The present disclosure relates to an improved automatic dishwashing composition. Specifically, the present invention relates to an automatic dishwashing composition which shows improvement in the removal of bleachable stains in automatic ware washing machines, a use of said composition and a method of automatic dishwashing using said composition.

The primary focus of dishwashing is the removal of soils and stains from wares. One component of this is the removal of bleachable stains from ware. To this end dishwashing compositions and products include bleaches. Automatic dishwashing processes also involve the drying of wares. Accordingly, automatic dishwashing compositions and products contain a number of components aimed at achieving the various desired effects including removal of soils and stains and drying.

In order to minimise the use of potentially expensive components and to ensure compatibility with existing automatic dishwashers there is a demand to optimise wash performance without significantly increasing the quantity of dishwashing composition or product required per wash. Accordingly, there is a desire to improve the performance of the various components.

In particular, there is a desire for a dishwashing composition that can provide an improved performance on bleachable stains, without the addition of a greater quantity of bleaches and/or bleach activators/catalysts.

It is in an object of the present invention to provide an improved automatic dishwashing composition, which provides improved bleach performance with respect to prior art compositions or, at least, provide a commercially useful alternative thereto.

According to a first aspect the present disclosure provides an automatic dishwashing composition comprising a sulfonic acid copolymer, wherein the copolymer comprises monomer units derived from:

(a) a first a,b-unsaturated carboxylic acid monomer,

(b) a second a,b-unsaturated carboxylic acid monomer, and

(c) a sulfonic acid group-containing monomer;

wherein the first a,b-unsaturated carboxylic acid monomer is different from the second a,b-unsaturated carboxylic acid monomer. The present inventors have surprisingly found that the inclusion of a sulfonic acid copolymers comprising two distinct a,b-unsaturated carboxylic acid monomers in an automatic dishwashing composition significantly improves bleaching performance, even when included in only a small amount.

In another aspect the present disclosure provides an automatic dishwashing product comprising the composition as claimed in any of the preceding claims, which is: in a unit dose form; and/or

housed within a water soluble or water dispersible film or container, preferably a polyvinyl alcohol film or container; and/or

in form of one or more tablets.

By tablets we include all forms of compressed power, such as micro-tablets comprised of compressed powder. These micro-tablets, which could also be described as granules, can be dosed as part of separate chemical steps in the dishwashing process.

In another aspect the present disclosure provides a method of automatic dishwashing, comprising supplying a composition or a product as disclosed herein to an automatic dishwasher, and releasing the composition or product into a wash cycle of the automatic dishwasher.

In another aspect the present disclosure provides the use of a sulfonic acid copolymer for improving bleach performance in an automatic dishwashing process, wherein the copolymer comprises monomer units derived from:

(a) a first a,b-unsaturated carboxylic acid monomer,

(b) a second a,b-unsaturated carboxylic acid monomer, and

(c) a sulfonic acid group-containing monomer;

wherein the first a,b-unsaturated carboxylic acid monomer is different from the second a,b-unsaturated carboxylic acid monomer.

The present invention will now be further described. In the following passages different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

The invention relates to an automatic dishwashing composition comprising a sulfonic acid copolymer. Advantageously the composition of the present disclosure provides improved bleaching performance with respect to prior art automatic dishwashing compositions.

The sulfonic acid copolymer comprises monomer units derived from:

(a) a first a,b-unsaturated carboxylic acid monomer,

(b) a second a,b-unsaturated carboxylic acid monomer, and

(c) a sulfonic acid group-containing monomer;

wherein the first a,b-unsaturated carboxylic acid monomer is different from the second a,b-unsaturated carboxylic acid monomer.

By“copolymer” it is meant a polymer derived from at least two (in the present case at least three) monomer units. By“different” it is meant that the first a,b-unsaturated carboxylic acid monomer and the second a, b-un saturated carboxylic acid monomer are chemically distinct, that is, they have different structural formulae.

Suitable a, b-un saturated carboxylic acid monomers for use in the present invention include, but are not limited to, (meth)acrylic acid, maleic acid, itaconic acid, ethacrylic acid, a-chloroacrylic acid, a-cyanoacrylic acid, crotonic acid and a-phenyl-acrylic acid.

Preferably the first a,b-unsaturated carboxylic acid monomer is itaconic acid, or an anhydride, ester or salt thereof. More preferably the first a,b-unsaturated carboxylic acid monomer is itaconic acid.

Preferably the second a,b-unsaturated carboxylic acid monomer is (meth)acrylic acid, or an anhydride, ester or salt thereof. More preferably the second a,b- unsaturated carboxylic acid monomer is acrylic acid.

Preferably the copolymer comprises monomer units derived from the first and second a,b-unsaturated carboxylic acid monomers in a total amount of from 1 to 99.9 wt.%, more preferably from 50 to 95 wt.%. Preferably the sulfonic acid group-containing monomer has the formula (i):

R ¹ R ² C=CR ³ C(=0)NHCR ⁴ R ⁵ CH ₂ S03X (i) wherein R ¹ -R ⁵ are independently H or C1-C16 alkyl and X is H or a cation.

The alkyl groups of formula (i) may be linear, branched or cyclic. Preferably the alkyl groups are linear.

Preferably the sulfonic acid group-containing monomer has the formula (i) wherein: each of R ¹ , R ² , and R ³ are H; and/or

R ⁴ and R ⁵ are each independently methyl or a linear CM alkyl; and/or

X is H or sodium, potassium, ammonium or alkylated ammonium cation.

Preferably the first a,b-unsaturated carboxylic acid monomer is itaconic acid, the second a, b-un saturated carboxylic acid monomer is (meth)acrylic acid, and the sulfonic acid group-containing monomer is either 2-acrylamido-2-methylpropane sulfonic acid or 2-acrylamidohexadecane-1 -sulfonic acid.

Preferably the copolymer comprises:

from 50 to 89.9 wt.% monomer units derived from itaconic acid, preferably from 60 to 80 wt.%;

from 10 to 30 wt.% monomer units derived from (meth)acrylic acid, preferably from 15 to 25 wt.%; and

from 0.1 to 30 wt.% monomer units derived from 2-acrylamido-2- methylpropane sulfonic acid or 2-acrylamidohexadecane-1 -sulfonic acid, preferably 1 to 25 wt.%.

In a preferred embodiment the copolymer is a copolymer comprising:

from 50 to 70 wt.% monomer units derived from itaconic acid, preferably 60 to 65 wt.%, preferably about 63.5 wt.%;

from 15 to 25 wt.% monomer units derived from acrylic acid, preferably 15 to 20 wt.%, preferably about 17.5 wt.%; and

from 15 to 25 wt.% monomer units derived 2-acrylamido-2-methylpropane sulfonic acid, preferably about 19 wt.%.

In a preferred embodiment the copolymer is a copolymer comprising: from 55 to 79 wt.% monomer units derived from itaconic acid, preferably 65 to 75 wt.%, preferably about 71 wt.%;

from 20 to 30 wt.% monomer units derived from acrylic acid, preferably from 20 to 25 wt.%, preferably about 23 wt.%; and

from 1 to 15 wt.% monomer units derived from 2-acrylamidohexadecane-1 - sulfonic acid, preferably 1 to 10 wt.%, preferably about 6 wt.%.

It has been found that these sulfonic acid copolymers are particularly effective at increasing the bleaching effect achieved in an automatic dishwashing method.

Optionally, the monomer units derived from the first and second a,b-unsaturated carboxylic acid monomers in the copolymer are from 0.1 to 60 mol% esterified. Partial esterification may be the result of the presence of alcohol solvents (such as isopropyl alcohol, ethanol or methanol) during production or storage of the polymers.

In some embodiments the polymer may be substantially, essentially or completely free of esterified monomer units.

Suitable sulfonic acid polymers for use in the present invention are disclosed in WO 2015/042013, WO 2014/143773, and WO 2015/138872.

Preferably the copolymer is present in the automatic dishwashing composition in an amount of up to 12 wt.% based on the total weight of the product, preferably up to 10 wt.%, preferably up to 8 wt.%, or even up to 6 wt.%. The present inventors have surprisingly found that the inclusion of even a low amount of the copolymer significantly improves bleaching performance. The minimum quantity of the copolymer may be 1 wt%, 0.9 wt%, 0.5 wt%, or even 0.1 wt%, based on the total weight of the product.

Preferably, the automatic dishwashing composition further comprises:

one or more additional bleaches, and/or

one or more bleach activators and/or catalysts, and/or

one or more builders, and/or

one or more surfactants, and/or

one or more enzymes. The automatic dishwashing composition may be in a solid of liquid form, such as a solution, a gel, a powder or a compressed tablet. Methods of producing such forms are well known in the art.

The automatic dishwashing composition may be an automatic dishwashing detergent composition.

Bleaches

The automatic dishwashing compositions preferably comprises a bleach component or material.

The bleach component (also referred to as the bleaching agent) is present in an amount up to 40% by weight of the total composition, preferably from 0.1 to 35% by weight, such as from 1 to 30% by weight, from 5 to 28% by weight, or preferably from 10 to 25% by weight.

In a preferred embodiment, the bleach component is present in an amount of from 15.5% or greater, such as from 15.5 to 25% by weight, or even 16 to 20% by weight.

For example, the bleach material may comprise an oxygen or chlorine based bleach. The bleach material may be selected from any conventional bleach material known to be used in automatic dishwashing compositions. The material may comprise the active bleach species itself or a precursor to that species. For example, the bleach material may comprise at least one inorganic peroxide or organic peracid or a chlorine based bleach including derivatives and salts thereof or mixtures thereof. Inorganic peroxides include percarbonates, perborates, persulphates, hydrogen peroxide and derivatives and salts thereof. The sodium and potassium salts of these inorganic peroxides are suitable, especially the sodium salts. Sodium percarbonate and sodium perborate are most preferred, especially sodium percarbonate.

The automatic dishwashing compositions may also comprise bleach additives or bleach activation catalysts. The composition may preferably comprise one or more bleach activators or bleach catalysts depending upon the nature of the bleaching compound. Any suitable bleach activator may be included, for example TAED, if this is desired for the activation of the bleach material. Bleach activators are preferably present in an amount of from 0.6 to 9% by weight of the composition, such as from 3 to 8.5%, or advantageously from 4% to 7.5%.

Any suitable bleach catalyst may be used, for example manganese acetate or dinuclear manganese complexes such as those described in EP 1 ,741 ,774.

Such manganese catalysts are preferably present in an amount of from less than 1 .8% by weight, such as from 0.01 to 1 .5% by weight, or 0.02 to 0.45%, or advantageously from 0.3 to 0.9% by weight.

The organic peracids such as perbenzoic acid and peroxycarboxylic acids e.g. PAP do not require the use of a bleach activator or catalyst as these bleaches are active at relatively low temperatures such as about 30°C and this contributes to such bleach materials being especially preferred according to the present invention.

The bleach system combining the bleach, bleach activator and bleach catalyst in the preferred quantities set our above has been found to have particularly beneficial effect in combination with the copolymer as described above.

Builders

The automatic dishwashing compositions may comprise a builder (or co-builder). The builder / co-builder may be either a phosphorous-containing builder or a phosphorous-free builder as desired. In many jurisdictions, phosphate builders are banned. In an embodiment, the automatic dishwashing composition is phosphate- free. In an embodiment, the automatic dishwashing product is phosphate-free.

If phosphorous-containing builders are to be used it is preferred that mono- phosphates, di-phosphates, tri-polyphosphates or oligomeric-polyphosphates are used. The alkali metal salts of these compounds are preferred, in particular the sodium salts. An especially preferred builder is sodium tripolyphosphate (STPP). Conventional amounts of the phosphorous-containing builders may be used typically in the range of from 15 % by weight to 60 % by weight, such as from 20 % by weight to 50 % by weight or from 25 % by weight to 40 % by weight.

If phosphorous-free builder is included, it is preferably chosen from succinate based compounds. The terms 'succinate based compound' and 'succinic acid based compound' are used interchangeably herein. Conventional amounts of the succinate based compounds may be used, typically in the range of from 5% by weight to 80% by weight, such as from 15 % by weight to 70% by weight or from 20 % by weight to 60 % by weight. The compounds may be used individually or as a mixture.

Other suitable builders are described in US 6,426,229 which are incorporated by reference herein. Particular suitable builders include; for example, aspartic acid-N- monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N- monopropionic acid (ASMP), iminodisuccinic acid (IDA), N-(2-sulfomethyl) aspartic acid (SMAS), N- (2-sulfoethyl)aspartic acid (SEAS), N- (2-sulfomethyl)glutamic acid (SMGL), N-(2- sulfoethyl)glutamic acid (SEGL), N- methyliminodiacetic acid (MIDA), a- alanine- N,N-diacetic acid (a-ALDA), -alanine-N,N-diacetic acid (b-ALDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine- N,N-diacetic acid (PHDA), anthranilic acid-N,N- diacetic acid (ANDA), sulfanilic acid- N,N-diacetic acid (SLDA), taurine-N, N-diacetic acid (TUDA) and sulfomethyl-N,N- diacetic acid (SM DA) and alkali metal salts or ammonium salts thereof.

Further preferred succinate compounds are described in US-A-5,977,053 and have the formula:

in which R, R ¹ , independently of one another, denote H or OH; R ² , R ³ , R ⁴ , R ⁵ , independently of one another, denote a cation, hydrogen, alkali metal ions and ammonium ions, ammonium ions having the general formula R ⁶ R ⁷ R ⁸ R ⁹ N+ and R ⁶ , R ⁷ , R ⁸ , R ⁹ , independently of one another, denote hydrogen, alkyl radicals having 1 to 12 C atoms or hydroxyl-substituted alkyl radicals having 2 to 3 C atoms.

Preferred examples include tetrasodium imminosuccinate. Iminodisuccinic acid (IDS) and (hydroxy)iminodisuccinic acid (HIDS) and alkali metal salts or ammonium salts thereof are especially preferred succinate based builder salts. The phosphorous-free co-builder may also or alternatively comprise non-polymeric organic molecules with carboxylic group(s). Builder compounds which are organic molecules containing carboxylic groups include citric acid, fumaric acid, tartaric acid, maleic acid, lactic acid and salts thereof. In particular, the alkali or alkaline earth metal salts of these organic compounds may be used, and especially the sodium salts. An especially preferred phosphorous-free builder is sodium citrate. Such polycarboxylates which comprise two carboxyl groups include, for example, water-soluble salts of, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid. Such polycarboxylates which contain three carboxyl groups include, for example, water-soluble citrate. Correspondingly, a suitable hydroxycarboxylic acid is, for example, citric acid.

Three other highly preferred builders are MGDA, GLDA and malonyl lactate, particularly MGDA.

Preferred secondary builders include homopolymers and copolymers of polycarboxyl ic acids and their partially or completely neutralized salts, monomeric polycarboxyl ic acids and hydroxycarboxylic acids and their salts, phosphates and phosphonates, and mixtures of such substances. Preferred salts of the abovementioned compounds are the ammonium and/or alkali metal salts, i.e. the lithium, sodium, and potassium salts, and particularly preferred salts is the sodium salts. Secondary builders which are organic are preferred. A polymeric polycarboxyl ic acid is the homopolymer of acrylic acid. Other suitable secondary builders are disclosed in WO 95/01416, to the contents of which express reference is hereby made.

Preferably the total amount of builder present in the composition is at least 20 % by weight, and most preferably at least 25 % by weight, preferably in an amount of up to 70 % by weight, preferably up to 60 % by weight, more preferably up to 45 % by weight. The actual amount used in the compositions will depend upon the nature of the builder used. If desired a combination of phosphorous-containing and phosphorous-free builders may be used.

Surfactants

Surfactant may also be included in the automatic dishwashing compositions and any of nonionic, anionic, cationic, amphoteric or zwitterionic surface active agents or suitable mixtures thereof may be used. Many such suitable surfactants are described in Kirk Othmer's Encyclopaedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360- 379, "Surfactants and Detersive Systems", incorporated by reference herein. In general, bleach-stable surfactants are preferred according to the present invention.

In the case of ADW compositions, it is preferred to minimise the amount of anionic surfactant. Preferably the composition comprises no more than 2 wt %, no more than

1 wt %, or no, anionic surfactant. Preferably the composition comprises no more than

2 wt %, no more than 1 wt %, or no, ionic surfactant of any type. Non-ionic surfactants are especially preferred instead for automatic dishwashing compositions.

A preferred class of non-ionic surfactants is ethoxylated non-ionic surfactants prepared by the reaction of a monohydroxy alkanol or alkylphenol with 6 to 20 carbon atoms. Preferably the surfactants have at least 12 moles, particularly preferred at least 16 moles, and still more preferred at least 20 moles, such as at least 25 moles, of ethylene oxide per mole of alcohol or alkylphenol. Particularly preferred non-ionic surfactants are the non-ionics from a linear chain fatty alcohol with 16-20 carbon atoms and at least 12 moles, particularly preferred at least 16 and still more preferred at least 20 moles, of ethylene oxide per mole of alcohol.

According to one embodiment of the invention, the non-ionic surfactants additionally may comprise propylene oxide units in the molecule. Preferably these PO units constitute up to 25 % by weight, preferably up to 20 % by weight, and still more preferably up to 15 % by weight of the overall molecular weight of the non-ionic surfactant.

Surfactants which are ethoxylated mono-hydroxy alkanols or alkylphenols, which additionally comprises polyoxyethylene-polyoxypropylene block copolymer units may be used. The alcohol or alkylphenol portion of such surfactants constitutes more than 30 % by weight, preferably more than 50 % by weight, more preferably more than 70 % by weight of the overall molecular weight of the non-ionic surfactant.

Another class of suitable non-ionic surfactants includes reverse block copolymers of polyoxyethylene and polyoxypropylene and block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane.

Another preferred class of nonionic surfactant can be described by the formula: Ri0[CH2CH(CH3)0]x[CH2CH20]y[CH2CH(0H)R2] where Ri represents a linear or branched chain aliphatic hydrocarbon group with 4-18 carbon atoms or mixtures thereof, R2 represents a linear or branched chain aliphatic hydrocarbon rest with 2- 26 carbon atoms or mixtures thereof, x is a value between 0.5 and 1 .5, and y is a value of at least 15.

Another group of preferred non-ionic surfactants are the end-capped polyoxyalkylated non-ionics of formula:

Ri0[CH2CH(R3)0]x[CH2]kCH(0H)[CH2]j0R2 where R1 and R2 represent linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1 -30 carbon atoms, R3 represents a hydrogen atom or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, x is a value between 1 and 30 and, k and j are values between 1 and 12, preferably between 1 and 5. When the value of x is >2 each R3 in the formula above can be different. R1 and R2 are preferably linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 6-22 carbon atoms, where groups with 8 to 18 carbon atoms are particularly preferred. For the group R3, H, methyl or ethyl is particularly preferred. Particularly preferred values for x are comprised between 1 and 20, preferably between 6 and 15.

As described above, in case x>2, each R3 in the formula can be different. For instance, when x=3, the group R3 could be chosen to build ethylene oxide (R3=FI) or propylene oxide (R ₃ = methyl) units which can be used in every single order for instance (PO)(EO)(EO), (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO),

(PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x is only an example and bigger values can be chosen whereby a higher number of variations of (EO) or (PO) units would arise. Particularly preferred end-capped polyoxyalkylated alcohols of the above formula are those where k=1 and j=1 originating molecules of simplified formula:

RI0[CH2CH(R ₃ )0]XCH2CH(0H)CH ₂ 0R2

Another group of preferred non-ionic surfactants are mixed alkoxylate fatty alcohol nonionic surfactants The standard non-ionic surfactant structure is based on a fatty alcohol with a carbon C8 to C20 chain, wherein the fatty alcohol has been ethoxylated or propoxylated. The degree of ethoxylation is described by the number of ethylene oxide units (EO), and the degree of propoxylation is described by the number of propylene oxide units (PO). Such surfactants may also comprise butylene oxide units (BO) as a result of butoxylation of the fatty alcohol. Preferably, this will be a mix with PO and EO units. The surfactant chain can be terminated with a butyl (Bu) moiety.

Preferably the mixed alkoxylate fatty alcohol non-ionic surfactants comprise between 3 to 5 moles of the higher alkoxylate group and between 6 to 10 moles the higher lower group. Especially preferred are mixed alkoxylate fatty alcohol nonionic surfactants having 4 or 5 moles of the higher alkoxylate group and 7 or 8 moles of the lower alkoxylate group. According to one aspect of the invention a mixed alkoxylate fatty alcohol nonionic surfactant having 4 or 5 PO moles and 7 or 8 EO moles is especially preferred and good results have been obtained with for surfactants with 4 PO moles and 8 EO moles. In an especially preferred embodiment the mixed alkoxylate fatty alcohol nonionic surfactant is C12-15 8EO/4PO (commercially available as Genapol EP 2584 ex Clariant, Germany).

The use of mixtures of different non-ionic surfactants is suitable in the context of the present invention, for instance mixtures of alkoxylated alcohols and hydroxy group containing alkoxylated alcohols.

Other suitable surfactants are disclosed in WO 95/01416, to the contents of which express reference is hereby made.

Preferably the non-ionic surfactants are present in the detergent composition in an amount of from 0.1 % by weight to 20 % by weight, more preferably 1 % by weight to 15 % by weight, such as 2 % to 10 % by weight, based on the total weight of the detergent composition.

The skilled person will be aware of the kinds of ingredients needed to form effective ADW (automatic dishwashing) compositions. The compositions may comprise any other suitable ingredients known in the art. For example, the compositions may include enzymes. It is preferred that the enzyme is selected from proteases, lipases, amylases, cellulases and peroxidases, with proteases and amylases, especially proteases being most preferred. It is most preferred that protease and/or amylase enzymes are included in the compositions according to the invention as such enzymes are especially effective in dishwashing detergent compositions. Any suitable species of these enzymes may be used as desired. More than one species may be used.

Additional components

The ADW compositions may comprise one or more additional anti-corrosion agents. These anti-corrosion agents may provide further benefits against corrosion of glass and/or metal and the term encompasses agents that are intended to prevent or reduce the tarnishing of non-ferrous metals, in particular of silver and copper.

It is known to include a source of multivalent ions in detergent compositions, and in particular in automatic dishwashing compositions, for anti-corrosion benefits. For example, multivalent ions and especially zinc, bismuth and/or manganese ions have been included for their ability to inhibit such corrosion. Organic and inorganic redox- active substances which are known as suitable for use as silver/copper corrosion inhibitors are mentioned in WO 94/26860 and WO 94/26859. Suitable inorganic redox-active substances are, for example, metal salts and/or metal complexes chosen from the group consisting of zinc, bismuth, manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and/or complexes, the metals being in one of the oxidation states II, III, IV, V or VI. Particularly suitable metal salts and/or metal complexes are chosen from the group consisting of MnS04, Mn(ll) citrate, Mn(ll) stearate, Mn(ll) acetylacetonate, Mn(ll) [1 -hydroxyethane-1 , 1 -diphosphonate], V2O5, V2O4, VO2, T1OSO4, K2T1F6, K2ZrF6, C0SO4, CO(N03)2, Zinc acetate, zinc sulphate and Ce(N03)3. Any suitable source of multivalent ions may be used, with the source preferably being chosen from sulphates, carbonates, acetates, gluconates and metal-protein compounds. Zinc salts are especially preferred corrosion inhibitors.

Preferred silver/copper anti-corrosion agents are benzotriazole (BTA) or bis- benzotriazole and substituted derivatives thereof. Other suitable agents are organic and/or inorganic redox-active substances and paraffin oil. Benzotriazole derivatives are those compounds in which the available substitution sites on the aromatic ring are partially or completely substituted. Suitable substituents are linear or branch- chain C1 -20 alkyl groups and hydroxyl, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine. A preferred substituted benzotriazole is tolyltriazole. Any conventional amount of the anti-corrosion agents may be included. Flowever, it is preferred that they are present in an total amount of from 0.01 % by weight to 5% by weight, preferably 0.05 % by weight to 3 % by weight, more preferably 0.1 % by weight to 2.5% by weight, such as 0.2% by weight to 2 % by weight based on the total weight.

Polymers intended to improve the cleaning performance of the detergent compositions may also be included therein. The composition may include further sulfonated polymers in addition to the sulfonic acid copolymer comprising monomer units of two different carboxylic acid as required by the present disclosure. Preferred examples include copolymers of CH2=CRI-CR2R3-0-C4H3R4-S03X wherein Ri , R2, R3, R4 are independently 1 to 6 carbon alkyl or hydrogen, and X is hydrogen or alkali with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof. Other suitable sulfonated monomers for incorporation in sulfonated (co)polymers are 2- acrylamido-2-methyl-1 -propanesulphonic acid, 2- methacrylamido-2-methyl-1 - propanesulphonic acid, 3-methacrylamido-2-hydroxy- propanesulphonic acid, allysulphonic acid, methallysulphonic acid, 2-hydroxy-3-(2- propenyloxy)propanesulphonic acid, 2-methyl-2-propenen-1 -sulphonic acid, styrenesulphonic acid, vinylsulphonic acid, 3-sulphopropyl acrylate, 3- sulphopropylmethacrylate, sulphomethylacrylamide, sulphomethylmethacrylamide and water soluble salts thereof. Suitable sulphonated polymers are also described in US 5308532 and in WO 2005/090541 . When a sulfonated polymer is present, it is preferably present in an amount of at least 0.1 % by weight, preferably at least 0.5 % by weight, more preferably at least 1 % by weight, and most preferably at least 3 % by weight, up to 40 % by weight, preferably up to 25 % by weight, more preferably up to 15 % by weight, and most preferably up to 10 % by weight. The detergent composition may also comprise one or more foam control agents. Suitable foam control agents for this purpose are all those conventionally used in this field, such as, for example, silicones and their derivatives and paraffin oil. The foam control agents are preferably present in amounts of 0.5 % by weight or less. The detergent compositions may also comprise minor, conventional, amounts of preservatives, fragrance etc..

The ADW compositions may also comprise a source of acidity or a source of alkalinity, to obtain the desired pH, on dissolution, especially if the composition is to be used in an automatic dishwashing application. A source of acidity may suitably be any suitable acidic compound for example a polycarboxyl ic acid. For example, a source of alkalinity may be a carbonate or bicarbonate (such as the alkali metal or alkaline earth metal salts). A source of alkalinity may suitably be any suitable basic compound for example any salt of a strong base and a weak acid. When an alkaline composition is desired silicates are amongst the suitable sources of alkalinity. Preferred silicates are sodium silicates such as sodium disilicate, sodium metasilicate and crystalline phyllosilicates. In an embodiment, the composition is free of silicates.

In a further aspect the present disclosure provides an automatic dishwashing product comprising the composition disclosed herein.

Preferably the automatic dishwashing product is:

in a unit dose form; and/or

housed within a water soluble or water dispersible film or container, preferably a polyvinyl alcohol film or container.

Preferably the copolymer is present in the automatic dishwashing product in an amount of up to 12 wt.% based on the total weight of the product, preferably up to 10 wt.%, preferably up to 8 wt.%.

Preferably the automatic dishwashing product further comprises:

one or more bleaches, and/or

one or more builders, and/or

one or more surfactants, and/or

one or more enzymes.

Suitable bleaches, builders, surfactants and enzymes are described above. The bleaches, builders, surfactants and enzymes may form part of the same composition as the copolymer. Alternatively, they may be provided in one or more separate compositions. Each composition may be separately packaged.

Product format

Preferably the ADW compositions of the present invention are provided in monodose or unit-dose products, i.e. compositions pre-supplied in a product form in the quantity required for a single wash cycle.

The terms monodose and unit-dose are used interchangeably throughout this disclosure. The monodose product may comprise a tablet with a gel portion or layer. If compressed tablets form a portion of the ADW detergent product, they may be homogeneous or composed of multi-layers. If the tablets are multi-layered then different layers may comprise different parts of the detergent. This may be done to increase stability or increase performance, or both.

In an embodiment, the product is contained within a water-soluble film or container, preferably a polyvinylalcohol film or container. The ADW products may be housed in PVOH capsules or film blisters. These PVOH capsules or blisters may have a single compartment or may be multi-compartment. Multi-compartment blisters or capsules may have different portions of the product in each compartment, or the same composition in each compartment. The distinct regions / compartments may contain any proportion of the total amount of ingredients as desired. The PVOH capsules or film blisters may be filled with tablets, powders, gels, pastes or liquids, or combinations of these, within the scope of the invention.

The PVOH containers comprising the composition are preferably thermoformed.

The monodose may comprise an injection moulded PVOH capsule with multiple compartments. Each compartment may comprise a different composition. Optionally, one or more of the compartments may contain a gel or liquid composition. Each compartment may comprise the sulfonic acid copolymer, and/or one or more bleaches, and/or one or more builders, and/or one or more surfactants, and/or one or more enzymes. Dishwashing products may include one or more compositions comprising a sulfonic acid copolymer as described herein.

In a further aspect the disclosure provides a method of automatic dishwashing, comprising supplying a composition or product disclosed herein to an automatic dishwasher, and releasing the composition or product into a wash cycle of the automatic dishwasher.

In a further aspect the present disclosure provides use of a sulfonic acid copolymer for improving bleach performance in an automatic dishwashing process, wherein the copolymer comprises monomer units derived from:

(a) a first a,b-unsaturated carboxylic acid monomer,

(b) a second a,b-unsaturated carboxylic acid monomer, and (c) a sulfonic acid group-containing monomer;

wherein the first a,b-unsaturated carboxylic acid monomer is different from the second a,b-unsaturated carboxylic acid monomer.

Preferably the use of the present disclosure comprises the use of the composition or product of the present disclosure, optionally in the process of the present disclosure.

All percentages used in this disclosure are by weight unless otherwise specified.

The invention will now be described in relation to the following non-limiting figures. Further advantages of the disclosure are apparent by reference to the detailed description when considered in conjunction with the Examples.

Example 1

Test Set-Up:

Dishwasher: Miele GSL 2

Program: P2 (R45° 8’ KI55°)

Water hardness: 21 °dH

Detergent: 17.7g Powder composition comprising percarbonate bleach, MGDA builder, surfactant, alkali, and enzymes. Soil: 50 g of IKW soil, dosed in the beginning of the cycle

No. of tea-stained cups per test: 4

Copolymer comprising itaconic acid, acrylic acid and AMPS, pre-dissolved in 5 ml_ of Dl water, was dosed in varying amounts with detergent composition.

Table 1 :

As shown by table 1 , the bleach performance of the powder detergent composition was significantly improved by the inclusion of the copolymer. Increasing the copolymer dosage increased the bleach score. Example 2

Dishwasher: Miele GSL 2

Program: P3 / 8 min (standard IKW program)

Water hardness 21 °dH

Detergent: 17.24g of a multi-compartment dishwashing products A and B containing different enzymes

Soil: Stained tea-cups: 3x Tea & 3x Tea with Milk + IKW soil

Table 2:

Inclusion of the copolymer significantly improved the bleach score for both detergent A and B.

Inclusion of the copolymer significantly improved the bleach score even in this phosphate free composition.

All the examples show the improved removal of bleachable stains when adding the sulfonic acid group containing copolymer to automatic dishwashing products. This effect is shown even at low amounts of the copolymer.