WO2023072457A1 - Films and capsules - Google Patents

Abstract

A water-soluble capsule comprising a film, the film comprising a polysaccharide and an anti-oxidant. Also provided is a water-soluble capsule utilising said film.

Description

Films and Capsules

The present invention relates to capsules of water soluble film for containing homecare substrate treatment compositions.

Despite the prior art there remains a need for renewable films which have pleasing aesthetics.

Accordingly, and in a first aspect, there is provided a film comprising a polysaccharide and an anti-oxidant.

Preferably the antioxidant excludes ammonium bisulfite or metabisulfite.

Preferably the film is in contact with a home care composition. This means the film may support a home care compositon e.g. a sheet of film carrying said composition; or be supported by a home care composition e.g. a sheet of film lying on top of said composition; or the film may be impregnated with the composition. Such films may be the form of a unit dose product. The film may be in the form of a capsule.

Accordingly, in a further aspect, there is provided a water-soluble capsule comprising a water-soluble film carrying or enclosing a home care composition, the water-soluble capsule comprising a polysaccharide and an anti-oxidant.

In a further aspect, there is provided a water soluble capsule comprising a water-soluble film and at least one internal compartment enclosed by the water-soluble film, the compartment having an internal space and containing a home care composition within the internal space, where the film comprises polysaccaride and an anti-oxidant.

The applicant has surprisingly found that unit dose products made from renewable films comprising polysaccharide and an anti-oxidant reduces discolouration of liquid compositions which contact e.g. are stored in said renewable films.

The following terms, as used here are defined below:

“A” and “an”, are understood to mean one or more of what is claimed or described. "Alkyl" refers to a straight or branched chain monovalent hydrocarbon radical having a specified number of carbon atoms. Alkyl groups may be unsubstituted or substituted with substituents that do not interfere with the specified function of the composition and may be substituted once or twice with the same or different group. Substituents may include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, nitro, carboxy, carbonyl, carbonyloxy, cyano, methylsulfonylamino, or halogen, for example. Examples of "alkyl" include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, n- pentyl, n-hexyl, 3-methylpentyl, and the like.

“Biodegradable” means the complete breakdown of a substance by microorganisms to carbon dioxide water biomass, and inorganic materials.

"Film" refers to a water soluble material and may be be sheet-like material. The length and width of the material may far exceed the thickness of the material, however the film may be of any thickness.

“Polymer" refers to a macromolecule comprising repeat units where the macromolecule has a molecular weight of at least 1000 Daltons. The polymer may be a homopolymer, copolymer, terpoymer etc.

“Substrate” mean any suitable substrate including fabric articles or garments, bedding, towels etc., and dishes, where “dishes" is used herein in a generic sense, and encompasses essentially any items which may be found in a dishwashing load, including crockery chinaware, glassware, plasticware, hollowware and cutlery, including silverware. “Thermoforming” means a process in which the film is deformed by heat, and in particular it may involve the following: a first sheet of film is subjected to a moulding process to form an enclosure in the film e.g. forming a recess in the film. Preferably this involves heating prior to deformation. The deformation step is preferably enabled by laying the film over a cavity and applying a vacuum or an under pressure inside the cavity (to hold the film in the cavity). The recesses may then be filled. The process may then include overlaying a second sheet over the filled recesses and sealing it to the first sheet of film around the edges of the recesses to form a flat sealing web, thus forming a capsule which may be a unit dose product. The second film may be thermoformed during manufacture. Alternatively, the second film may not be thermoformed during manufacture.

“Substrate treatment composition” means any type of treatment composition for which it is desirable to provide a dose thereof in a water-soluble and is designed for treating a substrate as defined herein. Such compositions may include, but are not limited to, laundry cleaning compositions, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewashing compositions, laundry pretreating compositions, laundry additives (e.g., rinse additives, wash additives, etc.), post-rinse fabric treatment compositions, dry cleaning compositions, ironing aid, dish washing compositions, hard surface cleaning compositions, and other suitable compositions that may be apparent to one skilled in the art in view of the teachings herein.

“Unit dose” means an amount of composition suitable to treat one load of laundry, such as, for example, from about 0.05 g to about 100 g, or from 10 g to about 60 g, or from about 20 g to about 40 g. A unit dose product may be in the form of a film package containing the composition, the package may be referred to as a capsule or pouch. “Water-soluble” means the article (film or package) dissolves in water at 20° C.

Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

Except in the examples and comparative experiments, or where otherwise explicitly indicated, all numbers are to be understood as modified by the word “about”.

All percentages ( expressed as “%”) and ratios contained herein are calculated by weight unless otherwise indicated. All conditions herein are at 20° C. and under the atmospheric pressure, unless otherwise specifically stated. All polymer molecular weights are determined by weight average number molecular weight unless otherwise specifically noted.

Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated. In specifying any range of values or amounts, any particular upper value or amount can be associated with any particular lower value or amount.

Polysaccharide

Preferably the polysaccharide is pectin.

Other polysaccharides include starch (sweet potato), soy polysaccharides and seaweeds Pectin

The pectin may be unmodified or modified and such modification includes substitution (alkylation, amidation, quaternization, thiolation, sulfation, oxidation, etc.), chain elongation (cross-linking and grafting) and depolymerization (chemical, physical, and enzymatic degradation).

Pectins comprise helical chains of galacturonic acid (GalA) residues linked by a-1 , 4 glycosidic linkages, wherein the carboxyl groups may be esterified to any degree with methyl groups or may be partially or completely converted into salts.

The pectin may comprise any type of galacturonan including heterogalacturonans (HG), substituted galacturonans, rhamnogalacturonan I pectins (RG-I), rhamnogalacturonan II (RG-II), xylogalacturonan (XGA) or any mixture thereof.

Esterification

The esterification level or degree of esterification (DE) is the ratio of esterified galacturonic acid groups to total galacturonic acid groups (and thus having a value between 0% and 100%). Preferably the degree of esterification is from 1% to 49%, more preferably from 25% to 48%, most preferably from 24 to 35%.

The level of esterification by methyl groups may be such that the pectin is a high methoxy pectin (HM pectin) - with more than half of all the galacturonic acid esterified; or a low methoxy pectin (LM pectin) with less than half of all the galacturonic acid esterified. Preferably the degree of methoxylation is from 1% to 49%, more preferably from 25% to 48%, most preferably from 24 to 35%.

Preferably the pectin is a low methoxy pectin.

Amidated Pectin

Preferably the pectin is amidated.

A representative segment of a nonacetylated, non-amidated pectin molecule:

R « -CO₂CH₃. -COj. cr -COjH

By “amidated pectin” it is intended to mean that the pectin is modified by conversion of a portion of the carboxylic groups to carboxylic acid amide, e.g. as with the amidated unit shown below:

Preferably the degree of amidation is from 1% to 90%, more preferably from 10 to 50% even more preferably from 20% to 40% most preferably from 20 to 30%. Degree of amidation (DA) can be measure by various known methods for example near infrared spectroscopy, based on the total number of galacturonic acid units in the molecule.

Pectins may be amidated by any suitable method e.g. by ammonia which may be dissolved in methanol or in aqueous form. This converts the methyl ester groups into carboxamide [-CONH2] groups. Because in the process, methyl ester groups are lost as they are converted into carboxamide groups a low methoxy (LM) pectin (by definition) is formed. Amdiated (LM) pections may have 15 - 25% of the carboxyl groups converted into carboxamide groups.

Low Methoxy Amidated Pectin

Amidation may achieve reduced methyl levels and so providing a low methoxy, amidated pectin. Source

The pectin is preferably plant derived and may be sourced from any suitable source such as citrus peel or pomace from e.g., both by-products of fruit production. Pomace may also be obtained from sugar beet.

Pectin Levels

The pectin may be present at any suitable level e.g. from 1 - 99 %wt. Suitably, the pectin may be present from 35%wt. Preferably, the pectin is present from 40%wt of the film, more preferably from 50%wt of the film, even more preferably from 60% wt. of the film.

Preferably the pectin is present at no more than 99%wt of the film, more preferably no more than 80%wt. of the film, most preferably no more than 70%wt. of the film.

The pectin may be present from 50 - 99%wt of the film.

Suitable pectin amounts are selected from the range of 40 to 90 %wt., more preferably 50 to 80 %wt.

Pectin MW

The pectin has an average molecular weight in the range 150,000 g/mol - 500,000 g/mol.

Suitably the pectin has an average molecular weight not greater than 450K g/mol, preferably not greater than 350 g/mol, more preferably not greater than 300 g/mol.

Suitably the pectin has an average molecular weight not less than 300 g/mol, preferably not less than 250 g/mol, more preferably not less than 200 g/mol.

PVOH

It is preferred that the film is substantially free of polyvinyl alcohol (PVOH) and more preferably 0%, by weight of the composition, of the component.

Anti-oxidant

Any suitable antioxidants may be used.

Suitable antioxidants include sulphite salts, such as Sodium Sulfite, Potassium Sulfite, Sodium Bisulfite and Sodium Metabisulfite or potassium sulphite. Organic acids like citric acid, ascorbic acid, tartaric acid, adipic acid and sorbic acid, or amines like lecithin, or amino acids like glutamine, methionine and cysteine, or esters like ascorbil palmitate, ascorbil stearate and triethylcitrate, or mixtures thereof.

Anti-oxidants also include free radical scavengers, except where the context would make this impossible. Suitable free radical scavengers for use herein include the well- known'substituted mono* and drhydroxy benzenes -and- their analogs, alkyl and aryl carboxylates and mixtures thereof. Preferred such radical scavengers for use herein include di- tert-butyl hydroxy toluene (BHT) , hydroquinone, ditert -butyl hydroquinone , mono-tert -butyl hydroquinone, tert-butyl- hydroxy anysole, benzoic acid, toluic acid, catechol, t- butyl catechol, benzylamine, 1 , 1 , 3-tris (2-methyl-4-hydrox-5- t-butylphenyl) butane, n-proyl-gallate or mixtures thereof and highly preferred is di-tert-butyl hydroxy toluene. Such radical scavengers like N-propyl-gallate may be commercially available from Nipa Laboratories under the trade name Nipanox SI®. Radical scavengers when used, are typically present herein in amounts ranging from up to 10% and preferably from 0.001% to 0.5% by weight of the total composition.

The anti-oxidant excludes ammonium bisulfite or metabisulfite.

Preferably the anti-oxidant is present in the film.

The anti-oxidant is suitably present at a level no less than 0.01 %wt, preferably no less than 0.4%wt, more preferably no less than 2 %wt of the film even more preferably no less than 4%wt of the film (based on total weight of dry e.g cast film).

The anti-oxidant is suitably present at a level no more than 10 %wt, preferably no more than 5 %wt, more preferably no more than 3 %wt of the film (based on total weight of dry e.g. cast film).

Film Thickness

The film thickness (before incorporation into a product e.g. capsule ) is from 40 to 200 micrometres (microns). This combined with the molecular weight as described herein, provides for a film that is strong enough to withstand handling especially when it contains quantities of a home care composition but that also dissolves in water during aqueous washing processes in which that home care composition is used.

Preferably the film thickness is from 40 to 150 micrometres (microns), more preferably from 40 to 100 microns, even more preferably from 60 to 90 micrometres (microns), most preferably from 70 to 80 micrometres (microns).

Water-soluble capsules may be made using two films, e.g one (second) film superposed over another (first) film and sealed around edge regions e.g. as described herein. Where two films are used to make a capsule, the second film is typically of a similar type to that used for the first film, but slightly thinner. Thus, in embodiments, the second film is thinner than the first film. In embodiments the ratio of thickness of the first film to the thickness of the second film is from 1 :1 to 2:1.

In embodiments the first film thickness (pre-thermoforming) is preferably from 40 to 200 micrometres, from 40 to 150 micrometres, from 60 to 120 micrometres, or from 80 to 100 micrometres. After capsule manufacture the average thickness of the first film is preferably from 30 to 90 micrometres, or from 40 to 80 micrometres.

In embodiments the second film thickness (pre-thermoforming) is preferably from 20 to 100 micrometres, from 25 to 80 micrometres, or from 30 to 60 micrometres.

Layer

Preferably the film comprises a single layer, that is to say it comprises no more than one layer. One way this may be achieved is that the film is made by forming a solution of carrageenan with a solvent e.g. water and any other ingredients (plasticisers, bittering agent as examples) and this is then cast e.g. poured on to a surface such as a moving belt and then dried. Preferably, no further layers of the film are added by casting.

Preferably the capsule comprises film having a single layer.

Bittering Agent

The film may comprise a bittering agent.

Preferably the bittering agent is selected from: capsicinoids (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'- methoxy-4'-hydroxy-phenyl)-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.

Preferred bittering agents include pungents e.g. capsaicinoids, which includes capsaicin, dihydrocapsaicin, nordihydrocapsaicin, homodihydrocapsaicin, homocapsaicin, and nonivamide. A particularly preferred bittering agent is capsaicin.

Bittering agents may also be selected from from other pungents which can act as bittering agents include pungents, piperine, allyl isothiocyanate, and resinferatoxin), benzoic benzylamine amide, trichloroanisole, methyl anthranilate and quinine (and salts of quinine). Further examples of bittering agents include flavonoids such as quercefin and naringenin, naringin, sucrose octaacetate, , quassinoids such as quassin and brucine and agents derived from plant or vegetable matter, such as chemical compounds derived from chilli pepper plants, those derived from a plant species of the genus cynaro, alkaloids and amino acids. Preferably, the bittering agent is selected from the group consisting of denatonium benzoate, denatonium saccharide, quinine or a salt of quinine. The chemical name of denatonium is phenylmethyl-[2-[(2,6-dimethylphenyl)amino]-2-oxoethyl]- diethylammonium. In particular embodiments, the bittering agent is denatonium benzoate or denatonium saccharide.

The bittering agent may be incorporated within the film or in a film-coating on the exterior surface of the film (prior to making the capsule) or water-soluble capsule. Preferably the bittering agent is incorporated into the film.

The bittering agent may be incorporated into the matrix of a water-soluble polymer included in the film by dissolving the bittering agent in a water-soluble polymer solution before the unprinted region of the film is formed. The bittering agent may be present in film material in a range of 100 to 5000 ppm, preferably 200 to 3000 ppm, more preferably 500 to 2000 ppm, based on the weights of the bittering agent and film. For example, 1 mg of bittering agent may be incorporated into 1 g of film to provide the bittering agent at 1000 ppm. Additionally or alternatively, the bitter agent may be included in the water-soluble package as a powdered bittering agent in a powder coating applied to the exterior surface of the water-soluble package (described in more detail below)

Preferably, the water-soluble package includes a powder coating on an exterior surface of the film, and the powder coating includes a powdered lubricating agent. The powder coating, when present, may coat printed region or regions and/or unprinted region or regions (if present) of the film. In any printed regions of the film, the powder coating may be indirectly on the exterior surface of the film where there is a layer of dye or pigment. The powder coating may be applied to least 50%, preferably at least 60%, at least 70% even more preferably at least 80%, most preferably at least 90%percent by area of the exterior surface of the film. The powder coating can be applied by any known technique such as spray-coating or passing the film through a falling curtain of powder coating composition. The powder coating may be applied to the exterior surface of the film at a rate of 0.5 to 10mg per 100cm², in some embodiments not more than 5mg per 100cm², and in further embodiments in the range of 1.25 to 2.5mg per 100cm². The powder coating may be applied to or present on the exterior surface of the film in an amount of 100 ppm or more, preferably 200 ppm or more, more preferably 300 ppm or more, based on the weights of the powder coating and the film. For example, a 1 mg of powder coating may be applied to a 1 g film to provide a 1000 ppm coating on the substrate. In certain embodiments, the powder coating is applied to or present on the exterior surface of the film in a range of 100 to 5000 ppm, preferably 200 to 3000 ppm, more preferably 300 to 2000 ppm.

Lubricating Agent

The powder coating may include a powdered lubricating agent. Typical powdered lubricating agents include oligosaccharide, polysaccharide and inorganic lubricating agents. The powdered coating may include one or more of the group selected from starch, modified starches (including, but limited to, corn starch, potato starch or hydroxyethyl starch) silicas, siloxanes, calcium carbonate, magnesium carbonate, clay, talc, silicic acid, kaolin, gypsum, zeolites, cyclodextrins, calcium stearate, zinc stearate, alumina, magnesium stearate, sodium sulphate, sodium citrate, sodium tripolyphosphate, potassium sulphate, potassium citrate, potassium tripolyphosphate and zinc oxide. In a preferred embodiment, the powdered lubricating agent includes talc. The powder coating can include a bittering agent in addition to or as an alternative to a bittering agent being present within or film-coated on the film. The powdered bittering agent may be a powdered form of any one of the bittering agents described herein.

When a bittering agent is included in a powder coating, the powdered bittering agent may form 5 weight percent or more of the powder coating based on the total weight of the powder coating. In some embodiments, the powdered bittering agent forms 10 weight percent or more, 15 weight percent or more, 20 weight percent or more, or 25 weight percent or more of powder coating based on the total weight of the powder coating. In some embodiments, the powdered bittering agent forms 75 weight percent or less, 70 weight percent or less, 65 weight percent or less, 60 weight percent or less, or 55 weight percent or less of the powder coating based on the total weight of the powder coating. In further embodiments, the powdered bittering agent forms 5 to 75 weight percent, 10 to 70 weight percent, 15 to 65 weight percent, 20 to 60 weight percent, or 25 to 55 weight percent of the powder coating based on the total weight of the powder coating. In alternative embodiments, the powdered bittering agent forms 50 weight percent or less, 40 weight percent or less, 30 weight percent or less of the powder coating based on the total weight of the powder coating. In these embodiments, it is advantageous to include a relatively low amount of powdered bittering agent in the powder coating while maintaining a bitter taste when a user tries to ingest the water-soluble package.

The powdered bittering agent, when present, may have an average particle diameter of at least about 0.1 microns. The powdered bittering agent may have an average particle diameter of about 200 microns or less. In some embodiments, the powdered bittering agent has an average particle diameter of in the range of about 0.1 to 100 microns, in other embodiments in the range of about 0.1 to 20 microns and in further embodiments in a range of about 5 and 15 microns. Average particle diameter can be measured by known optical imaging techniques.

In some embodiments, the powder coating further includes one or more additional active agents. The additional active agent may be selected from one or more of the group of enzymes, oils, odour absorbers, fragrances, bleaches, bleach components, cleaning polymers, soil release polymers, EPEI, water softeners, dyes and fabric softeners.

Plasticising surfactant

Preferably the film further includes a surfactant which may be anionic, cationic, nonionic or amphoteric. Preferably, surfactant is an anionic surfactant. Preferably the surfactant is a sugar-based surfactant, comprising at least one sugar group. Sugar-based Surfactant

The sugar group is preferably a monosaccharide or disaccharide.

Sugar-based surfactants may be selected from alkyl polyglycosides, sorbitan esters, sucrose esters, and fatty acid glucamides, or rhamnose sugar-based surfactants e.g. rhamnolipids or sophorolipids. Preferably the surfactant is a biodegradable surfactant.

Surfactant Volume

Preferably the surfactant has a volume greater than 350 cubic angstron, more preferably greater than 400 cubic angstrom.

Functionalised APGS

Preferably the surfactant comprises a functionalised alkylpolyglucosides (APGs).

APGs are non-ionic surfactants defined by the following chemical structure, wherein m is 2 or greater and n is generally 5 or greater.

As shown, the APGs are defined by an oligomer or polymer of glucose residues and terminal alkyl group. The glucosidic portion of the compounds is hydrophilic, while the alkyl component of the compounds is lipophilic.

A cross-linking agent will usually be used to functionalise the APG, in such a reaction to create a 'cross-polymer' . Functional groups include quaternary, or polyquaternary functionalized alkyl polyglycosides. Functional group/s are preferably selected from quaternary compounds (including quaternary ammonium groups), betaines, carboxymethylates, maleates, sulfonates (including hydroxyalkylsulfonates and polysulfonates), succinates and sulfosuccinates. The synthesis of these functionalised APGs is described in US 6,627,612 and US 7,507,399. Sulfate groups and hydroxy groups can also be added. Preferably, the APG derivatives have molecular weights of the order of about 2000 to about 6000Da. and therefore these do not bio- accumulate in the environment.

The functionalized APGs may comprise any of hydroxypropylsulfonate-functionalized APGs, hydroxypropylphosphate-functionalized APGs, and inorganic salts thereof APG crosspolymers, such as sorbitan ester APG crosspolymers, hydroxypropylphosphate APG crosspolymers, hydroxypropylsulfonate APG crosspolymers, betaine-functionalized APG crosspolymers, quaternized APG crosspolymers, and sulfosuccinate functionalized APG crosspolymers.

The functionalised APG derivatives of the present disclosure preferably includes, APG hydroxypropylsulfonates, and inorganic salts thereof. The general chemical structure of APG hydroxypropylsulfonates is shown below.

In the formula above, n is preferably between about 2 to about 11 and R1 is preferably a C2 -C24 alkyl group. Accordingly, APG derivatives of the present invention may include decylpolyglucoside hydroxypropylsulfonate, laurylpolyglucoside hydroxypropylsulfonate, and sodium salts thereof (e.g., sodium decylglucosides hydroxypropylsulfonate and sodium laurylglucosides hydroxypropylsulfonate), which are commercially available from Colonial Chemicals, Inc. (US) as SugaONate 100NC and SugaONate 160NC, respectively. These and related compounds can be synthesized according to methods known in the art. Structure of SugaONate 100NC

Likewise, in certain embodiments, the APG derivatives of the present disclosure can include, without limitation, hydroxypropylsulfonate functionalized APG crosspolymers, and inorganic salts thereof. A representative structure of hydroxypropylsulfonate functionalized APG crosspolymers is shown below.

Wherein n is preferably between about 2 to about 11 and R1 is a C2 -C24 alkyl group. The APG derivatives may include sodium hydroxypropylsulfonate decylglucoside crosspolymer, and sodium hydroxypropylsulfonate laurylglucoside crosspolymer, which are commercially available from Colonial Chemicals, Inc. (US) as PolySugaONate 100P and PolySugaONate 160P, respectively. These and related compounds can be synthesized according to methods known in the art.

The surfactant may be present at any suitable level e.g. from 1 to 60% wt. of the film. Preferably the surfactant is present from 10%wt of the film, more preferably from 20%wt. of the film, more preferably from 30%wt. of the film.

Preferably the surfactant is present at no more than 50%wt. of the film, more preferably at no more than 40% of the film.

Co-plasticizers

The film preferably contains one or more further or co-plasticizers. Such include, but are not limited to polyols, poly-alcohols, or sugar alcohols and may be selected from glycerol, poly glycerol, diglycerin, hydroxypropyl glycerine, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, monopropylene glycol, propylene glycol, polyethylene glycol, neopentyl glycol, trimethylpropane polyether polyols, sorbitol, manninol, ethanolamines and mixtures thereof.

Preferably the co-plasticiser is not a surfactant.

The co-plasticiser may be present at any suitable level e.g.,from 1 to 50%. Preferably the co-plasticiser is present at from 10%wt. of the film more preferably from 20%wt of the film.

Preferably the co-plasticiser is present at no more than 40%wt. of the film, more preferably at no more than 30%wt. of the film.

Preferably the capsule film comprises 60-70% pectin, 10-30% plasticising surfactant and 10-30% co-plasticiser.

The plasticising surfactant and the co-plasticiser may be present in equal amounts. A particularly preferred embodiment is a film having pectin, further plasticiser and surfactant in the ratio 6:2:2 (pectin: second plasticiser: plasticising surfactant)

The capsule film may have a thickness before incorporation into a product such as a capsule of between 40 microns and 100 microns, preferably between 60 microns and 90 microns, more preferably between 70 microns and 80 microns.

The capsules may be formed in any suitable manner using the water soluble pectin film.

The film may be folded and/or sealed to create the at least one internal compartment with an internal space which is then filled with a home care composition, and then optiionally the compartment is closed by sealing.

Alternatively the water soluble capsule may comprising a first film comprising a thermoformed recess, said recess containing a substrate treatment composition and a second film superposed over said first film, said first and second films sealed around the edges, wherein said first and second films are according to the first aspect of the invention and any preferred/optional features as described herein. Packages comprising a film such as those described herein may be manufactured using a form fill seal approach or using a vacuum form, fill seal approach. Pouches may be formed on a continuously moving process where a film is drawn into a mould, filled from above and then sealed by application of a second film. The pouches are then separated from one another to form individual unit dose products.

Substrate treatment capsules e.g. laundry capsules maybe thermoformed which involves a moulding process to deform sheet film to provide recesses therein. The process involves heating sheet film to soften and deform the film to stretch and fill a cavity in a mould and also the application of vacuum. The recesses are filled and the capsules completed by overlaying a second sheet of film over the filled recesses and sealing it to the first sheet of film around the edges of the recesse to form a flat seal. Relaxation of the first film typically then causes the applied second sheet to bulge out when the vacuum is released from the first sheet of film in the mould. For high performance laundry or machine dish wash treatment capsules there is a need to fill the capsule with sufficient liquid. The fill volume results in a greater stretch imposed on the water-soluble and provides a capsule with a bulbous, convex outer profile as the first and second sheets bulge out and stretch under the pressure. Films need to be strong and sufficiently stretchy to allow for this process. Films according to the invention are advanatageous for thermoforming such capsules as they exhibit strength and stretch.

The two films may be heat or water sealed depending on the process machinery used.

In a second aspect there is provided a unit dose substrate product comprising a substrate treatment formulation within a sealed container, said container comprising a film according to any preceding claim.

The water-soluble packages of the present invention can be manufactured using standard known techniques. The film may be printed, for example, a sheet of film (e.g. film) may be printed with one or more layers of dye or pigment in a pattern. The pattern may be indicia, such as words, symbols or drawings. The layer or layers of dye or pigment may be printed onto the film using an ink. The ink type is not particularly limited, and includes non-aqueous solvent- based inks (such as organic solvent-based inks), aqueous-based inks and/or UV cured inks. In some embodiments, the ink is a non-aqueous-based ink. The film may be printed with a primer layer before printing of the layer or layers of dye or pigment. After printing with the layer or layers of dye or pigment, the film may be printed with a protective or lacquer layer. The printed layer or layers may be then dried, for example using heat and/or air flow. The resulting printed film may be stored, transported or used immediately to form the printed water-soluble packages of the present invention. When the bittering agent is contained within at least part of the film, the bittering agent is typically present in the film before printing. In one embodiment, the bittering agent is included at least on part of the exterior surface of the film as a film coating. The film coating of bittering agent may be deposited on the water-substrate before, during or after the printing of the printed regions.

The film is typically formed (preferably thermoformed) into a film enclosure (e.g. a film pocket, open capsule or container). The film enclosure may then be filled with a composition such as a dishwashing or laundry detergent composition. The water-soluble enclosure containing the composition or material can then be sealed, for example by sealing the edges of the enclosure or joining the enclosure with one or more additional pieces of film, in order to enclose the material or composition in the water-soluble package. The powder coating may then be applied to the exterior surface of the film. The powder coating may be applied to the film by any known powder technique. Preferably, the powder is applied to the film using no solvent or a non-aqueous solvent. Such an application reduces the risk of dissolving the film. The above optional and preferred features are equally combinable and applicable to all aspects of the invention, unless indicated otherwise.

In a particular embodiment, the present invention provides a printed water-soluble package comprising a film of the first aspect, the film enclosing a composition, the film having an exterior surface with one or more printed regions, the bittering agent is selected from the group consisting of denatonium benzoate, denatonium saccharide, quinine or a salt of quinine and is substantially homogenously contained within the film, and wherein the water-soluble package further includes a powder coating coated on the exterior surface of the film, the powder coating a including a powdered lubricating agent, the powdered lubricating agent being talc.

When carrying or containing a substrate treatment composition, this may be a laundry treatment composition such as a laundry liquid or powder composition. Such formulations are well known in the art and comprise water up to around 15% wt. of the composition; surfactants such as anionic surfactants, non-ionic surfactants, zwitterionic surfactants and mixtures thereof. Further, polymeric cleaning aids such as soil release polymers and polyamines are commonly employed to improve cleaning performance. Fragrances are added for providing a fragrance benefit to the fabric after treatment.

Visual cues such as dyes are used to provide improved aesthetics.

Home Care Composition preferably comprises liquid laundry detergent.

Liquid laundry detergents

Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid colour care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines.

The term “liquid” in the context of this invention denotes that a continuous phase or predominant part of the composition is liquid and that the composition is flowable at 15°C and above. Accordingly, the term “liquid” may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, known as gels or pastes. The viscosity of the composition may suitably range from about 200 to about 10,000 mPa.s at 25°C at a shear rate of 21 sec¹. This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle. Pourable liquid detergent compositions generally have a viscosity of from 200 to 1 ,500 mPa.s, preferably from 200 to 500 mPa.s.

Liquid detergent compositions which are pourable gels generally have a viscosity of from 1 ,500 mPa.s to 6,000 mPa.s, preferably from 1 ,500 mPa.s to 2,000 mPa.s.

A liquid composition according to the invention may also have a low water content. Low water content compositions will generally comprise no more than 20%, and preferably no more than 10%, such as from 5 to 10% water (by weight based on the total weight of the composition).

A liquid composition of the invention with an aqueous continuous phase preferably has a pH in the range of 5 to 9, more preferably 6 to 8, when measured on dilution of the composition to 1% using demineralised water. The term “detersive surfactant” in the context of this invention denotes a surfactant which provides a detersive (i.e. cleaning) effect to laundry treated as part of a domestic laundering process.

Non-soap anionic surfactants for use in liquid compositions are typically salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha-olefin sulfonates and mixtures thereof. The alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule. The counterion for anionic surfactants is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA).

Mixtures of such counterions may also be employed.

A preferred class of non-soap anionic surfactant for use in liquid compositions includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the “para" position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1-phenyl isomer. LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ.

Also suitable are alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3EO units per molecule.

Some alkyl sulfate surfactant (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulphates with an alkyl chain length of from 10 to 18. Mixtures of any of the above described materials may also be used. A preferred mixture of non-soap anionic surfactants for use in the invention comprises linear alkylbenzene sulfonate (preferably Cn to C15 linear alkyl benzene sulfonate) and sodium lauryl ether sulfate, (preferably C10 to C18 alkyl sulfate ethoxylated with an average of 1 to 3 EO)

In a liquid composition of the invention the total level of non-soap anionic surfactant may suitably range from 8 to 20%, preferably from 12 to 16% (by weight based on the total weight of the composition).

Nonionic surfactants for use in liquid compositions are typically polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkyl phenols. Where the starter molecule is an alcohol, the reaction product is known as an alcohol alkoxylate. The polyoxyalkylene compounds can have a variety of block and heteric (random) structures. For example, they can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates. Within the block structures, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides. Examples of such materials include Cs to C22 alkyl phenol ethoxylates with an average of from 5 to 25 moles of ethylene oxide per mole of alkyl phenol; and aliphatic alcohol ethoxylates such as Cs to Cis primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.

A preferred class of nonionic surfactant for use in liquid compositions includes aliphatic Cs to Cis, more preferably C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.

Mixtures of any of the above described materials may also be used.

In a liquid composition of the invention the total level of non-ionic surfactant will suitably range from 1 to 10% (by weight based on the total weight of the composition). A mixture of non-soap anionic and non-ionic surfactants for use in the invention comprises linear alkylbenzene sulfonate (preferably Cn to C15 linear alkyl benzene sulfonate), sodium lauryl ether sulfate (preferably C10 to C18 alkyl sulfate ethoxylated with an average of 1 to 3 EO) and ethoxylated aliphatic alcohol (preferably C12 to C15 primary linear alcohol ethoxylate with an average of from 7 to 9 moles of ethylene oxide per mole of alcohol).

The weight ratio of total non-soap anionic surfactant to total nonionic surfactant in a composition of the invention suitably ranges from about 3: 1 to about 1.1 :1.

NON-AQUEOUS CARRIERS

A liquid composition of the invention may incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (M_w) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulfonates).

Mixtures of any of the above described materials may also be used.

Non-aqueous carriers, when included, may be present in an amount ranging from 0.1 to 20%, preferably from 1 to 15%, and more preferably from 3 to 12% (by weight based on the total weight of the composition).

COSURFACTANTS

A liquid composition of the invention may contain one or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the non-soap anionic and/or nonionic detersive surfactants described above. Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof. Cationic surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

Mixtures of any of the above described materials may also be used.

POLYAMINES

The ethoxylated polyamines (EPEI) are generally linear or branched poly (>2) amines. The amines may be primary, secondary or tertiary. A single or a number of amine functions are reacted with one or more alkylene oxide groups to form a polyalkylene oxide side chain. The alkylene oxide can be a homopolymer (for example ethylene oxide) or a random or block copolymer. The terminal group of the alkylene oxide side chain can be further reacted to give an anionic character to the molecule (for example to give carboxylic acid or sulphonic acid functionality).

The liquid composition comprises from about 0.5% to about 4% polyamine, more preferably from 2.0 to 3.5% wt. of the composition.

BUILDERS

A liquid composition of the invention may contain one or more builders.

Suitable inorganic builders include hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, zeolites, and mixtures thereof. Specific examples of such materials include sodium and potassium hydroxide, sodium and potassium carbonate, sodium and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof.

Suitable organic builders include polycarboxylates, in acid and/or salt form. When utilized in salt form, alkali metal (e.g. sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium and potassium citrates, sodium and potassium tartrates, the sodium and potassium salts of tartaric acid monosuccinate, the sodium and potassium salts of tartaric acid disuccinate, sodium and potassium ethylenediaminetetraacetates, sodium and potassium N(2-hydroxyethyl)- ethylenediamine triacetates, sodium and potassium nitrilotriacetates and sodium and potassium N-(2-hydroxyethyl)-nitrilodiacetates. Polymeric polycarboxylates may also be used, such as polymers of unsaturated monocarboxylic acids (e.g. acrylic, methacrylic, vinylacetic, and crotonic acids) and/or unsaturated dicarboxylic acids (e.g. maleic, fumaric, itaconic, mesaconic and citraconic acids and their anhydrides). Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic and maleic acid. The polymers may be in acid, salt or partially neutralised form and may suitably have a molecular weight (Mw) ranging from about 1,000 to 100,000, preferably from about 2,000 to about 85,000, and more preferably from about 2,500 to about 75,000

Mixtures of any of the above described materials may also be used. Preferred builders for use in the invention may be selected from polycarboxylates (e.g. citrates) in acid and/or salt form and mixtures thereof.

Builder, when included, may be present in an amount ranging from about 0.1 to about 20%, preferably from about 0.5 to about 15%, more preferably from about 1 to about 10% (by weight based on the total weight of the composition).

TRANSITION METAL ION CHELATING AGENTS

A liquid composition of the invention may contain one or more chelating agents for transition metal ions such as iron, copper and manganese. Such chelating agents may help to improve the stability of the composition and protect for example against transition metal catalyzed decomposition of certain ingredients. Suitable transition metal ion chelating agents include phosphonates, in acid and/or salt form. When utilized in salt form, alkali metal (e.g. sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotris(methylene phosphonic acid) (ATMP), 1-hydroxyethylidene diphosphonic acid (HEDP) and diethylenetriamine penta(methylene phosphonic acid (DTPMP) and their respective sodium or potassium salts. HEDP is preferred. Mixtures of any of the above described materials may also be used.

Transition metal ion chelating agents, when included, may be present in an amount ranging from about 0.1 to about 10%, preferably from about 0.1 to about 3% (by weight based on the total weight of the composition).

FATTY ACID

A liquid composition of the invention will preferably contain one or more fatty acids and/ or salts thereof.

Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

The fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.

Mixtures of any of the above described materials may also be used.

Fatty acids and/or their salts, when included, may be present in an amount ranging from about 0.25 to 5%, more preferably from 0.5 to 5%, most preferably from 0.75 to 4% (by weight based on the total weight of the composition). For formula accounting purposes, in the formulation, fatty acids and/or their salts (as defined above) are not included in the level of surfactant or in the level of builder.

POLYMERIC CLEANING BOOSTERS

To further improve the environmental profile of liquid laundry detergents it may be preferred in some cases to reduce the volume of laundry detergent dosed per wash-load and to add various highly weight efficient ingredients to the composition to boost cleaning performance. In addition to the soil release polymers of the invention described above, a composition of the invention will preferably contain one or more additional polymeric cleaning boosters such as anti-redeposition polymers.

Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil. Suitable soil release polymers for use in the invention include alkoxylated polyethyleneimines. Polyethyleneimines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. Preferred alkoxylated polyethyleneimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (M_w). The polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification. A preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.

Mixtures of any of the above described materials may also be used.

When included, a composition of the invention will preferably comprise from 0.25 to 8%, more preferably from 0.5 to 6% (by weight based on the total weight of the composition) of one or more anti-redeposition polymers such as, for example, the alkoxylated polyethyleneimines which are described above. SOIL RELEASE POLYMERS

Soil release polymers help to improve the detachment of soils from fabric by modifying the fabric surface during washing. The adsorption of a SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.

SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped. The SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity. The weight average molecular weight (M_w) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.

SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol). The copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate

Other types of SRP for use in the invention include cellulosic derivatives such as hydroxyether cellulosic polymers, C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; polymers with poly(vinyl ester) hydrophobic segments such as graft copolymers of poly(vinyl ester), for example Ci-Ce vinyl esters (such as poly(vinyl acetate)) grafted onto polyalkylene oxide backbones; poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

POLYMERIC THICKENERS

A composition of the invention may comprise one or more polymeric thickeners. Suitable polymeric thickeners for use in the invention include hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of a monomer mixture including at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e. methacrylic acid and/or acrylic acid); and at least one associative monomer. The term “associative monomer” in the context of this invention denotes a monomer having an ethylenically unsaturated section (for addition polymerization with the other monomers in the mixture) and a hydrophobic section When included, a composition of the invention will preferably comprise from 0.1 to 5% (by weight based on the total weight of the composition) of one or more polymeric thickeners such as, for example, the HASE copolymers which are described above.

ENZYMES

A composition of the invention may comprise an effective amount of one or more enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present with corresponding enzyme stabilizers.

FURTHER OPTIONAL INGREDIENTS

The laundry liquid composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability. Examples of such ingredients include foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, antishrinking agents, anti-wrinkle agents, , sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally, these optional ingredients are included individually at an amount of up to 5% (by weight based on the total weight of the composition). DOSING

A method of laundering fabric using a home care composition of the invention will usually involve diluting the dose of detergent composition with water to obtain a wash liquor, and washing fabrics or other substrates with the wash liquor so formed.

The dilution step preferably provides a wash liquor which comprises inter alia from about 3 to about 20 g/wash of detersive surfactants (as are further defined above).

In automatic washing machines the dose of detergent composition is typically put into a dispenser and from there it is flushed into the machine by the water flowing into the machine, thereby forming the wash liquor. From 5 up to about 65 litres of water may be used to form the wash liquor depending on the machine configuration. The dose of detergent composition may be adjusted accordingly to give appropriate wash liquor concentrations. For example, dosages for a typical front-loading washing machine (using 10 to 15 litres of water to form the wash liquor) may range from about 10 ml to about 60 ml, preferably about 15 to 40 ml. Dosages for a typical top-loading washing machine (using from 40 to 60 litres of water to form the wash liquor) may be higher, e.g. up to about 100 ml.

A subsequent aqueous rinse step and drying the laundry is preferred.

Combinations of aspects

A number of proposals and aspects are described herein, which proposals and aspects are intended to be combined to achieve improved or cumulative benefits. Thus, any one aspect may be combined with any other aspect. Similarly the optional features associated with any one of the aspects may apply to any one of the other aspects.

EXAMPLES

Example 1 : Exemplary films were made with varying ratios of pectin, surfactants (suganate) and glycerol as in the Table 1 below.

Film combinations are given as pectin:glycerol:surfactant ratios

Table 1: Film Compositions

Pectin:

Aglupectin LA- 520 from Silvateam, via Torre, 7, 12080 San Michele Mondovi CN - Italy

Glycerol (95% cone.)

Surfactants:

Suganate type “100NC” is SugaONate 100NC, available from Colonial Chemical, Inc., located in South Pittsburg, TN (CAS NUMBER 742087-48-5).

Suganate type “160NC” is SugaONate 160NC, available from Colonial Chemical, Inc., located in South Pittsburg, TN (CAS NUMBER 742087-49-6).

Suganate type “poly” is Poly Suga ©Nate 160P (primarily C12 poly sulfonate functionalized alkyl polyglucoside), available from Colonial Chemical, Inc., located in South Pittsburg, TN.

BitrexTM when used, it was used as granules at a level of 1000ppm of BitrexTM in the dry film.

Method for making the pectin film compositions of Table 1.

Preparation of polymer solutions to cast films of Table 1

1. Film components were mixed with water to provide a casting solution in a ratio of 18%wt. film to 82% wt. water as follows.

2. Pectin was dissolved in boiling water with overhead stirrer (added gradually) then left for approx. 5-10 minutes to dissolve and glycerine added - in ratios according to the table. 3. Three types of anionic surfactant (100NC, 160NC or poly) were used as shown in Table 1)

4. The solution was left to stir for approximately 5 minutes until full dissolution and mixing, ensuring the stirrer was fully immersed to avoid formation of bubbles.

5. The mixture was then centrifuged for 100minutes at 6000rpm to degas and remove bubbles.

6. The total solution weighed 45g and is sufficient to cast a film the size of an A4 sheet

Casting

1. Films were cast on to a polyacrylate substrate using a Elcometer 4340 Motorised I Automatic Film Applicator and Elcometer 3570 Micrometric Film Applicators.

2. The casting knife was set at different thickness (for clarity this is the thickness of the cast solution or wet film, before the film has set and water evaporated from the solution).

3. The optimum speed for an 18wt% casting solutions is 800pm to give a dry film thickness of 80pm. Thicknesses were varied.

4. Casting speed 3 (1.2m per minute) was used and this advantageously reduces bubbles.

5. Any bubbles observed can be popped e.g. with a sharp spatula.

6. The films were dried in ambient laboratory conditions for 12 - 48 hours (the time depends on ambient conditions) and then tested for peeling from the substrate. For increased drying speed, films can be dried in an oven at 40°C for 2hours.

Example 2 Film Dissolution Tests

Film pieces were cut to the size 4cm x 2.5cm were dissolved in 150mL of demineralised water at 40°C in a 250mL beaker stirring at 150 rpm and recorded time until total film dissolution.

It was observed that thicker films take longer to dissolve. Also, dissolution time decreases in the following order (pectin:glycerol:suganate) 6:1 :3>6:2:2>6:3:1 ; dissolution time decreases when the amount of glycerol increases, and the amount of suganate decreases. Increasing the glycerol decreases dissolution time. Dissolution time increases in the following order for type of suganate: 100NC<poly<160NC.

This data showed that the inclusion of bitrex improved (that is to say, reduced) the dissolution time.

Example 3: Methods of making the capsules containing a substrate treatment formulation.

Two sheets of the film were prepared as described above. The sheets can be sealed around the edges (except for one edge) to form an open package, the package filled with a substrate treatment composition, and then the edge sealed. This forms a simple pillowshaped package.

In another method, the capsule is produced by a process of thermoforming:

(a) the first sheet of water-soluble polyvinyl alcohol film was placed over a mould having a cavity;

(b) the cavity is heated and also a vacuum applied to the film to mould the film into the cavities and hold it in place to form a corresponding recess in the film;

(c) the recess is then filled with a substrate treatment composition;

(d) the second sheet of film is superposed over the first sheet of film across the formed recess and sealed around the edge to produce a capsule having a compartment bounded by a continuous seal (referred to as a sealing web);

(e) the capsule is trimmed to remove excess sheet.

Relaxation of the first film typically then causes the applied second sheet to bulge out when the vacuum is released from the first sheet of film in the mould. Where mulitple capsules are made from a single sheet (which may be fed from a roll) the film is cut between the capsules so that a series of capsules are formed.

Sealing can be done by any suitable method for example heat-sealing, solvent sealing or UV sealing or ultra-sound sealing or any combination thereof. Particularly preferred is water-sealing. Water sealing may be carried out by applying water/moisture to the second sheet of film before it is sealed to the first sheet of film to form the seal areas. Example 4 Liquid Capsules dissolution Tests

Capsules are made according to the above example 5, filled with a commercially available laundry detergent composition. The capsules are tested for dissolution.

1. Add 4.5 litres of demineralised water into a 5-litre beaker at

2. Heat up the water to 30°C

3. Place the beaker on the magnetic stirrer plate and add a large magnetic stirrer

4. Turn on the magnetic stirrer so that the vortex is 3cm in depth

5. Place the capsule in the centre of the open holed net, gather the net up above the capsule and fasten with an elastic band (the capsule is held in a net to simulate the capsule being held in-between fabrics and it allows the water to flow through the net)

6. Clamp the stirrer paddle with the capsule in a net attached above the beaker

7. Lower the net into the water up to the mark indicated on the paddle and start the clock immediately

8. Time how long it takes for the capsule to dissolve by noting the following: Bubble from liquid, Liquid leaking time, Liquid gone, film dissolved.

All capsules dissolve in the target range 30s - 30 mins releasing the formulation into the water.

Example 5

Bitrex impregnated films as described above are printed with a UV-curable ink , and the thin film is UV-cured. Capsules are made as described above using this film and then filled with two different commercially available laundry detergent compositions. The capsules are loaded into standard laundry detergent capsule containers.

The containers are placed in storage at a range of climatic conditions: 20°C & 65% relative humidity (RH); 28°C & 70% RH; and 37°C & 70% RH. Such conditions simulate west European ambient conditions and accelerated testing. The capsules are assessed visually at various time points.

The features disclosed in the foregoing description, or in the following claims, or in the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for obtaining the disclosed results, as appropriate, may, separately, or in any combination of such features, be utilised for realising the invention in diverse forms thereof. While the invention has been described in conjunction with the exemplary embodiments described above, many equivalent modifications and variations will be apparent to those skilled in the art when given this disclosure. Accordingly, the exemplary embodiments of the invention set forth above are considered to be illustrative and not limiting. Various changes to the described embodiments may be made without departing from the scope of the invention.

Pectin Films with Antioxidants

Pectin films with and without antioxidant are prepared by adding the film ingredients in 50mL of DI water to a total solids’ concentration of 2%(w/w) and mixing at room temperature for 10min (see table). The solution is then poured into a petri dish and left to dry for 2 days to form a film. The films with antioxidant were prepared by adding different amounts of a 45% Potassium Sulphite solution into the mixture. A dried piece of film (0.025g) was added to 5g of formulation containing 0.2% active levels of Potassium Sulphite in a glass vial with a cap and stability tests were carried out for 8 weeks.

Amidated low methoxy pectin film 50:30:20 (50% pectin, 30% glycerol and 20% suganate 100NC) without potassium sulphite causes discolouration of laundry liquid formulation from light yellow to dark brown after 8 weeks. The discolouration decreases with increasing levels of potassium sulphite in the film (see table and photo below).

A dried piece of film (0.025g) without antioxidant or 0.025g of pectin powder were added to 5g of formulation containing different levels of potassium sulphite. A glass vial with a cap and stability tests were carried out for 8 weeks. Amidated low methoxy pectin powder and CL1835 pectin film 50:30:20 (50% pectin, 30% glycerol and 20% suganate 100NC) cause discolouration of laundry liquid formulation from light yellow to dark brown after 8 weeks.

The discolouration decreases with increasing levels of potassium sulphite in the formulation (see table and photo below).

EXAMPLE CAPSULE - LAUNDRY TREATMENT COMPOSITION

The water soluble capsules comprise laundry treatment compositions dispensed to each of the three compartments is as follows:

Compartment #1 Compartment #2 Side compartment #2

Surfactant Surfactants Surfactants

Polymer cleaning Polymer cleaning Polymer cleaning

Sequestrant Sequestrant Sequestrant

Water Enzyme -cellulase Enzyme - protease

Hydroptrope Fluorescer Water 8%wt.

Opacifier Water 8%wt Hydrotrope

Hydrotrope Dyes

Dyes

Perfume

The unit dosed products comprise water soluble film printed on the inside.

Further example formulations of unit dose products are provided below.

The unit dosed products comprise water soluble film.

Claims

- 38 - CLAIMS

1. A water-soluble capsule comprising a film, the film comprising a polysaccharide and an anti-oxidant and wherein the polysaccharide comprises pectin.

2. A water-soluble film according to claim 1 wherein the anti-oxidant comprises an inorganic component.

3. A water-soluble film according to any preceding claim wherein the anti-oxidant comprises an organic component selected from organic acids, amines or mixtures thereof.

4. A water-soluble film according to any preceding claim wherein the pectin is a low methoxy amidated pectin.

5. A water-soluble film according to any preceding claim further comprising a plasticising surfactant.

6. A water-soluble film according to claim 5 or 6 wherein the surfactant is present at a level of at least 8 %wt based on total weight of the film.

7. A water-soluble film according to any preceding claim comprising at least one coplasticiser preferably polyol, a poly glycerol or a poly alcohol or mixtures thereof.

8. A water-soluble film according to any preceding claim wherein the film comprises a bittering agent.

9. A water-soluble film according to any preceding claim wherein the film is in contact with a home care composition.

10. A water-soluble capsule comprising a water-soluble film according to any of claims 1 - 9.

11. A water soluble capsule according to claim 11 or 12 comprising at least one internal compartment enclosed by the water-soluble film, the compartment having an internal space and containing a home care composition within the internal space.

12. A water soluble capsule according to claim 12 or 13 wherein the home care composition is in liquid form.

13. A water soluble capsule comprising a water soluble film and containing a home care composition, said film comprising a polysaccharide, preferably pectin, wherein the capsule further comprises an anti-oxidant in the film and/or the home care composition. - 39 -

14. A water-soluble capsule comprising a first film comprising a thermoformed recess, said recess containing a home care composition and a second film superposed over said first film, said first and second films sealed around the edges, wherein said first and second films are according to any of claims 1 - 11.

15. A method of making a water-soluble capsule comprising the steps of a. thermoforming a first film of to provide a thermoformed recess in said first film; b. filling said recess with a home care composition c. superposing a second film over said first film d. sealing said first film to said second film to provide a seal around edge regions of the films; wherein the at least the first or second film and preferably both the first and the second film are according to any of claims 1 -11.