-200 polymer from Lubrizol Advanced Materials, Inc.

²Carbopol® 676 polymer from Lubrizol Advanced Materials, Inc.

³Chemoxide™ MO surfactant from Lubrizol Advanced Materials, Inc.

[0096] The composition S1 comprising Acrylates/C 10-30 Alkyl Acrylate Crosspolymer was translucent and had a viscosity of 12000 cps. The formulation was stable for 1 month when stored at 50 °C, i.e. no phase separation was observed.

[0097] In contrast, the composition S2 with Crosslinked polyacrylic acid polymer had a much lower viscosity of 2920 cps and was unstable after 1 month at 50°C (i.e. phase separation was observed).

EXAMPLE 3

[0098] The stability of different compositions at 50 °C as set out in Table 3 was compared.

TABLE 3

¹Carbopol® SC-200 polymer from Lubrizol Advanced Materials, Inc.

²Chemoxide™ MO surfactant from Lubrizol Advanced Materials, Inc.

[0099] None of the formulations were stable after 1 month as white precipitate was observed. This demonstrates that at least 10 wt.% of nonionic surfactant is necessary. EXAMPLE 4

[00100] Different compositions as set out in TABLE 4 were formulated and stability monitored for 1 month at 50 °C.

TABLE 4

¹Carbopol® SC-200 polymer from Lubrizol Advanced Materials, Inc.

EXAMPLE 5 [00101] A cleaning composition was prepared containing the following ingredients:

¹Carbopol® 676 polymer from Lubrizol Advanced Materials, Inc.

²Chemoxide™ MO surfactant from Lubrizol Advanced Materials, Inc.

[00102] The viscosity of the composition was 100 cps. The composition was not stable at 1 month at 50 °C, i.e. phase separation was observed.

EXAMPLE 6

[00103] Different compositions with different amounts of Acrylates/C 10-30 Alkyl Acrylate crosspolymer were prepared and stability monitored for 1 month at 50 °C.

TABLE 6

¹Carbopol® SC-200 polymer from Lubrizol Advanced Materials, Inc.

²Chemoxide™ MO surfactant from Lubrizol Advanced Materials, Inc. [00104] All compositions were stable, i.e. no phase separation was observed. All compositions showed satisfactory viscosity, except composition S8 which was not viscous. [00105] The invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

CLAIMS:

1. A hard surface cleaning composition comprising: a) water; b) from about 1 to about 20 wt.% of an inorganic acid; c) from about 10 to about 40 wt.% of a nonionic surfactant; and d) from about 1 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and C to Cso-alkyl esters of (meth)acrylic acid; wherein the composition has a pH of 1 or lower, and wherein all percentages are based on the weight of the total composition.

2. The composition of claim 1 , wherein the concentration of inorganic acid is from about 5 to about 15 wt.% based on the total weight of the composition, preferably from about 10 to about 14 wt.%.

3. The composition of any one of the previous claims, wherein the weight ratio of nonionic surfactant c) to anionic polymer d) is of at least 10:1.

4. The composition of any one of the previous claims wherein the nonionic surfactant is selected from the group consisting of fatty alcohol ethoxylates and alkylphenol ethoxylates, and mixtures thereof.

5. The composition of any one of previous claims, wherein the noninonic surfactant comprises 13 or more alkylene oxide groups.

6. The composition of claim 5, wherein the nonionic surfactant is an alkyl phenol ethoxylate, preferably a nonylphenol ethoxylate.

7. The composition of any one of claims 1 to 4, wherein the nonionic surfactant comprises 12 or less alkylene oxide groups.

8. The composition of claim 7, comprising: c) from about 12 to about 40 wt.%, or from about 12 to 20 wt.% of a nonionic surfactant comprising 12 or less alkylene oxide groups; and, d) from about 1.25 to about 10 wt.% of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to Cso-alkyl esters of (meth)acrylic acid.

9. The composition of any one of the previous claims, wherein the inorganic acid is selected from the group consisting of hydrochloric acid (HCI) and phosphoric acid (H3PO4).

10. The composition of any of the previous claims, wherein the inorganic acid is hydrochloric acid (HCI).

11. The composition of any of the previous claims, wherein the anionic polymer is a crosslinked copolymer of acrylic acid and C10 to C30 alkyl esters of acrylic acid.

12. The composition of any one of the previous claims having a viscosity of at least 3,000, cps as measured by Brookfield viscosity at 20 rpm at 25 °C.

13. The composition of claim 12 having a viscosity of at least 10,000 cps as measured by Brookfield viscosity at 20 rpm at 25 °C.

14. The composition of claim 13 having a viscosity from 10,000 to 15,000 cps as measured by Brookfield viscosity at 20 rpm at 25 °C.

15. The composition of any one of the previous claims further comprising e) an amphoteric surfactant.

16. The composition of claim 15, wherein the amphoteric surfactant is selected from the group consisting of betaine-based surfactants, amine oxides, and mixtures thereof.

17. The composition of any one of claims 15 or 16, wherein the amphoteric surfactant is at a concentration of from about 1 to about 10 wt.% based on the total weight of the composition.

18. The composition of any one of the previous claims further comprising at least a benefit agent selected from the group consisting of fragrances, fragrance solubilizers, botanicals, antimicrobials, enzymes, odor control agents, preservatives, coloring agents, hydrotropes, chelating agents, and mixtures thereof.

19. A process for preparing a composition according to any one of the previous claims comprising the steps of: i) mixing a dispersion of an anionic polymer comprising a crosslinked copolymer of (meth)acrylic acid and Cw to C30 alkyl esters of (meth)acrylic acid with a nonionic surfactant; ii) optionally, adding an amphoteric surfactant; and iii) adding an inorganic acid in an amount to obtain a pH of 1 or lower in the composition.

20. A method for cleaning a hard surface comprising the step of applying a cleaning composition according to any one of claims 1 to 18 onto said hard surface.

21. Use of a cleaning composition according to any one of claims 1 to 18 for cleaning a hard surface.