Automatic dishwashing composition

Abstract

The present invention provides an automatic dishwashing composition comprising: a) 0.1 to 25 wt% carboxyalkyl tamarind having a carboxyalkyl degree of substitution DSCA of from 0.01 to 0.390, b) 0.001 to 10 wt% pH independent cationic polymer, c) 1 to 70 wt% builder, d) 0.2 to 40 wt% surfactant. The compositions inhibit the formation of scale spots and scale film on articles treated with the composition during an automatic dishwashing operation to provide good levels of shine to the treated articles. The compositions are especially effective on plastic articles (e.g. polypropylene articles), stainless steel articles and articles with non-stick coatings, such as ceramic coatings. The compositions are preferably multi-phase compositions which are preferably contained within a multi-compartment water-soluble container. The use of the compositions in automatic dishwashing operations and a method of manufacture of the compositions are also provided.

Description

[0001] PAT15863-WO-PCT

[0002] AUTOMATIC DISHWASHING COMPOSITION

[0003] Technical Field

[0004] The present invention relates automatic dishwashing compositions. The compositions comprise a biodegradable and preferably natural (biosourced) scale inhibition system. The present invention also relates to the preparation of these compositions and their use for inhibiting scale formation and / or providing shine on articles during an automatic dishwashing process. The compositions comprise a biodegradable, and preferably natural (biosourced), scale inhibition system comprising a carboxyalkyl tamarind, preferably a carboxymethyl tamarind, and a pH independent cationic polymer, preferably one having at least one quaternary ammonium group.

[0005] Compositions for dishwashing, including automatic dishwashing, are well known. Such compositions, especially automatic dishwashing compositions, typically include a scale inhibition system to inhibit the formation of limescale (hereinafter referred to as 'scale') on the articles being washed with the composition. The formation of scale on such articles is typically observed as scale spots and / or scale filming which can dull the surface of the articles and reduce their post-wash shine. Consumers generally consider dishwashed articles exhibiting minimal or no scale spotting and / or filming to be effectively cleansed particularly if they exhibit desirable levels of shine. Therefore, the control of scale deposition on the articles, and preferably a post-wash shine, are desirable properties for dishwashed articles, especially articles which have been washed in an automatic dishwasher.

[0006] Scale inhibition systems are known in the art for inclusion in automatic dishwashing compositions and acrylic acid-based polymers or co-polymers are used commercially for this purpose. Such materials are also referred to as dispersants. Whilst such acrylic-acid based polymers or co-polymers are effective scale inhibitors in automatic dishwashing operations they are synthetic in origin and are not biodegradable.PAT15863-WO-PCT

[0007] There is a growing desire by manufacturers and consumers to produce and use dishwashing compositions which contain as low a level of synthetic and / or non-biodegradable ingredients as possible. To improve the green credentials and sustainability characteristics of such compositions, and therefore be more environmentally friendly than current formulations, natural (biosourced) and biodegradable alternatives for use in scale inhibition systems are desirable.

[0008] However, the consumer is generally unwilling to accept a reduction in performance from dishwashing compositions which comprise higher levels of natural (non-synthetic) and / or biodegradable ingredients. Whilst consumers seek a more environmentally friendly dishwashing product, especially an automatic dishwashing product, they still require a high level of performance from the products they use. This generally requires dishwashed articles to have minimal, or no, levels of scale spotting and / or scale filming and ideally the articles should show good levels of shine.

[0009] Acrylic acid-based polymers or co-polymers, such as the Acusol™ range, e.g. Acusol™ 588 (available from Dow) and Sokalan CP7™ (a copolymer of maleic acid and acrylic acid, available from BASF) are commercially available and are known for the inhibition of scale in both phosphate containing and non-phosphate containing dishwashing detergent compositions. Such polymers are used in many commercially available dishwashing compositions as scale inhibitors. However, these polymers whilst excellent scale inhibitors, are of synthetic origin and are non-biodegradable.

[0010] Biodegradable ingredients for use in automatic dishwashing compositions are known. US5431846 discloses certain polycarboxylate copolymers and their use as biodegradable builders in detergent compositions and in rinse aid compositions for use in the final rinse step of a dish or ware-washing machine. The disclosed block copolymers of itaconic acid or a homologue thereof and vinyl alcohol or a lower vinyl ester (as such, or in hydrolyzed form) are said to exhibit excellent calcium binding capacity and their use is said to be especially beneficial under energy-saving conditions (low wash temperature, short washPAT15863-WO-PCT

[0011] time). Film-forming is also said to be better than that of polyitaconic acid. They are disclosed to provide an anti-scaling and rinse aid effect in automatic dishwashers.

[0012] US5191048 discloses partially biodegradable polymers which are terpolymers containing as polymerized units at least one first monomer selected from the group of vinyl acetate, vinyl ethers and vinyl carbonates, at least one second monomer of an ethylenically unsaturated monocarboxylic acid, and at least one third monomer of an anhydride of a dicarboxylic acid. The terpolymers are disclosed for use in detergents, in cleaner formulations for hard surfaces, and as antiscalants, dispersants, incrustation inhibitors, deflocculants, drilling fluid aids and corrosion inhibitors.

[0013] Despite the development of some partially biodegradable, or biodegradable, scale inhibitor systems which are suitable for inclusion in compositions for use in automatic dishwashing compositions, there remains a need for automatic dishwashing compositions which comprise a biodegradable scale inhibition system. In particular, a need remains for such compositions which comprise a natural (biosourced) biodegradable scale inhibition system. There is a particular need for such compositions which provide good anti-spotting and / or anti-filming benefits to the articles treated with these dishwashing compositions. There is a further need for such compositions which provide good shine characteristics to the articles treated with the compositions.

[0014] An object of the present invention is to provide automatic dishwashing compositions comprising a biodegradable scale inhibition system.

[0015] A further object of the present invention is to provide automatic dishwashing compositions comprising a biodegradable, natural (biosourced), scale inhibition system.

[0016] A particular objective is to provide automatic dishwashing compositions which provide good anti-spotting and / or anti-filming benefits to the articles treated with the compositions. It is a particular objective of the invention to provide such benefits on plasticPAT15863-WO-PCT

[0017] articles, stainless steel articles and articles with non-stick coatings, such as ceramic coatings, as it can be difficult to achieve the aforementioned benefits on these substrates.

[0018] Another object of the present invention is to provide automatic dishwashing compositions which provide good shine characteristics to the articles treated with the dishwashing compositions. It is a particular objective of the invention to provide good shine characteristics on plastic articles, stainless steel articles and articles with non-stick coatings, such as ceramic coatings, as it can be difficult to achieve the aforementioned benefits on these substrates.

[0019] It is a further object of the present invention to provide automatic dishwashing compositions which comprise a biodegradable, natural (biosourced), scale inhibition system and which provide good anti-spotting and / or anti-filming benefits and / or shine characteristics to the articles treated with the dishwashing compositions particularly as above for plastic articles, stainless steel articles and articles with non-stick coatings, such as ceramic coatings.

[0020] Surprisingly, it has been found that one or more of the aforementioned objectives can be addressed by the inclusion of a scale inhibition system comprising a carboxyalkyl tamarind and a pH independent cationic polymer, especially such a polymer having at least one quaternary ammonium group, in automatic dishwashing compositions. In particular, it has been found that the inclusion of a combination of a natural (biosourced), biodegradable, carboxyalkyl tamarind and a pH independent cationic polymer, especially such a polymer having at least one quaternary ammonium group, as a scale inhibition system in such compositions provides good anti-spotting and / or anti-filming benefits and / or shine characteristics to the articles treated with the dishwashing compositions especially for plastic articles, stainless steel articles and articles with non-stick coatings, such as ceramic coatings.

[0021] Carboxyalkyl tamarinds, such as carboxymethyl tamarind, are commercially available natural (biosourced) and biodegradable water-soluble polymers derived from tamarindPAT15863-WO-PCT

[0022] seeds. They are typically available in powder form. Carboxyalkyl tamarinds may also be referred to as a biopolymer. They are produced by reacting tamarind kernel powder with a carboxyalkyl acid to produce the carboxyalkyl tamarind. For example, carboxymethyl acid is reacted with tamarind kernel powder to produce carboxymethyl tamarind. These polymers have found use in a variety of applications.

[0023] CN110240977B discloses carboxymethyl hemicellulose in combination with cationic cellulose as a biodegradable and biosourced "synergist" ingredient in a household detergent composition to improve the cleaning performance of the detergent composition extend the cleaning agent attachment. The detergent is disclosed to be suitable for household buildings (such as walls, doors and windows etc) and industrial equipment. No reference is made to dishwashing compositions, including automatic dishwashing compositions. The carboxymethyl hemicellulose is included in the detergent composition in an amount of from 1-4 wt%.

[0024] US10954317B2 discloses a process for preparing an alkali metal salt of carboxyalkyl ether of tamarind gum. This material is said to have thickening properties, suspension-stabilising properties and film-forming properties. Disclosed uses are in the fiber industry and in food processing, paints, construction materials, cosmetics, ceramics, pharmaceuticals, agriculture, home care, detergents and drilling muds. No reference is made to dishwashing compositions, including automatic dishwashing compositions.

[0025] US2013 / 0048292A1 discloses a method of using fracturing fluids containing carboxyalkyl tamarind for production of hydrocarbons from a hydrocarbon bearing subterranean formation. The carboxyalkyl tamarind acts as a viscosity enhancing agent orgelling agent and as a friction reducer.

[0026] WO 2019 / 030183 discloses a method for improving the water retention of soil by the application of a derivatized tamarind gum.PAT15863-WO-PCT

[0027] JP2000166380A discloses a biodegradable gel composition comprising a natural water-soluble anionic polymeric compound which may be a carboxylated tamarind for growing plants.

[0028] WO 2004 / 061067 discloses a composition for inhibiting scale, film and / or spot formation on a surface treated with an aqueous solution containing calcium and / or magnesium ions, the composition comprising certain functionalized materials which may include tamarind gum.

[0029] CN 111822304 relates to a surface treatment process for a steel pipe pole, comprising the step of placing the steel pipe pole in a detergent solution comprising 2.5 wt% carboxymethyl tamarind powder.

[0030] PH independent cationic polymers are known for inclusion in automatic dishwashing compositions, for example in W02023 / 105006.

[0031] Statement of invention

[0032] According to a first aspect, the present invention provides an automatic dishwashing composition comprising:

[0033] (a) 0.1 to 25 wt% carboxyalkyl tamarind having a carboxyalkyl degree of substitution DSCA of from 0.01 to 0.390,

[0034] (b) 0.001 to 10 wt% pH independent cationic polymer,

[0035] (c) 1 to 70 wt% builder,

[0036] (d) 0.2 to 40 wt% surfactant.

[0037] It has been found that automatic dishwashing compositions of the present invention surprisingly provide good scale inhibition properties resulting in good control of scale spotting and / or scale filming on articles cleaned with the compositions. This in turn results in the articles washed with the compositions of the invention exhibiting good levels of shine which is a feature desired by consumers using automatic dishwashing compositions. The compositions of the invention have been found to be particularly effective on plasticPAT15863-WO-PCT

[0038] articles (e.g. polypropylene), stainless steel articles and articles with non-stick coatings, such as ceramic coatings.

[0039] The automatic dishwashing compositions of the invention preferably comprise 2 to 15 wt% carboxyalkyl tamarind. The carboxyalkyl tamarind preferably comprises carboxymethyl tamarind.

[0040] The automatic dishwashing compositions of the invention preferably comprise 0.01 to 0.5 wt%, pH independent cationic polymer. The pH independent cationic polymer preferably has at least one quaternary ammonium group. Preferably the pH independent cationic polymer having at least one quaternary ammonium group is of Formula (IV):

[0041] (IV) -(R-O-R-N+R2X-R-NH-C(=O)-NH-R-N+R2X-)n

[0042] wherein each R is independently a C1-C4 alkyl group, n=l-1000, and X=halide, preferably Cl.

[0043] Preferably the pH independent cationic polymer having at least one quaternary ammonium group of Formula (IV) is selected from the group consisting of Polyquaternium-2, Polyquaternium-4, Polyquaternium-6, Polyquaternium-7 or Polyquaternium-10, most preferably it is Polyquaternium-2.

[0044] The automatic dishwashing compositions of the invention preferably comprise 20 to 60 wt% builder. The builder is preferably selected from the group consisting of citrate salts, carbonate salts, phosphonates and aminocarboxylates.

[0045] The automatic dishwashing compositions of the invention preferably comprise 1 to 35 wt% surfactant. The surfactant is preferably selected from the group consisting of fatty alcohol alkoxylates, fatty acid alkoxylates and alkyl phenol alkoxylates.

[0046] Preferably the automatic dishwashing composition is a multi-phase composition. The compositions of the invention are preferably contained within a water-soluble container, most preferably a multi-compartment water-soluble container.PAT15863-WO-PCT

[0047] In a second aspect, the present invention provides the use of an automatic dishwashing composition according to the invention to inhibit the formation of scale on articles treated with the composition during an automatic dishwashing operation. In particular, the compositions of the invention have been found to be especially effective on plastic articles, stainless steel articles and articles with non-stick coatings, such as ceramic coatings. In particular, the present invention provides the use of an automatic dishwashing composition according to the invention to provide a shiny appearance of the treated articles, especially on treated plastic articles, stainless steel articles and articles with non-stick coatings, such as ceramic coatings.

[0048] It has been found that the use of the automatic dishwashing compositions of the present invention in an automatic dishwashing operation provides effective scale inhibition for articles cleaned with the composition and those articles exhibit low levels of, or no, scale spotting and / or filming which provides for a shiny appearance of the articles. This is especially the case for plastic articles, stainless steel articles and articles with non-stick coatings, such as ceramic coatings.

[0049] In a third aspect, the present invention provides a method of producing an automatic dishwashing composition according to the present invention, which method comprises the addition of a carboxyalkyl tamarind and a pH independent cationic polymer, either simultaneously or sequentially, to at least one other ingredient of the composition.

[0050] Detailed Description

[0051] a) Definitions

[0052] As used herein, the terms "wt%", "%wt.", "weight %” , and “% by weight" are synonyms to each other. All these expressions refer to a weight percentage of the respective component. Unless otherwise stated all amounts are given herein as the weight percentage of the respective component based on the total weight of the composition.PAT15863-WO-PCT

[0053] Where used herein, the term "about" means plus or minus 10 percent of the value stated.

[0054] The term 'molecular weight' as used herein means the number average molecular weight as determined by the well-known standard process of gel permeation chromatography (GPC) measured against the appropriate reference standard.

[0055] By the term "automatic dishwashing" as used herein is meant a dishwashing operation which is carried out in an automatic dishwashing machine.

[0056] By the term "scale" as used herein is meant limescale (which is mainly composed of calcium carbonate).

[0057] By the term "water-soluble container" as used herein, it is meant a container which at least partially dissolves in water or disperses in water at 40°C within 10 minutes to allow for egress of the contents of the container into the surrounding water.

[0058] The term 'pH independent cationic polymer' as used herein means that the cationic polymer has a positive charge irrespective of the pH of its solution.

[0059] The term 'substituted' as used herein, e.g. for the pH independent cationic polymer, refers to a group in which one, or more than one, of the hydrogen atoms present have been replaced with one or more groups such as, but not limited to, alkyl, heteroalkyl, haloalkyl, heterohaloalkyl, cycloalkyl, aryl, arylalkyl, heteroaryl, non-aromatic heterocycle, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, cyano, halo, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, trihalomethanesulfonyl, and amino, including mono- and di-substituted amino groups. In embodiments in which two or more hydrogen atoms have been substituted, the substituent groups may be linked to form a ring.PAT15863-WO-PCT

[0060] The pH of the compositions as referred to herein is the pH of the composition at room temperature, typically 21°C ±1°C. The pH is measured as a 1% w / w aqueous solution.

[0061] Unless otherwise specified, all the amounts herein refer to the active amounts of ingredients in the composition based on the total weight of the composition.

[0062] b) Form of the compositions

[0063] The compositions of the invention are automatic dishwashing compositions. The compositions may be of any suitable form, for example liquid, gel, paste, foam or a solid form such as a powder, granulate or tablet (such as a compressed tablet). In some embodiments of the invention the automatic dishwashing compositions are preferably solid compositions.

[0064] The compositions of the invention may be used as a liquid, gel, foam or in a solid form directly in an automatic dishwashing application. Alternatively, the compositions of the invention may be contained within a water-soluble container, which container is used in the automatic dishwashing process to dose an appropriate amount of composition for a single machine wash cycle. The water-soluble container is at least partially filled with the automatic dishwashing composition.

[0065] The compositions of the invention may be single-phase compositions, such as a liquid, gel, foam or a solid phase (for example a powder, granulate or a tablet, such as a compressed tablet). In single-phase composition embodiments of the invention all the essential ingredients of the automatic dishwashing composition are present in that single phase. Accordingly, such single-phase compositions can be used on their own in automatic dishwashing operations to cleanse articles. However, dishwashing auxiliary products, such as rinse aids, may also be used in the automatic dishwashing operation.

[0066] A water-soluble container containing the compositions of the invention may have a single compartment containing the single-phase composition, for example a powder, gel or liquid composition.PAT15863-WO-PCT

[0067] In another embodiment of the invention, the compositions of the invention may be multiphase compositions. In this embodiment, the composition has two or more phases, such as three or more phases. Each phase of the composition may have the same form, two or more phases may have the same form, or, each phase may have a different form. For example, the composition may comprise one or more solid phase(s) (e.g. a powder or a granulate), one of more gel phase(s) and one or more liquid phase(s). A multi-phase composition comprising a solid phase, especially a granulate, a gel phase and a liquid phase is especially preferred according to the invention. All phases of the composition are dosed together in the automatic dishwashing process to provide the essential ingredients of the composition. In multi-phase composition embodiments of the invention all the essential ingredients of the automatic dishwashing composition are present in the overall composition, but they may not all be present in each phase. In this embodiment one or more of the essential ingredients of the composition may be present in one phase and one or more essential ingredients may be present in at least one other phase of the composition. However, the multiple phases of the composition, taken together as a whole provide all the essential ingredients of the composition as they are all dosed together in the dishwashing operation.

[0068] According to one embodiment of the invention, preferably the water-soluble container is a multi-compartment container having at least two compartments, preferably at least three compartments, each compartment being separate from the other compartments (the compartments not being interconnected). Multi-compartment water-soluble containers are especially suitable for use with multi-phase compositions of the invention. Preferably, each compartment holds one phase of the multi-phase compositions of the invention, which phases may be of the same or different form.

[0069] c) Carboxyalkyl Tamarind

[0070] The automatic dishwashing compositions of the invention comprise 0.1 to 25 wt% carboxyalkyl tamarind having a carboxyalkyl degree of substitution (DSCA) of from 0.01 to 0.390. The carboxyalkyl tamarind forms part of the scale inhibition system in thePAT15863-WO-PCT

[0071] dishwashing compositions of the invention. The carboxyalkyl tamarind is a commercially available biodegradable, natural (biosourced), material.

[0072] The compositions of the invention preferably comprise 1 to 20 wt% carboxyalkyl tamarind, more preferably 2 to 15 wt% carboxyalkyl tamarind, especially 3 to 12wt% carboxyalkyl tamarind, most especially 5 to 10 wt% carboxyalkyl tamarind, such as 6 to 9.5wt% carboxyalkyl tamarind.

[0073] The carboxyalkyl is preferably selected from the group consisting of carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl and mixtures thereof. More preferably the carboxyalkyl is preferably selected from the group consisting of carboxymethyl, carboxyethyl and mixtures thereof. The carboxyalkyl tamarind most preferably comprises carboxymethyl tamarind, and especially is carboxymethyl tamarind.

[0074] Preferably the carboxyalkyl tamarind has a carboxyalkyl degree of substitution (DSCA) of from 0.05 to 0.380, more preferably of from 0.1 to 0.375, most preferably 0.2 to 0.370. The carboxyalkyl degree of substitution (DSCA) of the carboxyalkyl tamarind is measured according to ASTM D1439-15. The carboxyalkyl tamarind comprises a base tamarind gum substituted with carboxyalkyl groups (of the types listed hereinabove), wherein 90-100 mol%, preferably 92 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 98 to 100 mol% and most preferably 99 to 100 mol% of the carboxyalkyl substitutions are on galactose moieties of the base tamarind gum.

[0075] It is especially preferred that the compositions of the invention comprise a carboxymethyl tamarind having a carboxyalkyl degree of substitution (DSCA) of from 0.01 to 0.390, and more preferably withing the preferred (DSCA) values and preferred wt% amounts recited above.

[0076] When the composition of the invention is a multi-phase composition, it is preferred that the carboxyalkyl tamarind is part of a solid phase. For multi-phase compositions it is alsoPAT15863-WO-PCT

[0077] preferred that the carboxyalkyl tamarind and the pH independent cationic polymer are present in the same phase. For multi-phase compositions it is also preferred that the carboxyalkyl tamarind and at least a part of the builder are present in the same phase.

[0078] The carboxyalkyl tamarind may be included in the automatic dishwashing compositions of the invention using any suitable method of manufacture of the composition dependent upon the format of the composition.

[0079] d) pH independent cationic polymer

[0080] The compositions of the invention comprise 0.001 to 10 wt% pH independent cationic polymer. Such polymers have a pH-independent permanent positive charge. The cationic polymer is preferably obtained from renewable materials. It is preferably a biobased cationic polymer or a modified biopolymer and is preferably biodegradable. It is especially preferred that both the carboxyalkyl tamarind and the pH independent cationic polymer are natural (biosourced) materials and biodegradable.

[0081] In one embodiment of the present invention, the compositions preferably comprise 0.001 to 2 wt% pH independent cationic polymer, more preferably 0.005 to 1 wt% , even more preferably 0.01 to 0.5 wt%, most preferably 0.015 to 0.25 wt%, such as 0.02 to 0.15 wt%. In another embodiment of the invention higher amounts of the pH independent cationic polymer may be preferred and in this embodiment the compositions preferably comprise 0.1 to 8 wt% pH independent cationic polymer, more preferably 0.5 to 5 wt% , even more preferably 1 to 7.5 wt%.

[0082] It is preferred that the pH independent cationic polymer has at least one quaternary ammonium group (referred to herein as a 'polyquaternium' polymer). The at least one quaternary ammonium group is an ammonium cation that is permanently charged, independent of the pH of its solution. The at least one quaternary ammonium group may be selected from alkylammonium, dialkylammonium, trialkylammonium, iminium, amidinium, formamidinium, guanidinium and biguanidinium quaternary ammonium groups.PAT15863-WO-PCT

[0083] The alkylammonium, dialkylammonium, trialkylammonium quaternary ammonium groups may comprise any linear or branched alkyl group. The alkyl group may be any Ci to C20, preferably Ci to C10, even more preferably Ci to C5, linear or branched alkyl group.

[0084] Examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, pentyl, hexyl, heptyl and octyl. The alkyl group may be a substituted alkyl group.

[0085] The at least one quaternary ammonium group may comprise a group selected from an aryl group, a heteroaryl group, a cycloalkyl group, a heterocycloalkyl group, an alkoxy group, an aryloxy group, an alcohol group, a carboxylate ester group or an ether group.

[0086] The aryl group may comprise 5, 6, 7, 8, 9 or more carbon atoms. The aryl group may be substituted. Examples of aryl groups include, but are not limited to, 3-methylphenyl, 4-methylphenyl and dimethylphenyl.

[0087] The heteroaryl group may comprise 4, 5, 6, 7, 8, 9, or more than 9 atoms. The heteroaryl group may be substituted. Examples of heteroaryl groups include, but are not limited to, aromatic C3-C8 heterocyclic groups comprising one oxygen or sulphur atom or up to four nitrogen atoms, or a combination of one oxygen or sulphur atom and up to two nitrogen atoms, and their substituted as well as benzo- and pyrido-fused derivatives, for example, connected via one of the ring-forming carbon atoms. The heteroaryl group may be substituted with one or more substituents, independently selected from halo, hydroxy, amino, cyano, nitro, alkylamido, acyl, Ci to Ce-alkoxy, Ci to Ce-alkyl, Ci to Ce-hydroxyalkyl, Ci to Ce-aminoallcyl, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, sulfamoyl, or trifluoromethyl. Examples of heteroaryl groups include, but are not limited to, unsubstituted and mono- or di-substituted derivatives of furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, pyrazole, pyrylium, imidazole, indole, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, imidazole, benzimidazole, pyrazole,PAT15863-WO-PCT

[0088] indazole, tetrazole, quinoline, isoquinoline, pyridazine, pyrimidine, purine and pyrazine, 1.2.4-triazine, 1,3,5-triazine, furazan, 1,2,3-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1.2.4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, thiophene, triazole, benzotriazole, pteridine, phenoxazole, oxadiazole, benzopyrazole, quinolizine, cinnoline, phthalazine, quinazoline, and quinoxaline.

[0089] The cycloalkyl group may be any C3 to C20, preferably C3 to C10, cycloalkyl group. The cycloalkyl group may be substituted. Examples of cycloalkyl groups include, but are not limited to, cyclopropane, cyclobutane, cyclopentane and cyclohexane.

[0090] The heterocycloalkyl group may comprise 4, 5, 6, 7, 8, 9, or more than 9 atoms. The heterocycloalkyl group may be substituted. Examples of heterocycloalkyl group include, but are not limited to, C3 to Ca heterocyclic groups comprising one, two, three or more oxygen or sulphur atoms or up to four nitrogen atoms, or a combination of one, two, three or more oxygen or sulphur atoms and up to two nitrogen atoms, and their substituted as well as fused derivatives, for example, connected via one of the ring-forming carbon atoms.

[0091] The heterocycloalkyl group may be substituted with one or more substituents, independently selected from halo, hydroxy, amino, cyano, nitro, alkylamido, acyl, Ci to Ce-alkoxy, Ci to Ce-alkyl, Ci to Ce-hydroxyalkyl, Ci to Ce-aminoallcyl, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, sulfamoyl, or trifluoromethyl. Examples of heterocycloalkyl groups include, but are not limited to, unsubstituted and mono- or di-substituted derivatives of pyrrolidine, pyrroline, pyrazolidine, imidazolidine, pyrazoline, imidazoline, tetrahydrofuran, 1,3-dioxolane, tetrahydrothiophene, 1,2-oxathiolane, 1,3-oxathiolane, sulpholane, 2,4-thiazolidinedione, succinimde, 2-oxazolidone, hydantoin, piperidine, piperazine, tetrahydropyran, 2H-pyran, 4H-pyran, 1,4-dioxane, 1,4-dioxine, thiane, 2H-thiopyran, 4H-thiopyran, 1,3-dithiane, 1,4-dithiane, 1,3,5-trithiane, morpholine, 4H-l,2-oxazine, 21-1-1,2-oxazine, 6H-l,2-oxazine, 4H-l,3-oxazine, 2H-l,3-oxazine, 6H-l,3-oxazine, 4H-l,4-oxazine, 2H-l,4-oxazine, thiomorpholine, thiazine, 4H-l,4-thiazine, 2H-l,2-thiazine, 6H-l,2-thiazine, 2H-l,4-thiazine, cytosine, thymine, uracil, and thiomorpholine dioxide.PAT15863-WO-PCT

[0092] The alkoxy group may be any Ci to Cio alkoxy group, for example a methoxy or ethoxy group. The alkoxy group may be substituted.

[0093] The aryloxy group may comprise 5, 6, 7 , 8, 9 or more carbon atoms. The aryloxy group may be substituted. The aryloxy group may be a phenoxy group.

[0094] The alcohol group may comprise any Ci to C20, preferably Ci to Cio, more preferably Ci to Ce alcohol. The alcohol group may be substituted. The alcohol group may be any primary, secondary or tertiary alcohol group. The alcohol group may be any linear or branched alcohol group. The alcohol group may comprise more than one hydroxyl group, for example, two hydroxyl groups (diol) or three hydroxyl groups (triol).

[0095] The carboxylate ester group may be any carboxylate ester group of the formula (II):

[0096] (II) R1CO2R2

[0097] wherein R1and R2comprise any alky or aryl group. The alkyl and / or aryl group may be substituted.

[0098] The at least one quaternary ammonium group may have the formula (III):

[0099] (III) -+N(R1)(R2)-wherein R1and R2are each independently selected from a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a cycloalkyl group, a heterocycloalkyl group, an alkoxy group, an aryloxy group, an alcohol group, a carboxylate ester group and an ether group. R1and R2may be identical or different.

[0100] At least one of R1and R2may be a linear or branched Ci to Cio alkyl group, preferably a linear or branched Ci to C5 group. At least one of R1and R2may be a Ci, C2 or C3 alkyl group. R1and R2may each be a linear or branched Ci to Cio alkyl group, preferably a linear or branched Ci to C5 alkyl group. R1and R2may each be a Ci, C2 or C3 alkyl group. R1and R2may each be a methyl group.PAT15863-WO-PCT

[0101] The degree of quaternization of the cationic polymer may be between about 1 and about 100 mol%, between about 10 and about 90 mol%, between about 20 and about 80 mol%, between about 30 and about 70 mol%, between about 40 and about 60 mol%, or about 50 mol%, based on quaternizable N-atoms in the cationic polymer.

[0102] The degree of quaternization of the cationic polymer may be up to about 10 mol%, up to about 20 mol%, up to about 30 mol%, up to about 40 mol%, up to about 50 mol%, up to about 60 mol%, up to about 70 mol%, up to about 80 mol%, up to about 90 mol%, or up to about 100 mol%, based on quaternizable N-atoms in the cationic polymer.

[0103] The cationic polymer may further comprise a urea group and / or a urethane group, or a derivative thereof, for example a thio-derivative such as thiourea. Each of the urea and / or urethane groups comprise at least one oxygen and at least one nitrogen atom.

[0104] Advantageously, the oxygen and / or nitrogen atoms confer strong hydrogen-bonding properties to the cationic polymer which facilitates the efficacy of the cationic polymer in providing shine on dishwashed goods.

[0105] The urea group and / or the urethane group may comprise at least one quaternized N-atom. Specifically, a urea group comprises two nitrogen atoms and none, one or both of these nitrogen atoms may be quaternized. Moreover, a urethane group comprises one nitrogen atom and this nitrogen atom may be quaternized. Advantageously, a cationic polymer comprising a urea group and / or a urethane group allows for a greater mole percent of the cationic polymer to be quaternized, therefore, increasing the charge density of the polymer which facilitates the efficacy of the cationic polymer in providing shine on dishwashed goods.

[0106] The cationic polymer may further comprise a pyrrolidine group. The pyrrolidine group may be substituted with one or more substituents, independently selected from halo, hydroxy, amino, cyano, nitro, alkylamido, acyl, Ci to Ce -alkoxy, Ci to Ce -alkyl, Ci to Ce -hydroxyalkyl,PAT15863-WO-PCT

[0107] Ci to Ce -aminoallcyl, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, sulfamoyl, or trifluoromethyl. The cationic polymer may be a polydiallyldimethylammonium chloride (polyDADMAC or polyDDA) cationic polymer. Advantageously, polyDADMAC has a high permanent charge density of about 6.2 meq / g. As such, polyDADMAC can provide various consumer-relevant benefits such as shine when used in dishwashing compositions, especially for automatic dishwashing compositions.

[0108] The cationic polymer may be a polyurethane cationic polymer, a polyepoxide cationic polymer, a polyether cationic polymer or a polyester cationic polymer. The polyether cationic polymer may be a polyoxymethylene (POM) cationic polymer, polyethylene glycol (PEG) cationic polymer, polyethylene oxide (PEO) cationic polymer, polyoxyethylene (POE) cationic polymer, polytetramethylene glycol (PTMG) cationic polymer, polytetramethylene ether glycol (PTMEG) cationic polymer or polytetra hydrofuran (PTHF) cationic polymer. The cationic polymer may be a homopolymer (for example, comprising repeat unit 'A', -A-A-A-A-A-A-), an alternating copolymer (for example, comprising repeat units 'A' and 'B', -A-B-A-B-A-B-A-), a random copolymer (for example, -A-B-B-B-A-B-A-B-A-A-), a block copolymer (for example, -A-A-A-B-B-B-), a graft copolymer (for example, -A-A-A(-B-B-B-)-A-A-A(-B-B-B-)-A-A-A-), a periodic copolymer (for example, A-B-A-B-B-A-A-A-A-B-B-B), a stereoblock copolymer or a gradient copolymer.

[0109] The cationic polymer may have a pH-independent permanent positive charge having a permanent charge density of at least about 1 meq / g, at least about 2 meq / g, at least about 3 meq / g, at least about 4 meq / g, at least about 5 meq / g, at least about 6 meq / g, at least about 7 meq / g, at least about 8 meq / g, at least about 9 meq / g, or at least about 10 meq / g. The cationic polymer may have a pH-independent permanent positive charge having a permanent charge density of between about 1 and about 10 meq / g, between about 2 and about 9 meq / g, between about 3 and about 8 meq / g, between about 4 and about 7 meq / g, between about 4 and about 6 meq / g, or about 5 meq / g. The cationic polymer may have a pH-independent permanent positive charge having a permanent charge density of between about 2.0 and about 9.0 meq / g, between about 2.5 and about 8.5 meq / g, between about 3.0 and about 8.0 meq / g, between about 3.5 and about 7.5 meq / g, between about 4.0 andPAT15863-WO-PCT

[0110] about 7.0 meq / g, between about 4.5 and about 6.5 meq / g, between about 5.0 and about 6.0 meq / g, or between about 5.0 and about 5.5 meq / g.

[0111] Preferably the pH independent cationic polymer has at least one quaternary ammonium group (referred to herein as a polyquaternium cationic polymer). Most preferably the polyquaternium cationic polymer is of Formula (IV):

[0112] (IV) -(R-O-R-N+R2X-R-NH-C(=O)-NH-R-N+R2X-)n

[0113] wherein each R is independently a C1-C4 alkyl group, n=l-1000, and X=halide, preferably Cl.

[0114] The pH independent cationic polymer having at least one quaternary ammonium group may be selected from the family of polycationic polymers designated as polyquaternium polymers under the International Nomenclature for Cosmetic Ingredients, in particular the pH independent cationic polymer may be selected from the group consisting of Polyquaternium-2, Polyquaternium-4, Polyquaternium-6, Polyquaternium-7 or Polyquaternium-10, or any polycationic polymer which exhibits strong hydrogen bonding and adsorption to SiOz surfaces. An especially preferred pH independent cationic polymer (polyquaternium) for use in the dishwashing compositions of the invention is polyquaternium-2, also known as N,N'-bis[3-(dimethylamino)propyl]-urea polymer with l,l'-oxybis[2-chloroethane], Polyquaternium-2 is commercially available from BASF under the tradename Luga Ivan™ P or as Mirapol™ 15 available from Solvay.

[0115] The carboxyalkyl tamarind and the pH independent cationic polymer together form the scale inhibition system used in the compositions of the present invention.

[0116] When the composition of the invention is a multi-phase composition, it is preferred that the pH independent cationic polymer is part of a solid phase. For multi-phase compositions it is also preferred that the pH independent cationic polymer and the carboxyalkyl tamarind are present in the same phase. For multi-phase compositions it is also preferred that the pH independent cationic polymer and at least a part of the builder are present in the same phase.PAT15863-WO-PCT

[0117] In according to one embodiment, the carboxyalkyl tamarind is typically present in a greater wt% in the compositions of the invention than the pH independent cationic polymer.

[0118] According to this embodiment, it is preferred that the weight ratio of the carboxyalkyl tamarind: pH independent cationic polymer in the compositions of the invention is in the range of from 800 to 50:1, more preferably 700 to 100:1, even more preferably 600 to 200:1, such as preferably 500 to 300:1, for example 400 to 300:1.

[0119] The pH independent cationic polymer may be included in the automatic dishwashing compositions of the invention using any suitable method of manufacture of the composition dependent upon the format of the composition.

[0120] e) builder

[0121] The automatic dishwashing compositions of the invention comprise 1 to 70 wt% of builder, preferably 10 to 65 wt%, more preferably 20 to 60 wt%, even more preferably 30 to 55 wt% and especially 35 to 50 wt%. This amount is the total amount of builder materials in the compositions of the invention including any co-builder materials included therein. The actual amount used in the automatic dishwashing compositions of the invention will depend upon the nature of the builder(s) and any co-builders used. The builder may comprise a mixture of different builder materials and / or co-builder materials having 'builder' properties.

[0122] The builder may be an inorganic builder. For example, the builder may comprise an alkali or alkaline earth metal carbonate salt, especially sodium carbonate.

[0123] The builder may be an organic builder. The builder may be selected from the group containing hydroxycarboxylates, aminocarboxylates, dicarboxylic acid amines and / or phosphates, orthe salts thereof, or mixtures thereof. The builder may comprise one or more small molecule builders selected from hydroxycarboxylates (such as alkali or alkaline earth metal citrate salts, for example trisodium citrate, which may be anhydrous), aminocarboxylates (such as methyl glycine diacetic acid (MGDA), or N,N-dicarboxymethyl glutamic acid (GLDA), dicarboxylic acid amines (such as iminodisuccinic acid (IDS)) and / or phosphates (such asPAT15863-WO-PCT

[0124] tripolyphosphate), or the salts thereof, especially the alkali or alkaline earth metal salts thereof. Aminocarboxylates, and especially MGDA, GLDA and IDS are preferred builders.

[0125] The builder may be a phosphate-free builder. In many countries, including the United States and in the European Union, the use of phosphate builders is restricted, or the amount of phosphate permitted in a detergent composition is strictly limited. Therefore, it is preferred according to one embodiment of the invention, that the automatic dishwashing compositions of the invention are substantially phosphate-free.

[0126] According to one embodiment of the invention, the builder preferably comprises a combination of trisodium citrate and sodium carbonate. According to another embodiment of the invention, the builder preferably an aminocarboxylate such as MGDA, GLDA and IDS.

[0127] The automatic dishwashing compositions of the invention may comprise a co-builder compound as part of the builder. The compositions may comprise a phosphonate or a polymer as a co-builder. Tetrasodium-HEDP is an example of a suitable phosphonate cobuilder.

[0128] The compositions of the invention may comprise at least one polymer having co-builder properties, preferably at least one polycarboxylate. By the term 'polycarboxylate', is meant any polymeric species comprising a carboxylic acid or carboxylate groups available for chelation. The polycarboxylate polymer may be a homopolymer and / or a copolymer and / or a terpolymer. The polymer may be a polycarboxylate polymer comprising an acrylic acid homopolymer. The homopolymer may have a number average molecular weight of between about 2,000 and about 10,000, between about 3,000 and about 9,000, or between about 4,000 and about 8,000.

[0129] The at least one polycarboxylate may comprise a sulphonic acid monomer. The sulphonic acid monomer may be present in an amount of from about 4 to about 14 wt%, from about11

[0130] PAT15863-WO-PCT

[0131] 5 to about 13 wt%, from about 6 to about 12 wt% or from about 7 to about 11 wt% based on the total weight of the at least one polycarboxylate.

[0132] Preferred monomers containing sulphonic acid groups are those of Formula (V):

[0133] (V) R1(R2)C=C(R3)-X-SO3H

[0134] in which R1to R3mutually independently denote -CH3 , a straight-chain or branched saturated alkyl residue with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl residue with 2 to 12 carbon atoms, alkyl or alkenyl residues substituted with -NH2 , -OH or -COOH, or denote -COOH or -COOR4, R4being a saturated or unsaturated, straight-chain or branched hydrocarbon residue with 1 to 12 carbon atoms, and X denotes an optionally present spacer group which is selected from -(CH2)n- with n=0 to 4, -COO-(CH2)k- with k=l to 6, -C(O)-NH-C(CH3)2- and CH(CH2CH3)-.

[0135] Preferred monomers of the above formula include, for example, those of the formulae (VI to VIII):

[0136] (VI) H2C=CH-X-SO3H

[0137] (VII) H2C=C(CH3)-X-SO3H

[0138] (VIII) HO3S-X-(R5)C=C(R6)-X-SO3H

[0139] in which R5and R6are mutually independently selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2and X denotes an optionally present spacer group which is selected from-(CH2)n-with n= 0 to 4, -COO-(CH2)k with k=l to 6, -C(O)-NH-C(CH3)2- and -C(O)-NH-CH(CH2CH3)-. Preferred monomers containing sulphonic acid groups are here 1-acrylamido-l-propanesulphonic acid, 2-acrylamido-2-propanesulphonic acid, 2-acrylamido-2-methyl-l-propanesulphonic acid, 2-methacrylamido-2-methyl-l-propanesulphonic acid, 3-methacrylamido-2-hydroxypropane-sulphonic acid, al lylsul phonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulphonic acid, 2-methyl-2-propene-l-sulphonic acid, styrenesulphonic acid, vinylsulphonic acid, 3-sulphopropyl acrylate, 3-sulfopropyl methacrylate, sulphomethacrylamide, sulphomethylmethacrylamide and mixtures of thePAT15863-WO-PCT

[0140] stated acids or the water-soluble salts thereof. Particularly preferred is 2-acrylamido-2-methyl-l-propanesulphonic acid.

[0141] The sulphonic acid groups may be present in the polymers entirely or in part in neutralized form, i.e. the acidic hydrogen atom of the sulphonic acid group may be replaced in some or all the sulphonic acid groups with metal ions, preferably alkali metal ions and in particular with sodium ions. It is preferred according to the invention to use copolymers containing partially or completely neutralized sulphonic acid groups.

[0142] The polymer may comprise polyepoxysuccinic acid (PESA) or derivatives thereof.

[0143] Polyepoxysuccinic acid is also known as epoxysuccinic acid homopolymer, polyoxirane-2,3-dicarboxylic acid, 2,3-oxiranedicarboxylic acid homopolymer, or poly(l-oxacyclopropane-2,3-dicarboxylic acid); and has the general structure (IX):

[0144] (IX)

[0145]

[0146] and where the derivatives thereof have the general structure (X):

[0147] (X)

[0148]

[0149] where R may be hydrogen or any organic chain (but preferably an ester such as C1-4 alkyl) and where M may be any cation (preferably Na+, H+, K+, and / or NH4+).PAT15863-WO-PCT

[0150] All references to PESA hereafter are to be taken to refer to polyepoxysuccinic acid or derivatives thereof, unless otherwise stated.

[0151] The PESA may have a number average molecular weight (Mw) of from about 100 to about 10,000 g mol-1, from about 400 to about 2000 g mol-1, from about 1000 to about 1800 g mol-1. The PESA may have from about 2 to about 100 repeating monomer units, such as from about 2 to about 50, about 2 to about 45, about 2 to about 20 or from about 2 to about 10 repeating monomer units.

[0152] According to one preferred embodiment of the invention, the builder is selected from the group consisting of citrate salts, carbonate salts, phosphonates and aminocarboxylates. In particular, the builder is selected from the group consisting of trisodium citrate, sodium carbonate, phosphonate co-builders and aminocarboxylates, especially MGDA. According to one embodiment of the invention, most preferably the builder comprises a combination of trisodium citrate, sodium carbonate and a phosphonate co-builder, especially 1-hydroxyethylidene-l,l-diphosphonic acid (HEDP).

[0153] When the composition of the invention is a multi-phase composition, it is preferred that the builder is at least in part, within a solid phase. For multi-phase compositions it is also preferred that at least a part of the builder is present in the same phase as the pH independent cationic polymer and / or the carboxyalkyl tamarind.

[0154] f) Surfactants

[0155] The automatic dishwashing compositions of the invention comprise 0.2 to 40 wt% of surfactant, preferably 1 to 35 wt%, more preferably 2 to 30 wt%, even more preferably 2.5 to 25 wt% most preferably 5 to 20 wt%, such as 7.5 to 15 wt%. This amount is the total amount of surfactant in the compositions of the invention. The actual amount used in the automatic dishwashing composition will depend upon the nature of the surfactant used. The surfactant may comprise a mixture of different surfactants.PAT15863-WO-PCT

[0156] The automatic dishwashing compositions of the present invention may comprise one or more surfactants. Any of non-ionic, 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. Preferably, bleach-stable surfactants may be used especially if the composition also comprises a bleaching agent.

[0157] Non-ionic surfactants are preferred surfactants for inclusion in the automatic dishwashing compositions of the invention. The composition may comprise the non-ionic surfactant in the amounts stated above.

[0158] Any suitable non-ionic surfactant may be included in the compositions of the invention. Alkoxylated surfactants are especially preferred according to the present invention, including those selected from the group consisting of fatty alcohol alkoxylates, fatty acid alkoxylates and alkyl phenol alkoxylates. The ethoxylates, and mixed ethoxylates / propoxylates of these alkoxylated nonionic surfactants are especially preferred. The alkyl chain length of these surfactants is preferably C6-C22, more preferably C8-C20, most preferably Cio-Cis, such as C12 to Ci6. Preferred nonionic surfactants include Cio-Cis alkoxylated fatty alcohols, more preferably C12 to Ci6 alkoxylated fatty alcohols, especially C12 to Ci6 ethoxylated and mixed ethoxylated / propoxylated fatty alcohols.

[0159] The non-ionic surfactant may be an ethoxylated non-ionic surfactant prepared by the reaction of a monohydroxy alkanol with 6 to 20 carbon atoms. The surfactant may have at least 3 moles, or at least 5 moles, or at least 8 moles, or at least 10 moles, or at least 12 moles, or at least 16 moles, or at least 20 moles, or at least 25 moles of alkylene oxide, such as ethylene oxide or mixed ethylene oxide and propylene oxide, per mole of alcohol. The non-ionic surfactant may be from a linear or branched chain fatty alcohol with 6 to 20 carbon atoms, preferably with 8 to 18 carbon atoms, more preferably 10 to 18 carbon atoms, such as 12-16 carbon atoms. Suitable non-ionic surfactants include all thePAT15863-WO-PCT

[0160] aforementioned linear or branched chain fatty alcohol carbon chains with all the aforementioned moles of alkylene oxide, especially ethylene oxide or mixed ethylene oxide and propylene oxide per mole of alcohol.

[0161] The surfactant may be an ethoxylated mono-hydroxy alkanol which additionally comprises polyoxyethylene-polyoxypropylene block copolymer units. The alcohol portion of the ethoxylated mono-hydroxy alkanols may constitute more than 30 % by weight, more than 50 % by weight, or more than 70 % by weight of the overall number average molecular weight of the non-ionic surfactant. The non-ionic surfactant may comprise reverse block copolymers of polyoxyethylene and polyoxypropylene and block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane.

[0162] The non-ionic surfactant may be a surfactant described by the formula (XI):

[0163] (XI) R1O[CH2CH(CH3)O]X[CH2CH2O]Y[CH2CH(OH)R2]

[0164] where R1represents a linear or branched chain aliphatic hydrocarbon group with 4-18 carbon atoms or a mixture thereof, R2represents a linear or branched chain aliphatic hydrocarbon rest with 2-26 carbon atoms or a mixture thereof, x is a value between 0.5 and 1.5, and y is a value of at least 15.

[0165] The non-ionic surfactant may be an optionally end capped alkyl alkoxylate, such as an endcapped polyoxyalkylate described by the formula (XII):

[0166] (XII) R1O[CH2CH(R3)O]X[CH2]kCH(OH)[CH2]jOR2

[0167] where R1and R2represent linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1 -30 carbon atoms, R3represents 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, more preferably k = 1 and j = 1. When the value of x is greater than 2, each R3in the formula above may be different. R1and R2are preferably linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 6-22 carbon atoms, preferably 8 to 18 carbon atoms. For the group R3, H, methyl or ethyl is particularlyPAT15863-WO-PCT

[0168] preferred. Particularly preferred values for x are comprised between 1 and 20, preferably between 6 and 15.

[0169] As described above, where the value of x is greater than 2, each R3in the formula can be different. For example, when x=3, R3may be ethylene oxide (EO) (R3= H) or propylene oxide (PO) (R3= methyl) units which can be used in any order, for example (PO)(EO)(EO), (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO).

[0170] A preferred class of non-ionic surfactants are ethoxylated non-ionic surfactants prepared by the reaction of a monohydroxy alkanol or alkyl phenol with 6 to 20 carbon atoms.

[0171] Preferably the surfactants have at least 3, preferably at least 5 moles, more preferably at least 8 moles, even more preferably at least 10 moles, or at least 12 moles, or at least 16 moles, or at least 20 moles, or at least 25 moles of alkylene oxide moles, preferably moles of ethylene oxide or mixed ethylene oxide and propylene oxide per mole of alcohol or alkyl phenol. Particularly preferred non-ionic surfactants are the non-ionics from a linear chain fatty alcohol with 10-20 carbon atoms and at least 5 moles of ethylene oxide per mole of alcohol. The non-ionic surfactant may comprise propylene oxide (PO) units in the molecule. The propylene oxide (PO) units may constitute up to 40 %wt., 35 %wt., 30 %wt., 25 %wt., 20 %wt. or up to 15 %wt. of the overall number average molecular weight of the non-ionic surfactant.

[0172] Alkyl polyglycosides, such as alkyl polyglucoside, are also suitable non-ionic surfactants for inclusion in the compositions of the invention. The alkyl chain is typically a C2 to C12 alkyl chain.

[0173] The use of a mixture of any of the aforementioned non-ionic surfactants is suitable in compositions of the present invention.

[0174] In automatic dishwashing compositions it is generally preferred to limit the amount of anionic surfactant present as these surfactants generally have high foaming characteristics and some types of anionic surfactant foam too much to be suitable for use in a dishwashingPAT15863-WO-PCT

[0175] machine. However, provided the foaming characteristics of the compositions of the invention are acceptable, the compositions of the invention may comprise anionic surfactants, preferably in an amount of up to 15 wt%, more preferably 0.5 to 10 wt%, most preferably 1 to 5 wt%. For some compositions of the invention it is preferred that the compositions comprise no more than 15 %wt., more preferably no more than 10 %wt., most preferably no more than 5 %wt., especially no more than 2 %wt., such as no more than 1 %wt., or no anionic surfactant. When anionic surfactant is used, the compositions of the invention typically comprise at least 0.5 wt%, more preferably at least 1 wt%, such as at least 2 wt%, for example at least 5 wt% of anionic surfactant. In the compositions of the invention, any type of anionic surfactant may be included provided the foaming properties of the composition are acceptable.

[0176] In a particular embodiment the compositions of the invention may comprise a combination of one or more non-ionic surfactants and one or more anionic surfactants.

[0177] The surfactant may be present in two or more phases in a multi-phase composition. It is preferred that the surfactant is present in a non-solid phase. When the composition of the invention is a multi-phase composition, it is preferred that the less than 30 wt% of the total amount of surfactant is present within a solid phase, preferably less than 20 wt% and most preferably less than 10 wt% such as less than 5 wt%. In some embodiments it is preferred that no surfactant is present in a solid phase. It is preferred that the carboxyalkyl tamarind and the surfactant are present in the different phases of the composition.

[0178] g) Bleaching agents

[0179] The automatic dishwashing compositions of the present invention may optionally, but preferably, comprise one or more bleaching agents, preferably in combination with one or more bleach activators and / or one or more bleach catalysts. The one or more bleaching agent is preferably selected from the group consisting of an oxygen-releasing bleaching agent, a chlorine-releasing bleaching agent and mixtures thereof.

[0180] The bleaching agent may comprise the active bleach species itself or a precursor to that species. The bleaching agent may be selected from the group consisting of an inorganicPAT15863-WO-PCT

[0181] peroxide, an organic peracid and mixtures thereof. The terms "inorganic peroxide" and "organic peracid" encompass salts and derivatives thereof. Inorganic peroxides include percarbonates, perborates, persulphates, hydrogen peroxide and derivatives and salts thereof.

[0182] An oxygen-releasing bleaching agent is preferably used in the compositions of the invention when a bleaching agent is included. Inorganic peroxides are preferred bleaching agents according to the present invention. The sodium and potassium salts of these inorganic peroxides are preferred, especially the sodium salts. Percarbonates, and especially sodium percarbonate, are preferred bleaching agents.

[0183] It is preferred that the bleaching agent present in the compositions of the invention is in the form of granules and especially coated granules. Coated granules of sodium percarbonate are especially preferred. The coating for the bleaching agent may be made of any suitable material which allows the bleaching agent to perform well in the dishwashing composition. Preferably coated granules of sodium percarbonate having an active oxygen content ranging from 5 to 25 wt%, preferably from 11 to 18 wt%, and more preferably from 12 to 15 wt% are used in the compositions of the invention.

[0184] It is preferred that at least 90%, preferably at least 96 %, and more preferably at least 98% of the coated granules of sodium percarbonate have a particle size ranging from 150 to 1600 micrometers. It is also preferred that at least 86%, preferably at least 88 %, and more preferably at least 94% of said coated granules of sodium percarbonate have a particle size ranging from 150 to 1400 micrometers.

[0185] It is preferred that the sodium percarbonate content of the coated granules of sodium percarbonate ranges from 80 to 95 wt%, preferably from 82 to 91 wt%, and more preferably from 84 to 88 wt%.

[0186] Typically, the compositions of the invention comprise 5 to 40 wt%, preferably from 10 to 35 wt%, and more preferably from 12 to 30 wt% such as 15 to 25 wt% of the bleaching agent.PAT15863-WO-PCT

[0187] For multi-phase compositions of the invention, bleaching agents are preferably present in a solid phase if such a phase is present.

[0188] h) Bleach activators / catalysts

[0189] The compositions of the present invention preferably comprise one or more bleach activators and / or one or more bleach catalysts when the compositions comprise a bleaching agent which is advantageously used with a bleach activator and / or catalyst.

[0190] Any suitable bleach activator may be included, for example Tetraacetylethylenediamine (TAED), if this is desired for the activation of the bleaching agent. Any suitable bleach catalyst may be used, for example manganese acetate or dinuclear manganese complexes such as those described in EP 1741774 Al, the contents of which are incorporated herein by reference. The bleach catalyst may be a manganese complex comprising 1,4,7-Triazacyclononane (TACN), or any derivatives of a TACN ligand, for example 1,4,7-trimethyl-TACN, manganese oxalate, manganese acetate or a dinuclear manganese complex, for example a dinuclear manganese complex comprising TACN or any derivatives of a TACN ligand, for example 1,4,7-trimethyl-TACN. The compositions of the invention may preferably comprise both a bleach activator and a bleach catalyst.

[0191] The one or more bleach activators and / or one or more bleach catalysts may be present in the compositions of the invention in conventional amounts. Typically, the bleach activator, when present, is included in the compositions in amounts of 0.05 to 8 wt%, more preferably 1 to 7 wt%, such as 2 to 6 wt%. Typically, the bleach catalyst, when present, is included in the compositions in amounts of 0.005 to 2 wt%, more preferably 0.01 to 1.5 wt%, such as 0.1 to 1 wt%.

[0192] For multi-phase compositions of the invention, bleaching activators and / or catalysts may be present in any phase.PAT15863-WO-PCT

[0193] i) enzymes

[0194] The automatic dishwashing compositions of the present invention may, and preferably comprise one or more enzymes. It is preferred that the one or more enzymes are selected from protease, lipase, amylase, cellulase and peroxidase, with protease and amylase 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 compositions for the removal or proteinaceous and starch-based soils respectively. A preferred enzyme combination to be used in the compositions of the invention is a mixture of alpha-amylase and protease (subtilisin). Typically the protease will be used in a higher amount than the alpha-amylase.

[0195] The one or more enzymes may be present in a total amount from 0.05 to 5 %wt., preferably 0.1 to 4 wt%., more preferably 0.25 to 3 wt%., especially 0.5 to 2 wt%., such as 0.57 to 1.5 wt%., based on the weight of the dishwashing composition.

[0196] For multi-phase compositions of the invention, enzymes are preferably present in a solid phase if such a phase is present.

[0197] j) Optional additives.

[0198] The compositions of the invention may comprise one or more of the following optional additives: dyes, perfumes, antifoams, corrosion inhibitors (such as benzotriazole) and thickeners. Any types of these ingredients may be included in the compositions of the invention. Such ingredients may be included in the compositions of the invention in conventional amounts depending upon the effect desired from their inclusion.

[0199] For multi-phase compositions of the invention, optional additives may be included in any appropriate phase.

[0200] k) water

[0201] The compositions of the present invention may comprise some water even if only present through the raw materials used in the compositions. If the composition has added waterPAT15863-WO-PCT

[0202] (not part of an ingredient in the composition) it may be added in any suitable amount dependent upon the format of the composition and its desired properties e.g. viscosity if not a solid composition. If the composition of the invention is held within a water-soluble container, for example a PVOH container, it is preferred to keep the water content of the composition low to ensure the integrity of the container. Therefore, for compositions held within a water-soluble container and also for solid compositions, the compositions preferably contain less than 10 wt% water, more preferably less than 5 wt% water and especially less than 2 wt%, and they may contain no added water and may be anhydrous.

[0203] l) pH of the compositions

[0204] The automatic dishwashing compositions of the present invention typically have a pH in the range of from 9 to 13, preferably 9.2 to 12, more preferably 9.5 to 11.5, most 9.7 to 11, for example 10 to 10.8. The pH of the composition is measured at room temperature, typically 21°C ±1°C. The pH is measured as a 1% w / w aqueous solution.

[0205] m) water-soluble containers and automatic dosing systems

[0206] The water-soluble film used to produce the water-soluble container may be rigid or flexible at room temperature. The container may be formed by any suitable method, preferably by a thermoforming process. Preferably the water-soluble container comprises a water-soluble film comprising poly(vinyl alcohol). Preferably, the poly(vinyl alcohol) film (PVOH) may be partially or fully alcoholised or hydrolysed, for example, it may be from 40 to 100%, preferably 70 to 92%, most preferably 85% to 92%, alcoholised or hydrolysed, polyvinyl acetate film. The degree of hydrolysis is known to influence the temperature at which the PVOH starts to dissolve in water. 88% hydrolysis corresponds to a film soluble in cold (i.e. room temperature of 20°C) water, whereas 92% hydrolysis corresponds to a film soluble in warm water. The film may be cast, blown or extruded. It may further be unoriented, mono-axially oriented or bi-axia lly oriented.

[0207] In a preferred embodiment, said water-soluble container comprises two or more compartments, preferably 3 or more compartments. In this embodiment, at least one compartment of the water-soluble container contains an automatic dishwashingPAT15863-WO-PCT

[0208] composition in any form according to the invention. In another preferred embodiment of the present invention, the compositions contained in two or more compartments may together form the composition according to the invention. In this embodiment, the essential ingredients of the compositions of the invention may be present across two or more different compartments in the water-soluble container, provided the container is used to dose the composition of the invention into a dishwashing machine to carry out a dishwashing operation. Preferably, at least one compartment of the water-soluble container contains a solid composition according to the invention.

[0209] The dishwashing compositions of the invention may also be included in an auto-dosing automatic dishwashing system. For example, the auto-dosing automatic dishwashing system may comprise at least one cartridge, for example at least a first cartridge and at least a second cartridge arranged inside or connected with, a dishwashing machine, wherein at least one cartridge contains an automatic dishwashing detergent composition according to the present invention.

[0210] n) manufacture of the dishwashing compositions

[0211] The compositions of the present invention may be produced by any suitable method.

[0212] According to one aspect of the present invention there is provided a method of producing an automatic dishwashing composition according to the present invention, which method comprises the addition of a carboxyalkyl tamarind and a pH independent cationic polymer, either simultaneously or sequentially, to at least one other ingredient of the composition. Typically, the carboxyalkyl tamarind and the pH independent cationic polymer will be added with any other solid ingredients during the production process, especially if the composition is in solid form. If the composition is a liquid (e.g. a liquid, gel or foam) any suitable method of manufacture of the composition may be used.

[0213] o) use of the dishwashing compositions

[0214] The compositions of the invention are used in automatic dishwashing applications. The compositions of the invention are suitable for use in conventional dishwashing machinesPAT15863-WO-PCT

[0215] and using conventional conditions with water temperatures typically being between 20°C and 85°C, such as 30°C to 70°C, or, 35°C to 60°C. The compositions of the invention are suitable for use in conventional dishwashing cycles including shorter cycles and are dosed typically in amounts of 5 to 25 grams, such as 10 to 20 grams per machine dishwashing cycle. The compositions of the invention of intended for use in pre-wash and main wash cycles of a dishwashing machine, especially main wash cycles. However, the compositions may be used in a rinse cycle in addition to, or as an alternative to, the wash cycles if the compositions of the invention are formulated appropriately for rinse cycle use.

[0216] The automatic dishwashing composition according to the invention are used to inhibit the formation of scale on articles treated with the composition during an automatic dishwashing operation, and in particular to provide a shiny appearance of the treated articles. The compositions of the present invention have been found to be especially effective to provide the aforementioned benefits to plastic articles (e.g. polypropylene articles), stainless steel articles and articles with non-stick coatings, such as ceramic coatings. The compositions of the invention may also be used to treat glass articles and metal articles such as cutlery and to provide the benefits of the invention.

[0217] The ability of the automatic dishwashing compositions of the present invention to inhibit (to either reduce or prevent) the build-up of scale on articles treated therewith is observed as reduced scale spotting and / or scale filming on the treated articles compared to the same type of articles treated with a composition which does not comprise a scale inhibition system. This reduction in scale spotting and / or scale filming can be observed on the treated articles as fewer spots and / or a less noticeable film compared to articles washed in a composition which does not comprise a scale inhibition system. The reduction in scale spotting and / or filming also generally results in an appearance of 'shine' on the surface of the articles washed with the compositions or system of the invention. A further benefit of the invention is the present invention provides a biodegradable and natural (biosourced) scale inhibition system and dishwashing compositions, especially automatic dishwashing compositions, comprising the system. Biodegradable and natural (biosourced) materials and compositions are desirable on sustainability grounds. It has been found that thePAT15863-WO-PCT

[0218] biodegradable and natural (biosourced) compositions and system of the present invention have at least equal performance to conventional non-biodegradable, synthetic, scale inhibition systems and compositions comprising them.

[0219] The invention will now be described in more detail with reference to the following nonlimiting examples. Further examples within the scope of the present invention will be apparent to the person skilled in the art.

[0220] Examples

[0221] The following examples illustrate comparative compositions and preferred embodiments of the invention. It is to be understood that these examples are provided by way of illustration only and that further useful compositions falling within the scope of the present invention and the claims may be readily produced by one skilled in the art without deviating from the scope and spirit of the invention.

[0222] Example 1, Comparative Composition 1 and Comparative Composition 2 are tested within a multi-compartment water-soluble container having three compartments. The first compartment contains the powder composition, the second compartment contains the gel composition and the third compartment contains the liquid composition. The ingredients included in the powder, gel and liquid phases are shown in Table 1. Therefore, the compositions in Table 1 are all multi-phase compositions.

[0223] Example 1 is a composition according to the invention. It comprises a combination of carboxyalkyl tamarind (carboxymethyl tamarind) and a pH independent cationic polymer having a least one quaternary ammonium group (polyquaternium 2) as a biodegradable (and biosourced) scale inhibition system.

[0224] Comparative Composition 1 comprises a combination of a known non-biodegradable acrylic acid based polymer, namely, poly(acrylic acid co 2-acrylamido-2-methylpropane sulfonic acid) polymer (available as Acusol™ 588 ex DOW) and a pH independent cationic polymerPAT15863-WO-PCT

[0225] having a least one quaternary ammonium group (polyquaternium 2) as a scale inhibition system.

[0226] Comparative Composition 2 comprises carboxyalkyl tamarind (carboxymethyl tamarind) as a scale inhibition system in the absence of a polyquaternium.

[0227] The solid compositions in Table 1 were produced using the following method:

[0228] The solids were mixed together for 1 minute to produce a solid pre-mix. The liquid ingredients, namely the perfume and the polyquaternium 2, were added dropwise to the solid pre-mix and the resultant mixture was mixed until no lumps were visible (mixing took approximately 4 minutes).

[0229] The gel composition was produced by mixing the ingredients together.

[0230] Table 1: Automatic dishwashing compositions used in a multi-compartment water-soluble container.

[0231]

[0232] PAT15863-WO-PCT

[0233]

[0234] *1The carboxymethyl tamarind used in Comparative Composition 2 and Example 1 is a powder with an active carboxymethyl tamarind concentration of about 85%. The active concentration of this ingredient in Comparative Composition 2 and Example 1 in Table 1 is about 7.99wt%. The carboxymethyl tamarind has a carboxymethyl degree of substitution,PAT15863-WO-PCT

[0235] DSCA, of 0.336 (measured value according to ASTM D1439-15). This material is available from Shree Krishna Industries and Group.

[0236] *2The polyquaternium (polyquaternium 2) (bio-)polymer used in Comparative Composition 1 and Example 1 is a 25wt% solution of polyquaternium 2 (available as Lugalvan™ P ex BASF). The active concentration of this ingredient in Comparative Composition 1 and Example 1 in Table 1 is 0.025wt%.

[0237] □

[0238] * l-hydroxyethylidene-l,l-diphosphonic acid (HEDP), about 88 wt% active.

[0239] *4Sodium percarbonate granules, about 80% active sodium percarbonate.

[0240] *5Poly(acrylic acid co 2-acrylamido-2-methylpropane sulphonic acid) available as Acusol™ 588 from Dow is a non-biodegradable scale inhibitor.

[0241] *6The nonionic surfactant used in Comparative Composition 1 was ROKAnol ™ L5P5 (an alkoxylated fatty alcohol, C12-C14 EO-PO alcohol, nonionic surfactant (also known as PPG-5 laureth 5), 99.5% active, available from PCC Exol S.A.). The nonionic surfactant used in Comparative Composition 2 and Example 1 was Genapol™ EP2584 (an alkoxylated fatty alcohol, C12-C14 EO-PO alcohol, nonionic surfactant, 100% active, available from Clariant). *7a bleach catalyst / bleach activator mixture available as Peractive FDO X, available from Weylchem. It is a combination of 2 wt% MnTACN and 75 wt% TAED. The compositions comprise 0.12 wt% MnTACN and 4.5 wt% TAED from the Peractive FDO X.

[0242] Q

[0243] * The enzyme mixture contained alpha-amylase and protease as the enzymes and provided 0.15 wt% alpha-amylase and 0.71 wt% protease (subtilisin) to the composition (based on the total weight of the composition).

[0244] *9The additives were: 0.01 wt% liquid dye, 0.8 wt% Polyglycol P41 / 12000 (a liquid polyalkylene glycol available from Dow) used as a thickener, 0.1 wt% benzotriazole and 0.1 wt% antifoam.

[0245] *10Sokalan CP7™ (a copolymer of maleic acid and acrylic acid) available from BASF is a non-biodegradable scale inhibitor.PAT15863-WO-PCT

[0246] For each of the compositions in Table 1, 13.4g in total of the compositions was included in a water-soluble container. The compositions were used in the relative proportions given in Table 1. Each phase of the composition was included in a separate chamber of the multicompartment PVOH water soluble container. Thus, each PVOH water soluble container had one powder compartment, one gel compartment and one liquid compartment.

[0247] The multi-compartment PVOH water soluble containers (comprising the aforementioned compositions) were produced using conventional thermoforming techniques and were of a conventional size used for automatic dishwashing applications. The PVOH water soluble containers were used in the experimental testing as described below.

[0248] The multi-compartment compositions in Table 1 were used in an automatic dishwasher to wash polypropylene plates, stainless steel casseroles and non-stick pans with a ceramic non-stick coating as detailed below. After the dishwashing cycle was complete, the washed items were assessed to evaluate the level of scale filming on them and the level of shine exhibited by the items.

[0249] The level of filming and the shine performance of each of the compositions in Table 1 was assessed using the following method.

[0250] The test was conducted under EU consumer relevant conditions using a Bosch dishwasher SMS6ECW57E / 10 run on program Eco 50°C, 21 °GH water hardness. No rinse aid or dishwasher salt was added to the machine. A PVOH water soluble container above (one for each of the Comparison Compositions and one for Example 1) was added to the dispensing draw of the dishwasher. Each composition was used in the dishwasher for a total of 6 dishwasher cycles with a new water-soluble container added for each cycle. The first 3 cycles used 16 grams of artificial soil and the last 3 cycles used 48 grams of artificial soil. The composition of the artificial soil is shown below in Table 2. The results were assessed at the end of the 6 cycles. The items being washed in the dishwasher were not removed until the end of the sixth cycle when they were removed and allowed to air dry. PolypropylenePAT15863-WO-PCT

[0251] plates, stainless steel casseroles and stainless-steel pans with ceramic non-stick coating were placed in the dishwasher, together with other non-evaluated tableware.

[0252] Table 2: artificial soil

[0253]

[0254] The artificial soil of Table 2 was prepared using the following method. The eggs are mixed in a container until homogenous (without the shells). The water is added to a separate container and the potato flour, wheat flour and cornstarch are added to the water and the mixture is heated up to approx. 70°C with continuous stirring. The container is then placed in a cold water bath and left to cool to about 40°C while stirring occasionally to produce Mixture 1. The sunflower oil and margarine are melted separately in a container on a low heat and then allowed to cool to approx. 30 °C to produce Mixture 2. The tomato ketchup,PAT15863-WO-PCT

[0255] mustard, whipped cream and sugar are added to a separate container and mixed well with a whisk to produce Mixture 3. The skimmed-milk powder and benzoic acid are combined in a separate container. The benzoic acid must not contain any lumps. If lumps are present or if it is too coarse, it must be crushed with a mortar. This produces Mixture 4. Mixture 2 is added to the egg container and the resultant mixture is stirred for 5 minutes. Mixture 3 is added thereto and the resultant mixture is stirred for a further 5 minutes. Mixture 4 is added to this mixture (by hand with a whisk) and the resultant mixture is stirred for 10 minutes. Finally, Mixture 1 is added to this stirred mixture and the resultant mixture is stirred for a further 5 minutes. Once the final mixture has been prepared, it is sieved with a conventional kitchen sieve to remove any large lumps of mixture.

[0256] For testing the compositions of Table 1, prior to the testing of a new composition the dishwasher sieve system and the dishwasher main wash chamber was cleaned with a strong alkaline detergent followed by a clean with citric acid. Once the dishwasher had been prepared, the dishwasher was run for a total of 6 cycles as detailed above.

[0257] The items were visually evaluated by two trained experts (wearing cotton gloves) together to assess the level of scale "filming" on the items. The evaluations were made by putting a washed item into a black box (black interior lining with a halogen lamp light source fixed to the ceiling of the box) and viewing the level of filming against the light through a viewing window.

[0258] The filming scores are assessed and recorded according to the following scale. To provide the level of shine on the washed articles typically desired by the consumer, the filming score should be no higher than 3 and ideally 2 or below. The lower the assessed score for filming, the lower the level of filming and the better the performance of the composition:

[0259] 5 = Extremely strong filming

[0260] 4 = Very strong filming

[0261] 3 = Strong filming

[0262] 2 = Slight filmingPAT15863-WO-PCT

[0263] 1 = No filming.

[0264] Table 3 shows the results of the assessment of the items washed in the dishwasher for 6 cycles under the stated conditions. The results given in the table below are the scores at the end of the 6 wash cycles for each composition.

[0265] Table 3: Assessment of scale film formation

[0266]

[0267] The scale filming results in Table 3 demonstate that the combination of the carboxymethyl tamarind and the polyquaternium (polyquaternium 2) as the scale inhibition system in Example 1 is the more effective in inhibiting the formulation of a scale film on polypropylene plates than the non-biodegradable poly(acrylic acid co 2-acrylamido-2-methylpropane sulfonic acid) polymer and polyquaternium scale inhibition system of Comparative Composition 1, and, more effective than the carboxymethyl tamarind used alone as the scale inhibition system of Comparative Composition 2.

[0268] The scale filming results in Table 3 also demonstate that the combination of the carboxymethyl tamarind and the polyquaternium as the scale inhibition system in Example 1 is the more effective in inhibiting the formulation of a scale film on stainless steel casseroles than the non -biodegradable poly(acrylic acid co 2-acrylamido-2-methylpropane sulfonic acid) polymer and polyquaternium (polyquaternium 2) scale inhibition system ofPAT15863-WO-PCT

[0269] Comparative Composition 1, and, the carboxymethyl tamarind used alone as the scale inhibition system of Comparative Composition 2.

[0270] The scale filming results in Table 3 also demonstate that the combination of the carboxymethyl tamarind and the polyquaternium as the scale inhibition system in Example 1 is effective in inhibiting the formulation of a scale film on stainless steel pans with nonstock ceramic coating. For these items the scale inhibition system of Example 1 performs as well as the non-biodegradable poly(acrylic acid co 2-acrylamido-2-methylpropane sulfonic acid) polymer and polyquaternium (polyquaternium 2) scale inhibition system of Comparative Composition 1. Example 1 outperforms the carboxymethyl tamarind used alone as the scale inhibition system of Comparative Composition 2 showing the benefit of using the combination of the carboxymethyl tamarind and the polyquaternium (polyquaternium 2) scale inhibition system.

[0271] The carboxymethyl tamarind and the polyquaternium (polyquaternium 2) scale inhibition system of Example 1 achieves the lowest scale filming results of the 3 compositions tested across the tested items (which are of different materials) resulting in the highest level of shine on those items.

Claims

PAT15863-WO-PCTClaims1. An automatic dishwashing composition comprising:(a) 0.1 to 25 wt% carboxyalkyl tamarind having a carboxyalkyl degree of substitution DSCA of from 0.01 to 0.390,(b) 0.001 to 10 wt% pH independent cationic polymer,(c) 1 to 70 wt% builder,(d) 0.2 to 40 wt% surfactant.

2. An automatic dishwashing composition according to Claim 1, wherein the composition comprises 2 to 15 wt% carboxyalkyl tamarind.

3. An automatic dishwashing composition according to Claim 1 or 2, wherein the carboxyalkyl tamarind comprises carboxymethyl tamarind.

4. An automatic dishwashing composition according to any one of the preceding claims, wherein the composition comprises 0.01 to 0.5 wt% pH independent cationic polymer.

5. An automatic dishwashing composition according to any one of the preceding claims, wherein the pH independent cationic polymer has at least one quaternary ammonium group.

6. An automatic dishwashing composition according to Claim 5, wherein the pH independent cationic polymer having at least one quaternary ammonium group is of Formula (IV):(IV) -(R-O-R-N+R2X-R-NH-C(=O)-NH-R-N+R2X-)nwherein each R is independently a C1-C4 alkyl group, n=l-1000, and X=halide, preferably Cl.

7. An automatic dishwashing composition according to Claim 6, wherein the pH independent cationic polymer having at least one quaternary ammonium group is ofPAT15863-WO-PCTFormula (IV) is selected from the group consisting of Polyquaternium-2, Polyquaternium-4, Polyquaternium-6, Polyquaternium-7 or Polyquaternium-10.

8. An automatic dishwashing composition according to Claim 7 , wherein the pH independent cationic polymer having at least one quaternary ammonium group is of Formula (IV) is Polyquaternium-2.

9. An automatic dishwashing composition according to any one of the preceding claims, wherein the composition comprises 20 to 60 wt% builder.

10. An automatic dishwashing composition according to any one of the preceding claims, wherein the builder is selected from the group consisting of citrate salts, carbonate salts, phosphonates and aminocarboxylates.

11. An automatic dishwashing composition according to any one of the preceding claims, wherein the composition comprises 1 to 35 wt% surfactant.

12. An automatic dishwashing composition according to any one of the preceding claims, wherein the surfactant is selected from the group consisting of fatty alcohol alkoxylates, fatty acid alkoxylates and alkyl phenol alkoxylates.

13. An automatic dishwashing composition according to any one of the preceding claims, wherein the composition is a multi-phase composition.

14. An automatic dishwashing composition according to any preceding claim, wherein the composition is contained within a water-soluble container.

15. An automatic dishwashing composition according to Claim 14, wherein the water- soluble container is a multi-compartment water-soluble container.

16. The use of an automatic dishwashing composition according to any one of Claims 1 to 15, to inhibit the formation of scale on articles treated with the composition during an automatic dishwashing operation.PAT15863-WO-PCT17. A method of producing an automatic dishwashing composition according to any one of Claims 1 to 15, which method comprises the addition of a carboxyalkyl tamarind and a pH independent cationic polymer, either simultaneously or sequentially, to at least one other ingredient of the composition.

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