Method, composition, product and use

Abstract

A method of treating a surface, the method comprising the step of contacting the surface with a composition comprising a polymer, wherein the polymer is obtainable by polymerising a mixture of monomers comprising: (a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and (b) a monomer comprising a cationic moiety and an alkenyl group; wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

Description

[0001] Method, composition, product and use

[0002] Field of the Invention

[0003] The present invention relates to methods of treating a surface with a composition comprising a polymer, compositions comprising a polymer, treatment products comprising a polymer, and uses of a polymer as a treatment agent, in particular where the polymer is prepared from a monomer comprising an anionic moiety and an alkenyl group and a monomer comprising a cationic moiety and an alkenyl group.

[0004] Background

[0005] Hard surfaces, such as ceramics, glass and metals, are repeatedly contaminated with foulants during their lifetimes. This fouling may be a result of the viscoelastic and chemical character of foulants, e.g. faeces, allowing spreading and adsorption to the surface, or the precipitation and adhesion of salts onto the surface e.g. limescale. This adsorption can be either chemical or physical, or a mixture of the two. Water (e.g. flushing) alone cannot wholly remove these foulants. Although typical cleaning agents such as surfactants in a cleaning product such as a toilet block, or spray, can aid in their removal, these surfactants are washed away with the foulants and are oftentimes not sufficient to remove the foulant without mechanical aids (e.g. brushing).

[0006] An alternative approach would be to apply a coating to the surface that has antifouling properties and therefore either prevents fouling of the surface or facilitates removal of the foulant from that surface. Such antifouling coatings must both be able to stick to the surface and be able to provide a coating that repels any foulant that the surface comes into contact with. There have been solutions proposed based on organosilicon and fluorine chemistries but these are undesirable due to environmental concerns around their persistence.

[0007] Thus, there remains a need for improved methods of combatting fouling of hard surfaces, in particular bathroom or toilet surfaces.

[0008] Detailed Description

[0009] Unless otherwise stated, the following terms used in the specification and claims have the meanings set out below.

[0010] As used herein, the term "hydrocarbyl” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having hydrocarbon character. Examples of hydrocarbyl groups include hydrocarbon groups, i.e. aliphatic (which may be saturated or unsaturated, linear or branched, for example alkyl or alkenyl), alicyclic (for example cycloalkyl or cycloalkenyl), aromatic (for example phenyl) groups, and combinations thereof, such as aralkyl (i.e. aryl substituted alkyl) or alkaryl (i.e. alkyl substituted aryl) groups.

[0011] The term “alkyl” includes both linear and branched chain alkyl groups. References to individual alkyl groups such as “propyl” are specific for the straight chain version only and references to individual branched chain alkyl groups such as “isopropyl” are specific for the branched chain version only. For example, “Cs to C30 alkyl” includes C10 to C25, C5 to Cs alkyl, pentyl, isopentyl and octyl.

[0012] The term “alkenyl” includes both linear and branched chain alkenyl groups. References to individual alkenyl groups such as “propenyl” are specific for the straight chain version only and references to individual branched chain alkenyl groups such as “isopropenyl” are specific for the branched chain version only. For example, “C10 to C20 alkenyl” includes C12 to C alkenyl, C13 to Cie alkenyl and octenyl.

[0013] Any hydrocarbyl groups herein may be optionally substituted (unless stated otherwise). By “optionally substituted” groups we mean that the hydrocarbyl groups are substituted or unsubstituted. Suitable substituents may include non-hydrocarbon groups provided that they do not alter the predominantly hydrocarbon nature of the hydrocarbyl group. Suitable substituents may include hydroxyl, oxo, alkoxy (such as Ci to C4 alkoxy), amino, halo (especially fluoro and chloro), trifluoromethyl, trifluoromethoxy, and cyano groups. The hydrocarbyl groups herein may be unsubstituted.

[0014] Any group ending in “-ylene” herein is intended to refer to a divalent group (i.e. which has two bonds to other groups). For example, hydrocarbylene groups, alkylene groups, and alkenylene groups are respectively hydrocarbyl groups, alkyl groups and alkenyl groups which are divalent instead of monovalent.

[0015] References to “solid” and “liquid” herein refer to the state of compositions or components under normal atmospheric conditions (i.e. at a pressure of 1 atmosphere and 298 K).

[0016] As used in the specification and the appended claims, the singular forms "a", "an," and "the" include both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a polymer" means one polymer or more than one polymer. Throughout this specification, the term “comprising” or “comprises” means including the component(s) specified but not to the exclusion of the presence of other components. The term “consisting essentially of’ or “consists essentially of’ means including the components specified but excluding other components except for components added for a purpose other than achieving the technical effect of the invention. The term “consisting of’ or “consists of’ means including the components specified but excluding other components.

[0017] Whenever appropriate, depending upon the context, the use of the term “comprises” or “comprising” may also be taken to include the meaning “consists essentially of’ or “consisting essentially of’, and also may also be taken to include the meaning “consists of’ or “consisting of’.

[0018] In this specification, unless otherwise indicated any amounts referred to relate to the amount of active component present in the composition. The skilled person will appreciate that commercial sources of some of the components referred to herein may include impurities, side-products and / or residual starting material. However, the amounts specified refer only to the active material and do not include any impurity, side-product, starting material or diluent that may be present.

[0019] As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts of percentages may be read as if prefaced by the word “about”, even if the term does not expressly appear.

[0020] The term "about" as used herein when referring to a measurable value such as a parameter, an amount, a temporal duration, and the like, indicate that a value includes the standard deviation of error for the device or method being employed to determine the value. The term "about" is meant to encompass variations of + / -10% or less, + / -5% or less, or + / -0.1 % or less of and from the specified value, insofar such variations are appropriate to perform in the disclosure. It is to be understood that the value to which the modifier "about" refers is itself also specifically disclosed.

[0021] The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein. The optional features set out herein may be used either individually or in combination with each other where appropriate and particularly in the combinations as set out in the accompanying claims. The optional features for each exemplary embodiment of the invention, as set out herein are also applicable to any other aspects or exemplary embodiments of the invention, where appropriate. In other words, the skilled person reading this specification should consider the optional features for each aspect or embodiment of the invention as interchangeable and combinable between different aspects of the invention.

[0022] As used herein, the term "and / or," when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a list is described as comprising group A, B, and / or C, the list can comprise A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

[0023] According to a first aspect of the present invention, there is provided a method of treating a surface, the method comprising the step of contacting the surface with a composition comprising a polymer,

[0024] wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0025] (a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and

[0026] (b) a monomer comprising a cationic moiety and an alkenyl group;

[0027] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

[0028] The method of the present invention may be used to treat any suitable surface. Suitable surfaces include but are not limited to dishes, textiles, and household surfaces. Suitable household surfaces include but are not limited to floors, kitchen surfaces and bathroom surfaces. In some embodiments, the surface is a hard surface. The hard surface is suitably a ceramic surface, a metal surface, a glass surface, or a hard plastic surface.

[0029] The surface may be a polar surface or a non-polar surface.

[0030] The surface may be a non-polar surface. By “non-polar surface” we mean to refer to a surface having no overall charge, i.e. an electrically neutral surface. Suitable non-polar surfaces include silicone surfaces, polytetrafluoroethylene (PTFE) surfaces, polypropylene surfaces, polyethylene surfaces, powder coated surfaces, and painted surfaces.

[0031] Preferably, the surface is a polar surface. By “polar surface” we mean to refer to a surface having an overall charge. The overall charge may be negative or positive. Suitable polar surfaces include stainless steel surfaces, polycarbonate surfaces, glass surfaces, and ceramic surfaces. In one embodiment, the surface may be the surface of a textile. Examples of suitable textiles include clothing and soft furnishings such as carpets, curtains, and bedding. The method of the first aspect may be a method of laundering items, for example a method of washing laundry.

[0032] In another embodiment, the surface may be the surface of dishes. The method of the first aspect may be a dishwashing process, such as a manual dishwashing process or an automatic dishwashing process. By “dishes” we mean any article which may be washed in a dishwashing process. Examples of such articles include kitchen utensils, tableware and cookware.

[0033] By “kitchen utensil” we mean tools (other than cookware) typically used in the preparation of food and / or beverages, such as spoons, kitchen knives, forks, ladles, spatulas, whisks, sieves, and colanders.

[0034] By “tableware” we mean equipment used to consume food or beverages, such as forks, knives, spoons, plates, bowls, drinking glasses, cups and / or mugs.

[0035] By “cookware” we mean equipment used in the preparation of food or beverages, such as pots, pans, baking trays and roasting dishes.

[0036] In another embodiment, the surface may be a household surface. The household surface may be selected from floors, kitchen surfaces or bathroom surfaces. Other household surfaces are also within the scope of the invention.

[0037] The household surface may be the surface of a pipe, in particular the internal surface of a pipe. Suitable pipes may be found in a kitchen or bathroom. Suitably, the pipe is a drainpipe connected to a kitchen sink, a bathroom sink, a toilet, a bath, or a shower cubicle. The pipe may be formed from any suitable material, for example plastic (such as polyvinyl chloride (PVC)), metal (such as stainless steel), or ceramic.

[0038] The surface is preferably a bathroom surface. By “bathroom surface” we mean any surface in a bathroom, shower room, or toilet, especially a surface which comes into contact with water during the use thereof. Examples of suitable bathroom surfaces include the surfaces of toilets, bathtubs, sinks, tiles, acrylic wall panels, taps, shower heads, bath screens, shower cubicles, pipes and mirrors, preferably the surfaces of toilets, bathtubs, sinks, tiles, acrylic wall panels, taps, shower heads, bath screens, and shower cubicles.

[0039] Preferably, the bathroom surface is a surface of a toilet. Preferably, the surface is a surface of a toilet bowl. The bathroom surface contacted with the polymer may be unfouled. The bathroom surface may have no visible fouling. Fouling on bathroom surfaces may include soil (e.g. faeces), limescale and / or soap scum.

[0040] The method of the first aspect may optionally comprise a step of cleaning the bathroom surface prior to contacting the bathroom surface with the polymer. The step of cleaning the bathroom surface suitably removes any fouling on the bathroom surface.

[0041] Contact of the bathroom surface with the polymer suitably results in the formation of a coating on the bathroom surface. The coating may advantageously prevent or reduce the adhesion of foulants (e.g. soil, limescale and / or soap scum) on the bathroom surface. The coating may show better adhesion to the bathroom surface when the bathroom surface is unfouled.

[0042] Following contact of the bathroom surface with the polymer, the bathroom surface is suitably not rinsed or washed (e.g. with water) for at least 1 minute, preferably for at least 5 minutes. This prolongs contact of the bathroom surface with the polymer and may aid the formation of a coating on the bathroom surface.

[0043] In some embodiments, the surface is not a glass surface.

[0044] In some preferred embodiments, the first aspect of the present invention provides a method of treating a surface of a toilet, the method comprising the step of contacting the surface of the toilet with a composition comprising a polymer, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0045] (a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and

[0046] (b) a monomer comprising a cationic moiety and an alkenyl group;

[0047] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

[0048] The surface of the toilet is preferably a surface of a toilet bowl.

[0049] The polymer used in the present invention is obtainable by polymerising a mixture of monomers comprising monomer (a) and monomer (b), wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers. The polymer is suitably obtained by polymerising a mixture of monomers comprising monomer (a) and monomer (b), wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers. The mixture of monomers may comprise one or more further monomers. References herein to “a polymer” also include embodiments in which mixtures of two or more polymers are present. Therefore, the polymer may comprise a mixture of two or more polymers obtainable (or obtained) by polymerising a mixture of monomers comprising monomer (a) and monomer (b), wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

[0050] Monomer (a) and monomer (b) provide anionic and cationic moieties, respectively, to the polymer. The polymer is therefore a zwitterionic polymer.

[0051] Suitably, monomer (a) and monomer (b) provide at least 97 wt%, such as at least 99 wt% of the mixture of monomers. In some embodiments, the mixture of monomers consists of monomer (a) and monomer (b).

[0052] The mixture of monomers may comprise monomer (a) and monomer (b) in a weight ratio of from 75:25 to 25:75, such as from 60:40 to 40:60, for example from 55:45 to 45:55. In some embodiments, the weight ratio of monomer (a) to monomer (b) is 52:48 or 48:52.

[0053] The mixture of monomers may comprise monomer (a) and monomer (b) in a molar ratio of from 75:25 to 25:75, such as from 60:40 to 40:60, for example from 55:45 to 45:55. In some embodiments, the molar ratio of monomer (a) to monomer (b) is 52:48 or 48:52.

[0054] Monomer (a) is a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof.

[0055] References herein to “a monomer” also include embodiments in which mixtures of two or more monomers are present. Therefore, monomer (a) may comprise one or more monomers comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof. Monomer (a) is suitably an anionic monomer.

[0056] Monomer (a) comprises an anionic moiety selected from a sulfate ester group, a sulfonic acid group, or a salt thereof. By “anionic moiety” we mean to refer to a group having a negative charge or a group having a negative charge after salt formation. Monomer (a) may be in the form of a free acid or a salt. By "sulfate ester" group we mean a group having the formula -O-SO3H. By “sulfonic acid group” we mean a group having the formula -SO3H that is attached to a carbon atom on the remainder of the monomer. Suitably, the anionic moiety is a salt of a sulfate ester group or a salt of a sulfonic acid group (i.e. a sulfate or sulfonate group). The salt comprises a cation as a counterion. The cation may be ammonium, a substituted ammonium, or an alkali metal. The cation may be a substituted ammonium, such as ammonium substituted with one to four alkyl and / or hydroxyalkyl groups, preferably ammonium substituted with one to three alkyl and / or hydroxyalkyl groups. The cation is suitably an alkali metal, such as lithium, sodium, or potassium. Preferably, the cation is sodium.

[0057] Preferably, the anionic moiety is a sulfonic acid group or a salt thereof. Preferably, the anionic moiety comprises a sulfonate group.

[0058] Preferably, monomer (a) does not comprise a cationic moiety. Such monomers do not comprise a cationic moiety in the same molecule as the anionic moiety and the alkenyl group, but may comprise a cationic counterion when the anionic moiety is in the form of a salt.

[0059] Monomer (a) also includes an alkenyl group. By “alkenyl group” we mean to refer to a hydrocarbyl group comprising an aliphatic carbon-carbon double bond. The alkenyl group may be linear or branched. The alkenyl group may have from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms. Preferably, the alkenyl group comprises a vinyl group. By “vinyl group” we mean to refer to the presence of a terminal carboncarbon double bond, i.e. wherein one of the carbon atoms is bound to two hydrogen atoms. In some embodiments, the alkenyl group is a vinyl group, i.e. an alkenyl group having 2 carbon atoms.

[0060] In some preferred embodiments, monomer (a) comprises a sulfonate group and a vinyl group.

[0061] Suitably, the anionic moiety is covalently bound to the alkenyl group, either directly or by a linking group. Preferably, the anionic moiety and the alkenyl group are covalently bound to a linking group. The linking group may comprise an alkylene group, an arylene group, an ester group, an amide group, or a combination thereof. Suitably, the linking group comprises an alkylene group or an arylene group directly bound to the anionic moiety. The linking group may comprise an arylene group, an ester group, or an amide group directly bound to the alkenyl group. The alkylene group may be linear or branched. The alkylene group may have from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. The arylene group is preferably a phenylene group.

[0062] Monomer (a) may comprise from 3 to 10 carbon atoms, preferably from 5 to 8 carbon atoms, for example 6 or 7 carbon atoms.

[0063] In some embodiments, monomer (a) is selected from sulfoalkyl methacrylates, sulfoalkyl acrylates, alkenyl aryl sulfonic acids, alkenyl aryl sulfuric acids, sulfoalkyl methacrylamides, sulfoalkyl acrylamides, alkenyl sulfonic acids, alkenyl sulfuric acids, salts thereof, or mixtures thereof. In some preferred embodiments, monomer (a) is selected from sulfoethylmethacrylate, sulfopropyl acrylate, 4-styrenesulfonic acid, 4-styrenesulfuric acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), vinylsulfonic acid, vinylsulfuric acid, allylsulfonic acid, allylsulfuric acid, 2-methyl-2-propene-1 -sulfonic acid, 2-methyl-2-propene-1 -sulfuric acid, salts thereof, or mixtures thereof.

[0064] Monomer (a) is suitably represented by formula (I):

[0065] H2C=CR1-CO-X1-R2-X2-SO3M (I)

[0066] wherein R1is hydrogen or an optionally substituted hydrocarbyl group;

[0067] R2is an optionally substituted hydrocarbylene group;

[0068] X1is O or NR3;

[0069] R3is hydrogen or an optionally substituted hydrocarbyl group;

[0070] X2is a bond or O; and

[0071] M is hydrogen or a cation.

[0072] R1is suitably hydrogen or an unsubstituted hydrocarbyl group, such as an unsubstituted alkyl group. Suitably, R1is hydrogen or an unsubstituted alkyl group having from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms. R1may be hydrogen or a methyl group. Preferably, R1is hydrogen.

[0073] R2is suitably an unsubstituted hydrocarbylene group, such as an unsubstituted alkylene group. The unsubstituted alkylene group may be linear or branched. Suitably, R2is an unsubstituted alkylene group having from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 2 to 4 carbon atoms. R2may be CH2-CH2, CH2-CH2-CH2 or C(CH3)2-CH2, preferably CH2-CH2-CH2 or C(CH3)2-CH2, further preferably C(CH3)2-CH2.

[0074] X1is suitably NR3.

[0075] R3is suitably hydrogen or an unsubstituted hydrocarbyl group, such as an unsubstituted alkyl group. Suitably, R3is hydrogen or an unsubstituted alkyl group having from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms. R3may be hydrogen or a methyl group. Preferably, R3is hydrogen. Preferably, X1is O or NH.

[0076] X2is preferably a bond. M is hydrogen or any suitable cation. Suitable cations will be well known to the skilled person. M may be ammonium, a substituted ammonium, or an alkali metal. M may be a substituted ammonium, such as ammonium substituted with one to four alkyl and / or hydroxyalkyl groups, preferably ammonium substituted with one to three alkyl and / or hydroxyalkyl groups. M is suitably an alkali metal, such as lithium, sodium, or potassium. Preferably, M is sodium.

[0077] In some preferred embodiments, R1is hydrogen or an unsubstituted hydrocarbyl group;

[0078] R2is an unsubstituted hydrocarbylene group;

[0079] X1is O or NR3;

[0080] R3is hydrogen or an unsubstituted hydrocarbyl group;

[0081] X2is a bond or O; and

[0082] M is hydrogen or a cation.

[0083] In some preferred embodiments, monomer (a) is represented by formula (IA):

[0084] H2C=CR1-CO-X1-R2-SO3M (IA)

[0085] wherein R1is hydrogen or an unsubstituted alkyl group having from 1 to 12 carbon atoms; R2is an unsubstituted alkylene group having from 1 to 12 carbon atoms;

[0086] X1is O or NR3;

[0087] R3is hydrogen or an unsubstituted alkyl group having from 1 to 12 carbon atoms; and

[0088] M is hydrogen, ammonium, a substituted ammonium, or an alkali metal.

[0089] In some preferred embodiments, monomer (a) is represented by formula (IA):

[0090] H2C=CR1-CO-X1-R2-SO3M (IA)

[0091] wherein R1is hydrogen or a methyl group;

[0092] R2is CH2-CH2, CH2-CH2-CH2or C(CH3)2-CH2;

[0093] X1is O or NH; and

[0094] M is an alkali metal.

[0095] In some preferred embodiments, monomer (a) is 2-acrylamido-2-methyl-1 -propanesulfonic acid (AMPS), 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, or a salt thereof. The salt may be an alkali metal salt, such as a lithium, sodium, or potassium salt. Preferably, monomer (a) is acrylic sodium 2-acrylamido-2-methyl-1 -propanesulfonate (AMPS), potassium 3-sulfopropyl acrylate (SPAK), or potassium 3-sulfopropyl methacrylate (SPMAK). In some preferred embodiments, monomer (a) is a salt of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS). The salt may be an alkali metal salt, such as a lithium, sodium, or potassium salt. Preferably, monomer (a) is sodium 2-acrylamido-2-methyl-1 -propanesulfonate (AMPS).

[0096] Monomer (b) is a monomer comprising a cationic moiety and an alkenyl group. Monomer (b) may comprise one or more monomers comprising a cationic moiety and an alkenyl group. Monomer (b) is suitably a cationic monomer.

[0097] Monomer (b) comprises a cationic moiety. Preferably, the cationic moiety comprises a quaternary ammonium group.

[0098] The cationic moiety comprises an anion as a counterion. The anion may be a halide, hydroxide, sulfate, hydrogensulfate, phosphate, or a carboxylate. The anion is suitably a halide, such as fluoride, chloride, or bromide. The anion may be a carboxylate, such as formate or acetate. Preferably, the anion is chloride.

[0099] Preferably, monomer (b) does not comprise an anionic moiety. Such monomers do not comprise an anionic moiety in the same molecule as the cationic moiety and the alkenyl group, but comprise an anionic counterion.

[0100] Monomer (b) comprises an alkenyl group. The alkenyl group may be linear or branched. The alkenyl group may have from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms. Preferably, the alkenyl group comprises a vinyl group. In some embodiments, the alkenyl group is a vinyl group. Monomer (b) may comprise one or more alkenyl groups, such as 1 or 2 alkenyl groups, wherein each alkenyl group suitably comprises a vinyl group.

[0101] In some preferred embodiments, monomer (b) comprises a quaternary ammonium group and one or more alkenyl groups.

[0102] Suitably, the cationic moiety is covalently bound to the alkenyl group, either directly or by a linking group. When monomer (b) comprises two or more alkenyl groups, each alkenyl group may be independently covalently bound to the cationic moiety directly or by a linking group. The linking group may comprise an alkylene group, an arylene group, an ester group, an amide group, or a combination thereof. The linking group may comprise an alkylene group or an arylene group directly bound to the cationic moiety. The linking group may comprise an arylene group, an ester group, or an amide group directly bound to the alkenyl group. The alkylene group may be linear or branched. The alkylene group may have from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. The arylene group is preferably a phenylene group.

[0103] Monomer (b) may comprise from 4 to 16 carbon atoms, preferably from 6 to 12 carbon atoms, for example 8 to 10 carbon atoms.

[0104] In some embodiments, monomer (b) is selected from (acrylamidoalkyl)trialkylammonium salts, (methacrylamidoalkyl)trialkylammonium salts, (acryloyloxyalkyl)trialkylammonium salts, (methacryloyloxyalkyl)trialkylammonium salts, and diallyldialkylammonium salts.

[0105] In some embodiments, monomer (b) is selected from (acrylamidoethyl)trimethylammonium halides, (acrylamidopropyl)trimethylammonium halides, (methacrylamidoethyl)trimethylammonium halides, (methacrylamidopropyl)trimethylammonium halides, (acryloyloxyethyl)trimethylammonium halides, (acryloyloxypropyl)trimethylammonium halides, (methacryloyloxyethyl)trimethylammonium halides, (methacryloyloxypropyl)trimethylammonium halides, diallyldimethylammonium halides, and diallyldiethylammonium halides.

[0106] Monomer (b) is suitably represented by formula (II):

[0107] N+R4R5R6R7A- (||)

[0108] wherein R4, R5, R6and R7are each independently an optionally substituted hydrocarbyl group, wherein at least one of R4, R5, R6and R7independently comprises an alkenyl group and two or more of R4, R5, R6and R7may be optionally combined to form a cyclic moiety; and

[0109] A- is an anion.

[0110] Suitably, at least one of R4, R5, R6and R7is independently represented by formula (A):

[0111] CH2=CR8-L- (A)

[0112] wherein R8is hydrogen or an optionally substituted hydrocarbyl group; and

[0113] L is a linker moiety.

[0114] R8is suitably hydrogen or an unsubstituted hydrocarbyl group, such as an unsubstituted alkyl group. The hydrocarbyl group or the alkyl group may be linear or branched. Suitably, R8is hydrogen or an unsubstituted alkyl group having from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms. Preferably, R8is hydrogen or a methyl group. L may be an optionally substituted hydrocarbylene group, such as an unsubstituted hydrocarbylene group. In such embodiments, R8is preferably hydrogen. L may be an unsubstituted alkylene group having from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms. L may have the formula (CH2)n wherein n is from 1 to 12, such as from 1 to 6, for example from 1 to 4. Preferably, L is a methylene group.

[0115] Alternatively, L may have the formula:

[0116] -CO-X3-R9-

[0117] wherein R9is an optionally substituted hydrocarbylene group;

[0118] X3is O or NR10; and

[0119] R10is hydrogen or an optionally substituted hydrocarbyl group.

[0120] R9is suitably an unsubstituted hydrocarbylene group, such as an unsubstituted alkylene group. The unsubstituted alkylene group may be linear or branched. Suitably, R9is an unsubstituted alkylene group having from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 2 to 4 carbon atoms. R9may be CH2-CH2, CH2-CH2-CH2 or C(CH3)2-CH2, preferably CH2-CH2or CH2-CH2-CH2.

[0121] R10is suitably hydrogen or an unsubstituted hydrocarbyl group, such as an unsubstituted alkyl group. Suitably, R10is hydrogen or an unsubstituted alkyl group having from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms. R10may be hydrogen or a methyl group. Preferably, R10is hydrogen.

[0122] Preferably, X3is O or NH.

[0123] In some embodiments, at least two of R4, R5, R6and R7are independently represented by formula (A). In such embodiments, each group represented by formula (A) may be the same or different. Preferably each group represented by formula (A) is the same. Suitably, two of R4, R5, R6and R7are independently represented by formula (A) wherein each L is independently an optionally substituted hydrocarbylene group and the other two of R4, R5, R6and R7are not represented by formula (A). In such embodiments, each group independently represented by formula (A) is suitably independently represented by formula (A1)

[0124] CH2=CH-(CH2)n- (A1)

[0125] wherein n is as defined above. In some embodiments, only one of R4, R5, R6and R7is represented by formula (A). In such embodiments, formula (A) is suitably represented by formula (A2):

[0126] CH2=CR8-CO-X3-R9- (A2)

[0127] wherein R8, R9and X3are as defined above.

[0128] The rest of R4, R5, R6and R7(i.e. that are not represented by formula (A), (A1) or (A2)) are each independently an optionally substituted hydrocarbyl group, wherein two or more of the rest of R4, R5, R6and R7may be optionally combined to form a cyclic moiety.

[0129] Suitably, the rest of R4, R5, R6and R7are each independently an optionally substituted hydrocarbyl group. The rest of R4, R5, R6and R7may each independently be an unsubstituted hydrocarbyl group, such as an unsubstituted alkyl group. Suitably, the rest of R4, R5, R6and R7are each independently an unsubstituted alkyl group having from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms. Preferably, the rest of R4, R5, R6and R7are each a methyl group.

[0130] In some embodiments, two or more of R4, R5, R6and R7are combined to form a cyclic moiety. The cyclic moiety is suitably a heterocycle optionally substituted (i.e. other than at the nitrogen atom) with one or more unsubstituted hydrocarbyl groups, such as unsubstituted alkyl or alkenyl groups. The heterocycle may be unsubstituted. The heterocycle may be a 5, 6, or 7-membered ring. Preferably, the atoms forming the heterocycle are carbon atoms and one nitrogen atom. The heterocycle may be saturated or unsaturated. The heterocycle may be aromatic.

[0131] A-is any suitable anion. Suitable anions will be well known to the skilled person. A-may be selected from a halide, hydroxide, sulfate, hydrogensulfate, phosphate, or a carboxylate. A-is suitably a halide, such as F-, Ch or Br. A-may be a carboxylate, such as formate or acetate. Preferably, A- is Ck.

[0132] In some preferred embodiments, monomer (b) is represented by formula (II):

[0133] N+R4R5R6R7a- ((I)

[0134] wherein R4is independently represented by formula (A);

[0135] R5is independently represented by formula (A) or is an unsubstituted hydrocarbyl group;

[0136] R6and R7are each independently an unsubstituted hydrocarbyl group or are combined to form a heterocycle optionally substituted with one or more unsubstituted hydrocarbyl groups; and A- is an anion;

[0137] wherein formula (A) is as defined above.

[0138] In some preferred embodiments, monomer (b) is represented by formula (II):

[0139] N+R4R5R6R7A- (||)

[0140] wherein R4and R5are each independently represented by formula (A1) and R6and R7are each independently an unsubstituted alkyl group; or

[0141] R4is represented by formula (A2) and R5, R6and R7are each independently an unsubstituted alkyl group; and

[0142] A-is an anion;

[0143] wherein formula (A1) and formula (A2) are as defined above.

[0144] In some preferred embodiments, monomer (b) is represented by formula (II):

[0145] N+R4R5R6R7A- (II)

[0146] wherein R4and R5are each independently represented by formula (A1):

[0147] CH2=CH-(CH2)n- (A1)

[0148] n is from 1 to 4;

[0149] R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms; and

[0150] A- is an anion; or

[0151] R4is represented by formula (A2):

[0152] CH2=CR8-CO-X3-R9- (A2)

[0153] R5, R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms;

[0154] R8is hydrogen or a methyl group;

[0155] R9is an unsubstituted alkylene group having from 2 to 4 carbon atoms;

[0156] X3is O or NH; and

[0157] A-is an anion.

[0158] In some embodiments, monomer (b) is selected from (3-acrylamidopropyl) trimethylammonium chloride (APTAC), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), 2- (acryloyloxy)ethyl trimethylammonium chloride (AETAC), 2-(methacryloyloxy)ethyl trimethylammonium chloride (MAETAC), diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldiethylammonium chloride, or diallyldiethylammonium bromide, or mixtures thereof.

[0159] In some preferred embodiments, monomer (b) is selected from (3-acrylamidopropyl) trimethylammonium chloride (APTAC), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), 2-(methacryloyloxy)ethyl trimethylammonium chloride (MAETAC), diallyldimethylammonium chloride (DADMAC), or mixtures thereof.

[0160] In some embodiments, monomer (b) is selected from (3-acrylamidopropyl) trimethylammonium chloride (APTAC), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)ethyl trimethylammonium chloride (AETAC), 2-(methacryloyloxy)ethyl trimethylammonium chloride (MAETAC), or mixtures thereof.

[0161] In some preferred embodiments, monomer (b) is selected from (3-acrylamidopropyl) trimethylammonium chloride (APTAC), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), 2-(methacryloyloxy)ethyl trimethylammonium chloride (MAETAC), or mixtures thereof.

[0162] In some preferred embodiments, monomer (b) is selected from diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldiethylammonium chloride, or diallyldiethylammonium bromide, or mixtures thereof. Suitably, monomer (b) is diallyldimethylammonium chloride (DADMAC).

[0163] Preferably, monomer (b) is (3-acrylamidopropyl) trimethylammonium chloride (APTAC).

[0164] Monomer (a) is preferably different from monomer (b).

[0165] The mixture of monomers may polymerised in the presence of a chain transfer agent. The chain transfer agent reduces the molecular weight of the resulting polymer. Any suitable chain transfer agent may be used. Suitable chain transfer agents include salts of sulfites, halogen containing compounds, aldehydes, thiols, thioesters, alcohols, and combinations thereof.

[0166] The chain transfer agent may comprise a salt of a sulfite, such as a salt of sulfite, bisulfite or metabisulfite. The salt of a sulfite is suitably an alkali metal salt or an ammonium salt of a sulfite, such as sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium metabisulfite, potassium metabisulfite, or ammonium metabisulfite. The chain transfer agent may comprise a halogen containing compound, such as carbon tetrachloride, bromoform or bromotrichloromethane.

[0167] The chain transfer agent may comprise an aldehyde, such as a Ci to C4 aldehyde.

[0168] The chain transfer may comprise a thiol, such as a monofunctional thiol or a polyfunctional thiol. Suitable monofunctional thiols include propyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, n-dodecanethiol (DDT), t-dodecanethiol, tetradecyl mercaptan, hexadecyl mercaptan, thioglycolic acid (TG), mercaptopropionic acid, alkyl thioglycolates (such as butyl thioglycolate, 2-ethylhexyl thioglycolate, n-octyl thioglycolate, isooctyl thioglycolate, or dodecyl thioglycolate), mercaptoethanol, mercaptoundecanoic acid, thiolactic acid, and thiobutyric acid. Suitable polyfunctional thiols include trifunctional compounds such as trimethylol propane tris(3-mercaptopropionate); tetrafunctional compounds such as pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathio lactate, and pentaerythritol tetrathiobutyrate; hexafunctional compounds such as dipentaerythritol hexa(3-mercaptopropionate) and dipentaerythritol hexathioglycolate; and octafunctional compounds such as tri penta erythritol octa(3-mercaptopropionate) and tripentaerythritol octathioglycolate.

[0169] The chain transfer agent may comprise an alcohol, such as a secondary alcohol. The secondary alcohol may be isopropyl alcohol (IPA).

[0170] Preferably the chain transfer agent is selected from n-dodecanethiol (DDT), thioglycolic acid (TG), and isopropyl alcohol (IPA). Preferably, the chain transfer agent is n-dodecanethiol (DDT).

[0171] The chain transfer agent may be present an amount of from 0.1 to 5 wt%, preferably from 1 to 3 wt%, such as 2 wt% based on the total weight of monomer (a) and monomer (b).

[0172] The chain transfer agent may be present an amount of from 0.1 to 5 wt%, preferably from 1 to 3 wt%, such as 2 wt% based on the total weight of the mixture of monomers.

[0173] The chain transfer agent may be present an amount of from 0.1 to 10 mol%, such as from 1 to 5 mol%, preferably from 1 to 3 mol% based on the total molar amount of monomer (a) and monomer (b).

[0174] The chain transfer agent may be present an amount of from 0.1 to 10 mol%, such as from 1 to 5 mol%, preferably from 1 to 3 mol% based on the total molar amount of mixture of monomers. The chain transfer agent may be present an amount of from 0.1 to 5 wt%, preferably from 1 to 3 wt%, such as 2 wt% based on the total weight of monomer (a) monomer (b), and the chain transfer agent.

[0175] The chain transfer agent may be present an amount of from 0.1 to 5 wt%, preferably from 1 to 3 wt%, such as 2 wt% based on the total weight of the mixture of monomers and the chain transfer agent.

[0176] The chain transfer agent may be present an amount of from 0.1 to 10 mol%, such as from 1 to 5 mol%, preferably from 1 to 3 mol% based on the total molar amount of monomer (a) monomer (b), and the chain transfer agent.

[0177] The chain transfer agent may be present an amount of from 0.1 to 10 mol%, such as from 1 to 5 mol%, preferably from 1 to 3 mol% based on the total molar amount of mixture of monomers and the chain transfer agent.

[0178] Preferably, the mixture of monomers is not polymerised in the presence of a chain transfer agent.

[0179] In some preferred embodiments, the mixture of monomers comprises monomer (a) and monomer (b) in a weight ratio of from 75:25 to 25:75;

[0180] monomer (a) is represented by formula (I):

[0181] H2C=CR1-CO-X1-R2-X2-SO3M (I)

[0182] wherein R1is hydrogen or an optionally substituted hydrocarbyl group;

[0183] R2is an optionally substituted hydrocarbylene group;

[0184] X1is O or NR3;

[0185] R3is hydrogen or an optionally substituted hydrocarbyl group;

[0186] X2is a bond or O; and

[0187] M is hydrogen or a cation;

[0188] and

[0189] monomer (b) is represented by formula (II):

[0190] N+R4R5R6R7A- (||)

[0191] wherein R4, R5, R6and R7are each independently an optionally substituted hydrocarbyl group, wherein at least one of R4, R5, R6and R7comprises an alkenyl group and two or more of R4, R5, R6and R7are optionally combined to form a cyclic moiety; and

[0192] A- is an anion. In some preferred embodiments, the mixture of monomers comprises monomer (a) and monomer (b) in a weight ratio of from 60:40 to 40:60;

[0193] monomer (a) is represented by formula (IA):

[0194] H2C=CR1-CO-X1-R2-SO3M (IA)

[0195] wherein R1is hydrogen or a methyl group;

[0196] R2is CH2-CH2, CH2-CH2-CH2 or C(CH3)2-CH2;

[0197] X1is O or NH; and

[0198] M is an alkali metal;

[0199] and

[0200] monomer (b) is represented by formula (II):

[0201] N+R4R5R6R7A- (II)

[0202] wherein R4and R5are each independently represented by formula (A1):

[0203] CH2=CH-(CH2)n- (A1)

[0204] n is from 1 to 4;

[0205] R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms; and

[0206] A- is an anion; or

[0207] R4is represented by formula (A2):

[0208] CH2=CR8-CO-X3-R9- (A2)

[0209] R5, R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms;

[0210] R8is hydrogen or a methyl group;

[0211] R9is an unsubstituted alkylene group having from 2 to 4 carbon atoms;

[0212] X3is O or NH and

[0213] A-is an anion.

[0214] In some preferred embodiments, the mixture of monomers comprises monomer (a) and monomer (b) in a weight ratio of 52:48 to 48:52, monomer (a) is sodium 2-acrylamido-2-methyl-1 -propanesulfonate (AMPS) and monomer (b) is selected from (3-acrylamidopropyl) trimethylammonium chloride (APTAC), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), 2-(methacryloyloxy)ethyl trimethylammonium chloride (MAETAC), or diallyldimethylammonium chloride (DADMAC).

[0215] The polymer may be prepared by any suitable method. Suitable polymerisation methods will be well known to the skilled person. The polymer is suitably prepared by free radical polymerisation. The free radical polymerisation may be carried out in any suitable solvent. The solvent may comprise water, an alcohol such as methanol or ethanol, or a mixture thereof. Preferably, the solvent is a mixture of water and ethanol. An initiator is typically used. Any suitable initiator may be used, such as peroxide initiators or azo initiators. Suitable peroxide initiators include dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, and persulfate salts such as potassium persulfate or ammonium persulfate. Suitable azo initiators include 4,4’-azobis(4-cyanovaleric acid) and azobisisobutryonitrile (AIBN). Preferably, the initiator is azobisisobutryonitrile (AIBN). The initiator may be used in an amount of from 0.1 to 10 wt%, preferably from 1 to 5 wt%, such as from 1 to 3 wt% based on the total weight of monomers in the monomer mixture. The free radical polymerisation is suitably carried out at a temperature of from 40 to 100 °C, preferably from 60 to 80 °C.

[0216] The polymer is suitably a random copolymer.

[0217] The polymer may have a number average molecular weight of from 100,000 to 3,000,000 Da, such as from 300,000 to 2,500,000 Da, for example from 400,000 to 600,000 Da.

[0218] The polymer may have a weight average molecular weight of from 100,000 to 5,000,000 Da, such as from 300,000 to 4,000,000 Da, for example from 400,000 to 600,000 Da.

[0219] The polymer may have a polydispersity index of from 1 to 5, such as from 1 to 3.5, for example from 1.0 to 1.5.

[0220] The composition comprising the polymer used in the first aspect of the present invention may consist essentially of the polymer. For example, the composition may consist of the polymer.

[0221] Preferably, the composition comprising the polymer comprises a surfactant. The surfactant may be selected from anionic surfactants, cationic surfactants, non-ionic surfactants, amphoteric or zwitterionic surfactants, and mixtures thereof. Biosurfactants falling within these classes may also be useful.

[0222] Suitably, the surfactant comprises a cationic surfactant and / or an amphoteric or zwitterionic surfactant, and optionally one or more further surfactants. According to a second aspect of the present invention, there is provided a composition comprising a polymer and a surfactant, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0223] (a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and

[0224] (b) a monomer comprising a cationic moiety and an alkenyl group;

[0225] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

[0226] According to the second aspect of the present invention, there is preferably provided a composition comprising a polymer, and a cationic surfactant and / or an amphoteric or zwitterionic surfactant, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0227] (a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and

[0228] (b) a monomer comprising a cationic moiety and an alkenyl group;

[0229] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

[0230] Suitable features of the polymer in the second aspect are as defined in relation to the first aspect of the present invention.

[0231] In some preferred embodiments, the composition used in the first aspect may be the composition of the second aspect of the present invention.

[0232] Suitable features of the composition of the second aspect of the present invention will now be described.

[0233] The composition preferably comprises a cationic surfactant and / or an amphoteric or zwitterionic surfactant.

[0234] In some embodiments, the composition comprises a cationic surfactant.

[0235] In some embodiments, the composition comprises an amphoteric or zwitterionic surfactant. For the avoidance of doubt, the amphoteric or zwitterionic surfactant is different to the polymer described herein.

[0236] In some embodiments, the composition comprises a cationic surfactant and an amphoteric or zwitterionic surfactant. The composition may comprise a cationic surfactant. The cationic surfactant may be an ammonium salt such as an alkyl trimethyl ammonium salt, a dialkyl dimethyl ammonium salt, an alkyl-(N-hydroxyethyl)-dimethyl ammonium salt, or an alkyldimethylbenzylammonium salt (i.e. a benzalkonium salt). The salt may be a halide, hydroxide, sulfate, hydrogensulfate, phosphate, or carboxylate salt. The salt is suitably a halide salt, such as a fluoride, chloride, or bromide salt. The salt may be a carboxylate salt, such as formate or acetate salt. Preferably, the salt is chloride.

[0237] Examples of suitable cationic surfactants include hydroxyethyl laurdimonium chloride, lauryl trimethyl ammonium chloride, tallowtrimonium chloride, cetrimonium chloride, didecyldimethylammonium chloride, an amidoalkyl amine (such as stearamidopropyl dimethyl amine (SAPDMA) or cocamidopropyl dimethyl amine) in acidic media, and an alkyldimethylbenzylammonium chloride (i.e. a benzalkonium chloride). Preferably, the cationic surfactant comprises hydroxyethyl laurdimonium chloride, lauryl trimethyl ammonium chloride, or an alkyldimethylbenzylammonium chloride (i.e. a benzalkonium chloride). More preferably, the cationic surfactant comprises hydroxyethyl laurdimonium chloride or a benzalkonium chloride.

[0238] The composition may comprise an amphoteric or zwitterionic surfactant. The amphoteric or zwitterionic surfactant may be selected from betaines (such as alkyl betaines and alkylamidopropyl betaines), amphoacetates, diamphoacetates, and amine oxides (such as alkylamine oxides and alkylamidopropyl amine oxides). Suitable amphoteric surfactants include lauryl betaine, cocamidopropyl betaine, sodium lauroamphoacetate, sodium cocoamphoacetate, disodium cocoamphodiacetate, lauramine oxide, C12-18 alkyldimethylamine oxide, myristamine oxide, and cocamidopropyl amine oxide. Preferably, the amphoteric or zwitterionic surfactant comprises lauramine oxide.

[0239] Suitable amphoteric surfactants for use in the present invention include those based on fatty nitrogen derivates and those based on betaines.

[0240] Suitable amphoteric or zwitterionic surfactants may be selected from betaines, for example alkyl betaines, alkylamidopropyl betaines, for example cocamidopropyl betaine, alkylamidopropyl hydroxy sultaines, alkylamphoacetates, alkylamphodiacetates, alkyl propionates, alkylamphodipropionates, alkylamphopropionates, alkyliminodipropionates alkyliminodiacetates, and amine oxides.

[0241] Amphoteric or zwitterionic surfactants for use herein may include those which have an alkyl or alkenyl group of 7 to 22 carbon atoms and comply with an overall structural formula:

[0242]

[0243] where R11is alkyl or alkenyl of 7 to 22 carbon atoms; R12and R13are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 6 carbon atoms; m is 2 to 4; n is 0 or 1 ; X is alkylene of 1 to 6 carbon atoms optionally substituted with hydroxyl; and Y is -CO2-or-SCh'.

[0244] Amphoteric or zwitterionic surfactants may include simple betaines of formula:

[0245]

[0246] and amido betaines of formula:

[0247]

[0248] where m is 2 or 3.

[0249] In both formulae R11, R12and R13are as defined previously. R11may, in particular, be a mixture of C12 and Cu alkyl groups derived from coconut so that at least half, preferably at least three quarters, of the groups R11has 10 to 14 carbon atoms. R12and R13are preferably methyl.

[0250] Amphoteric or zwitterionic surfactants may include sulfobetaines of formula:

[0251] R12

[0252] R11-N— (CH2)3SO3_

[0253] R13or O R12

[0254] R n11-C1 1-NH(CH2)m— Nl+— (CH2)3SO3- R13

[0255] where m is 2 or 3, or variants of these in which

[0256] -(CH2)3SO3_is replaced by

[0257]

[0258] where R11, R12and R13in these formulae are as defined previously.

[0259] Amphoteric or zwitterionic surfactants may include amphoacetates and diamphoacetates. Amphoacetates generally conform to the following formula:

[0260] R14CONHCH2CH2— N— CH2CH2OH

[0261] CH2COO~ M2+

[0262] Diamphoacetates generally conform to the following formula:

[0263]

[0264] where R14is an aliphatic group of 8 to 22 carbon atoms and M2+is a cation such as sodium, potassium, ammonium, or substituted ammonium.

[0265] Suitable acetate-based surfactants include lauroamphoacetate; alkyl amphoacetate; sodium alkyl amphoacetate; cocoampho(di)acetate; cocoamphoacetate; disodium cocoamphodiacetate; sodium cocoamphoacetate; disodium capryloamphodiacete; disodium lauroamphoacetate; sodium lauroamphoacetate and disodium wheat germamphodiacetate.

[0266] Suitable betaine surfactants include alkylamido betaine; alkyl betaine, C12 / 14 alkyldimethyl betaine; cocoamidopropylbetaine; tallow bis(hydroxyethyl) betaine; hexadecyldimethylbetaine; cocodimethylbetaine; alkyl amido propyl sulfo betaine; alkyl dimethyl amine betaine; coco amido propyl dimethyl betaine; alkyl amido propyl dimethyl amine betaine; cocamidopropyl betaine; lauryl betaine; laurylamidopropl betaine, coco amido betaine, lauryl amido betaine, alkyl amino betaine; alkyl amido betaine; coco betaine; lauryl betaine; diemethicone propyl PG-betaine; oleyl betaine; N-alkyldimethyl betaine; coco biguamide derivative, Cs amido betaine; C12 amido betaine; lauryl dimethyl betaine; alkylamide propyl betaine; amido betaine; alkyl betaine; cetyl betaine; oleamidopropyl betaine; isostearamidopropyl betaine; lauramidopropyl betaine; 2-alkyl- / V-carboxymethyl- / V-hydroxyethyl imidazolinium betaine; 2-alkyl- / V-carboxyethyl- / V-hydroxyethyl imidazolinium betaine; 2-alkyl- / V-sodium carboxymethyl- / V-carboxymethyl oxyethyl imidazolinium betaine; / V-alkyl acid amidopropyl- / V, / V-dimethyl- / V-(3-sulfopropyl)-ammonium-betaine; / V-alkyl- / V, / V-dimethyl- / V-(3-sulfopropyl)-ammonium-betaine; cocodimethyl betaine; apricotamidopropyl betaine; isostearamidopropyl betaine; myristamidopropyl betaine; palmitamidopropyl betaine; alkamidopropyl hydroxyl sultaine; cocamidopropyl hydroxyl sultaine; undecylenamidopropyl betaine; cocoamidosulfobetaine; alkyl amido betaine; C12 / 18 alkyl amido propyl dimethyl amine betaine; lauryldimethyl betaine; ricinol amidobetaine; tallow aminobetaine.

[0267] Preferred acetate-based amphoteric surfactants for use herein include sodium lauroamphoacetate, disodium lauroamphoacetate and mixtures thereof.

[0268] Preferred betaine surfactants for use as herein include cocoamidopropyl betaine (CAPB).

[0269] Preferred sultaine surfactants for use as herein include cocoamidopropylhydroxy sultaine.

[0270] The amphoteric or zwitterionic surfactant may comprise one or more amine oxide surfactants, preferably one or more alkyl or amidoalkyl dimethyl amine oxides.

[0271] The one or more amine oxide surfactants may comprise a mixture of compounds, suitably a mixture of homologues. The skilled person will understand that amines obtained from natural sources typically comprise mixtures of compounds.

[0272] The one or more amine oxide surfactants may be oxides of tertiary amines. Suitable amine oxide surfactants may be represented by the following formula:

[0273]

[0274] wherein R11, R12and R13are as defined in relation to betaines, m may be 2 or 3 and n may be 1 or 0. Suitably the amine oxide is an oxide of a tertiary alkylamine or alkenylamine having 6 to 36, preferably 6 to 30, more preferably 8 to 24, for example 10 to 20 or 12 to 18, carbon atoms.

[0275] Preferably the amine oxide surfactant comprises a mixture of C12 to C or C12 to Cw amine oxides.

[0276] Preferred amine oxides are lauramine oxide (N,N-dimethyllaurylamine oxide), lauryl myristyl amidoamine oxide, lauryl amidoamine oxide and cocamidopropylamine oxide (CAPAO).

[0277] In some embodiments the composition comprises a cationic surfactant and / or an amphoteric or zwitterionic surfactant, and one or more further surfactants. The one or more further surfactants are in addition to the cationic surfactant and / or the amphoteric or zwitterionic surfactant described above. The one or more further surfactants may be selected from anionic surfactants, cationic surfactants, non-ionic surfactants and amphoteric or zwitterionic surfactants. Preferably, the one or more further surfactants are selected from anionic surfactants and non-ionic surfactants.

[0278] The composition may comprise an anionic surfactant. This may or may not be in addition to a cationic surfactant and / or an amphoteric or zwitterionic surfactant. Suitable anionic surfactants may include sulfate surfactants (such as mono- or di-alkyl sulfates or alkyl ether sulfates), sulfonate surfactants, alkyl ether carboxylate surfactants, sarcosinate surfactants, phosphate surfactants, succinate surfactants, sulfosuccinate surfactants, sulfoacetate surfactants, isethionate surfactants, taurate surfactants, amino acid surfactants such as glutamates and glycinates, lactylate surfactants, and fatty acid salts. Particularly exemplary salts of the above, where applicable, are the sodium, potassium, ammonium, magnesium and triethanolamine salts.

[0279] Preferred anionic surfactants include sodium alkyl benzene sulfonates, sodium alkyl sulfates, sodium alkyl ether sulfates, methyl ester sulfonates, acyl glutamates, fatty acid isethionates, fatty acid alkyl isethionates, acylamino alkanesulfonates (fatty acid taurides) and fatty acid salts (soaps).

[0280] Examples of suitable anionic surfactants include magnesium laureth sulfate, ammonium laureth sulfate, ammonium lauryl sulfate, MEA lauryl sulfate, TEA lauryl sulfate, sodium lauryl sulfate, sodium coco sulfate, sodium Cu- olefin sulfonates, sodium dodecylbenzene sulfonate, laureth-11 carboxylic acid, laureth-5 carboxylic acid, sodium laureth-5 carboxylate, capryleth-6 carboxylic acid, disodium laureth-3 sulfosuccinate, diethylhexyl sodium succinate, sodium lauroyl sarcosinate, sodium lauroyl methyl isethionate (SLMI), sodium cocoyl isethionate (SCI), sodium cocoyl methyl isethionate (SCMI), sodium methyl cocoyl taurate (SMCT), and sodium methyl oleoyl taurate (SMOT). Preferably, the anionic surfactant comprises a sulfonate surfactant, more preferably an alkyl benzene sulfonate.

[0281] In some embodiments, the composition is substantially free or completely free of anionic surfactants.

[0282] The composition may comprise a non-ionic surfactant. Suitable non-ionic surfactants for use herein include alcohol alkoxylates (such as alcohol ethoxylates, alcohol propoxylates, and ethylene oxide / propylene oxide copolymer derived surfactants), aliphatic esters, aromatic esters, sugar esters (such as sorbitan esters), alkyl glucosides, fatty acid alkoxylates (such as fatty acid ethoxylates and fatty acid propoxylates), amine alkoxylates, especially amine ethoxylates (such as bis (2-hydroxyethyl) tallow alkylamine, PEG-2 oleamine, oleyl amine ethoxylate, dihydroxyethyl tallowamine), or polyethylene glycol esters (including partial esters), glycerol esters (including glycerol partial esters and glycerol triesters), fatty alcohols (such as cetearyl alcohol, lauryl alcohol, stearyl alcohol, behenyl alcohol), and alkanolamides. Preferably, the non-ionic surfactant is selected from alcohol alkoxylates (such as alcohol ethoxylates, alcohol propoxylates, and ethylene oxide / propylene oxide copolymer derived surfactants), aliphatic esters, aromatic esters, sugar esters (such as sorbitan esters), alkyl glucosides, fatty acid alkoxylates (such as fatty acid ethoxylates and fatty acid propoxylates), or polyethylene glycol esters (including partial esters), glycerol esters (including glycerol partial esters and glycerol triesters), fatty alcohols (such as cetearyl alcohol, lauryl alcohol, stearyl alcohol, behenyl alcohol), and alkanolamides.

[0283] Suitably, the non-ionic surfactant comprises an alcohol alkoxylate and / or an alkanolamide. Preferably, the non-ionic surfactant comprises an alcohol ethoxylate or a surfactant derived from an alcohol and an ethylene oxide / propylene oxide copolymer.

[0284] In some embodiments the non-ionic surfactant comprises an amine alkoxylate, for example an amine ethoxylate or a surfactant derived from an amine and an ethylene oxide / propylene oxide copolymer.

[0285] Examples of suitable non-ionic surfactants include deceth-5, C12-15 pareth-7, C12-15 pareth-9, C12-15 pareth-11 , trideceth-6, trideceth-7, trideceth-8, C9-11 pareth-5, C9-11 pareth-6, 09-11 pareth-8, deceth-7, ceteareth-20, ceteareth-25, ceteareth-30, ceteareth-50, ceteareth-80, C -is alcohol ethoxylates, cetyl oleyl alcohol ethoxylates, PPG-4-undeceth-7; PPG-5-undeceth-7, coconut methyl ester ethoxylate (10 EG), cocamide DEA, cocamide MIPA, and cocamide MEA. Preferably, the non-ionic surfactant comprises deceth-5, C12-15 pareth-7, C12-15 pareth-9, C12-15 pareth-11 , trideceth-6, C9-11 pareth-5, C9-11 pareth-6, C9-11 pareth-8, deceth-7, PPG-4- undeceth-7; PPG-5-undeceth-7, coconut methyl ester ethoxylate (10 EO), cocamide DEA, cocamide MIPA, or cocamide MEA. More preferably, the non-ionic surfactant comprises deceth-5 or PPG-4-undeceth-7.

[0286] Suitable biosurfactants include rhamnolipids, trehalolipids, sophorolipids, mannosylerythritol lipids, and glycolipids produced by Meyerozama guilliermondii, Saccharomyces cerevisiae, Candida utilis, Candida bombicola and / or Marinobacter hydrocarbonoclasticus.

[0287] The composition may comprise one or more further components. The composition may comprise a diluent or carrier. Suitable components include chelating agents (such as tetrasodium EDTA), solvents, hydrotropes (such as sodium cumene sulfonate), perfumes, builders, thickeners, fillers, colourants, biocides, enzymes, additional limescale removers, pH buffers, solubility controllers, bleaching agents, bleach activators, biofilm removal agents, soil-adhesion inhibitors, acids (such as citric acid), bases (such as sodium metasilicate), additional polymers (i.e. other than those defined herein), probiotics, redeposition additives, and dye transfer inhibitors.

[0288] The composition may be a laundry composition or dishwashing composition. Laundry and dishwashing compositions typically comprise ingredients such as fillers, builders, bleaching agents, bleach activators, redeposition additives, dye transfer inhibitors, enzymes, colourants and perfumes.

[0289] The composition may comprise a solvent. The solvent may comprise a polar solvent and / or an nonpolar or low polarity solvent. Suitable polar solvents include alcohols, glycols, glycol ethers, and glycerol. Examples of suitable polar solvents include dipropylene glycol monobutyl ether and propylene glycol. Suitably nonpolar or low polarity solvents include oils (such as hydrocarbon oils or vegetable oils) and esters. An example of a suitable nonpolar or low polarity solvent is white mineral oil.

[0290] The composition may be acidic or alkaline. Preferably, the composition is acidic. The acidic composition may have a pH of 6 or less, such as 5 or less, for example 3.5 or less. The acid composition may have a pH of from 0 to 6, such as from 1 to 5, for example from 1.5 to 3.5. The acidic composition suitably comprises an acid. The acid may be an organic acid or an inorganic acid. Examples of suitable acids include citric acid, acetic acid, lactic acid, glycolic acid, oxalic acid, boric acid, gluconic acid, sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, salicylic acid, tartaric acid, formic acid, and malic acid.

[0291] Suitably, the acid is an organic acid, preferably a polycarboxylic acid. The polycarboxylic acid is suitably selected from citric acid (for example, in the form of citric acid monohydrate), oxalic acid, tartaric acid and malic acid. The composition may consist essentially of or consist of the polymer, citric acid and water. The inventors have found that the inclusion of an acid such as citric acid in the composition may prevent or reduce fouling (in particular, limescale) on a surface treated with the composition.

[0292] The composition may be alkaline and have a pH of at least 8, such as at least 10, for example at least 12.5. The alkaline composition may have a pH of from 8 to 14, such as from 10 to 14, for example from 12.5 to 13.5. The alkaline composition suitably comprises a base.

[0293] The composition may comprise the polymer in any suitable amount. The composition may comprise the polymer in a total amount of from 0.1 to 10 wt%, such as from 0.5 to 5 wt%, for example from 1 to 2 wt% based on the total weight of the composition. Amounts referto the total amount of the polymers if two or more are present.

[0294] The composition may comprise surfactants (i.e. cationic, amphoteric or zwitterionic, anionic and non-ionic) in a total amount of from 0.1 to 60 wt%, such as from 0.5 to 50 wt%, for example from 1 to 40 wt% based on the total weight of the composition. Amounts refer to the total amount of the surfactants if two or more are present.

[0295] Cationic surfactants and amphoteric or zwitterionic surfactants may provide from 10 to 95 wt% of the surfactants in the composition, such as from 20 to 90 wt%, for example from 25 to 50 wt% of the surfactants in the composition.

[0296] The composition may comprise cationic surfactants and amphoteric or zwitterionic surfactants in a total amount of from 0.1 to 60 wt%, such as from 0.5 to 50 wt%, for example from 1 to 40 wt% based on the total weight of the composition.

[0297] The cationic surfactant or the amphoteric or zwitterionic surfactant in the composition of the second aspect may provide from 10 to 95 wt% of the surfactants in the composition, such as from 20 to 90 wt%, for example from 25 to 50 wt% of the surfactants in the composition.

[0298] The composition of the second aspect may comprise the cationic surfactant or the amphoteric or zwitterionic surfactant in a total amount of from 0.1 to 60 wt%, such as from 0.5 to 50 wt%, for example from 1 to 40 wt% based on the total weight of the composition.

[0299] Nonionic surfactants may provide from 10 to 95 wt% of the surfactants in the composition, such as from 20 to 90 wt%, for example from 25 to 50 wt% of the surfactants in the composition. The composition may comprise nonionic surfactants in a total amount of from 0.1 to 60 wt%, such as from 0.25 to 50 wt%, for example from 0.5 to 40 wt% based on the total weight of the composition.

[0300] The non ionic surfactant in the composition of the second aspect may provide from 10 to 95 wt% of the surfactants in the composition, such as from 20 to 90 wt%, for example from 25 to 50 wt% of the surfactants in the composition.

[0301] The composition of the second aspect may comprise the nonionic surfactant in a total amount of from 0.1 to 60 wt%, such as from 0.25 to 50 wt%, for example from 0.5 to 40 wt% based on the total weight of the composition.

[0302] Anionic surfactants may provide from 10 to 100 wt% of the surfactants in the composition, such as from 20 to 95 wt%, for example from 25 to 80 wt% of the surfactants in the composition.

[0303] The composition may comprise anionic surfactants in a total amount of from 0.1 to 60 wt%, such as from 0.5 to 50 wt%, for example from 1 to 40wt% based on the total weight of the composition.

[0304] The anionic surfactant in the composition of the second aspect may provide from 10 to 100 wt% of the surfactants in the composition, such as from 20 to 95 wt%, for example from 25 to 00 wt% of the surfactants in the composition.

[0305] The composition of the second aspect may comprise the anionic surfactant in a total amount of from 0.1 to 60 wt%, such as from 0.25 to 50 wt%, for example from 0.5 to 40 wt% based on the total weight of the composition.

[0306] The composition is preferably a liquid composition. The liquid composition is suitably aqueous, and preferably comprises at least 50 wt% water, such as at least 90 wt% water based on the total weight of the liquid composition. The composition is suitably a liquid acidic composition. The liquid composition may be applied to the surface by pouring or by spraying. The liquid composition may be applied to the surface as a foam, for example by spraying the liquid composition through a foam-forming nozzle.

[0307] The liquid composition suitably comprises surfactants in a total amount of from 0.1 to 10 wt%, such as from 0.5 to 5 wt%, for example from 1 to 3 wt% based on the total weight of the composition. The liquid composition may comprise cationic surfactants and amphoteric or zwitterionic surfactants in a total amount of from 0.1 to 10 wt%, such as from 0.5 to 5 wt%, for example from 1 to 3 wt% based on the total weight of the composition.

[0308] Alternatively, the composition may be a solid composition.

[0309] The solid composition suitably comprises a filler. The filler suitably comprises a carbonate salt, a sulfate salt, a halide salt, a phosphate salt, a silicate, or a combination thereof. The filler may comprise an alkali metal or alkaline earth metal carbonate salt, an alkali metal or alkaline earth metal sulfate salt, an alkali metal or alkaline earth metal halide salt, an alkali metal or alkaline earth metal phosphate salt, or a combination thereof. Suitable fillers include sodium sulfate, sodium chloride, sodium carbonate, and sodium silicate.

[0310] The filler may be present in the solid composition in any suitable amount, such as in an amount of at least 10 wt%, such as at least 30 wt%, or even at least 50 wt%, based on the total weight of the solid composition. The filler may be present in the solid composition in an amount of from 10 to 90 wt%, such as from 30 to 70 wt%, or even from 50 to 60 wt% based on the total weight of the solid composition.

[0311] The solid composition suitably comprises surfactants in a total amount of from 0.1 to 60 wt%, suitably from 10 to 50 wt%, such as from 20 to 50 wt%, for example from 25 to 40 wt% based on the total weight of the composition.

[0312] The solid composition may comprise cationic surfactants and amphoteric or zwitterionic surfactants in a total amount of from 0.1 to 60 wt%, suitably from 10 to 50 wt%, such as from 20 to 50 wt%, for example from 25 to 40 wt% based on the total weight of the composition.

[0313] The solid composition may comprise anionic and / or nonionic surfactants in a total amount of from 0.1 to 60 wt%, suitably from 10 to 50 wt%, such as from 15 to 50 wt%, for example from 20 to 40 wt% based on the total weight of the composition.

[0314] The solid composition may comprise anionic surfactants in a total amount of from 0.1 to 60 wt%, suitably from 5 to 50 wt%, such as from 10 to 45 wt%, for example from 15 to 40 wt% or from 20 to 30 wt% based on the total weight of the composition.

[0315] The solid composition may be a powder.

[0316] The solid composition may be a solid gel. By solid gel we mean the gel is not pourable. The gel suitably comprises water in an amount of from 35 to 70 wt%, preferably from 40 to 65 wt%, for example from 42 to 62 wt% based on the total weight of the gel. The gel may be directly applied to the surface. The gel may be self-adhesive.

[0317] The solid composition may be a toilet block. Suitably the toilet block is a rim block or a cistern block. The method of the first aspect may comprise the step of affixing the toilet block (e.g. a rim block) to a toilet rim or placing the toilet block (e.g. a cistern block) within a toilet cistern.

[0318] The toilet block (e.g. the rim block) may be affixed to the rim of a toilet bowl via an attachment device. The attachment device suitably comprises an attachment element such as an arm or hook. The attachment device may comprise a holder for holding the toilet block. The holder may be in the form of a housing such as a basket. When the toilet is flushed, water suitably contacts a portion of the toilet block, for example, by passing through the basket, to dissolve a portion of the toilet block and provide treatment to the surface of the toilet.

[0319] The toilet block may be a solid gel. Suitably, the gel may be self-adhesive or the gel may be affixed to the rim of a toilet bowl via an attachment device.

[0320] The method of the first aspect of the present invention is a method of treating a surface, the method comprising the step of contacting the surface with a composition comprising a polymer.

[0321] In embodiments in which the composition comprising the polymer is a solid composition the method may involve direct contact of the surface with the solid composition or it may involve contact of the surface with an aqueous composition derived from passing water over, through or around the solid composition.

[0322] For example, in embodiments in which a toilet block is affixed to the rim of a toilet bowl via an attachment device contact of the surface will be with an aqueous composition derived from passing water over, through or around the solid toilet block.

[0323] In some preferred embodiments, the first aspect of the present invention provides a method of treating a bathroom surface, the method comprising the step of contacting the bathroom surface with a liquid acidic composition comprising a polymer and one or more further components, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0324] (a) a monomer represented by formula (I):

[0325] H2C=CR1-CO-X1-R2-X2-SO3M (I)

[0326] wherein R1is hydrogen or an optionally substituted hydrocarbyl group;

[0327] R2is an optionally substituted hydrocarbylene group; X1is O or NR3;

[0328] R3is hydrogen or an optionally substituted hydrocarbyl group;

[0329] X2is a bond or O; and

[0330] M is hydrogen or a cation;

[0331] and

[0332] (b) a monomer represented by formula (II):

[0333] N+R4R5R6R7A- (II)

[0334] wherein R4, R5, R6and R7are each independently an optionally substituted hydrocarbyl group, wherein at least one of R4, R5, R6and R7independently comprises an alkenyl group and two or more of R4, R5, R6and R7are optionally combined to form a cyclic moiety; and

[0335] A-is an anion;

[0336] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers; and

[0337] the mixture of monomers comprises monomer (a) and monomer (b) in a weight ratio of from 75:25 to 25:75.

[0338] In some preferred embodiments, the first aspect of the present invention provides a method of treating a surface of a toilet, the method comprising the step of contacting the surface of the toilet with an aqueous acidic composition comprising a polymer, at least one of a cationic surfactant and an amphoteric or zwitterionic surfactant, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0339] (a) a monomer represented by formula (IA):

[0340] H2C=CR1-CO-X1-R2-SO3M (IA)

[0341] wherein R1is hydrogen or a methyl group;

[0342] R2is CH2-CH2, CH2-CH2-CH2 or C(CH3)2-CH2;

[0343] X1is O or NH; and

[0344] M is an alkali metal;

[0345] and

[0346] (b) a monomer represented by formula (II):

[0347] N+R4R5R6R7a- ((I)

[0348] wherein R4and R5are each independently represented by formula (A1): CH2=CH-(CH2)n- (A1)

[0349] n is from 1 to 4; and

[0350] R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms; or

[0351] R4is represented by formula (A2):

[0352] CH2=CR8-CO-X3-R9- (A2)

[0353] R5, R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms;

[0354] R8is hydrogen or a methyl group;

[0355] R9is an unsubstituted alkylene group having from 2 to 4 carbon atoms; and

[0356] X3is O or NH;

[0357] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers; and

[0358] the mixture of monomers comprises monomer (a) and monomer (b) in a weight ratio of from 60:40 to 40:60.

[0359] In some preferred embodiments, the first aspect of the present invention provides a method of treating a bathroom surface, the method comprising the step of contacting the bathroom surface with a composition comprising a polymer and one or more further components;

[0360] wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0361] (a) a monomer represented by formula (I):

[0362] H2C=CR1-CO-X1-R2-X2-SO3M (I)

[0363] wherein R1is hydrogen or an optionally substituted hydrocarbyl group;

[0364] R2is an optionally substituted hydrocarbylene group;

[0365] X1is O or NR3;

[0366] R3is hydrogen or an optionally substituted hydrocarbyl group;

[0367] X2is a bond or O; and

[0368] M is hydrogen or a cation;

[0369] and

[0370] (b) a monomer represented by formula (II):

[0371] N+R4R5R6R7A- (II) wherein R4, R5, R6and R7are each independently an optionally substituted hydrocarbyl group, wherein at least one of R4, R5, R6and R7independently comprises an alkenyl group and two or more of R4, R5, R6and R7are optionally combined to form a cyclic moiety; and

[0372] A-is an anion;

[0373] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers; and

[0374] the mixture of monomers comprises monomer (a) and monomer (b) in a weight ratio of from 75:25 to 25:75;

[0375] wherein the composition contacted with the bathroom surface is a solid composition comprising the polymer and one or more further components or an aqueous composition derived from passing water over, through or around a solid composition comprising the polymer and one or more further components.

[0376] In some preferred embodiments, the first aspect of the present invention provides a method of treating a surface of a toilet, the method comprising the steps of providing a toilet block, affixing the toilet block to a toilet rim or placing the toilet block within a toilet cistern, and flushing the toilet, wherein the toilet block comprises a polymer and a surfactant, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0377] (a) a monomer represented by formula (IA):

[0378] H2C=CR1-CO-X1-R2-SO3M (IA)

[0379] wherein R1is hydrogen or a methyl group;

[0380] R2is CH2-CH2, CH2-CH2-CH2 or C(CH3)2-CH2;

[0381] X1is O or NH; and

[0382] M is an alkali metal;

[0383] and

[0384] (b) a monomer represented by formula (II):

[0385] N+R4R5R6R7A- (II)

[0386] wherein R4and R5are each independently represented by formula (A1):

[0387] CH2=CH-(CH2)n- (A1)

[0388] n is from 1 to 4; and R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms; or

[0389] R4is represented by formula (A2):

[0390] CH2=CR8-CO-X3-R9- (A2)

[0391] R5, R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms;

[0392] R8is hydrogen or a methyl group;

[0393] R9is an unsubstituted alkylene group having from 2 to 4 carbon atoms; and

[0394] X3is O or NH;

[0395] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers; and

[0396] the mixture of monomers comprises monomer (a) and monomer (b) in a weight ratio of from 60:40 to 40:60.

[0397] Treating a surface according to the method of the first aspect may provide a cleaning effect, a conditioning effect, an antifouling effect, and / or an appearance enhancing effect. Treating a surface according to the method of the first aspect preferably provides a cleaning effect, a conditioning effect, and / or antifouling effect.

[0398] When the surface is a textile, contact of the composition comprising the polymer with the textile may result in the cleaning and / or conditioning of the textile.

[0399] When the surface is dishes, contact of the composition comprising the polymer with the dishes may result in the cleaning of the dishes.

[0400] When the surface is a household surface (preferably a bathroom surface), contact of the household surface with the composition comprising the polymer may result in cleaning of the household surface, confer an antifouling effect on the household surface, and / or enhance the visual appearance of the household surface. Preferably, contact of the household surface with the composition comprising the polymer results in cleaning of the household surface, and / or confers an antifouling effect on the household surface. By “antifouling effect” we mean that it is easier to remove fouling from the household surface compared to a surface that has not been contacted with the composition.

[0401] The method of the first aspect of the present suitably enhances the visual appearance of the treated surface. Enhancing the visual appearance of the surface may comprise increasing the shine or gloss of the surface and / or repairing the surface. Enhancing the visual appearance may comprise increasing the shine or gloss of the surface. Enhancing the visual appearance may comprise repairing the surface. Repairing the surface suitably involves coating the surface to mask scratches or blemishes on the surface.

[0402] The method of the first aspect of present invention suitably provides the treated surface with an antifouling effect, preferably wherein the antifouling effect comprises a property selected from soil repellency, limescale repellency, soap scum repellency, or a combination thereof. The antifouling effect may comprise soil repellency. The antifouling effect may comprise limescale repellency. The antifouling effect may comprise soap scum repellency. The antifouling effect may comprise a combination of soil repellency, limescale repellency, and soap scum repellency.

[0403] According to a third aspect of the present invention, there is provided the use of a polymer as a treatment agent, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0404] (a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and

[0405] (b) a monomer comprising a cationic moiety and an alkenyl group;

[0406] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

[0407] Suitable features of the polymer in the third aspect are as defined in relation to the first aspect of the present invention.

[0408] The use of a polymer according to the third aspect may provide a cleaning effect, a conditioning effect, an antifouling effect, and / or an appearance enhancing effect. The use of a polymer according to the third aspect preferably provides a cleaning effect, a conditioning effect, and / or antifouling effect.

[0409] In some embodiments, the third aspect of the present invention may provide a cleaning effect, i.e. the use of the polymer as a cleaning agent. The polymer suitably provides cleaning, for example the removal of dirt, grease or staining.

[0410] In some embodiments, the third aspect of the present invention may provide a conditioning effect, i.e. the use of the polymer as a conditioning agent. The polymer suitably provides conditioning to textiles.

[0411] In some embodiments, the third aspect of the present invention may provide an appearance enhancing effect, i.e. the use of the polymer as an appearance enhancing agent. The polymer suitably provides the enhancement of visual appearance of a surface, for example increased shine or gloss, or surface repair. Preferably, the third aspect of the present invention may provide an antifouling effect, i.e. the use of the polymer as an antifouling agent. The polymer suitably combats fouling, e.g. prevents or reduces fouling or aids removal of fouling. The polymer is preferably applied before fouling occurs.

[0412] Preferably the antifouling effect comprises a property selected from soil repellency, limescale repellency, soap scum repellency, or a combination thereof. The use of the polymer as an antifouling agent may comprise the use of the polymer to provide soil repellency. The use of the polymer as an antifouling agent may comprise the use of the polymer to provide limescale repellency. The use of the polymer as an antifouling agent may comprise the use of the polymer to provide soap scum repellency. The use of the polymer as an antifouling agent may comprise the use ofthe polymerto provide a combination of soil repellency, limescale repellency and soap scum repellency.

[0413] The polymer may be used in combination with an acid to provide the antifouling effect. Preferably, the polymer is used in combination with an acid to provide limescale repellency. The combination of the polymer and the acid may provide an improved antifouling effect (preferably limescale repellency) compared to the polymer in the absence of the acid.

[0414] Examples of suitable acids include citric acid, acetic acid, lactic acid, glycolic acid, oxalic acid, boric acid, gluconic acid, sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, salicylic acid, tartaric acid, formic acid, and malic acid.

[0415] The polymer may be used in combination with an organic acid to provide the antifouling effect. Preferably, the polymer is used in combination with an organic acid to provide limescale repellency. The combination of the polymer and the organic acid may provide an improved antifouling effect (preferably limescale repellency) compared to the polymer in the absence of the organic acid.

[0416] The organic acid is preferably a polycarboxylic acid. The polycarboxylic acid is suitably citric acid (for example, in the form of citric acid monohydrate).

[0417] The polymer may be used as a treatment agent on a surface, such as a hard surface. Suitably, the surface is selected from dishes, textiles or household surfaces.

[0418] Suitable features ofthe dishes, textiles or household surfaces in the third aspect are as defined in relation to the first aspect ofthe present invention. The surface is preferably a bathroom surface. The bathroom surface is suitably a surface of a toilet, preferably a surface of a toilet bowl.

[0419] The polymer may be comprised in a composition as described herein, for example a composition according to the second aspect of the present invention. In some embodiments, the third aspect of the present invention may provide the use of the composition as a treatment agent.

[0420] The composition may be a liquid composition. The composition is suitably a liquid acidic composition. The liquid acidic composition suitably comprises an acid, suitably an organic acid, preferably a polycarboxylic acid, such as citric acid (for example, in the form of citric acid monohydrate), oxalic acid, tartaric acid and malic acid. The liquid composition may be applied to the surface by pouring or by spraying. The liquid composition may be applied to the surface as a foam, for example by spraying the liquid composition through a foam-forming nozzle.

[0421] Alternatively, the composition may be a solid composition. The solid composition may be a toilet block. Suitably the toilet block is a rim block or a cistern block. The toilet block may be a solid gel.

[0422] The use of the third aspect suitably combats fouling on a bathroom surface (e.g. a surface of a toilet). Combatting fouling may comprise preventing or reducing fouling or aiding removal of fouling on a bathroom surface. Preferably, the use of the third aspect aids removal of fouling on a bathroom surface. Combatting fouling may be achieved by reducing adherence of fouling on a bathroom surface. The polymer may be applied to the bathroom surface prior to the fouling, suitably forming a coating on the bathroom surface. Fouling on the bathroom surface may be removed by rinsing or washing the bathroom surface (e.g. with water). The fouling is suitably selected from soil (e.g. faeces), limescale and / or soap scum.

[0423] In some preferred embodiments, the third aspect of the present invention provides the use of the polymer as an antifouling agent on a bathroom surface.

[0424] According to a fourth aspect of the present invention, there is provided a bathroom treatment product comprising a composition and packaging, wherein the composition comprises a polymer and a surfactant, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0425] (a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and

[0426] (b) a monomer comprising a cationic moiety and an alkenyl group;

[0427] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers. According to the fourth aspect of the present invention, there is preferably provided a bathroom treatment product comprising a composition and packaging, wherein the composition comprises a polymer, and a cationic surfactant and / or an amphoteric or zwitterionic surfactant, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:

[0428] (a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and

[0429] (b) a monomer comprising a cationic moiety and an alkenyl group;

[0430] wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

[0431] Suitable features of the polymer in the fourth aspect are as defined in relation to the first aspect of the present invention. Suitable features of the composition in the fourth aspect are as defined in relation to the second aspect of the present invention.

[0432] The bathroom treatment product of the fourth aspect may be a bathroom cleaning product.

[0433] Suitable bathroom cleaning products include toilet gel cleaners, drain cleaners / treatments and toilet blocks.

[0434] The composition in the fourth aspect is preferably a liquid composition. The packaging may be any packaging suitable for holding a liquid composition.

[0435] The packaging may comprise a bottle. The bottle is suitably adapted for applying a liquid composition to a bathroom surface such as a toilet.

[0436] The bottle may be adapted to apply a liquid composition to the underside of a toilet rim.

[0437] The bottle may be a spray bottle. The spray bottle suitably comprises a spray nozzle and a trigger. The bathroom treatment product may be a spray detergent comprising a spray bottle.

[0438] A particular advantage of the polymers used in the present invention is their storage stability, even when stored in acidic conditions.

[0439] Suitably a composition comprising a polymer as defined in the present invention maintains its stability after storing for at least one month, for example after storing for at least 3 months or at least 6 months under ambient conditions.

[0440] Suitably an acidic composition comprising a polymer as defined in the present invention maintains its stability storing for at least one month, for example after storing for at least 3 months or at least 6 months under ambient conditions. By maintaining its stability we mean that the composition does not decompose or degrade or lose its efficacy.

[0441] Brief Description of the Drawings

[0442] Figure 1 shows photographs of ceramic tiles before and after cleaning of synthetic faeces, wherein the ceramic tiles have been coated with polymer solutions of the present invention.

[0443] Figure 2 shows photographs of ceramic tiles before and after cleaning of synthetic faeces, wherein the ceramic tiles have been coated with a formulation of the present invention.

[0444] Figure 3 shows photographs of ceramic tiles before and after cleaning of synthetic faeces, wherein the ceramic tiles have been coated with a control formulation.

[0445] The invention will now be described with reference to the following non-limiting examples.

[0446] Examples

[0447] Example 1 - Synthesis

[0448] Polymers were synthesised using free radical polymerisation in a water / ethanol mixture (50:50 vol%) for random copolymers with the selected monomers. AIBN was used as initiator (2 wt% by weight of monomers). The temperatures was held at 70 °C.

[0449] The polymers synthesised are shown in Table 1 below:

[0450] Table 1

[0451]

[0452] Comparative polymer AMPS: sodium 2-acrylamido-2-methyl-1 -propanesulfonate

[0453] APTAC: (3-acrylamidopropyl) trimethylammonium chloride

[0454] DADMAC: diallyldimethylammonium chloride

[0455] MAETAC: 2-(methacryloyloxy)ethyl trimethylammonium chloride

[0456] MAPTAC: (3-methacrylamidopropyl) trimethylammonium chloride

[0457] MAA: methacrylic acid

[0458] Example 2 - Antifouling Testing

[0459] A synthetic faeces formulation was prepared from the following ingredients:

[0460]

[0461] Antifouling was tested using a ceramic tile. 150 mL of a polymer solution (1 wt% in distilled water) was applied by pouring the polymer solution down the tile into a beaker and then allowing the tile to sit in the polymer solution in the beaker for 5 minutes. The section of the tile above the level of the solution was allowed to dry while the section of the tile below the level of the solution was coated with the polymer in a hydrated environment. The tile was removed from the solution. The tile was held at an angle of 45 degrees and two samples of the synthetic faeces formulation were applied where the water had run down the tile and then also where the tile had sat in the solution for 5 minutes. The faeces were subsequently washed off with 150 mL of a 1 wt% SLES (sodium lauryl ether sulfate) surfactant solution without agitation. The tile was then left for 2 minutes and the removal was assessed visually compared to the same test conducted on a noncoated tile (control) above and below the solution level in the beaker. The results are shown in Table 2 below.

[0462] Table 2

[0463]

[0464] Comparative polymer

[0465] Example 3 - Antifouling Test in a Toilet

[0466] A 1 kg synthetic faeces formulation was prepared from the following ingredients:

[0467]

[0468] The preparation procedure was as follows:

[0469] 1. The dry powders were added to a beaker and thoroughly mixed.

[0470] 2. Oleic acid was added and mixed thoroughly.

[0471] 3. Miso paste was added and the mixture was stirred until homogenised.

[0472] 4. Deionised (DI) water was slowly added while stirring.

[0473] 5. The beaker was covered with cling film and left to stand at room temperature for 1.5 hours.

[0474] A cleaned ceramic tile was coated in a polymer solution comprising Polymer 1. The synthetic faeces were applied (8.5 g) and within 5 minutes the tile was put in a toilet bowl in a horizontal position and flushed with 6 L of tap water. The tile was then allowed to dry in an oven for assessment. This was repeated 4 times. A picture ofthe tile was taken and analysed with Imaged as follows:

[0475] The picture was converted to a binary image (black and white) and pixel statistics were analysed. The software calculated the percentage ofthe total area with black pixels (corresponding to the amount of soil). The percentage of black pixels before flushing / cleaning and after flushing / cleaning was compared and expressed as the soil removal index. The results are shown in Table 3 below.

[0476] Table 3

[0477]

[0478] Figure 1 shows photographs of the ceramic tiles coated with (a) Polymer 1 (1 wt%) in distilled water and (b) Polymer 1 (1 wt%) and citric acid monohydrate (3 wt%) in distilled water.

[0479] Example 4 - Anti-Limescale Testing

[0480] One side of a black tile was treated with a polymer solution and the other side was treated with hard water (350 ppm CaCOs and 175 ppm MgCOs) by placing the polymer solution or hard water on the tile surface and uniformly spreading the polymer solution or hard water using a paper tissue. The tile surface was wiped until completely dry. Then, a concentrated salt solution (CaCh, MgCh in water / EtOH) was sprayed three times onto the whole tile and then sprayed with a solution of NaHCCh. The tile was allowed to dry for 15 minutes and the procedure was repeated two times. The whole tile was then rinsed with distilled tap water (600 mL / min) for 60 seconds and allowed to dry for 30 minutes before the appearance was evaluated. The results are shown in Table 4 below.

[0481] Table 4

[0482]

[0483] The polymer solution comprising citric acid resulted in significantly less limescale than the polymer solution without citric acid. Example 5 - Formulations

[0484] Formulations containing Polymer 1 were prepared as shown in Table 5. Amounts shown are in weight % based on the total weight of the formulation.

[0485] Table 5

[0486]

[0487] Example 6 - Antifouling Test in a Toilet

[0488] A 1 kg synthetic faeces formulation was prepared as described in Example 3.

[0489] A cleaned ceramic tile was coated in a formulation and allowed to dry. The controls were the corresponding formulations without Polymer 1. The synthetic faeces were applied (8.5 g) and within 5 minutes the tile was put in a toilet bowl in a horizontal position and flushed with 6 L of tap water. The tile was then allowed to dry in an oven for assessment. This was repeated 4 times and evaluation was completed visually. The results are shown in Table 6 below.

[0490] Table 6

[0491]

[0492]

[0493] Figure 2 shows photographs of the ceramic tiles coated with Formulation 1 before and after cleaning of the synthetic faeces. Figure 3 shows photographs of the ceramic tiles coated with the corresponding control formulation before and after cleaning of the synthetic faeces.

[0494] Example 7 - Anti-Limescale Testing

[0495] One side of a black tile was treated with a formulation and the other side was treated with hard water (350 ppm CaCOs and 175 ppm MgCOs) by placing the formulation or hard water on the tile surface and uniformly spreading the formulation or hard water using a paper tissue. The tile surface was wiped until completely dry. Then, a concentrated salt solution (CaCh, MgCh in water / EtOH) was sprayed three times onto the whole tile and then sprayed with a solution of NaHCOs. The tile was allowed to dry for 15 minutes and the procedure was repeated two times. The whole tile was then rinsed with distilled tap water (600 mL / min) for 60 seconds and allowed to dry for 30 minutes before the appearance was evaluated. The results are shown in Table 7 below.

[0496] Table 7

[0497]

[0498] Formulations 1 and 2 also resulted in less limescale compared to corresponding control formulations without Polymer 1. The tiles treated with the control formulations showed a large number of white limescale spots whereas tiles treated with Formulations 1 and 2 were completely free of limescale spots. The tiles treated with Formulations 1 and 2 showed good limescale prevention even after 3 to 4 applications of limescale.

[0499] Example 8 - Anti-Limescale Performance in Toilet Gels

[0500] The limescale prevention properties of the following samples were tested:

[0501] • Sample 1 : Commercial limescale remover aqueous gel based on 5-10 wt% HCI, <2.5 wt% tallowbis(2-hydroxyethyl)amine, 0.25 - 1 wt% Tallowtrimonium Chloride, and 0.25 - 1 wt% C10-16 ethoxylated alcohol.

[0502] • Sample 2: Sample 1 + 1 wt% Polymer 1 10 mL of each sample was applied uniformly onto individual cleaned black enamelled ceramic tiles (6 replicates for each sample). The tiles were allowed to stand and dry for 10 minutes. Each tile was then positioned inside a toilet bowl, and a flushing program was started. The flushing program consisted of flushing 6 L of tap water (330 ppm CaCCh), 17 times a day for 7 days. Photographs were taken after the 7thday and analysed with Image J as described in Example 3. The limescale deposit was calculated as the percentage of the tile surface covered with limescale spots. The average of the 6 replicates was recorded for each sample.

[0503]

[0504] Comparative

[0505] Sample 2 using Polymer 1 according to the invention reduced the limescale deposition for at least 1 week, compared to the commercial benchmark without the polymer (Sample 1).

[0506] Example 9 - Anti-Limescale Performance on Aged Samples

[0507] Samples 1 and 2 from Example 8 were stored for 2 months at 40 °C. The anti-limescale performance test from Example 8 was repeated for 2 replicates for each sample, but the tile was brushed homogeneously after applying the sample. The tile was then left to dry for 10 minutes. The tile area covered with limescale was calculated as described in Example 8 and averaged for the 2 replicates.

[0508]

[0509] Comparative

[0510] Example 10 - Anti-Fouling and Anti-Limescale Performance in Toilet Blocks

[0511] The following toilet rim block formulations were prepared. The table shows ingredients in active wt%.

[0512]

[0513]

[0514] Comparative

[0515] 11 :1 mixture of Acusol 445G (homopolymer of acrylic acid having a weight average molecular weight of approximately 4500) and Acusol 588G (copolymer of acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) having a weight average molecular weight of 14000 to 18000)

[0516] Anti-fouling

[0517] An aqueous solution of 0.033 g / L of each toilet block was prepared to simulate the amount of product dosed in the flush of a toilet. 100 mL of the toilet block solution was poured onto 10x10 cm white glazed ceramic tiles 5 times (total of 500 mL poured). The ceramic tile was left to dry in a vertical position. 8.5 g of the synthetic faeces formulation described in Example 3 was spread uniformly on the tile. A photograph of the soiled tile was taken and then the tile was flushed with 6 L of hard water (330 ppm CaCOs) in a toilet bowl. The tile was left to dry, and a second photograph was taken. The images were analysed with Imaged to determine the % of synthetic faeces removed. The test was performed in duplicate, and the average was recorded.

[0518]

[0519] Comparative

[0520] The Toilet block 2 of the invention repelled almost 100% of the organic soil applied to the tile.

[0521] Anti-limescale

[0522] 200 mL of the 0.033 g / L toilet block aqueous solution was poured onto 20x20 cm black glazed ceramic tiles 4 times (total of 800 mL poured). The ceramic tile was left to dry for 15 minutes in a vertical position. 0.2g of a solution of CaCh and MgCh was applied onto the tiles 3 times followed by 0.2g of a solution of NaHCOs to create a limescale deposit. This process was repeated 3 times. After each application, the tiles were left to dry in a vertical position. A photograph of the soiled tile was taken and then the tile was rinsed with 600 mL of distilled water at a speed of 10 mL / sec. The rinsed tiles were left to dry, and a second photograph was taken. The images were analysed with Imaged to determine the % of limescale deposited on the tile before and after rinsing.

[0523]

[0524] Comparative

Claims

Claims1. A method of treating a surface, the method comprising the step of contacting the surface with a composition comprising a polymer,wherein the polymer is obtainable by polymerising a mixture of monomers comprising:(a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and(b) a monomer comprising a cationic moiety and an alkenyl group;wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

2. The method of claim 1. wherein the surface is selected from dishes, textiles, or household surfaces.

3. The method of claim 1 or claim 2, wherein the surface is a bathroom surface.

4. The method of claim 3, wherein the bathroom surface is a surface of a toilet.

5. A composition comprising a polymer and a surfactant, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:(a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and(b) a monomer comprising a cationic moiety and an alkenyl group;wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

6. A bathroom treatment product comprising a composition and packaging, wherein the composition comprises a polymer and a surfactant, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:(a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and(b) a monomer comprising a cationic moiety and an alkenyl group;wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

7. The composition or product of claim 5 or claim 6, wherein the composition comprises a cationic surfactant and / or an amphoteric or zwitterionic surfactant.

8. The method, composition, or product of any preceding claim, wherein the composition is a liquid composition.

9. The method, composition, or product of any preceding claim, wherein the composition is acidic and has a pH of 6 or less.

10. Use of a polymer as a treatment agent, wherein the polymer is obtainable by polymerising a mixture of monomers comprising:(a) a monomer comprising an anionic moiety and an alkenyl group, wherein the anionic moiety is selected from a sulfate ester group, a sulfonic acid group, or a salt thereof; and(b) a monomer comprising a cationic moiety and an alkenyl group;wherein monomer (a) and monomer (b) provide at least 95 wt% of the mixture of monomers.

11. The use of claim 10, wherein the polymer is used in combination with an organic acid, preferably a polycarboxylic acid, to provide an antifouling effect, preferably limescale repellency.

12. The use of claim 10 or claim 11 , wherein the polymer is used as a treatment agent on a surface selected from dishes, textiles, or household surfaces.

13. The use of any of claims 10 to 12, wherein the polymer is used as a treatment agent on a bathroom surface.

14. The method, composition, product, or use of any preceding claim, wherein the mixture of monomers comprises monomer (a) and monomer (b) in a molar ratio of from 60:40 to 40:60.

15. The method, composition, product, or use of any preceding claim, wherein monomer (a) is represented by formula (I):H2C=CR1-CO-X1-R2-X2-SO3M (I)wherein R1is hydrogen or an optionally substituted hydrocarbyl group;R2is an optionally substituted hydrocarbylene group;X1is O or NR3;R3is hydrogen or an optionally substituted hydrocarbyl group;X2is a bond or O; andM is hydrogen or a cation.

16. The method, composition, product, or use of claim 15, wherein R1is hydrogen or an unsubstituted hydrocarbyl group;R2is an unsubstituted hydrocarbylene group;X1is O or NR3;R3is hydrogen or an unsubstituted hydrocarbyl group;X2is a bond or O; andM is hydrogen or a cation.

17. The method, composition, product, or use of any preceding claim, wherein monomer (a) is represented by formula (IA):H2C=CR1-CO-X1-R2-SO3M (IA)wherein R1is hydrogen or an unsubstituted alkyl group having from 1 to 12 carbon atoms; R2is an unsubstituted alkylene group having from 1 to 12 carbon atoms;X1is O or NR3;R3is hydrogen or an unsubstituted alkyl group having from 1 to 12 carbon atoms; andM is hydrogen, ammonium, a substituted ammonium, or an alkali metal.

18. The method, composition, product, or use of any preceding claim, wherein monomer (a) is represented by formula (IA):H2C=CR1-CO-X1-R2-SO3M (IA)wherein R1is hydrogen or a methyl group;R2is CH2-CH2, CH2-CH2-CH2or C(CH3)2-CH2;X1is O or NH; andM is an alkali metal.

19. The method, composition, product, or use of any preceding claim, wherein monomer (b) is represented by formula (II):N+R4R5R6R7A- (||)wherein R4, R5, R6and R7are each independently an optionally substituted hydrocarbyl group, wherein at least one of R4, R5, R6and R7independently comprises an alkenyl group and two or more of R4, R5, R6and R7are optionally combined to form a cyclic moiety; andA- is an anion.

20. The method, composition, product, or use of claim 19, wherein at least one of R4, R5, R6and R7is independently represented by formula (A):CH2=CR8-L- (A)wherein R8is hydrogen or an optionally substituted hydrocarbyl group; and L is a linker moiety.

21. The method, composition, product, or use of claim 20, wherein L may be an optionally substituted hydrocarbylene group; orL may have the formula:-CO-X3-R9-wherein R9is an optionally substituted hydrocarbylene group;X3is O or NR10; andR10is hydrogen or an optionally substituted hydrocarbyl group.

22. The method, composition, product, or use of any preceding claim, wherein monomer (b) is represented by formula (II):N+R4R5R6R7A- (II)wherein R4and R5are each independently represented by formula (A1):CH2=CH-(CH2)n- (A1)n is from 1 to 4;R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms; andA- is an anion; orR4is represented by formula (A2):CH2=CR8-CO-X3-R9- (A2)R5, R6and R7are each independently an unsubstituted alkyl group having from 1 to 4 carbon atoms;R8is hydrogen or a methyl group;R9is an unsubstituted alkylene group having from 2 to 4 carbon atoms;X3is O or NH; andA-is an anion.

23. The method, composition, product or use according to any preceding claim, wherein the mixture of monomers consists of monomer (a) and monomer (b).

24. The method, composition, product or use according to any preceding claim, which provides an antifouling effect, preferably wherein the antifouling effect comprises a property selected from soil repellency, limescale repellency, soap scum repellency, or a combination thereof.

25. The method, composition, product or use according to any preceding claim which provides a cleaning effect, a conditioning effect, an antifouling effect, and / or an appearance enhancing effect.

Images