CA2892827A1 - Water soluble unit dose article - Google Patents

Abstract

A water-soluble unit dose article comprising a water-soluble film and at least one internal compartment, wherein said compartment contains a liquid cleaning composition, wherein when the water-soluble unit dose article is placed in water at 20°C, the liquid cleaning composition is retained within the water-soluble unit dose article for at least 30 seconds.

Description

la WATER SOLUBLE UNIT DOSE ARTICLE
FIELD OF THE INVENTION
The present invention relates to water-soluble unit dose articles.
BACKGROUND OF THE INVENTION
Water-soluble unit dose articles are known in the art. Such articles comprise unitised doses of liquid compositions such as laundry or automatic dish washing compositions enveloped in a water-soluble film. Upon addition of the water-soluble unit dose article to water, the water-soluble film dissolves allowing the film to rupture and release the unitized dose of the liquid composition into the water.
It was found that it is preferred that the liquid cleaning composition is retained within the water-soluble unit dose article for at least 30 seconds. The benefit of this is that if the water-soluble unit dose article is accidentally put in the mouth of a user or ingested by a user then the contents are held within the unit dose article for sufficient time to allow the unit dose article to be removed from mouth or regurgitated.
SUMMARY OF THE INVENTION
A water-soluble unit dose article comprising a water-soluble film and at least one internal compartment, wherein said compartment contains a liquid cleaning composition, wherein when the water-soluble unit dose article is placed in water at 20 C, the liquid cleaning composition is retained within the water-soluble unit dose article for at least 30 seconds.
A water-soluble unit dose article comprising a water-soluble film and at least one internal compartment, wherein said compartment comprises a powder composition, wherein when the water-soluble unit dose article is placed in water at 20 C, the powder composition is retained within the water-soluble unit dose article for at least 30 seconds.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a water-soluble unit dose article comprising a water-soluble film and at least one internal compartment, wherein said compartment comprises a liquid cleaning composition, wherein when the water-soluble unit dose article is placed in water at 20 C, the liquid cleaning composition is retained within the water-soluble unit dose article for at least 30 seconds. The average temperature of the human mouth is approximately between 36.5 C and 37.5 C. Preferably, when the water¨soluble unit dose article is placed in water at a temperature

2 of between 35 C and 38 C the liquid cleaning composition is retained within the water-soluble unit dose article for at least 30 seconds.
Alternatively, the water-soluble unit dose article comprises a water-soluble film and at least one internal compartment, wherein said compartment comprises a powder composition, wherein when the water-soluble unit dose article is placed in water at 20 C, the powder composition is retained within the water-soluble unit dose article for at least 30 seconds or when the water¨soluble unit dose article is placed in water at a temperature of between 35 C and 38 C
the powder composition is retained within the water-soluble unit dose article for at least 30 seconds The water-soluble unit dose article comprises at least one water-soluble film shaped such that the unit dose article comprises at least one internal compartment surrounded by the water-soluble film. The at least one compartment comprises the liquid cleaning composition. The water-soluble film is sealed such that the composition does not leak out of the compartment during storage. However, upon addition of the water-soluble unit dose article to water, the water-soluble film dissolves and releases the contents of the internal compartment into the wash liquor.
The unit dose article is manufactured such that the water-soluble film completely surrounds the composition and in doing so defines the compartment in which the composition resides. The unit dose article may comprise two films, or even three films. A
first film may be shaped to comprise an open compartment into which the composition is added. A
second film is then laid over the first film in such an orientation as to close the opening of the compartment.
The first and second films are then sealed together along a seal region.
Water-soluble unit dose articles include products supplied by The Procter and Gamble Company under the following names TIDE PODS, CASCADE ACTION PACS, CASCADE
PLATINUM, CASCADE COMPLETE, ARIEL 3 IN I PODS, TIDE BOOST ORIGINAL DUO
PACs, TIDE BOOST FEBREZE SPORT DUO PACS, TIDE BOOST VIVID WHITE BRIGHT
PACS, DASH, FAIRY PLATINUM.
By 'cleaning composition' we herein mean any treatment composition such as detergent, softener, rinse aid or the like, and any mixture thereof.
By 'retained within the water-soluble unit dose article' we herein mean that preferably the liquid or powder composition does not contact the water, more preferably the unit dose article does not rupture sufficiently and/or the water-soluble film does not disintegrate or dissolve sufficiently to allow the liquid or powder composition to contact the water until after at least 30 seconds. Preferably, the water-soluble film does not disintegrate or dissolve to the

3 extent that a hole is formed wherein said hole is sufficiently large to allow water to access the internal compartment through the film and contact the liquid or powder composition. Also, preferably, the water-soluble film does not disintegrate or dissolve to the extent that a hole is formed wherein said hole is sufficiently large to allow the liquid or powder composition to exit through the hole and contact the water.
Preferably, the water-soluble unit dose article is placed in water at 20 C, the liquid or powder composition is retained within the water-soluble unit dose article for at least 30 seconds when the unit dose article is not subjected to any shear force. In other words there water is not subjected to any mixing or other turbulence. Alternatively, the water-soluble unit dose article is placed in water at 20 C, the liquid cleaning composition is retained within the water-soluble unit dose article for at least 30 seconds when the unit dose article is subjected to any shear force. In other words there water is mixed such that turbulence is created in the water.
The liquid or powder composition may be retained within the water-soluble unit dose article for between 30 seconds and 60 seconds, preferably between 30 seconds and 50 seconds, more preferably between 30 seconds and 40 seconds, most preferably between 30seconds and 35 seconds once the unit dose article has been contacted with water at 20 C.
Alternatively, the liquid or powder composition may be retained within the water-soluble unit dose article for at least 30 seconds, or even at least 3 seconds, or even at least 40 seconds, or even at least 50 seconds, or even at least 60 seconds.
The water-soluble unit dose article may be freshly made, or may have been aged for a period of time. The aging may have been conducted at room temperature such as during storage of the unit dose article or at an elevated or decreased temperature to that of room temperature.
The unit dose article may have been aged at a temperature of between 0 C and 50 C, or between C and 40 C or between 10 C and 30 C. The unit dose article may be at least 1 day old, or even at least 10 days old, or even at least 25 days old, or even at least 50 days old, or even at least 100 days old.
The water-soluble unit dose article may dissolve substantially or completely in the water in less than 10 minutes, or even less than 9 minutes, or even less than 8 minutes, or even less than 7 minutes, or even less than 6 minutes, or even less than 5 minutes or even less than 4 minutes, or even less than 3 minutes, or even less than 2 minutes or even less than 1 minute, or even less than 45 seconds, or even less than 30 seconds, or even less than 15 seconds, or even less than 10 seconds, or even less than 5 seconds, or even less than 2 seconds. By dissolve completely, we herein mean the film has substantially or completely dissolved in the water and the liquid or powder composition has substantially or completely dispersed within the water. By

4 'substantially dissolves' we herein mean the film is not visible by the naked eye or only minute quantities of the film are visible by the naked eye in the water. Preferably dissolution is tested in 800m1 of water placed in a standard 1L beaker, wherein the water is at 20 C in the absence of agitation, wherein the water is deionized water. Alternatively the water may have a hardness of 2.5mmol/L or 4mmol/L.
The water-soluble film may comprise polyvinyl alcohol. Suitable films are described in more detail below.
The water-soluble unit dose article may comprise an aversive agent, preferably a bittering agent and wherein the aversive agent is contained within the film, comprised out the outside of the unit dose article, comprised within the liquid composition or a mixture thereof. By 'aversive agent' we herein mean any compound that provides an unpleasant taste when placed in the mouth or ingested. Such unpleasant tastes include bitterness, heat/spice, unpleasant odour, sourness, coldness or a mixture thereof. The aversive agent may be a bittering agent. Preferably the aversive agent is at a concentration which is safe and which elicits oral repulsive behaviour within a maximum time of 6 seconds in case of accidental oral exposure.
Suitable bittering agents include naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate and mixtures of these. The bittering agent may have a bitter value of between 1000 and 10,000,000 as measured using the standardized process is used that is set forth in the European Pharmacopoeia (5th Edition, Stuttgart 2005, Volume 1, General Monograph Groups, 2.8.15 Bitterness Value, p. 278).
The aversive agent may be selected from the group comprisingcapsicinoids (including capsaicin); vanillyl ethyl ether; vanillyl propyl ether; vanillyl butyl ether;
vanillin propylene;
glycol acetal; ethylvanillin propylene glycol acetal; capsaicin; gingerol; 4-(1-menthoxymethyl)-2-(3'-rnethoxy-4'-hydroxy-pheny1)-1, 3-dioxolane; pepper oil; pepperoleoresin;
gingeroleoresin;
nonylic acid vanillylamide; jamboo oleoresin; Zanthoxylum piperitum peel extract; sanshool;
sanshoamide; black pepper extract; chavicine; piperine; spilanthol; and mixtures thereof.
The aversive agent may be present on or in the film or in the composition or a mixture thereof at a concentration of between 10 and 4000ppm, or even between 10 and 3000ppm, or even between 10 and 2000ppm, or even between 10 and 1000ppm.
The water-soluble unit dose article may comprise an area of print. The water-soluble unit dose article may be printed using flexographic techniques, ink jet printing techniques or a mixture thereof. The printed are may be on the film, preferably on the outside of the film, within the film, on the inside of the film or a mixture thereof. The printed area may convey information such as usage instructions, chemical safety instructions or a mixture thereof.
Alternatively, the entire surface of the pouch, or substantially the entire surface of the pouch is printed in order to make the pouch opaque. The print may convey an image that reduces the risk of confusion and hence accidental ingestion of the pouch.
The water-soluble film prior to being made into a water-soluble unit dose article has a thickness between 30 m and 100 m, preferably between 5011m and 100 m, even more preferably between 65 m and 88 rrk, most preferably between 76 m and 85p.m.
Herein we mean the thickness of the film before it has been subjected to any thermoforming, elastic strain or plasticization techniques such as thermoforming into a mould for example or stretching from general film handling.
The liquid cleaning composition is selected from laundry cleaning compositions, automatic dishwashing compositions or a mixture thereof. Suitable liquid cleaning compositions are described in more detailed below.
The unit dose article may comprise an air bubble, preferably the air bubble is within the internal compartment. Without wishing to be bound by theory, the presence of the air bubble helps increase the time taken for the unit dose article to retain the liquid composition once placed in water. The volume of the air bubble may be between 0.1m1 and 15m1, or even between 0.2ml and 10 ml or even between 0.5ml and 5m1.
The unit dose article may comprise at least two internal compartments, or even at least three compartments or even at least four compartments. The compartments may be arranged in a superposed orientation, side-by-side orientation or a mixture thereof. The compartments may be arranged such that two side-by-side compartments are superposed onto a third compartment wherein the third compartment is larger than the first and/or second compartments.
Alternatively, the compartments may be arranged such that three side-by-side compartments are superposed onto a fourth compartment wherein the fourth compartment is larger than the first and/or second and/or third compartments.
The water-soluble unit article may further comprise a powder composition. The powder composition is preferably in at least a second compartment. Alternatively, a second compartment may comprises a second liquid composition. The compartments may be arranged such that two side-by-side compartments are superposed onto a third compartment wherein the third compartment is larger than the first and/or second compartments and wherein all the compartments comprise a liquid composition wherein the liquid compositions may be the same or different. Alternatively, the third compartment may comprise a powder and the first and second compartments comprise liquids, wherein the liquids may be the same or different.

Alternatively, the first and/or second compartments may comprise a powder and the third compartment comprises a liquid.
The unit dose article may be transparent, translucent or opaque. The water-soluble film may be transparent, translucent or opaque, the liquid cleaning composition maybe transparent, translucent or opaque or a mixture thereof.
The unit dose article may be flow wrapped in a flexible external film. The flow wrap film may comprise non-woven materials, woven materials or mixtures thereof. For the avoidance of confusion, the flow wrap film is different to the external container, and the external container may comprises one or more flow wrapped pouches.
The unit dose articles according to the present invention are preferably made by thermoforming / vacuum forming process. Preferably a heated film is drawn into a mould by vacuum to create an open cavity. The open cavity is then filled with the composition after which the open cavity is closed with another film or closed compartment. Sealing can be achieved via heat or solvent or a mixture thereof. A preferred solvent sealing process is water sealing.
The present invention is also to a packaged product comprising an external container and at least water-soluble unit dose article according to the present invention, wherein the external container is opaque. The external container could be in the form of a tub or a bag. The tub or bag could be of any shape or orientation suitable to hold at least one unit dose article.
Preferably, the tub and/or bag are made from non-water-soluble materials such as polyolefin based materials.
Preferably the external container comprises a child resistant closure such as a child resistant lid opening mechanism or child resistant zipper.
The present invention is also to a method of laundering fabrics comprising the step of adding a water-soluble unit dose article according to the present invention to a volume of water.
Preferably the volume of water is sufficient to dilute the liquid cleaning composition by a factor of at least 100, or even at least 200, or even at least 300, or even at least 500.
The present invention is also to an automatic dishwashing method comprising the step of adding a water-soluble unit dose article according to the present invention to a volume of water.
Preferably the volume of water is sufficient to dilute the liquid cleaning composition by a factor of at least 100, or even at least 200, or even at least 300, or even at least 500.
Film The water-soluble film prior to being made into a water-soluble unit dose article has a thickness between 30p.m and 100 m, preferably between 50 m and 100p.m, even more preferably between 6511m and 8811m, most preferably between 76pm and 85pm.
Herein we mean the thickness of the film before it has been subjected to any thermoforming or plasticization techniques such as thermoforming into a mould for example.
The film of the present invention is soluble or dispersible in water.
Preferably, the film has a water-solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns:
50 grams 0.1 gram of film material is added in a pre-weighed 400 ml beaker and 245m1 lml of distilled water is added. This is stirred vigorously on a magnetic stirrer, Labline model No.
1250 or equivalent and 5 cm magnetic stirrer, set at 600 rpm, for 30 minutes at 24 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 fraction). Then, the percentage solubility or dispersability can be calculated.
Preferred film materials are preferably polymeric materials. The film material can, for example, be obtained by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art.
Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are 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, carboxymethyleellulose 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. Preferably, the level of polymer in the pouch material, for example a PVA polymer, is at least 60%. The polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.
Mixtures of polymers can also be used as the pouch material. This can be beneficial to control the mechanical and/or dissolution properties of the compartments or pouch, depending on the application thereof and the required needs. Suitable mixtures include for example mixtures wherein one polymer has a higher water-solubility than another polymer, and/or one polymer has a higher mechanical strength than another polymer. Also suitable are mixtures of polymers having different weight average moleailar weights, for example a mixture of PVA or a copolymer thereof of a weight average molecular weight of about 10,000-40,000, preferably around 20,000, and of PVA or copolymer thereof, with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000. Also suitable herein are polymer blend compositions, for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35% by weight polylactide and about 65%
to 99% by weight polyvinyl alcohol. Preferred for use herein are polymers which are from about 60% to about 98% hydrolysed, preferably about 80% to about 90% hydrolysed, to improve the dissolution characteristics of the material.
Preferred films exhibit good dissolution in cold water, meaning unheated distilled water.
Preferably such films exhibit good dissolution at temperatures of 24 C, even more preferably at 10 C. By good dissolution it is meant that the film exhibits water-solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns, described above.
Of the total PVA resin content in the film described herein, the PVA resin can comprise about 30 to about 85 wt% of the first PVA polymer, or about 45 to about 55 wt%
of the first PVA polymer. For example, the PVA resin can contain about 50 w.% of each PVA
polymer, wherein the viscosity of the first PVA polymer is about 13 cP and the viscosity of the second PVA polymer is about 23 cP.
Naturally, different film material and/or films of different thickness may be employed in making the compartments of the present invention. A benefit in selecting different films is that the resulting compartments may exhibit different solubility or release characteristics.
The film material herein can also comprise one or more additive ingredients.
For example, it can be beneficial to add plasticisers, for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof. Other additives may include water and functional detergent additives, including surfactant, to be delivered to the wash water, for example organic polymeric dispersants, etc.
Alternatively for use herein are commercially available polyvinyl alcohols (PVA) obtained by hydrolysis of polyvinyl acetates. The solubility of these films can be selectively adjusted by the degree of hydrolysis of the PVA or by using a cross-linking agent. Preferably, the film comprises polyvinyl acetate with a degree of hydrolysis of from about 90 to about 99%, preferably from about 92 to about 98% and more preferably from about 94 to about 98%. The degree of hydrolysis is expressed as a percentage of vinyl acetate units converted to vinyl alcohol units.
Examples of commercially available PVA suitable for use herein are BP26 available from Aicello, L10 and L15 available from Aquafilm, VF-M and VM-S available from Kuraray and E-2060 available from Monosol, especially preferred for use herein is BP26 available from Aicello. The thickness of the material can influence the dissolution kinetics, films having a thickness between about 1 and about 200, more preferably between 10 and 100 gm are preferred for use herein.
Other preferred materials for use herein are starch, starch derivatives, cellulose and cellulose derivatives, more especially methyl cellulose and mixture thereof.
Especially preferred for use herein are polymers comprising hydroxypropylmethylcellulose.
Preferred films are those supplied by Monosol under the trade references M8630, M8900, M8779, M8310, M9467. Suitable films for use in the present invention include those supplied by Monosol for use in the following Procter and Gamble products: TIDE PODS, CASCADE
ACTION PACS, CASCADE PLATINUM, CASCADE COMPLETE, ARIEL 3 IN I PODS, TIDE BOOST ORIGINAL DUO PACs, TIDE BOOST FEBREZE SPORT DUO PACS, TIDE
BOOST VIVID WHITE BRIGHT PACS, DASH, FAIRY PLATINUM.
Liquid cleaning composition The at least one internal compartment comprises a liquid cleaning composition.
The cleaning composition may be a detergent, softener, rinse aid or the like, and any mixture thereof.
The term 'liquid' refers to any composition capable of wetting and treating a substrate and encompasses forms such as dispersions, gels, pastes and the like. A
dispersion, for example, is a liquid comprising solid or particulate matter contained therein. The liquid composition may also include gases in suitably subdivided form.
Preferably, the liquid composition comprises a substrate treatment agent. A
substrate treatment agent is any ingredient that provides a benefit, for example a cleaning benefit, softening benefit, freshness benefit, sequestering benefit and the like.
The substrate treatment agent may comprise a fabric treatment agent. As used herein, "fabric treatment agent" refers to any material that can provide fabric care benefits such as fabric cleaning, stain removal, softening, color protection, pill/fuzz reduction, anti-abrasion, anti-wrinkle, and the like to garments and fabrics, particularly on cotton and cotton-rich garments and fabrics, when an adequate amount of the material is present on the garment/fabric. Non-limiting examples of fabric treatment agents include anionic surfactants, non-ionic surfactants, cationic surfactants, polyethylene glycol polymers, ethoxylated polyethyleneimines, structu rants, hueing dyes, perfumes, perfume microcapsules, chelants, enzymes, silicones, polyolefin waxes, latexes, oily sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids, enzyme stabilizing

5 systems; antioxidants, opacifier, pearlescent agent and mixtures thereof.
Fabric treatment agents when present in the composition, are suitably at levels of up to about 30% by weight of the liquid composition, more typically from about 1% to about 20%, or even from about 2%
to about 10%.
The substrate treatment agent may be selected from anionic surfactants, non-ionic surfactants, cationic surfactants, polyethylene glycol polymers, ethoxylated polyethyleneimines, rheology modifier, hueing dyes, perfumes, perfume microcapsules, chelants, enzymes, silicones, polyolefin waxes, latexes, oily sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids, enzyme stabilizing systems; antioxidants, pacifier, pearlescent agent, deposition aid, builder, bleaching agent, bleach activator, bleach catalyst, organic shine polymers, surface modifying polymers, metal care agents, metal salts, anti-corrosion agents and mixtures thereof.
If a powder composition is present, the powder composition may comprise a substrate treatment agent selected from anionic surfactants, non-ionic surfactants, cationic surfactants, polyethylene glycol polymers, ethoxylated polyethyleneimines, rheology modifier, hueing dyes, perfumes, perfume microcapsules, chelants, enzymes, silicones, polyolefin waxes, latexes, oily sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids, enzyme stabilizing systems; antioxidants, pacifier, pearlescent agent, deposition aid, builder, bleaching agent, bleach activator, bleach catalyst, organic shine polymers, surface modifying polymers, metal care agents, metal salts, anti-corrosion agents and mixtures thereof, and such agents are preferably present at concentrations as detailed below by weight of the powder.
The substrate treatment agent may comprise a surfactant. The total surfactant level may be in the range of from about 1% to 80% by weight of the substrate treatment agent.
10 Further detersive surfactants utilized can be of the anionic, nonionic, zwitterionic, ampholytic, zwitterionic, semi-polar or cationic type or can comprise compatible mixtures of these types. The surfactants can be selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof.
Nonionic surfactants can be those of the formula R1(0C2H4)OH, wherein RI is a alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about 80.
Particularly practical are condensation products of C12-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., Cu-Cu alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
The substrate treatment agent may comprise a detersive enzymes. Suitable detersive enzymes for use herein include protease, amylase, lipase, cellulase, carbohydrasc including mannanase and endoglucanase, and mixtures thereof. Enzymes can be used at their art-taught levels, for example at levels recommended by suppliers. Typical levels in the substrate treatment agents are from about 0.0001% to about 5%. When enzymes are present, they can be used at very low levels, e.g., from about 0.001% or lower, in certain embodiments of the invention; or they can be used in heavier-duty laundry detergent formulations in accordance with the invention at higher levels, e.g., about 0.1% and higher. In accordance with a preference of some consumers for "non-biological" detergents, the present invention includes both enzyme-containing and enzyme-free embodiments.
The substrate treatment agent may comprise a deposition aid. As used herein, "deposition aid" refers to any cationic polymer or combination of cationic polymers that significantly enhance the deposition of a fabric care benefit agent onto the fabric during laundering.
The deposition aid can be a cationic or amphoteric polymer. The amphoteric polymers of the present invention can also have a net cationic charge, i.e.; the total cationic charges on these polymers will exceed the total anionic charge. Nonlimiting examples of deposition enhancing agents are cationic polysaccharides, chitosan and its derivatives and cationic synthetic polymers.
Suitable cationic polysaccharides include cationic cellulose derivatives, cationic guar gum derivatives, chitosan and derivatives, cationic starches and mixtures thereof.
The substrate treatment agent may comprise a rheology modifier. The rheology modifier can be selected from the group consisting of non-polymeric crystalline, hydroxy-functional materials, polymeric rheology modifiers which impart shear thinning characteristics to the aqueous liquid matrix of the substrate treatment agent 50. Crystalline, hydroxy-functional materials are rheology modifiers which form thread-like structuring systems throughout the matrix of the liquid composition upon in situ crystallization in the matrix.
Specific examples of suitable crystalline, hydroxyl-containing rheology modifiers include castor oil and its derivatives. Also practical are hydrogenated castor oil derivatives such as hydrogenated castor oil and hydrogenated castor wax. Commercially available, castor oil-based, crystalline, hydroxyl-containing rheology modifiers include TH1XCIN from Rheox, Inc. (now Elementis).
Polymeric rheology modifiers can be selected from polyacrylates, polymeric gums, other non-gum polysaccharides, and combinations of these polymeric materials. Practical polymeric gum materials include pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, guar gum and mixtures thereof.
The substrate treatment agents of the present invention may optionally comprise a builder. Suitable builders include polycarboxylate builders include cyclic compounds, particularly alicyclic compounds. Particularly suitable are citrate builders, e.g., citric acid and soluble salts thereof, particularly sodium salts thereof.
Other suitable organic builders include aminocarboxylate builders such as salts of MGDA (methyl-glycine-diacetic acid), GLDA (glutamic-N,N- diacetic acid), EDDS
(ethylene diamine disuccinates) iminodisuccinic acid (IDS) and carboxymethyl inulin.
Salts of MGDA
and GLDA are especially suitable, with the tri-sodium salt thereof being practical and a sodium/potassium salt being particularly practical for the favourable hygroscopicity and fast dissolution properties when in particulate form.
Other suitable aminocarboxylate builders include; for example, salts of aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP) , iminodisuccinic acid (IDA), N- (2-sulfomethyl) aspartic acid (SMAS), N- (2-sulfoethyl) aspartic acid (SEAS), N- (2- sulfomethyl) glutamic acid (SMGL), N-(2- sulfoethyl) glutamic acid (SEGL) and IDS (iminodiacetic acid) such as salts of N-methyliminodiacetic acid (MIDA), alpha- alanine-N,N-diacetic acid (alpha -ALDA) , serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid- N ,N - diacetic acid (ANDA), sulfanilic acid-N, N-diacetic acid (SLDA), taurine-N, N-diacetic acid (TUDA), ethylene diamine tetraacetic acid and salts thereof (EDTA), diethylene triamine penta acetates (DTPA) and sulfomethyl-N,N-diacetic acid (SMDA).
Other practical builders include aluminosilicates such as zeolite A, B or MAP;
fatty 25, acids or salts, suitably sodium salts, thereof, suitably C 12-C18 saturated and/or unsaturated fatty acids; and alkali or alkali earth metal carbonates such as sodium carbonate.
The substrate treatment agent may comprisie a bleaching agent. Bleaching agents suitable herein include chlorine and oxygen bleaches, especially inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and sodium percarbonate optionally coated to provide controlled rate of release preformed organic peroxyacids and mixtures thereof with organic peroxyacid bleach precursors and/or transition metal-containing bleach catalysts (especially manganese or cobalt). Inorganic perhydrate salts are typically incorporated at levels in the range from about 1% to about 60% by weight, optionally from about 2% to about 30% by weight or even from about 5% to about 25% by weight of the liquid composition.

Peroxyacid bleach precursors suitable for use herein include precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid precursors;
peracetic acid precursors such as TAED, sodium acetoxybenzene sulfonatc and pentaacetylglucose;
pernonanoic acid precursors such as sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacid precursors;
and benzoxazin peroxyacid precursors. Bleach precursors are typically incorporated at levels in the range from about 0.5% to about 25%, suitably from about 1% to about 10% by weight of the liquid composition while the preformed organic peroxyacids themselves are typically incorporated at levels in the range from 0.5% to 25% by weight, or even from 1% to 10% by weight of the liquid composition. Bleach catalysts practical for use herein include the manganese triazacyclononane and related complexes; Co, Cu, Mn and Fe bispyridylamine and related complexes; and pentamine acetate cobalt(III) and related complexes.
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.
Alkali metal percarbonates, particularly sodium percarbonate, are practical for use herein.
The percarbonate can be 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 d:peroxyhexadecanedioc 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. Practical representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-a-acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, c-phthalimidoperoxycaproic acid[phthaloiminoperoxyhexanoic acid (PAP)1, o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperad ipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-d iperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassyl ie. acid, the di peroxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyldi(6-aminopercaproic acid).
The level of bleaching agent in the liquid composition can be from about Ito about 20%, optionally from about 2 to about 15%, even from about 3 to about 12%, or even from about 4 to about 10% by weight of the liquid composition.
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 from 1 to 12 carbon atoms, in particular from 2 to 10 carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances bear 0-acyl and/or N-acyl groups of the number of carbon atoms specified and/or optionally substituted benzoyl groups. Suitable substances include polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacety1-2,4-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). Bleach activators if included in the substrate treatment agents are at a level of from about 0.01 to about 10%, or from about 0.1 to about 5% or from about Ito about 4% by weight of the liquid composition.
The substrate treatment agent may comprise a bleach catalyst, such as a metal containing bleach catalyst. The metal containing bleach catalyst can be a transition metal containing bleach catalyst, such as a manganese or cobalt-containing bleach catalyst.
Bleach catalysts suitable for use herein include the manganese triazacyclononane and related complexes; Co, Cu, Mn and Fe bispyridylamine and related complexes;
and pentamine acetate cobalt(III) and related complexes.
Manganese bleach catalysts are practical for use in the substrate treatment agent. A
suitable catalyst for use herein is a dinuclear manganese-complex having the general formula:
LMn ____________________________ X ________ MnL

wherein Mn is manganese which can individually be in the Ill or IV oxidation state; each x represents a coordinating or bridging species selected from the group consisting of H20, 022-, 02-, OH-, 1102-, SH-, S2-, >S0, Cl-, N3-, SCN-, RC00-, NH2- and NR3, with R
being H, alkyl 5 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].
10 Suitable manganese-complexes are those wherein x is either CH3C00- or 02 or mixtures thereof, optionally wherein the manganese is in the IV oxidation state and x is 02-. Suitable ligands are those which coordinate via three nitrogen atoms to one of the manganese centres, optionally being of a macrocyclic nature. Suitable ligands include:
(1) 1,4,7-trimethy1-1,4,7-triazacyclononane, (Me-TACN); and 15 (2) 1,2,4,7-tetramethy1-1,4,7-triazacyclononane, (Me-Me TACN).
The type of counter-ion Y for charge neutrality may not be critical for the activity of the complex and can be selected from, for example, any of the following counter-ions: chloride;
sulphate; nitrate; methylsulphate; surfanctant anions, such as the long-chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate, trifluoromethylsulphonate, perchlorate (C104), BPh4", and PF6" though some counter-ions are more suitable than others for reasons of product property and safety.
Consequently, suitable manganese complexes useable in the present invention include:
(I) [(Me-TACN)mniv(A
0)3mn'v(me-TAcm24-(pF6)2 (II) [(Me-MeTACN)Mniv(Ap_0)3mniv(Me-MeTACN)12+(FF6-)2 (III) [(Me-TACN)Mnill(A.. -0)(4-0Ac)2Mnm(Me-TACN)]2+(PF6-)2 (IV) [(Me-MeTACN)Mnm(4-0)(A -0Ac)2Mni11(Me-MeTACN)]2f(PF6)2 which hereinafter may also be abbreviated as:
(I) rõ, iv , AN IRA A ',xi%
LiVin 2V-111-V)3kiVie- I IALIN)21 (PF6)2 (II) [Mniv2(A 1i-0)3(Me-MeTACN)2] (PF6)2 (III) [Mn1112(A1t-0) (4-0Ac)2(Me-TACN)21 (PF6)2 (IV) [Mni112(A -0) (Ail-OAc)2(Me-TACN) 2liFF6)2 The structure of I is given below.

2+
Me Me Cmo,N NI
__________________________ Mniv 0 __ Mniv ________ (PF6-)2 N
Me Me abbreviated as [Mniv2(4-0)3(Me-TACN)2] (PF6) 2.
The structure of II is given below:
Me 2+
Me Nç Me iv mn Me-N _________________ )0. 0 ___ Mn' ___________ NMe (PF6-)2 Me Me = Me abbreviated asm[ niv2.Ati_ k 0)3(Me-MeTACN)2] (PF6)2.
The liquid composition can generally be prepared by mixing the ingredients together. If a pearlescent material is used it should be added in the late stages of mixing. If a rheology modifier is used, it is suitable to first form a pre-mix within which the rheology modifier is dispersed in a portion of the water and optionally other ingredients eventually used to comprise the liquid composition. This pre-mix is formed in such a way that it forms a structured liquid.
To this structured pre-mix can then be added, while the pre-mix is under agitation, the surfactant(s) and other laundry adjunct materials, along with water and whatever optional detergent composition adjuncts are to be used.

Preferably, if the unit dose article comprises an automatic dish washing composition, the automatic dishwashing composition is phosphate free, or substantially phosphate free.
The composition may comprise an automatic dishwashing care benefit agent. As used herein, "automatic dishwashing care benefit agent" refers to any material that can provide shine, fast drying, metal, glass or plastic protection benefits. Non-limiting examples of automatic dishwashing care benefit agents include organic shine polymers, especially sulfonated /
carboxylated polymers, surface modifying polymers or surfactants inducing fast drying, metal care agents like benzatriazoles and metal salts including Zinc salts, and anti-corrosion agents including silicates e.g. sodium silicate.
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 examplz, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."
EXAMPLES
Example 1 Compositions for use in an automatic dishwasher can be as tabulated below (given in grams). The constituents are introduced into a dual-compartment water-soluble pack having a first compartment comprising a solid composition (in powder form) and a liquid compartment comprising the liquid composition. The water-soluble film used is preferably Monosol M8630 film as supplied by Monosol. In one example the water-soluble film has printing on the interior of one or both compartments. In another example the film comprises an aversive agent on the outside, within the film or a mixture thereof. In another example, the film comprises print and aversive agent. When added to an automatic dishwashing machine, the compositions below are diluted by a factor of at least 100.
Table 1 Powder A
Percarbonate 1.41 1.41 TAED 0.32 0.32 Cobalt catalyst 0.0013 Mn TACN 0.0013 Sodium carbonate 7.17 7.17 Sodium Sulphate 2.5 2.5 Amylase 0.0013 0.0013 Protease 0.013 0.013 Acusol 588 1.20 1.20 NI surfactant 0.10 0.10 BTA 0.0080 0.0080 HEDP 0.10 MGDA 2.20 2.20 Liquid Top NI surfactant 1.17 1.17 DPG 0.44 0.44 -Amine Oxide 0.05 0.05 Glycerine 0.08 0.08 PEI600 E07 P01 0.25 0.25 90% Quat Example water-soluble unit dose articles for fabric treatment are set forth in the following table. In one example the water-soluble film has printing on the interior of one or both compartments. In another example the film comprises an aversive agent on the outside, within the film or a mixture thereof. In another example, the film comprises print and aversive agent.
When added to a washing machine, the liquid composition is diluted by a factor of at least 200.
Table 2 3 compartments 2 compartments 3 compartments Compartment # 1 2 3 1 2 1 2 3 Dosage (g) 34.0 3.5 3.5 30.0 5.0 25.0 1.5 4.0 Ingredients Weight %
Alkylbenzene sulfonic 20.0 20.0 20.0 10.0 20.0 20.0 acid __________________________________________________________________________ _ Alkyl sulfate 2.0 C12-14 alkyl 7- 17.0 17.0 17.0 17.0 17.0 ethoxylate Cationic surfactant 1.0 _ Zeolite A 10.0 C12-18 Fatty acid 13.0 13.0 13.0 18.0 18.0 Sodium acetate 4.0 Enzymes 0-3 0-3 0-3 0-3 0-3 Sodium Percarbonate 11.0 TAED 4.0 Organic catalyst r 1.0 PAP granule 2 50 Polycarboxylate 1.0 Ethoxysulfated 2.2 2.2 2.2 Hexamethylene Diamine Dimethyl Quat Hydroxyethane 0.6 0.6 0.6 0.5 diphosphonic acid Ethylene diamine 0.4 tetra(methylene phosphonic) acid Brightener 0.2 0.2 0.2 0.3 0.3 Alkoxylated polyamine 5.0 4.0 7.0 Hueing dye 4 0.05 0.035 0.12 Perfume 1.7 - 1.7 0.6 1 .5 Water 10.0 10.0 10.0 4.1 1.0 Glycerol 5.0 6.0 10.0 Sorbitol 1 Propane diol 5.0 5.0 5.0 30.0 11.0 89.0 Buffers (sodium To pH 8.0 for liquids carbonate, To RA > 5.0 for powders monoethanolamine) 5 Minors (antioxidant, To 100%
aesthetics,...), sodium sulfate for powders Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-y1)-1-(2-ethyl-hexyloxymethyl)-ethylJester as described in US7169744 2 PAP = Phthaloyl-Amino-Peroxycaproic acid, as a 70% active wet cake Polyethylenimine (MW = 600) with 20 ethoxylate groups per -NH.
5 Ethoxylated thiophene, E0 (12.1+R2) =
5 RA = Reserve Alkalinity (g NaOH/dose)

6 PEI600 E020, available from BASF
The water-soluble films used in the examples of Table 2 were supplied by Monosol and have the trade name M9467.
Example 2 A packaged product was purchased from a UK supermarket on 21 May 2015 under the Arid l Pods 3in I brand. The outer container was an opaque rigid tub generally green in colour and comprised the barcode 4 015600 385392. The water-soluble unit dose articles comprised within were three compartment unit dose articles and comprised a first and a second compartment arranged side by side in a `ying yang' orientation, and were superposed onto a larger third compartment. All three compartments comprised a liquid composition. The third compartment comprised a green liquid, the first compartment comprised a blue compartment and the second compartment comprised a white compartment. The packaged product of the example 2 was a laundry detergent composition.
Example 3 A packaged product was purchased from a UK supermarket on 21 May 2015 under the Fairy Platinum All in One brand. The outer container was a flexible opaque bag generally silver in colour and comprised the barcode 5 410076 383825. The water-soluble unit dose articles comprised 4 compartments, wherein three smaller compartments were arranged on top of a larger fourth compartment. The fourth compartment comprised a powder composition and the first, second and third compartments comprised liquid compositions. The packaged product of example 3 was an automatic dishwashing composition.

Claims (23)

What is claimed is:

1. A water-soluble unit dose article comprising a water-soluble film and at least one internal compartment, wherein said compartment contains a liquid cleaning composition, wherein when the water-soluble unit dose article is placed in water at 20°C, the liquid cleaning composition is retained within the water-soluble unit dose article for at least 30 seconds.

2. The water-soluble unit dose article according to claim 1, wherein when the water-soluble unit dose article is placed in water at 20°C, essentially all of the liquid cleaning composition is retained within the water-soluble unit dose article for at least 30 seconds.

3. The water-soluble unit dose article according to any preceding claims, wherein when the water-soluble unit dose article is placed in water at 20°C, the liquid cleaning composition is retained within the water-soluble unit dose article for at least 30 seconds when the unit dose article is not subjected to any shear force.

4. The water-soluble unit dose -article according to any preceding claims wherein the unit dose article is at least 1 day old, or even at least 10 days old, or even at least 25 days old, or even at least 50 days old, or even at least 100 days old.

5. The water-soluble unit dose article according to any preceding claims wherein when the water-soluble unit dose article is placed in water at 20°C, the liquid cleaning composition is retained within the water-soluble unit dose article for between 30 seconds and 60 seconds, preferably between 30 seconds and 50 seconds, more preferably between seconds and 40 seconds, most preferably between 30seconds and 35 seconds.

6. The water-soluble unit dose article according to any preceding claims wherein the water-soluble unit dose article dissolves substantially or completely in the water in less than 10 minutes, or even less than 9 minutes, or even less than 8 minutes, or even less than 7 minutes, or even less than 6 minutes, or even less than 5 minutes or even less than 4 minutes or even less than 3 minutes, or even less than 2 minutes or even less than 1 minute, or even less than 45 seconds, or even less than 30 seconds, or even less than 15 seconds, or even less than 10 seconds, or even less than 5 seconds, or even less than 2 seconds..

7. The water-soluble unit dose article according to any preceding claims wherein the water-soluble film comprises polyvinyl alcohol.

8. The water-soluble unit dose article according to any preceding claims wherein the water-soluble unit dose article comprises an aversive agent, preferably a bittering agent and wherein the aversive agent is contained within the film, comprised out the outside of the unit dose article, comprised within the liquid composition or a mixture thereof and preferably wherein the aversive agent is at a concentration which is safe and which elicits oral repulsive behaviour within a maximum time of 6 seconds in case of accidental oral exposure.

9. The water-soluble unit dose article according to any preceding claims wherein the unit dose article comprises an area of print, or wherein the whole of the unit dose article is printed.

10. The water-soluble unit dose article according to any preceding claims, wherein the water-soluble film prior to being made into a water-soluble unit dose article has a thickness between 30µm and 100µm, preferably between 50µm and 100µm, even more preferably between 65µm and 88 µm, most preferably between 76µm and 85µm.

11. The water-soluble unit dose article according to any preceding claims wherein the liquid cleaning composition is selected from laundry cleaning compositions, automatic dishwashing compositions or a mixture thereof.

12. The water-soluble unit dose article according to claim 11 wherein the liquid cleaning composition comprises a substrate treatment agent and wherein the substrate treatment agent is preferably selected from the group comprising anionic surfactants, non-ionic surfactants, cationic surfactants, polyethylene glycol polymers, ethoxylated polyethyleneimines, rheology modifier, hueing dyes, perfumes, perfume microcapsules, chelants, enzymes, silicones, polyolefin waxes, latexes, oily sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids, enzyme stabilizing systems;
antioxidants, opacifier, pearlescent agent, deposition aid, builder, bleaching agent, bleach activator, bleach catalyst, organic shine polymers, surface modifying polymers, metal care agents, metal salts, anti-corrosion agents and mixtures thereof.

13. The unit dose article according to any preceding claims comprising an air bubble.

14. The water-soluble unit dose article according to any preceding claims wherein the unit dose article comprises at least two internal compartments, or even at least three compartments or even at least four compartments.

15. The water-soluble unit dose article according to claim 14, wherein the compartments are arranged in a superposed orieritation, side-by-side orientation or a mixture thereof.

16. The water-soluble unit dose article according to any preceding claims wherein the unit dose article is transparent, translucent or opaque.

17. The water-soluble unit dose article according to any preceding claims wherein the unit dose article is flow wrapped.

18. A water-soluble unit dose article comprising a water-soluble film and at least one internal compartment, wherein said compartment comprises a powder composition, wherein when the water-soluble unit dose article is placed in water at 20 C, the powder composition is retained within the water-soluble unit dose article for at least 30 seconds.

19. A packaged product comprising an external container and at least water-soluble unit dose article according to any preceding claims, wherein the external container is opaque.

20. The packaged product according to claim 19 wherein the external container comprises a child resistant closure.

21. A method of laundering fabrics comprising the step of adding a water-soluble unit dose article according to any preceding claims to a volume of water.

22. An automatic dishwashing method comprising the step of adding a water-soluble unit dose article according to any preceding claims to a volume of water.

23. The method of claim 21 or 22 wherein the volume of water is sufficient to dilute the liquid cleaning composition by a factor of at least 100, or even at least 200, or even at least 300, or even at least 500.