Patent Publication Number: US-2019194576-A1

Title: Detergent pack

Description:
TECHNICAL FIELD 
     The present invention is in the field of detergent packs. In particular it relates to detergent packs comprising a combination of a packaging container and a water-soluble cleaning product. The invention also relates to a method of preventing or reducing malodour in the interior of a packaging container containing a water-soluble cleaning product. 
     BACKGROUND OF THE INVENTION 
     Cleaning detergent compositions are usually perfumed. Powdered cleaning products usually include perfume sprayed onto the powder. Liquid cleaning products usually include perfume dissolved/emulsified therein. In traditional products, part of the perfume is released from the composition into the headspace of the pack providing a pleasant smell each time that the pack is opened or at least for the first few times. Consumers associate the pleasant smell with cleaning capacity and expect to perceive an agreeable smell time that the pack is opened. 
     Water-soluble cleaning products in unit dose form have become widely spread. The products consist of enveloping water-soluble material that wraps the cleaning composition. The water-soluble enveloping material, usually a polyvinyl alcohol film is usually permeable to relatively small molecules, such as water and amine based malodours. The products are stored in a pack, the pack is usually permeable to small molecules but in some case the rate of malodour generation is faster than the rate of permeation of the malodour to the surrounding environment, in this conditions the malodour can be concentrated in the headspace and it is released every time that the user opens the bag, this malodour is not very pleasant and may connote lack of cleaning. 
     Some amine-comprising cleaning actives can generate malodours either from by-products originating from the synthesis, from degradation or from interaction with other components in the cleaning product. The objective of the present invention is to find a cleaning composition containing malodour-generating amine-containing cleaning actives with improved smell. 
     SUMMARY OF THE INVENTION 
     According to a first aspect of the invention there is provided a detergent pack. The pack comprises a plurality of water-soluble unit-dose detergent products the products comprising a detergent composition and an enveloping material. The detergent composition comprises from 15% to 50%, preferably from 20 to 30% of amine-containing cleaning active. The amine-containing cleaning active generate malodours (nitrogen based compound). The composition also comprises a malodour reducing agent. The product presents a good olfactory profile. 
     The detergent pack can be impermeable or permeable to malodours however the malodours can generate faster that they can leave the pack thereby accumulating in the headspace. 
     By “unit-dose form” is herein meant that the composition is provided in a form sufficient to provide enough detergent for one wash. Suitable unit dose forms include sachets, capsules, pouches, etc. Preferred for use herein are compositions wrapped in water-soluble material made of polyvinyl alcohol. The detergent product of the invention preferably weighs from about 8 to about 25 grams, preferably from about 10 to about 20 grams. This weight range fits comfortably in a dishwasher dispenser. 
     The detergent composition of the pack of the invention is sometimes herein referred as “the composition of the invention”. 
     Detergent compositions may comprise amine-containing cleaning actives, these cleaning actives generate malodours that may be caused by impurities, degradation or interaction with other components of the composition, such as bleach. By “cleaning active” is herein understood an ingredient that is part of a detergent product and contributes to cleaning. 
     Preferred amine-containing cleaning active for use herein is selected from the group consisting of aminocarboxylic complexing agent, amine oxide surfactant and mixtures thereof. 
     The aminocarboxylic complexing agent is selected from the group consisting of methyl glycine diacetic acid, its salts and derivatives thereof, glutamic-N,N-diacetic acid, its salts and derivatives thereof and mixtures thereof. Especially preferred for use herein is the tri-sodium salt of methyl glycine diacetic acid. 
     Preferably the amine-containing cleaning active is in particulate form. The particulate composition is preferably in the form of loose powder. By “loose-powder” is herein meant a powder comprising a plurality of independent particles, i.e., the particles are not bound to one another. When the loose powder is delivered into the dishwasher the particles in the wash liquor are found as individual entities rather than in the form of a single entity constituted by a plurality of particles. The particulate loose-powder can be enveloped by a water-soluble wrapping or encasing material such as a water-soluble film or an injection-moulded container. Particulate loose-powder wrapped in water-soluble material is considered “loose powder” for the purpose of the invention because once the enveloping water-soluble material is dissolved the particles are found in the wash liquor as individual entities. Pressed tablets are not considered a product comprising a particulate loose powder composition. Malodour generation in a loose powder can be faster. 
     By “malodour reducing agent” is herein meant a material capable of reducing the amount of ammonia generated by 100 grams of a composition comprising a malodour-generating amine-containing cleaning active by at least 50%, more preferably at least 70% and especially 90%, when the composition is placed in a sealed PE/PET laminated bag and placed in an oven at 50° C. for 24 hours and the amount of malodour reducing agent is less than 15%, preferably less than 10% and more than 0.1% the weight of the malodour-generating amine-containing cleaning active. 
     Preferably, the malodour reducing agent is a monomeric or polymeric carboxylic acid having a pH of less than 7 as measured in 1% weight aqueous solution in distilled water at 20° C. The preferred carboxylic acid to use herein are citric acid and carboxylated/sulfonated polymers. 
     Preferably, the composition of the invention is alkaline, by “alkaline” is herein meant that the pH of the composition is greater than 7, preferably greater than 9 as measured in 1% weight aqueous solution in distilled water at 20° C. Alkaline composition can be more prone to chemical instability caused by moisture. Preferably the composition of the invention comprises bleach, more preferably sodium pecarbonate. Bleach can contribute to malodour generation by interacting with the amine-containing cleaning active. 
     Especially preferred herein are detergent products the products in which the enveloping material is a water-soluble film, more preferably a polyvinyl alcohol film, preferably having a thickness of less than 100 μm. These films are permeable to amine based malodours. Detergent packs comprising these detergent products can present acute malodour problems. 
     When the detergent is in particulate form, the enveloping material preferably has a pin hole to allow the escape of any gases that might form during the storage of the detergent product. This facilitates the escape of amine based malodours further contributing to the malodour of the detergent pack. 
     According to a second aspect of the invention, there is provided the use of a material comprising a carboxylic functionality for reducing malodour of an alkaline detergent composition comprising from about 15% to 50% of amine-containing cleaning active that generate malodour. 
     The elements of the composition of the invention described in connection with the first aspect of the invention apply mutatis mutandis to the second aspect of the invention. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention envisages a detergent pack. The detergent pack comprises a plurality of water-soluble unit-dose detergent products. The products comprise an enveloping material (preferably a polyvinyl alcohol film) and an amine-containing cleaning active that generates a malodour and a malodour reducing agent. The composition presents good olfactory profile. The invention also envisages the use of a malodour reducing agent comprising a carboxylic functionality for reducing malodour of an alkaline detergent composition comprising from about 15% to 50% of amine-containing cleaning active that generate malodour. 
     Detergent Pack 
     The detergent pack can be a tub, tray, jar, bottle, bag, box, etc, preferably the pack is reclosable. Preferably the pack is a reclosable flexible bag and preferably self-standing. 
     By “flexible” bag is understood a bag which can be easily deformed with a hand squeeze, preferably deformed by the mere act of holding the bag. 
     Water-Soluble Unit-Dose Detergent Products 
     The composition of the invention is presented in unit-dose form. Products in unit dose form include capsules, sachets, pouches, injection moulded containers, etc. Preferred packs are pouches, where the detergent composition is enveloped by a water-soluble film, preferably having a thickness of less than 100 μm and injection moulded containers wherein the detergent composition is placed in a container of water-soluble material made by injection moulding. Both the detergent composition and the enveloping material are water-soluble. They readily dissolve when exposed to water in an automatic dishwashing process, preferably during the main wash. The detergent products can have a single compartment or a plurality of compartments. The compartments can comprise a composition in liquid or solid form. Preferably the composition of the invention or part thereof is in particulate form and wrapped by a water-soluble film, preferably having a thickness of less than 100 μm. 
     Preferably, the unit dose detergent can by in the form of a multi-compartment pouch or injection moulded container. By “multi-compartment” is herein meant a pouch or injection moulded container having at least two compartments, preferably at least three compartments, each compartment contains a composition surrounded by enveloping material, preferably polyvinyl alcohol. The compartments can be in any geometrical disposition. The different compartments can be adjacent to one another, preferably in contact with one another. Especially preferred configurations for use herein include superposed compartments (i.e. one above the other), side-by-side compartments, etc. Especially preferred from a view point of automatic dishwasher dispenser fit, stability and enveloping material reduction are multi-compartment pouches or containers having some superposed compartments and/or some side-by-side compartments. 
     Enveloping Material 
     The enveloping material is water soluble. By “water-soluble” is herein meant that the material has a water-solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out herein after using a glass-filter with a maximum pore size of 20 microns. 50 grams +−0.1 gram of enveloping material is added in a pre-weighed 400 ml beaker and 245 ml +−1 ml of distilled water is added. This is stirred vigorously on a magnetic stirrer set at 600 rpm, for 30 minutes at 20° C. Then, the mixture is filtered through a folded qualitative sintered-glass filter with a pore size as defined above (max, 20 micron). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material is determined (which is the dissolved or dispersed faction). Then, the % solubility can be calculated. 
     The enveloping material is any water-soluble material capable of enclosing the cleaning composition of the product of the invention. The enveloping material can be a polymer that has been injection moulded to provide a casing or it can be a film. Preferably the enveloping material is made of polyvinyl alcohol. Preferably the enveloping material is a water-soluble polyvinyl alcohol film. 
     The pouch can, for example, be obtained by injection moulding or by creating compartments using a film. The enveloping material is usually moisture permeable. The pouch of the invention is stable even when the enveloping material is moisture permeable. The liquid composition confers stability to the pouch, in terms of both interaction among the different compositions and interaction with the surrounding environment. 
     Preferred substances for making the enveloping material include polymers, copolymers or derivatives thereof selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof. Especially preferred for use herein is polyvinyl alcohol and even more preferred polyvinyl alcohol films. 
     Most preferred enveloping materials are PVA films known under the trade reference Monosol M8630, as sold by Kuraray, and PVA films of corresponding solubility and deformability characteristics. Other films suitable for use herein include films known under the trade reference PT film or the K-series of films supplied by Aicello, or VF-HP film supplied by Kuraray. 
     The enveloping material herein may comprise other additive ingredients than the polymer or polymer material and water. For example, it may be beneficial to add plasticisers, for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, dipropylene glycol, sorbitol and mixtures thereof. Preferably the enveloping material comprises glycerol as plasticisers. Other useful additives include disintegrating aids. 
     Detergent Composition 
     The detergent composition of the invention is presented in unit-dose form and it can be in any physical form including solid, liquid and gel form. The composition of the invention is very well suited to be presented in the form of a multi-compartment pack, more in particular a multi-compartment pack comprising compartments with compositions in different physical forms, for example a compartment comprising a composition in solid form and another compartment comprising a composition in liquid form. The composition is preferably enveloped by a water-soluble film such as polyvinyl alcohol. The composition comprises malodour-generating amine-containing cleaning active, preferably an aminocarboxylic complexing agent, preferably the tri-sodium salt of MGDA, preferably a sulfonated polymer comprising 2-acrylamido-2-methylpropane sulfonic acid monomers, a bleach, preferably sodium percarbonate and preferably an inorganic builder, more preferably carbonate, a bleach activator, a bleach catalyst, protease and amylase enzymes, non-ionic surfactant, a crystal growth inhibitor, more preferably HEDP. The composition is preferably free of citrate. 
     The composition of the invention preferably has a pH as measured in 1% weight/volume aqueous solution in distilled water at 20° C. of from about 9 to about 12, more preferably from about 10 to less than about 11.5 and especially from about 10.5 to about 11.5. 
     The composition of the invention preferably has a reserve alkalinity of from about 10 to about 20, more preferably from about 12 to about 18 at a pH of 9.5 as measured in NaOH with 100 grams of product at 20° C. 
     Malodour-Generating Amine-Containing Cleaning Active 
     The malodour-generating amine-containing cleaning active are preferably selected from aminocarboxylic complexing agents, amine oxide surfactants and mixtures thereof. 
     Aminocarboxylic Complexing Agent 
     A complexing agent is a material capable of sequestering hardness ions, particularly calcium and/or magnesium. 
     The composition of the invention comprises from 5% to 50% of complexing agent, preferably from 10 to 40% by weight of the composition. The complexing agent is preferably selected from the group consisting of methyl-glycine-diacetic acid, its salts and derivatives thereof, glutamic-N,N-diacetic acid, its salts and derivatives thereof, and mixtures thereof. Especially preferred complexing agent for use herein is a salt of MGDA, in particular the tri-sodium salt of MGDA. 
     Preferably, the complexing agent is in particulate form. The particle preferably comprises:
         a) from 20 to 95%, more preferable from 40 to 60% by weight of the particle of aminocarboxylic acid, preferably a salt of methyl glycine diacetic acid, more preferably the tri-sodium salt;   b) from 5 to 80% by weight of the particle of material selected from the group consisting of:
           i) polyalkylene glycol, preferably polyethylene glycol   ii) nonionic surfactant;   iii) a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), and   iv) a mixture thereof.   
               

     Preferred polyethylene glycols in component (b) have an average molecular weight (weight-average molecular weight) of from 500 to 30,000 g/mol, more preferably of from 1000 to 5000 g/mol, most preferably from 1200 to 2000 g/mol. 
     Nonionic surfactants in component (b) are preferably selected from the group consisting of alkoxylated primary alcohols, alkoxylated fatty alcohols, alkylglycosides, alkoxylated fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides. Preferably the nonionic surfactant in component (b) has a melting point of above 20° C. 
     The particle may be produced by dissolving components (a) and (b) in a solvent and spray-drying the resulting mixture, which may be followed by a granulation step. In this process, components (a) and (b) may be dissolved separately, in which case the solutions are subsequently mixed, or a powder mixture of the components may be dissolved in water. Useful solvents are all of those which can dissolve components (a) and (b); preference is given to using, for example, alcohols and/or water, particular preference to using water. Spray-drying is preferably followed by a granulation step. 
     Preferably the particle has a weight geometric mean particle size of from about 700 to about 1000 um with less than about 3% by weight above about 1180 μm and less than about 5% by weight below about 200 μm. Preferably the particle has a bulk density of at least 550 g/l, more preferably from about 600 to about 1,400 g/l, even more preferably from about 700 g/l to about 1,200 g/l. This makes the particle suitable for use in detergent compositions, especially automatic dishwashing detergent compositions. 
     Amine Oxide Surfactant 
     Amine oxides surfactants are useful for use in the composition of the invention. Preferred are C10-C18 alkyl dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide. Amine oxide surfactants may be present in amounts from 0 to 15% by weight, preferably from 0.1% to 10%, and most preferably from 0.25% to 5% by weight of the composition. 
     Malodour Reducing Agent 
     Suitable materials for use as malodour reducing agents include monomeric or polymeric carboxylic acids, either in the form of the free acid or in partly neutralized form. In the context of the present invention, the term “acid” therefore includes both the acids in free form and in partly neutralized form. Preferably the acid should have a pH of less than 7 as measured in 1% weight aqueous solution in distilled water at 20° C. Preferred counterions are especially sodium ions. Preferred organic acids are citric acid, ascorbic acid, oxalic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, famaric acid, sugar acids, aminocarboxylic acids, fatty acids and mixtures thereof. Particularly preferred organic acids are oxalic acid, ascorbic acid, citric acid and fatty acids. The polymeric acids used herein can be polymers of acrylic acid and copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Especially preferred organic acids are citric acid, ascorbic acid and oxalic acid. 
     Dispersant polymers discussed in more detail herein below are very suitable for use as malodour reducing agent. In particular carboxylic based sulfonated polymers. 
     Dispersant Polymer 
     The polymer, if present, is used in any suitable amount from about 0.1% to about 30%, preferably from 0.5% to about 20%, more preferably from 1% to 10% by weight of the composition. Preferably the dispersant polymer is a sulfonated polymer, more preferably a sulfonated polymer comprising 2-acrylamido-2-methylpropane sulfonic acid monomers and carboxyl monomers. 
     Polycarboxylate Polymer 
     For example, a wide variety of modified or unmodified polyacrylates, polyacrylate/maleates, or polyacrylate/methacrylates are highly useful. It is believed these polymers are excellent dispersing agents and enhance overall detergent performance, particularly when used in the composition of the invention. 
     Suitable polycarboxylate-based polymers include polycarboxylate polymers that may have average molecular weights of from about 500 Da to about 500,000 Da, or from about 1,000 Da to about 100,000 Da, or even from about 3,000 Da to about 80,000 Da. Suitable polycarboxylates may be selected from the group comprising polymers comprising acrylic acid such as Sokalan PA30, PA20, PA15, PA10 and sokalan CP10 (BASF GmbH, Ludwigshafen, Germany), Acusol™ 45N, 480N, 460N and 820 (sold by Rohm and Haas, Philadelphia, Pa., USA) polyacrylic acids, such as Acusol™ 445 and Acusol™ 420 (sold by Rohm and Haas, Philadelphia, Pa., USA) acrylic/maleic co-polymers, such as Acusol™ 425N and acrylic/methacrylic copolymers. 
     Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to and can provide additional grease suspension. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are ester-linked to the polyacrylate “backbone” to provide a “comb” polymer type structure. The molecular weight can vary, but may be in the range of about 2000 to about 50,000. 
     Unsaturated monomeric acids that can be polymerized to form suitable dispersing polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments containing no carboxylate radicals such as methyl vinyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 50% by weight of the dispersant polymer. 
     Co-polymers of acrylamide and acrylate having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than about 20%, by weight of the dispersant polymer can also be used. Most preferably, such dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0% to about 15%, by weight of the polymer. 
     Sulfonated Polymers 
     Suitable sulfonated polymers described herein may have a weight average molecular weight of less than or equal to about 100,000 Da, preferably less than or equal to about 75,000 Da, more preferably less than or equal to about 50,000 Da, more preferably from about 3,000 Da to about 50,000, and specially from about 5,000 Da to about 45,000 Da. 
     The sulfonated polymers preferably comprises carboxylic acid monomers and sulfonated monomers. Preferred carboxylic acid monomers include one or more of the following: acrylic acid, maleic acid, itaconic acid, methacrylic acid, or ethoxylate esters of acrylic acids, acrylic and methacrylic acids being more preferred. Preferred sulfonated monomers include one or more of the following: sodium (meth) allyl sulfonate, vinyl sulfonate, sodium phenyl (meth) allyl ether sulfonate, or 2-acrylamido-methyl propane sulfonic acid. Preferred non-ionic monomers include one or more of the following: methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, methyl (meth) acrylamide, ethyl (meth) acrylamide, t-butyl (meth) acrylamide, styrene, or α-methyl styrene. 
     Specially preferred sulfonated polymers for use herein are those comprising monomers of acrylic acid and monomers of 2-acrylamido-methyl propane sulfonic acid. 
     In the polymers, all or some of the carboxylic or sulfonic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the carboxylic and/or sulfonic acid group in some or all acid groups can be replaced with metal ions, preferably alkali metal ions and in particular with sodium ions. 
     Preferred commercial available polymers include: Alcosperse 240, Aquatreat AR 540 and Aquatreat MPS supplied by Alco Chemical; Acumer 3100, Acumer 2000, Acusol 587G and Acusol 588G supplied by Rohm &amp; Haas; Goodrich K-798, K-775 and K-797 supplied by BF Goodrich; and ACP 1042 supplied by ISP technologies Inc. Particularly preferred polymers are Acusol 587G and Acusol 588G supplied by Rohm &amp; Haas, Versaflex Si™ (sold by Alco Chemical, Tennessee, USA) and those described in U.S. Pat. No. 5,308,532 and in WO 2005/090541. 
     Suitable styrene co-polymers may be selected from the group comprising, styrene co-polymers with acrylic acid and optionally sulphonate groups, having average molecular weights in the range 1,000-50,000, or even 2,000-10,000 such as those supplied by Alco Chemical Tennessee, USA, under the tradenames Alcosperse® 729 and 747. 
     Other dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of this group. 
     Other suitable dispersant polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates. Preferred cellulose-derived dispersant polymers are the carboxymethyl celluloses. 
     Yet another group of acceptable dispersing agents are the organic dispersing polymers, such as polyaspartates. 
     Amphilic graft co-polymer are useful for use herein. Suitable amphilic graft co-polymer comprises (i) polyethylene glycol backbone; and (ii) and at least one pendant moiety selected from polyvinyl acetate, polyvinyl alcohol and mixtures thereof. In other examples, the amphilic graft copolymer is Sokalan HP22, supplied from BASF. 
     Bleach 
     The composition of the invention preferably comprises from about 1 to about 20%, more preferably from about 2 to about 15%, even more preferably from about 3 to about 12% and especially from about 4 to about 10% by weight of the composition. 
     Inorganic and organic bleaches are suitable for use herein. Inorganic bleaches include perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. Alternatively, the salt can be coated. Suitable coatings include sodium sulphate, sodium carbonate, sodium silicate and mixtures thereof. Said coatings can be applied as a mixture applied to the surface or sequentially in layers. 
     Alkali metal percarbonates, particularly sodium percarbonate is the preferred bleach for use herein. The percarbonate is most preferably incorporated into the products in a coated form which provides in-product stability. 
     Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility herein. 
     Typical organic bleaches are organic peroxyacids, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid are also suitable herein. Diacyl and Tetraacylperoxides, for instance dibenzoyl peroxide and dilauroyl peroxide, are other organic peroxides that can be used in the context of this invention. 
     Further typical organic bleaches include the peroxyacids, particular examples being the alkylperoxy acids and the arylperoxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ϵ-phthalimidoperoxycaproic acid[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyldi(6-aminopercaproic acid). 
     Bleach Activators 
     Bleach activators are typically organic peracid precursors that enhance the bleaching action in the course of cleaning at temperatures of 60° C. and below. Bleach activators suitable for use herein include compounds which, under perhydrolysis conditions, give aliphatic peroxoycarboxylic acids having preferably from 1 to 12 carbon atoms, in particular from 2 to 10 carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances bear O-acyl and/or N-acyl groups of the number of carbon atoms specified and/or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), decanoyloxybenzoic acid (DOBA), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also triethylacetyl citrate (TEAC). If present the composition of the invention comprises from 0.01 to 1, preferably from 0.2 to 0.5% by weight of the composition of bleach activator, preferably TAED. 
     Bleach Catalyst 
     The composition herein preferably contains a bleach catalyst, preferably a metal containing bleach catalyst. More preferably the metal containing bleach catalyst is a transition metal containing bleach catalyst, especially a manganese or cobalt-containing bleach catalyst. Bleach catalysts preferred for use herein include manganese triazacyclononane and related complexes; Co, Cu, Mn and Fe bispyridylamine and related complexes; and pentamine acetate cobalt(III) and related complexes. A complete description of bleach catalysts suitable for use herein can be found in WO 99/06521, pages 34, line 26 to page 40, line 16. 
     Manganese bleach catalysts are preferred for use in the composition of the invention. Especially preferred catalyst for use here is a dinuclear manganese-complex having the general formula: 
     
       
         
         
             
             
         
       
     
     wherein Mn is manganese which can individually be in the III or IV oxidation state; each x represents a coordinating or bridging species selected from the group consisting of H2O, O22-, O2-, OH-, HO2-, SH-, S2-, &gt;SO, Cl-, N3-, SCN-, RCOO-, NH2- and NR3, with R being H, alkyl or aryl, (optionally substituted); L is a ligand which is an organic molecule containing a number of nitrogen atoms which coordinates via all or some of its nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q=z/[charge Y] 
     Preferred manganese-complexes are those wherein x is either CH 3 COO −  or O 2  or mixtures thereof, most preferably wherein the manganese is in the IV oxidation state and x is O 2− . 
     Preferred ligands are those which coordinate via three nitrogen atoms to one of the manganese centres, preferably being of a macrocyclic nature. Particularly preferred ligands are:
         (1) 1,4,7-trimethyl-1,4,7-triazacyclononane, (Me-TACN); and   (2) 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, (Me-Me TACN).       

     The type of counter-ion Y for charge neutrality is not critical for the activity of the complex and can be selected from, for example, any of the following counter-ions: chloride; sulphate; nitrate; methylsulphate; surfactant anions, such as the long-chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate, trifluoromethylsulphonate, perchlorate (ClO 4   − ), BPh 4   − , and PF 6   −  though some counter-ions are more preferred than others for reasons of product property and safety. 
     Consequently, the preferred manganese complexes useable in the present invention are:
         (I) [(Me-TACN)Mn IV (Âμ-0) 3 Mn IV (Me-TACN)] 2+ (PF 6   − ) 2      (II) [(Me-MeTACN)Mn IV  (Âμ-0) 3 Mn IV (Me-MeTACN)] 2+ (PF 6   − ) 2      (III) [(Me-TACN)Mn III (Âμ-0)(Âμ-OAc) 2 Mn III (Me-TACN)] 2+ (PF 6   − ) 2      (IV) [(Me-MeTACN)Mn III (Âμ-0)(Âμ-OAc) 2 Mn III (Me-MeTACN)] 2+ (PF 6   − ) 2  
 
which hereinafter may also be abbreviated as:
   (I) [Mn IV   2 (Âμ-0) 3 (Me-TACN) 2 ] (PF 6 ) 2      (II) [Mn IV   2 (Âμ-0) 3 (Me-MeTACN) 2 ] (PF 6 ) 2      (III) [Mn III   2 (Âμ-0) (Âμ-OAc) 2 (Me-TACN) 2 ] (PF 6 ) 2      (IV) [Mn III   2 (Âμ-0) (Âμ-OAc) 2 (Me-TACN) 2 ] (PF 6 ) 2          

     The structure of I is given below: 
     
       
         
         
             
             
         
       
     
     abbreviated as [Mn IV   2 (Âμ-0) 3 (Me-TACN) 2 ] (PF 6 ) 2 . 
     The structure of II is given below: 
     
       
         
         
             
             
         
       
     
     abbreviated as [Mn IV   2 (Âμ-0) 3 (Me-MeTACN) 2 ] (PF 6 ) 2 . 
     It is of note that the manganese complexes are also disclosed in EP-A-0458397 and EP-A-0458398 as unusually effective bleach and oxidation catalysts. In the further description of this invention they will also be simply referred to as the “catalyst”. 
     Preferably the composition of the invention comprises from 0.001 to 0.5, more preferably from 0.002 to 0.05% of bleach catalyst by weight of the composition. Preferably the bleach catalyst is a manganese bleach catalyst. 
     Inorganic Builder 
     The composition of the method of the invention preferably comprises an inorganic builder. Suitable inorganic builders are selected from the group consisting of carbonate, silicate and mixtures thereof. Especially preferred for use herein is sodium carbonate. Preferably the composition of the invention comprises from 5 to 50%, more preferably from 10 to 40% and especially from 15 to 30% of sodium carbonate by weight of the composition. 
     Surfactant 
     Surfactants suitable for use herein include non-ionic surfactants, preferably the compositions are free of any other surfactants. Traditionally, non-ionic surfactants have been used in automatic dishwashing for surface modification purposes in particular for sheeting to avoid filming and spotting and to improve shine. It has been found that non-ionic surfactants can also contribute to prevent redeposition of soils. 
     Preferably the composition of the invention comprises a non-ionic surfactant or a non-ionic surfactant system, more preferably the non-ionic surfactant or a non-ionic surfactant system has a phase inversion temperature, as measured at a concentration of 1% in distilled water, between 40 and 70° C., preferably between 45 and 65° C. By a “non-ionic surfactant system” is meant herein a mixture of two or more non-ionic surfactants. Preferred for use herein are non-ionic surfactant systems. They seem to have improved cleaning and finishing properties and better stability in product than single non-ionic surfactants. 
     Phase inversion temperature is the temperature below which a surfactant, or a mixture thereof, partitions preferentially into the water phase as oil-swollen micelles and above which it partitions preferentially into the oil phase as water swollen inverted micelles. Phase inversion temperature can be determined visually by identifying at which temperature cloudiness occurs. 
     The phase inversion temperature of a non-ionic surfactant or system can be determined as follows: a solution containing 1% of the corresponding surfactant or mixture by weight of the solution in distilled water is prepared. The solution is stirred gently before phase inversion temperature analysis to ensure that the process occurs in chemical equilibrium. The phase inversion temperature is taken in a thermostable bath by immersing the solutions in 75 mm sealed glass test tube. To ensure the absence of leakage, the test tube is weighed before and after phase inversion temperature measurement. The temperature is gradually increased at a rate of less than 1° C. per minute, until the temperature reaches a few degrees below the pre-estimated phase inversion temperature. Phase inversion temperature is determined visually at the first sign of turbidity. 
     Suitable nonionic surfactants include: i) ethoxylated non-ionic surfactants prepared by the reaction of a monohydroxy alkanol or alkyphenol with 6 to 20 carbon atoms with preferably at least 12 moles particularly preferred at least 16 moles, and still more preferred at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol; ii) alcohol alkoxylated surfactants having a from 6 to 20 carbon atoms and at least one ethoxy and propoxy group. Preferred for use herein are mixtures of surfactants i) and ii). 
     Another suitable non-ionic surfactants are epoxy-capped poly(oxyalkylated) alcohols represented by the formula: 
       R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2]  (I)
 
     wherein R1 is a linear or branched, aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5, more preferably about 1; and y is an integer having a value of at least 15, more preferably at least 20. 
     Preferably, the surfactant of formula I, at least about 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2]. Suitable surfactants of formula I, according to the present invention, are Olin Corporation&#39;s POLY-TERGENT® SLF-18B nonionic surfactants, as described, for example, in WO 94/22800, published Oct. 13, 1994 by Olin Corporation. 
     Enzymes 
     In describing enzyme variants herein, the following nomenclature is used for ease of reference: Original amino acid(s):position(s): substituted amino acid(s). Standard enzyme IUPAC 1-letter codes for amino acids are used. 
     Proteases 
     Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62) as well as chemically or genetically modified mutants thereof. Suitable proteases include subtilisins (EC 3.4.21.62), including those derived from  Bacillus , such as  Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus  and  Bacillus gibsonii.    
     Especially preferred proteases for the detergent of the invention are polypeptides demonstrating at least 90%, preferably at least 95%, more preferably at least 98%, even more preferably at least 99% and especially 100% identity with the wild-type enzyme from  Bacillus lentus , comprising mutations in one or more, preferably two or more and more preferably three or more of the following positions, using the BPN′ numbering system and amino acid abbreviations as illustrated in WO00/37627, which is incorporated herein by reference:V68A, N87S, S99D, S99SD, S99A, S101G, S101M, S103A, V104N/I, G118V, G118R, S128L, P129Q, S130A, Y167A, R170S, A194P, V2051 and/or M222S. 
     Most preferably the protease is selected from the group comprising the below mutations (BPN′ numbering system) versus either the PB92 wild-type (SEQ ID NO:2 in WO 08/010925) or the subtilisin 309 wild-type (sequence as per PB92 backbone, except comprising a natural variation of N87S).
         (i) G118V +S128L +P129Q +S130A   (ii) S101M +G118V +S128L +P129Q +5130A   (iii) N76D +N87R +G118R +S128L +P129Q +5130A +S188D +N248R   (iv) N76D +N87R +G118R +S128L +P129Q +S130A +S188D +V244R   (v) N76D +N87R +G118R +S128L +P129Q +S130A   (vi) V68A +N87S +S101G +V104N       

     Suitable commercially available protease enzymes include those sold under the trade names Savinase®, Polarzyme®, Kannase®, Ovozyme®, Everlase® and Esperase® by Novozymes A/S 
     (Denmark), those sold under the tradename Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3® , FN4®, Excellase®, Ultimase® and Purafect OXP® by Genencor International, those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes, those available from Henkel/Kemira, namely BLAP. 
     Preferred levels of protease in the product of the invention include from about 0.1 to about 10, more preferably from about 0.5 to about 7 and especially from about 1 to about 6 mg of active protease. 
     Amylases 
     Preferred enzyme for use herein includes alpha-amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha-amylase is derived from a strain of  Bacillus , such as  Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis , or other  Bacillus  sp., such as  Bacillus  sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (U.S. Pat. No. 7,153,818) DSM 12368, DSMZ no. 12649, KSM AP1378 (WO 97/00324), KSM K36 or KSM K38 (EP 1,022,334). Preferred amylases include:
         (a) the variants described in U.S. Pat. No. 5,856,164 and WO99/23211, WO 96/23873, WO00/60060 and WO 06/002643, especially the variants with one or more substitutions in the following positions versus the AA560 enzyme listed as SEQ ID No. 12 in WO 06/002643:   9, 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 195, 202, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 320, 323, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 458, 461, 471, 482, 484, preferably that also contain the deletions of D183* and G184*.   (b) variants exhibiting at least 95% identity with the wild-type enzyme from  Bacillus  sp.707 (SEQ ID NO:7 in U.S. Pat. No. 6,093, 562), especially those comprising one or more of the following mutations M202, M208, 5255, R172, and/or M261. Preferably said amylase comprises one of M202L or M202T mutations.       

     Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, POWERASE®, FUNGAMYL® and BAN® (Novozymes A/S, Bagsvaerd, Denmark), KEMZYM® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE® , PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS® and PURASTAR OXAM® (Genencor International Inc., Palo Alto, Calif.) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). Amylases especially preferred for use herein include NATALASE®, STAINZYME®, STAINZYME PLUS®, POWERASE® and mixtures thereof. 
     Preferably, the product of the invention comprises at least 0.01 mg, preferably from about 0.05 to about 10, more preferably from about 0.1 to about 6, especially from about 0.2 to about 5 mg of active amylase. 
     Additional Enzymes 
     Additional enzymes suitable for use in the product of the invention can comprise one or more enzymes selected from the group comprising hemicellulases, cellulases, cellobiose dehydrogenases, peroxidases, proteases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, amylases, and mixtures thereof. 
     Preferably, the protease and/or amylase of the product of the invention are in the form of granulates, the granulates comprise less than 29% of sodium sulfate by weight of the granulate or the sodium sulfate and the active enzyme (protease and/or amylase) are in a weight ratio of less than 4:1. 
     Crystal Growth Inhibitor 
     Crystal growth inhibitors are materials that can bind to calcium carbonate crystals and prevent further growth of species such as aragonite and calcite. 
     Especially preferred crystal growth inhibitor for use herein is HEDP (1-hydroxyethylidene 1,1-diphosphonic acid). Preferably, the composition of the invention comprises from 0.01 to 5%, more preferably from 0.05 to 3% and especially from 0.5 to 2% of a crystal growth inhibitor by weight of the product, preferably HEDP. 
     Metal Care Agents 
     Metal care agents may prevent or reduce the tarnishing, corrosion or oxidation of metals, including aluminium, stainless steel and non-ferrous metals, such as silver and copper. Preferably the composition of the invention comprises from 0.1 to 5%, more preferably from 0.2 to 4% and especially from 0.3 to 3% by weight of the product of a metal care agent, preferably the metal care agent is benzo triazole (BTA). 
     Glass Care Agents 
     Glass care agents protect the appearance of glass items during the dishwashing process. Preferably the composition of the invention comprises from 0.1 to 5%, more preferably from 0.2 to 4% and specially from 0.3 to 3% by weight of the composition of a metal care agent, preferably the glass care agent is a zinc containing material, specially hydrozincite. 
     The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”. 
     EXAMPLES 
     Example 1 
     Two compositions were made comprising the ingredients detailed herein below. 
     
       
         
           
               
               
               
               
             
               
                   
                   
               
               
                   
                 Ingredients (grams of 
                   
                   
               
               
                   
                 active material) 
                 Composition 1 
                 Composition 2 
               
               
                   
                   
               
             
            
               
                   
                 Solid compartment 
                   
                   
               
               
                   
                 Sodium carbonate 
                 4.00 
                 4.00 
               
               
                   
                 MGDA 
                 6.00 
                 6.00 
               
               
                   
                 Sodium percarbonate 
                 2.00 
                 2.00 
               
               
                   
                 Acusol 588 
                   
                 0.40 
               
               
                   
                 Sodium sulphate 
                 Balance to 15.26 
                 Balance to 15.26 
               
               
                   
                   
               
               
                   
                 MGDA Tri-sodium salt of methyl glycine diacetic acid. Trilon M SG available from BASF 
               
               
                   
                 Acusol 588 Sulphonated polycarboxylate supplied by Rohm &amp; Haas 
               
            
           
         
       
     
     Procedure 
     A 100 g of each composition were placed into a 34 count Fairy ActionPac bag (Procter &amp;Gamble) sealed. The bags are made of PE/PET laminate. The bags were then placed in a 50° C. oven for 24 hours. After this period, the bags were pierced with an ammonia detector tube fitted to a Kitagawa (AP-20) gas aspirating pump to measure the concentration of airborne ammonia in the headspace of the bag. 
     To measure the ammonia concentration two different detection ranges had to be used as the levels of ammonia were considerably different between the two samples. (105SD 0.2 to 20 ppm and 105SC 5-260 ppm). 
     To complement the measurement, the compositions were stored in 250 mL glass jars filling up to 2 cm in height from the bottom of the jar, the jars with the compositions were also stored in the oven at 50° C. for 24 hours, and the headspace on the jar was also given an olfactive grade by two independent judges. The olfactive scale from 1 to 20, where 1 is the lowest level of malodour and 20 is the highest level of malodour. The panels also judge the headspace in the bags after the Kitagawa measures had been conducted. 
     
       
         
           
               
               
               
            
               
                   
                   
               
               
                   
                   
                 Ammonia (ppm) measured 
               
               
                   
                 Olfactive malodour grade 
                 with Kitagawa kit. 
               
            
           
           
               
               
               
               
            
               
                   
                 In jar 
                 In bag 
                 In bag 
               
               
                   
                   
               
            
           
           
               
               
               
               
            
               
                 Composition 1 
                 20 
                 9 
                 200 ppm 
               
               
                 Composition 2 
                 5 
                 2 
                  0.3 ppm 
               
               
                   
               
            
           
         
       
     
     The tabulated data show that the malodour generated by composition 1 is greatly decreased by the addition of the sulfonated polymer to the composition. 
     Example 2 
     Two compositions were made comprising the ingredients detailed herein below. 
     
       
         
           
               
               
               
               
             
               
                   
                   
               
               
                   
                 Ingredients (grams of 
                   
                   
               
               
                   
                 active material) 
                 Composition 1 
                 Composition 2 
               
               
                   
                   
               
             
            
               
                   
                 Solid compartment 
                   
                   
               
               
                   
                 Sodium carbonate 
                 4.00 
                 4.00 
               
               
                   
                 MGDA 
                 6.00 
                 6.00 
               
               
                   
                 Sodium percarbonate 
                 2.00 
                 2.00 
               
               
                   
                 Citric acid 
                   
                 0.40 
               
               
                   
                 Sodium sulphate 
                 Balance to 15.26 
                 Balance to 15.26 
               
               
                   
                   
               
               
                   
                 MGDA Tri-sodium salt of methyl glycine diacetic acid. Trilon M SG available from BASF 
               
            
           
         
       
     
     Procedure 
     A 100 g of each composition were placed into a 34 count Fairy ActionPac bag (Procter &amp;Gamble) sealed. The bags are made of PE/PET laminate. The bags were then placed under controlled conditions at 32° C. and 80% relative humidity for 24 hours. After this period, the bags were pierced with an ammonia detector tube fitted to a Kitagawa (AP-20) gas aspirating pump to measure the concentration of airborne ammonia in the headspace of the bag. 
     To measure the ammonia concentration two different detection ranges had to be used as the levels of ammonia were considerably different between the two samples. (105SD 0.2 to 20 ppm and 105SC 5-260ppm). 
     The headspace in the bags was also given an olfactive grade by two independent judges after the Kitagawa measures had been conducted. The olfactive scale from 1 to 20, where 1 is the lowest level of malodour and 20 is the highest level of malodour. 
     
       
         
           
               
               
               
             
               
                   
               
               
                   
                   
                 Ammonia 
               
               
                 In bag 
                 Olfactive malodour grade 
                 measured with Kitagawa kit 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Composition 1 
                 10 
                 120 ppm 
               
               
                 Composition 2 
                 1 
                 0 ppm - below detection limit 
               
               
                   
               
            
           
         
       
     
     The tabulated data show that the malodour generated by composition 1 is greatly decreased by the addition of citric acid to the composition. 
     The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”. 
     Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern. 
     While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.