Water soluble capsules

Abstract

Disclosed is a water-soluble capsule manufactured from biopolymer films containing unrefined polysaccharide seaweed extract, which has a mixture of unrefined polysaccharides in the extract. The resultant water-soluble capsules when encapsulating laundry detergent systems have high resistance to short term dissolution and with compressive integrity.

Description

WATER SOLUBLE CAPSULESFIELD OF INVENTION

[0001] The present invention relates to water-soluble capsules and a method for their manufacture and in particular to water-soluble capsules manufactured using seaweed extracts.BACKGROUND ART

[0002] Conventional plastic materials are primarily derived from petrochemical sources and used for packaging materials and films. However, conventional plastics do not degrade effectively and result in the accumulation of waste in the environment. As well as slow degradation these plastics also degrade to produce or release by-products that can be toxic and can cause damage to the environment. Many conventional plastics are also difficult to effectively recycle, reuse and manage as waste.

[0003] An emerging alternative to conventional plastics are bioplastic materials derived from biological origin. One promising source of such bioplastic materials is seaweed.Of the many types of seaweed available brown seaweeds such as Ascophyllum nodosum and other brown seaweeds are of particular interest as a source of useful materials such as for example alginates. One active area or interest is to extract film forming polysaccharides from seaweed as alternatives to film forming polymers derived from crude oil and other fossil sources. Of particular interest is the use of polysaccharides from seaweed in the manufacture of biopolymer film packaging and in particular encapsulation films for liquid products such as for example unit dose pods and similar products, where a liquid and / or powder material is encapsulated between two polymer films that are sealed to each other at their periphery encapsulating the liquid or material.

[0004] One particularly challenging application for biopolymers and seaweed biopolymers in unit does pods applications is their use in the encapsulation of detergent systems for the manufacture of laundry pods or capsules. The technical requirements are challenging and there are strict regulatory standards that are required to be met. One such regulatory requirement is in relation to EU Commission Regulation (EU) No 1297 / 2014 andthe AISE (International Association for Soaps, Detergents and Maintenance Products) in respect of soluble laundry pod properties and integrity.

[0005] Whilst some progress has been made in the development of seaweed-based laundry pods there is still a need for further development of seaweed-based unit does pods that whilst meeting the needs of any particular application are also able to meet the required regulatory standards. There is also a general need for new biopolymer based water-soluble capsules for numerous applications.DISCLOSURE OF THE INVENTION

[0006] It has surprisingly been found that if a seaweed extract comprising a mixture of unrefined seaweed polysaccharides is used in the manufacture of biopolymer films the resultant use of these films in the manufacture of encapsulated materials such as a unitary dose pod provides unitary dose pods that are robust and have good properties for many applications and in certain applications meet regulatory requirements. In the context of the present invention unrefined means that the polysaccharide containing seaweed extract has not been subjected to further processes to isolate individual seaweed polysaccharide materials from the extract or to eliminate the presence of other materials from the extract other than solid material filtration and / or dilution or dewatering to concentrate the unrefined extract.

[0007] There is provided a water-soluble capsule comprising at least one sealed compartment containing a composition, the capsule walls comprising a first water soluble biopolymer film and a second water soluble biopolymer film, the first water soluble biopolymer film being sealed to the second water soluble film to form at least one sealed compartment, wherein the biopolymer film comprises unrefined seaweed polysaccharide extract.

[0008] It is envisaged that the water-soluble capsule may be a multicompartment unit-dose article comprising at least one water-soluble film shaped to define a plurality of sealed internal compartments. In certain laundry-based applications each compartment may contain a portion of a detergent composition (liquid, gel, paste or solid), with the compositions in different compartments being the same or different. Compartments may bearranged side-by-side and / or in superposed (stacked) orientation and may be separated by sealed film webs being areas of film between compartments that are sealed to each other. The multicompartment capsule may be surrounded by an outer flange formed by sealed films.

[0009] The water-soluble capsule, whilst being physically robust and handleable will dissolve when immersed into an aqueous environment. The rate of dissolution will depend on the biopolymer formulation used to manufacture the water-soluble capsule and its method of manufacture; in certain embodiments the biopolymer-based capsule may be treated e.g. with a cross-linking agent to reduce its rate of dissolution in an aqueous environment. The nature of the aqueous environment will also have an impact on the rate of dissolution. Factors such as pH, temperature and the presence of other materials in the aqueous environment may either accelerate or reduce the rate of dissolution.

[0010] The biopolymer film comprises unrefined seaweed extract. This may be unrefined brown seaweed extract, red seaweed extract or green seaweed extract or any combination thereof. Preferably the unrefined seaweed extract is an unrefined brown seaweed extract. The biopolymer film may comprise a mixture of unrefined fucoidan, and unrefined alginate. The biopolymer film may comprise a mixture of unrefined fucoidan and unrefined laminarian. The biopolymer film may comprise a mixture of unrefined alginate and unrefined laminarian. The biopolymer film may comprise any combination of unrefined fucoidan, unrefined alginate or unrefined laminarian with the addition of unrefined mannitol. In a preferred embodiment the biopolymer comprises, unrefined fucoidan and unrefined alginate. These polysaccharides will be present in any biopolymer film and products manufactured using brown seaweed extract without the use of additional polysaccharide refining steps in the manufacture of the polysaccharide extract solution used to manufacture the biopolymer film. Preferably the biopolymer film further comprises unrefined extract glucose present in the unrefined extract. In further embodiments the biopolymer comprises unrefined red seaweed extract and such extract may comprise unrefined carrageenan, unrefined agar or unrefined starch and mixtures of two or more of these unrefined polysaccharides. In further embodiments the biopolymer comprises unrefined green seaweed extract and such extract may comprise unrefined s or unrefined ulvan and mixtures of two or more of these unrefined polysaccharides.

[0011] The biopolymer films prepared using the unrefined polysaccharide extract will preferably comprise water and preferably comprise between 4-60 wt.% water, between 4-40 wt.% water and most preferably between 4-30 wt.% water.

[0012] This biopolymer film will typically comprise the unrefined polysaccharide extract produced by a seaweed extraction process and in addition various other materials and additives to aid film formation and to provide required final properties in the film for use in the manufacture of a water-soluble capsule. Typically, the unrefined polysaccharide extract and other materials are brought together in a biopolymer formulation that is in a form suitable for the film forming process to be used such as for example casting or extrusion.

[0013] The aqueous unrefined polysaccharide extract solution may be used in such biopolymer formulations directly from the polysaccharide extraction process and at the extraction temperature or it may be used at its storage temperature of between -21 °C and 20°C. The extract solution may be pre-conditioned before formulating by raising the temperature of the extract solution to between 50°C and 75°C for a period of 50 to 70 minutes; the extract may be used immediately after this conditioning or may be stored for future use by being cooled to a temperature of between -21 °C and 20°C for long term storage. It is preferred that the polysaccharide extract solution is used at ambient temperature of between 18°C and 25°C without thermal pre-conditioning for preparing formulations for coating and biopolymer film formation. Such thermal conditioning may be deferred to the formulation stages.

[0014] It is preferred that the biopolymer formulation is prepared by mixing components together at relatively low temperatures below 50°C, most preferably below 30°C, and most preferably between 19 to 23°C. During this mixing phase the temperature may be increased up to 50°C in stages to ensure complete dissolution of the various components with the polysaccharide extraction solution. It is preferred that once all of the components of the formulation are combined this mixture then goes through a 30 to 60 minute period of homogenization. It is further preferred that the formulation with or without homogenization is then post-conditioned before use in any coating or film forming process. This formulation post-conditioning requires the temperature of the formulation starting from a temperature ofbelow 50°C, preferably below 30°C, and most preferably between 19 to 23°C and then be raised to a temperature of between 50°C and 95°C, more preferably between 50°C and 85°C, and most preferably between 50°C and 75°C for a period of 50 to 70 minutes. Preferably the post-conditioning temperature is maintained at 72°C±2°C for 60±5 minutes. This postconditioning step may be commenced from the point of dissolution of the formulation components; once dissolution is determined the formulation is not allowed to cool and is raised to the post-conditioning temperature. The biopolymer formulation may have a target viscosity for film formation which depends on the film preparation conditions and this target viscosity may be achieved through adjustment of the conditioning temperature and / or water content of the formulation. On completion of this post formulation conditioning the formulation is ready for use in a biopolymer film forming operation such as casting.

[0015] In preparing the biopolymer film formulation the aqueous unrefined polysaccharide extract solution may be used as produced from the extraction process or may be diluted to provide the requisite level of unrefined polysaccharide seaweed extract in the final formulation. The extract may be diluted by a factor of 10 or less, preferably 5 or less and still be suitable for biopolymer film production. Alternatively, water may be removed from the unrefined polysaccharide extract solution in order to lower the water level in the formulation and raise viscosity to a level desired for biopolymer film formation.

[0016] The biopolymer film formulation may be dried to a powder and / or may be agglomerated with additives. One preferred drying method is spray drying. The biopolymer film formulation may be spray dried with an inlet temperature of 160 to 220 °C, more preferably of 180 to 190 °C, and with an exhaust temperature of 40 to 90 °C and most preferably 60 to 70 °C.

[0017] The biopolymer film forming composition may include other materials and additives that either aid in the film forming process and / or provide added benefits and properties to the biopolymer film when formed and during use in making the water-soluble capsule.

[0018] One such group of materials are polymeric film forming materials or additives that may aid or add to the film forming properties of the biopolymer film. Suitable additionalfilm forming materials may be selected from natural and / or water-soluble polymers. Preferably these are biodegradable polymers and more preferably natural polymers. One suitable source are other seaweed sourced biopolymers including refined polysaccharides from brown seaweed such as alginate or polysaccharides from other seaweeds such as red and green seaweed. From red seaweed these typically include refined seaweed products such as agar, kappa carrageenan, iota carrageenan, lambda carrageenan. For green seaweed these typically include refined seaweed products such as starch, hemicellulose, cellulose and ulvan.

[0019] Other film forming materials include but are not limited to one or more of modified cellulose derivatives e.g. carboxy methyl cellulose, methyl cellulose, hydroxyl ethyl cellulose, hydroxpropyl celluloses, starches such as natural starch for example potato starch and modified starches, plant and animal proteins, for example milk proteins, gluten, gelatines, zein, potato proteins etc. Gums e.g. gellan gum, locust bean etc, polyvinyl alcohols, and polyvinvyl alcohol polyvinyl amine co-polymers, polylactic acid, PLA, polyhydroxy alkonate PHA, polybutylene adipate terephthalate PBAT, casein, or pectins. The biopolymer film may comprise a seaweed extract-biopolymer system with homopolymer and / or copolymer blends.

[0020] The formulation may incorporate fillers. Suitable fillers can be selected from koalin, bentonites, silicas, TiCh, chalk and these materials can also function as colour modifiers, specifically lighteners and odour control agent. Suitably, a filler may be selected from, colour pigments, carbon black, or other active inorganic materials such as graphene or carbon nanotubes may be included. The formulation may comprise salts and mineral typically at < 2 wt.% and such salts and minerals include NaCl, NaCO3, CaCl, ZnO, or MgO. The formulation may incorporate essential oils or perfumes.

[0021] The formulation may incorporate functional additives and property modifiers such as hydrophobing agents including lipids, resin(s), wax(es), oil(s), shellac or shellac analogues. Suitably, waxes and oils may be selected from paraffin wax, calendula, bees wax, candelilla wax, polyethylene wax, fatty acids. Reactive hydrophobing agent such as Alkyl Ketene Dimers and Alkyl Succinic Anhydrides or Tall Oil Rosins and their functionalised derivatives may also be used. Suitably, a hydrophobing agent that may be provided to the processed residual seaweed of the invention may be selected from a lipid, resin(s), wax(ex), oil(s), shellac or shellac analogues. Suitably, waxes and oils may be selected from Alkylketene dimers, Alkenyl Succinic Anhydride, Tall Oil Rosin and its derivatives, paraffin wax, calendula, bees wax, candelilla wax, polyethylene wax, fatty acids. The formulation may incorporate other additives such as polyphenols for example tannic acid, carboxylic acids for example citric acid and salts such as calcium and sodium salts for example sodium chloride, minerals for example zinc oxide; some of these may aid crosslinking and film formation during manufacture of the biopolymer film.

[0022] The formulation may incorporate plasticisers. Suitable plasticisers may be selected from glycerol, sorbitol, mannitol, polyethelengyols (PEG), oils for example, mineral oil, vegetable oil, fatty acids, natural and synthetic waxes. Suitable examples are polyols such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, sorbitol, mannitol and xylitol, fatty acids, monosaccharides (glucose, fructose and sucrose), ethanolamine, urea, triethanolamine, vegetable oils, lecithin, waxes, amino acids, surfactants may be used. Also, glycerol triacetate mineral oil or vegetable oil, fatty acids, waxes Tall Oil Rosin and its derivative or the like. One suitable plasticiser is a combination of three plasticisers namely a combination of dipropylene glycol as a first plasticizer, a sugar alcohol such as sorbitol as a second plasticizer, and a polyol such as glycerin as a third plasticizer.

[0023] The biopolymer formulations used to manufacture water-soluble capsules may comprise from 10 to 95 wt.% water, preferably from 20 to 95 wt.% water, more preferably from 30 to 95 wt.% water, more preferably from 40 to 95 wt.% water, more preferably from 50 to 95 wt.% water and most preferably from 70 to 95 wt.% water.

[0024] The biopolymer formulations may comprise 100 wt.% of unrefined seaweed extract said extract comprising mainly unrefined polysaccharides as herein indicated and other minor unrefined components of the seaweed, in an aqueous basic environment. The resultant biopolymer films prepared from such biopolymer formulation, if no further materials are added to the formulation, will comprise 100 wt. % of unrefined seaweed extract.

[0025] It is preferred that the biopolymer formulations used comprise other materials in addition to the unrefined polysaccharide extract(s) in order to produce the biopolymer films for the water-soluble capsules.

[0026] The total unrefined polysaccharide extract present in the biopolymer formulations is preferably from 1 to 70 wt.%, more preferably from 1 to 50 wt.%, more preferably, 1 to 40 wt.%, more preferably 1 to 30 wt.%, more preferably 2 to 20 wt.%, and most preferably 2 to 16 wt.%. The exact wt.% of unrefined polysaccharide extract used will depend in part on the solids concentration of the unrefined polysaccharide extract, which can be variable depending on the seaweed used or even the batch of seaweed used to prepare the unrefined seaweed extract. The exact percentage of unrefined seaweed extract used will be selected to take into account the solids content of the extract and the desired level of unrefined polysaccharide in the biopolymer films prepared from the extract.

[0027] The biopolymer formulations preferably comprise one or more further refined polysaccharides and / or other film forming polymeric materials. Refined polysaccharides are typically substantially pure polysaccharide materials obtained from a natural source such as seaweed and other biomass. As an example, refined carrageenan is typically obtained through an extraction and refining process from red seaweed. Preferably the formulation comprises between 1 to 70 wt% of formulation DM or refined polysaccharide more preferably between 20 to 70 wt.% and most preferably between 30 to 60 wt.%. Preferred additional refined additives comprise starch or carrageenan and mixtures thereof, the most preferred is a mixture of unrefined polysaccharide extract with added refined starch and added refined carrageenan.

[0028] The plasticisers may be present in the formulation within the range of 1-80 wt.% of formulation DM..

[0029] Functional additives: may be present in the range of 0-10 wt.% of formulation DM.

[0030] Fillers may be present in the formulation in the range of 0 - 5 wt.% of formulation DM.

[0031] These unrefined polysaccharide formulations may then be used to make biopolymer films. These biopolymer films may comprise a mixture of components.Typically, water may be present within the range of 9 to 40 wt.%, preferably, 9 to 30 wt. % and most preferably 10 to 25 wt.% of film mass. The biopolymer film may comprise additional polysaccharide / film forming components e.g. starch and / or carrageenan at between 10 to 80 wt.%, more preferably 20 to 70 wt.%, and most preferably 30 to 60 wt.% of the film. The biopolymer film may comprise plasticisers at between 10 to 60 wt.%, more preferably 10 to 50 wt.%, and most preferably 20 to 40 wt.% of the film. Functional additives may be present within the range of 0 to 20 wt.% of the film. Fillers may be present within the range of 0 to 10 wt.% of the film.

[0032] The various components and wt.% of the components in the biopolymer formulation and resultant films are selected in order that the total additive wt.% of all components is 100 wt.%. Where the additive wt. % is less than 100 wt.% the balance to 100 wt.% for the formulation is preferably made up of water.

[0033] Most preferred composition ranges for the formulations and resultant films are as follows:

[0034] The biopolymer film may be and preferably is manufactured via a casting method, which method comprises preparing an aqueous formulation comprising unrefined polysaccharide extract, casting the formulation onto a material surface to provide a cast biopolymer film and drying the cast biopolymer film at elevated temperature to remove waterto form the biopolymer film. The cast biopolymer film is then delaminated from the surface of the material substrate to provide a self-supporting free standing biopolymer film.

[0035] Biopolymer film water-soluble capsules derived from the unrefined polysaccharide extract are composable and biodegradable. They may be dissolved and dispersed in water or aqueous environments, especially at room temperature or above.

[0036] The biopolymer film may be thermoformable. Athermoformable film is one that can be shaped through the application of heat and a force. Thermoforming can be performed by any one or more of the following processes, for example: the manual draping of a thermally softened film over a mold, or the pressure induced shaping of a softened film to a mold (e.g., vacuum forming), or the automatic high-speed indexing of a freshly extruded sheet having an accurately known temperature into a forming and trimming station, or the automatic placement, plug and / or pneumatic stretching and pressuring forming of a film. The extent of the film stretch is defined by the areal draw ratio which is the pocket (or cavity) surface area divided by the film surface area before thermoforming. The areal draw ratio (also called areal depth of draw) can be calculated according to the method described in Technology of Thermoforming, James L. Throne, Hanser publisher, (1996) Chapter 7.4, pg. 488-494 (ISBN 3-446-17812-0). Herein for thermoformed biopolymer films, the areal draw ratio can be in a range of 1.05 to 2.7; or in a range of 1.2 to 2.3; or in a range of 1.3 to 2.0.

[0037] In the alternative to or in addition to heating, the film can be wetted by any suitable means, for example directly by spraying a wetting agent (including water, a solution of the film composition, a plasticizer for the film composition, or any combination of the foregoing) onto the film, prior to feeding it onto the surface or once on the surface, or indirectly by wetting the surface or by applying a wet item onto the film. The film comprising extracted mixture of unrefined seaweed polysaccharides may be and preferably is vacuum formed without the application of heat. Once a film has been wetted, it may be drawn into an appropriate mold, preferably using a vacuum. The filling of the moulded film can be accomplished by utilizing any suitable means. In some embodiments, the most preferred method will depend on the product form and required speed of filling. In some embodiments, the moulded film is filled by in-line filling techniques. The filled, open packets are thenclosed forming the water-soluble capsules, using a second film, by any suitable method. This may be accomplished while in horizontal position and in continuous, constant motion. The closing may be accomplished by continuously feeding a second film over and onto the open packets and then preferably sealing the first and second film together, typically in the area between the mold and thus between the packets.

[0038] Any suitable method of sealing the water-soluble capsules may be utilized. Non-limiting examples of such means include heat sealing, solvent welding, solvent or wet sealing, and combinations thereof. Typically, only the area which is to form the seal is treated with heat or solvent. The heat or solvent can be applied by any method, typically on the closing material, and typically only on the areas which are to form the seal. If solvent or wet sealing or welding is used, it may be preferred that heat is also applied. Preferred wet or solvent sealing / welding methods include selectively applying solvent onto the area between the molds, or on the closing material, by for example, spraying or printing this onto these areas, and then applying pressure onto these areas, to form the seal. Sealing rolls and belts as described above (optionally also providing heat) can be used, for example. Preferred sealing solvents are aqueous and preferably aqueous formulations comprising one or more additives and preferably dilute aqueous formulations comprising additives. Preferred solutions are solutions that include starch / Ca2+ and / or glycerol and tannic acid, which may be added to the film contact surfaces to support heat sealing.

[0039] The formed water-soluble capsules may then be cut by a cutting device. Cutting can be accomplished using any known method. It may be preferred that the cutting is also done in continuous manner, and preferably with constant speed and preferably while in horizontal position. The cutting device can, for example, be a sharp item, or a hot item, or a laser, whereby in the latter cases, the hot item or laser ‘burns’ through the film / sealing area.

[0040] A preferred method of making the water-soluble capsule comprises the steps of vacuum forming a first water-soluble biopolymer film in a mould to form an open cavity, filling the cavity with a material e.g. laundry detergent, laying the second biopolymer film over the first film to close the cavity, and sealing the first and second films together preferably through heat sealing, or solvent sealing, the solvent preferably comprising water oran aqueous based sealing composition, to produce the water-soluble unit dose article. It is not necessary to heat the biopolymer film to allow vacuum forming although this may be used.

[0041] The present water-soluble capsules may contain various compositions. A multi-compartment water-soluble capsules may contain the same or different compositions in each separate compartment. Preferably the water-soluble capsules contain home laundry compositions such as detergent compositions.

[0042] The detergent composition may be in the form of free-flowing powder, a liquid, a compacted solid, a gel or a mixture thereof.

[0043] The detergent composition when in the form of a free-flowing powder may have an average particle size diameter of between 100 microns and 1500 microns, preferably between 100 microns and 1000 microns, more preferably between 100 microns and 750 microns. Those skilled in the art will be aware of standard techniques to measure particle size. The detergent composition may be a free-flowing laundry detergent composition.

[0044] The detergent composition may be a liquid. In relation to the liquid detergent composition of the present invention, the term ‘liquid’ encompasses forms such as dispersions, gels, pastes and the like. The liquid composition may also include gases in suitably subdivided form. However, the liquid composition excludes forms which are nonliquid overall, such as tablets or granules.

[0045] The detergent composition may be a liquid laundry detergent composition. The term ‘liquid laundry detergent composition’ refers to any laundry detergent composition comprising a liquid capable of wetting and treating fabric e.g., cleaning clothing in a domestic washing machine.

[0046] Laundry detergent compositions include fabric detergents, fabric softeners, 2- in-1 detergent and softening, pre-treatment compositions and the like.

[0047] The laundry detergent composition may comprise an ingredient selected from bleach, bleach catalyst, dye, hueing dye, brightener, cleaning polymers including alkoxylatedpolyamines and polyethyleneimines, soil release polymer, surfactant, solvent, dye transfer inhibitors, chelant, builder, enzyme, perfume, encapsulated perfume, polycarboxylates, rheology modifiers, structurant, hydrotropes, pigments and dyes, opacifiers, preservatives, anti-oxidants, processing aids, conditioning polymers including cationic polymers, antibacterial agents, pH trimming agents such as hydroxides and alkanolamines, suds suppressors, and mixtures thereof.

[0048] The laundry detergent composition may comprise surfactants e selected from anionic, cationic, zwitterionic, non-ionic, amphoteric or mixtures thereof. Preferably, the composition comprises anionic, non-ionic or mixtures thereof. The anionic surfactant may be selected from linear alkyl benzene sulfonate, alkyl ethoxylate sulphate and combinations thereof. Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate materials. The non-ionic surfactant may be selected from fatty alcohol alkoxylate, an oxosynthesised fatty alcohol alkoxylate, Guerbet alcohol alkoxylates, alkyl phenol alcohol alkoxylates or a mixture thereof. Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula: R1(CmH2mO)nOH wherein R' is a Cs-Ci6 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. In one aspect, R' is an alkyl group, which may be primary or secondary, that comprises from about 9 to 15 carbon atoms, or from about 10 to 14 carbon atoms. In one aspect, the alkoxylated fatty alcohols will also be ethoxylated materials that contain on average from about 2 to 12 ethylene oxide moi eties per molecule, or from about 3 to 10 ethylene oxide moi eties per molecule.

[0049] The shading dyes employed in the present laundry detergent compositions may comprise polymeric or non-polymeric dyes, pigments, or mixtures thereof.

[0050] The laundry detergent compositions can comprise one or more detergent enzymes which provide cleaning performance and / or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, B-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. Atypical combination is a cocktail of conventional applicable enzymes like protease, lipase, cutinase and / or cellulase in conjunction with amylase.

[0051] The laundry detergent compositions may comprise one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids and mixtures thereof.

[0052] The laundry detergent composition may comprise a brightener. Suitable brighteners are stilbenes, such as brightener 15. Other suitable brighteners are hydrophobic brighteners, and brightener 49. The brightener may be in micronized particulate form, having a weight average particle size in the range of from 3 to 30 micrometers, or from 3 micrometers to 20 micrometers, or from 3 to 10 micrometers. The brightener can be alpha or beta crystalline form.

[0053] The laundry detergent composition may also optionally contain one or more copper, iron and / or manganese chelating agents. The chelant may comprise 1- hydroxyethanediphosphonic acid (HEDP) and salts thereof; N,N-dicarboxymethyl-2- aminopentane-1, 5-dioic acid and salts thereof; 2-phosphonobutane-l,2,4-tricarboxylic acid and salts thereof; and any combination thereof.

[0054] The compositions may also include one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N- vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.

[0055] The laundry detergent composition may comprise one or more polymers. Suitable polymers include carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers such as terephthalate polymers, amine polymers, cellulosic polymers, dye transfer inhibition polymers, dye lock polymers such as a condensation oligomer produced bycondensation of imidazole and epichlorhydrin, optionally in ratio of 1 :4: 1, hexamethylenediamine derivative polymers, and any combination thereof.

[0056] Other suitable cellulosic polymers may have a degree of substitution (DS) of from 0.01 to 0.99 and a degree of blockiness (DB) such that either DS+DB is of at least 1.00 or DB+2DS-DS2is at least 1.20. The substituted cellulosic polymer can have a degree of substitution (DS) of at least 0.55. The substituted cellulosic polymer can have a degree of blockiness (DB) of at least 0.35. The substituted cellulosic polymer can have a DS+DB, of from 1.05 to 2.00. A suitable substituted cellulosic polymer is carboxymethylcellulose. Another suitable cellulosic polymer is cationically modified hydroxy ethyl cellulose.

[0057] Suitable perfumes include perfume microcapsules, polymer assisted perfume delivery systems including Schiff base perfume / polymer complexes, starch -encapsulated perfume accords, perfume-loaded zeolites, blooming perfume accords, and any combination thereof. A suitable perfume microcapsule is melamine formaldehyde based, typically comprising perfume that is encapsulated by a shell comprising melamine formaldehyde. It may be highly suitable for such perfume microcapsules to comprise cationic and / or cationic precursor material in the shell, such as polyvinyl formamide (PVF) and / or cationically modified hydroxyethyl cellulose (catHEC).

[0058] Suitable suds suppressors include silicone and / or fatty acid such as stearic acid.

[0059] The water-soluble capsules of the present invention may comprise other types of composition for encapsulation within water-soluble capsules. These may be a nondetergent composition and / or a non-household care composition. A fabric or household care composition includes fabric treatments, hard surfaces, air care, car care, dishwashing, fabric conditioning and softening, laundry detergency, laundry and rinse additive and / or care, hard surface cleaning and / or treatment, and other cleaning for consumer or institutional use. Nonhousehold care compositions are for other uses. For example, a non-household care composition can be selected from agricultural compositions, aviation compositions, food and nutritive compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, mercantile compositions, military and quasi -militarycompositions, office compositions, and recreational and park compositions, pet compositions, water-treatment compositions, including cleaning and detergent compositions applicable to any such use while excluding fabric and household care compositions.

[0060] In one type of embodiment, the composition can include an agrochemical, e.g. one or more insecticides, fungicides, herbicides, pesticides, miticides, repellants, attractants, defoliaments, plant growth regulators, fertilizers, bactericides, micronutrients, and trace elements. In another type of embodiment, the composition is a water-treatment agent. The composition can be a limescale removing composition.

[0061] The compositions for enclosure within the water-soluble capsules may be liquids, gels of solids or powders.

[0062] In further embodiments the compositions may be edible food products in liquid or solid or power form, or agricultural fertilisers, or bath salt.

[0063] The water-soluble capsules may contain water or other liquid beverages. In these arrangements the water-soluble capsules will comprise a biopolymer film that has been prepared to resist immediate dissolution in water or only allows dissolution in certain aqueous environments.

[0064] The water-soluble capsules may contain compositions comprising pharmaceutical compositions suitable for oral administration to a patient.

[0065] The biopolymer films will have a range of properties making them suitable for water-soluble capsules. For film applications various physical parameters are desirable and are typically measured. A water-soluble biopolymer film is typically characterized by or to be tested for tensile strain according to the Tensile Strain (TS) Test and e-modulus (elongation modulus or tensile stress). The procedures typically include the determination of tensile strain and the determination of e-modulus according to ASTM D 882 (“Standard Test Method for Tensile Properties of Thin Plastic Sheeting”). Water soluble films are typically preconditioned to the testing environmental conditions for a minimum of 48 h. Tests are typically conducted in the standard laboratory atmosphere of 23±2.0° C. and 35±5% relativehumidity. For tensile strain or modulus determination, l"-wide (2.54 cm) samples of a single film sheet having a thickness of 3.0±0.15 mil (or 76.2±3.8 pm) are typically prepared. For e- modulus testing virgin films are usually tested. For tensile strain testing test films are typically first pre-immersed in a testing detergent.

[0066] A further test important for characterizing water-soluble films is the Monosol Dissolution and Disintegration Test (MSTM 205), which is classed as an industry standard. A film can be characterized by or tested for Dissolution Time and Disintegration Time according to the MonoSol Test Method 205 (MSTM 205), a method known in the art and discussed in US20160024446. Another test is the OECD test; OECD Guideline 120 2.OECD Guideline 105. A further test is in relation to the regulatory requirement detailed in EU Commission Regulation (EU) No 1297 / 2014 and the AISE (International Association for Soaps, Detergents and Maintenance Products) in respect of soluble laundry pod properties and integrity. These require water-soluble capsules for laundry products to resist aqueous dissolution for at least 30 seconds and to resist an applied weight of 300 newtons. The water- soluble capsules of the present invention pass both of these regulatory requirements.

[0067] The manufacturing of the water-soluble capsules comprises a number of stages. The first stage comprises the manufacture of the unrefined seaweed polysaccharide extract for use in manufacturing the water-soluble capsules; this may be made using an extraction process comprising: a) forming a dispersion by dispersing seaweed in an aqueous basic solution of pH>7 or water, b) stirring the dispersion at a temperature of less than 100°C for at least 15 minutes, and c) filtering the dispersion to separate a solid seaweed residue from an aqueous unrefined polysaccharide extract solution.

[0068] In this process the seaweed preferably has not been acid pre-treated (pH<5) through the addition of added acids to convert the alginate salts within the seaweed into alginic acids before the dispersion of the seaweed in the aqueous basic solution.

[0069] Preferably, the water or aqueous basic solution is heated to a temperature of 100°C or less, more preferably 95°C or less, more preferably 80°C or less, and mostpreferably 70°C or less and ideally 65°C or less. The temperature of extraction is preferably from 40°C to 90°C, more preferably from 40°C to 80°C, more preferably between 40°C to 65°C, more preferably, 50°C to 65°C, and most preferably 60°C to 65°C.

[0070] Preferably, the water or aqueous basic solution of pH>>7 is heated to a desired temperature before dispersion of the seaweed into the water or aqueous basic solution of pH> 7. Preferably the aqueous basic solution is pH>7.5 and most preferably is pH>8 ideally pH>8. Heating to desired temperature before dispersion of the seaweed increases the extraction yield for any given extraction period.

[0071] Preferably, the filtration is undertaken using a filter which removes particulate material from the polysaccharide extract solution that is greater thanlOOpm, more preferably greater than 50pm, more preferably greater than 25 m and most preferably greater than 10pm. Preferably, the filtration comprises two or more filtration stages. The first stage preferably removes material of particle size greater thanlOOpm and the second stage removes material of particle size of greater than 10pm. It has been found that ensuring that the polysaccharide rich liquid extract from the process contains particles of less thanlOpm. provides good quality biopolymer films formed from the filtered but unrefined polysaccharide extract solution. Alternatively, or additionally the polysaccharide extract solution may be centrifuged.

[0072] It has been found that once filtered the unrefined polysaccharide extract solution may be used directly in formulations for the preparation of biofilms for the manufacture of unitary dose capsules. The s unrefined polysaccharide extract solution does not require, other than filtering, any further refinement processing or extraction of any materials contained therein in order for the extract to be usable in formulations for biopolymer film forming compositions and their subsequent use in the manufacture of capsules and in particular water-soluble capsules.

[0073] The aqueous basic solution may be prepared from alkali salts or basic salts or mixtures thereof. Examples of such salts include sodium carbonate, sodium bicarbonate, sodium acetate, sodium hydroxide, potassium carbonate, potassium acetate, potassium hydroxide and mixtures of these alkali or basic salts. It is preferred that the aqueous basicsolution is prepared from sodium salts or mixtures thereof. The preferred aqueous basic sodium solution is prepared from Na2COs. The aqueous Na2COs solution is preferably 10 % w / v or less Na2CO3, more preferably 8 % w / v or less Na2CO3, more preferably 6 % w / v or less Na2CO3, more preferably 5 % w / v or less Na2CO3, more preferably 3 % w / v or less Na2CO3, more preferably 2 % w / v or less Na2CO3, and most preferably 1 % w / v or less Na2CO3. Ideally and preferably the aqueous Na2CO3 solution is between 0.1 to 3% w / v Na2CO3, more preferably 0.1 to 2 % w / v Na2CO3, more preferably 0.1 to 1.5 % w / v Na2CO3, and most preferably 0.1 to 1 % w / v Na2CO3. It is preferred that the process uses aqueous basic solutions and not water.

[0074] The time for the extraction is preferably between 15 to 120 minutes, more preferably between 30 to 120 minutes, more preferably 60 to 120 minutes and most preferably between 70 to 120 minutes. Preferably, the time for extraction is for a minimum of 90 to 120 minutes. It is preferred that the dispersion is stirred throughout the extraction process. It is preferred that the means of stirring is isolated from the dispersed seaweed during the extraction process.

[0075] It is preferred that the seaweed used in the basic extraction process has a reduced fucoxanthin level compared to the raw seaweed. In a preferred embodiment the seaweed for use in the basic extraction process is the residual seaweed from a pigment extraction process that has removed at least lwt% of the fucoxanthin, more preferably at least 5 wt% and more preferably at least 10 wt%.

[0076] The seaweed and aqueous basic solution or water are typically combined in proportions to provide at least 1% w / v seaweed: to water or aqueous basic solution, preferably at least 2 % w / v seaweed: to water aqueous basic solution: preferably at least 10 % w / v seaweed: to water aqueous basic solution and a preferred maximum of 30% w / v seaweed : water or aqueous basic solution in the dispersion or slurry and preferably within the range of 1 to 30% w / v seaweed: to water aqueous basic solution, preferably within the range of 2 to 30% w / v seaweed: to water aqueous basic solution and most preferably within the range of 2 to 20% w / v seaweed: to water aqueous basic solution. Generally, at levels greater than 30% w / v the dispersion becomes too difficult to process due to the seaweed absorbing fluid and swelling. The ratio may be adjusted to ensure that in the final extract solution thepolysaccharides are present at between 1 to 20% w / v DM (dry matter) of the extract solution and more preferably 1 to 10% w / v DM of the extract solution. Ideally the dry matter content of the extract solution is within the range of 0.5 to 6 wt.% of the solution, preferably 2 to 3 wt.% of the solution and ideally at a total dissolved solids of > 5 g.l’1and preferably within the range of 5 to 10 g.l’1

[0077] There may be a further step d) where the polysaccharide extract solution is immediately cooled from the elevated temperature of extraction to a temperature of between - 20°C and 20°C, for storage. It is advantageous to keep the extract solution within this temperature range to avoid unwanted early uncontrolled gelation and polymerisation of the dissolved solids in the extract. At low storage temperatures on reheating of the polysaccharide extract solution stirring may be applied to homogenise the polysaccharide extract solution. Preferably, there is no temperature reduction for storage and step d) is maintenance of the extract fluidity through gentle agitation and temperature control to enable effective degassing of the extract whilst preventing gelation prior to use in biopolymer formulations.

[0078] The raw seaweed is typically and preferably water washed, dried and or dewatered and then processed into an easily handleable form prior to use in the process. The seaweed may be abraded, cut, shredded or milled to provide a handleable form. The seaweed will preferably be in flake form with thickness from 1 to 10 mm. more preferably 2 to 5 mm and most preferably 1 to 4 mm. A preferred grade of seaweed is 2 mm. If used in the milled form, it is preferred that the seaweed is milled to 500 micron or greater particle size.

[0079] Any seaweed may be used to prepare the unrefined polysaccharide extract including Phaeophyta (brown seaweed), Rhodophyta (red seaweed) or Chlorophyta (green seaweed) or mixtures thereof to provide unrefined polysaccharide extract solutions for polymer film formation and unitary pod manufacture. It is preferred that the seaweeds used in this extraction process to provide polysaccharides for the biopolymer film are brown seaweeds, which are typically alginate containing seaweeds collectively referred to as algenophytes. Suitable algenophytes may be selected from the orders Laminariales, Fucales or Ectocarpales, Macrocystis, for example M. pyrifera, Lessonia, and Sargassum. The brown seaweed may be selected from one of more of: Laminaria abyssalis, Laminaria agardhii, Laminaria appressirhiza, Laminaria brasiliensis, Laminaria brongardiana, Laminaria bulbosa,Laminaria bullata, Laminaria complanata, Laminaria digitate, Laminaria ephemera, Laminaria farlowii, Laminaria groenlandica, Laminaria hyperborean, Laminaria inclinatorhiza, Laminaria longipes, Laminaria multiplicata, Laminaria nigripes, Laminaria ochroleuca, Laminaria pallida, Laminaria platymeris, Laminaria rodriguezii, Laminaria ruprechtii, Laminaria sachalinensis, Laminaria setchellii, Laminaria sinclairii, Laminaria solidungula, and Laminaria yezoensis The brown seaweed may be from the order Fucales, suitably of the genus Ascophyllum. The seaweed may be selected from S.latissima, L.digitata, A. escuelnte, L. japonica, U. pinnatifida, Sargassum sp., Ascophyllum nodosum, Fucus sp., Fucus spiralis, Fucus vesiculosus, or P. caliculatata. The extraction process is however sufficiently robust to accommodate a mixture of one or more of any of the brown seaweeds listed and may be adapted to maximise the extraction from such mixtures.

[0080] The products of the extraction process are an unrefined polysaccharide seaweed extract in aqueous solution and a seaweed residue; the unrefined polysaccharide seaweed extract being of particular use for biopolymer film production and subsequent water- soluble capsule formation. This unrefined polysaccharide extract solution will typically comprise a mixture of unrefined seaweed polysaccharides and the liquid extract may be dried to provide a solid material. The unrefined polysaccharide extract solution may include other components of seaweed such as pigments,

[0081] Preferably this polysaccharide extract solution is in the form of an aqueous solution and more preferably a basic aqueous solution. This is a complex mixture comprising unrefined polysaccharides and as such is challenging to analyse. The presence or not of polysaccharides in a seaweed or processed seaweed material or such polysaccharide extract solutions may be determined by hydrolyzing the sample and using various techniques, including chromatographic techniques, to detect and quantify the sugar monomer units or derivatized monomer units of the relevant polysaccharide. Alginate, for example, is a complex mixture of oligo-polymers mainly consisting of polymannuronic acid and polyguluronic acid and after processing these provide mannuronic acid and guluronic acid that may easily be detected and quantified. The remaining non-alginate saccharides and sugars produce mannitol, glucose, manatose, galactose, xylose, fucose and other oligomers. Fucose, for example, is a sugar derived from fucoidan another major polysaccharide present in brown seaweed. Preferably the unrefined polysaccharide seaweed extract comprisespolysaccharides that upon hydrolysis produce one or more of: mannuronic acid, guluronic acid, mannitol, glucan, xylose, fucose, glucose, mannose, and galactose. Preferably the unrefined polysaccharide seaweed extract and resultant biopolymer films and unitary pods comprises a mixture of unrefined alginate, fucoidan, laminarian and mannitol. The unrefined polysaccharide extract may further comprise unrefined glucose.

[0082] The polysaccharide extract solution typically has a pH >7 and typically comprises 1-20 wt% dry matter, and most preferably between 1 to 10 wt% dry matter . The total dissolved solids in the aqueous extract are preferably 1.5 to 8.5 g / 1, most preferably 5 to 6 g / 1. Preferably the aqueous extract has a BRIX @20°C of >1, and most preferably >2. The aqueous polysaccharide extract solution will preferably have a viscosity at @20°C of between 2 and 120 mPas, more preferably 2 to 50 mPas, and most preferably between 2 and 20 mPas.

[0083] When the process utilizes the pigment extraction pretreatment described herein the resultant aqueous unrefined polysaccharide extract solution may have a relatively low level of colour due to the low level of extracted pigment, because significant quantities of pigment will have been removed via any pretreatment. Preferably, the normalizing optical density at absorbance 500 nm (OD 500nm / OD 600nm) is less than 4 to help ensure that any film-based products prepared from this extract solution are transparent and exhibiting no more than a light yellow / brown tint.

[0084] The water present in the aqueous unrefined polysaccharide extract solution may be removed through any suitable process to provide a substantially water free and solid or semi-solid unrefined polysaccharide extract.

[0085] With reference to the basic seaweed extraction process for producing a polysaccharide extract solution, the process may be undertaken with seaweed that has been washed and processed to produce the required form and particle sizes for the process as outlined above and may optionally but preferably be subjected to an additional pre-treatment stage prior to being used in the polysaccharide extraction process.

[0086] This pretreatment stage is an extraction process designed to extract a significant proportion of the natural colouring of the seaweed, which in the case of brownseaweed is primarily the xanthophyll pigment fucoxanthin. Fucoxanthin absorbs the bluegreen light to yellow-green light, and the peak value is observed at between 510-525 nm wavelength. Whilst fucoxanthin is the primary target of the pretreatment stage other materials will also be removed in the pretreatment process such as other dyes / pigments, proteins and polysaccharides, oligomers and sugars. The objective is to remove as much dye as possible whilst removing as little polysaccharides, oligomers and sugars as possible. The pigments may be present in the seaweed in their salt form or sugar form therefore a proportion of the overall sugar content of the seaweed will be reduced as some sugars will be extracted with the pigments.

[0087] The pretreatment may use water or a combination of aqueous solutions comprising low levels of solvents and / or hydrogen peroxide and low temperature. Suitable solvents include ethanol, industrial methylated spirits and / or methanol. Mixtures of solvents may be used in the aqueous solutions and mixtures of one or more solvents with hydrogen peroxide may also be used. The aqueous solutions are preferably free of any added acids or added bases. Preferably the solvents and / or hydrogen peroxide are present in the aqueous solution at between 2 to 40% v / v solutions in water, more preferably 5 to 30% v / v solutions in water more preferably 5 to 25% v / v solutions in water, more preferably 5 to 20 % v / v solutions in water, more preferably 5 to 15% v / v solutions in water and most preferably 5 to 12% v / v solutions in water. Preferably the aqueous solution is neutral or pH <7, preferably pH is within the range of 4 to 7. In one embodiment the pretreatment aqueous solution is mildly acidic or non-acidic. In one embodiment the pretreatment solution comprises hydrogen peroxide as a 10% aqueous solution. In one embodiment the pretreatment solution is hydrogen peroxide free. In one embodiment the aqueous pretreatment solution comprises an alcohol, preferably ethanol or industrial methylated spirits.

[0088] The pretreatment is ideally carried out at room temperature or lower. Preferably, the pre-treatment is carried out at < 25°C, more preferably within the range of 15 to 25°C., and most preferably within the range of 20 to 25°C.

[0089] In this pretreatment stage the seaweed is mixed with the aqueous pretreatment solution at an amount of between 5 to 30% (w / v), more preferably 5 to 20% (w / v) and most preferably 5 to 10% (w / v).

[0090] This pretreatment is ideally undertaken with mixing and stirring of the seaweed in the aqueous solvent for a period of between 30 and 120 mins, more preferably 30 and 90 mins and most preferably 60 to 90 mins. After the pretreatment is completed, the seaweed is filtered from the aqueous solvent and may then be used in the polysaccharide extraction process described in the first aspect.

[0091] The remaining aqueous solvent is a pretreatment extract that contains significant levels of the xanthophyll pigment fucoxanthin and inter alia some sugars. The neutrality or mild acidity of the aqueous solvent under these conditions is sufficient to remove the pigment but not to remove significant quantities of polysaccharides from the seaweed.

[0092] Depending on the starting volumes the pretreatment extract will contain between 1 to 5% by weight of the dry mass of the original seaweed and this will equate to total dissolved solids of <10 g / 1. The remaining seaweed for use in the further stages of the first aspect is between 95 to 99 % by weight of the dry mass of the original seaweed.

[0093] The pretreatment extract is highly coloured due to the high levels of pigment present. This may be assessed by measuring the optical density of the extract by reading the absorbance of the extract at 500 nm and normalizing against an absorbance measurement at 600 nm (OD 500nm / OD 600nm). This normalized optical density can indicate the level of extraction of the pigment and efficiency of the extraction process. Typically, the normalized optical density of this extract is within the range of 1.5 to 4 for each extraction.

[0094] The pretreatment may be repeated a number of times on the same source of seaweed to ensure maximum pigment extraction. Once the pre-treatment is completed it is preferred that the pre-treated residue is then washed with or soaked in water to remove as much of the absorbed pre-treatment from the pre-treated residue as possible before the pretreated residue is used in the basic extraction process.

[0095] All of the aqueous extraction solutions used may also extract varying minor amounts of oligomers, sugars and polysaccharides from the seaweed but none extracted anysignificant amount of polysaccharides. The solutions incorporating hydrogen peroxide for any given species of seaweed resulted in the lowest levels of polysaccharide, oligomer and sugar losses but these solutions were less efficient at pigment removal.

[0096] Embodiments of the invention will now be described by way of example only with reference to the accompanying figures in which:

[0097] Figure 1 illustrates a schematic of a biorefinery for the production of biopolymer films from unrefined polysaccharide extract,

[0098] Figure 2 illustrates analytical compositional data for various samples of Example 2,

[0099] Figure 3 illustrates analytical compositional data for various samples of Example 2, and

[0100] Figure 4 illustrates analytical compositional data for various samples of Example 2

[0101] With reference to Figure 1, there is shown a preferred biorefinery, which utilizes the key processes described herein to produce inter alia the unrefined polysaccharide extracts and biopolymer film used to manufacture water-soluble capsules.

[0102] In a first stage (Pigment Extraction) raw seaweed, typically 2-4 mm flake / powder is introduced to an extraction vessel at 2-10% w / v of the vessel and extraction solution typically a 10% hydrogen peroxide solution and / or ethanol in water is added (typically 10-30% v / v) are mixed at a low temperature. After a period of time (typically 1 hour) the mixture is filtered to provide two products; (1) a liquid pigment rich by-product (1- 10 wt% DM) and a wet seaweed solid residue (90-99 wt% DM). The liquid by-product (1) contains high levels of fucoxanthin, other pigment related extracts and relatively low levels of sugars and polysaccharides. The wet solid (retaining low levels of water and solvent from the first stage) may then be passed to a washing stage where it is washed with water and agitation and then passed to a solid de-watering stage to provide a washed seaweed solid residue and afurther dilute pigment solution (l)b. The washed seaweed solid residue comprises from 90 to 99 wt% DM and is then passed to a polymer extraction (polysaccharide extraction) stage.

[0103] In the polymer extraction stage, the wet solid from the dewatering stage is combined with a basic aqueous solution with mixing at moderate temperatures for typically 15 to 120 minutes. The seaweed is present in the vessel at typically 2-10 w / v to the extraction solution. The extraction is preferably carried out at between 40 to 65 ° C, with a 1% NaCO3 (pH 10-12) extraction solution for 30-90 minutes. The mixture is then passed to a further dewatering stage using a press or a centrifuge tor provide a wet solid (2) that may be recycled to the polymer extraction vessel for further base extractions. The liquid phase obtained from the second dewatering stage is an aqueous solution comprising a mixture of unrefined polysaccharides and other components of the seaweed. This liquid extract is then filtered to provide a final unrefined polysaccharide extract (3). Filtering is typically with a filter mesh of 100pm or less and preferably 10pm or less.

[0104] The unrefined polysaccharide extract (3) may then be used directly as the extract in a formulation stage with inter alia plant based plasticizers and other materials to provide a biopolymer formulation to prepare formulations for final products comprising the unrefined polysaccharide extract. Such formulations are then subjected to a thermal condition stage before use. Alternatively, the extract (3) may be further dewatered to a dry powder or flake and then formulated for desirable products. After thermal conditioning if the formulation is for a biopolymer film it may be cast to form a roll of biopolymer film (4), which may then be fed into a vacuum forming process to produce water-soluble capsules comprising for example laundry detergent.

[0105] The invention will now be further illustrated by means of the following nonlimiting examples.

[0106] Example 1 - Pre-treatment for pigment extraction

[0107] A raw brown seaweed Ascophyllum nodosum (1-4 mm flakes or milled powder -500 micron) was sourced and treated either with a solvent (Industrial MethylatedSpirit, Ethanol or Methanol) or with a weak oxidizing agent hydrogen peroxide to facilitate a preliminary pigment extraction.

[0108] Various aqueous solutions were prepared at 10% (v / v) IMS, Methanol or H2O2 in water. 0. IKg of raw seaweed provided as a water washed and particulate form (1-4 mm flakes) was added to IL of an aqueous solution to provide a 10% (w / v) seaweed: water solution mixture. Each solution containing the raw seaweed was stirred and mixed at room temperature for at least Ih. Optical density (OD) was measured by reading absorbance at 500nm, the peak wavelength value for the most abundant pigment, the xanthophyll pigment fucoxanthin. The OD was measured by normalization to the 600nm absorbance, considered as a blank value using the following equation:OD ~ A (500nm) / A (600nm)

[0109] The results are shown in Table 1.

[0110] The results show that both EtOH and MeOH extractions provide comparable and higher pigment extraction compared to H2O2. However, the pre-treatment with H2O2, an oxidising agent, showed lower pigment extraction efficiency yet effectively decolouring the pre-treated seaweed solids. It is important to say that when extracting pigment, either via alcohol or oxidizing agent, with a 10% v / v water solution, the main polar solvent is the water - water will naturally extract polar pigments. The 10% v / v Ethanol or Methanol water extraction can extract pigments, both hydrophilic and hydrophobic molecules, preserving their quality and resulting with pure pigments with minimal structural alteration. In contrast, the 10% v / v H2O2 water solution can extract mainly polar pigments yet leading to oxidation of these and therefore altering their structure, therefore resulting in lower yield when compared to alcohol: water solutions.

[0111] A further set of extractions were undertaken to compare extraction time and concentration of the extraction solution. This series of extraction re-treatments were conducted with IMS or desaturated Ethanol at three different concentration levels (10%, 20% and 40% v / v). The results are shown in Table 2. These results confirmed that a Ih extraction pre-treatment at 10% v / v IMS: water solution is sufficient to extract enough pigment, presenting a similar OD500 / OD600 ratio to Ethanol (3.24 vs. 3.27), to allow decolouring of wet solid seaweed prior to any alkaline extraction. IMS is a good solvent for pigment extraction and analyses, providing comparable efficacy to ethanol, potentially preserving chemical structure of pigments (the pigment containing extract may be used for further processing in other industries).

[0112] In general, the higher the absorbance in optical density at 500nm or OD(500), the higher is the pigment density in the pre-treatment extract, indicating a higher pigment extraction yield and in turn a higher pigmen extraction efficiency. Hence the OD can be used as proxy to determine pigment extraction efficiency.

[0113] A further set of extractions were evaluated to determine the impact of multiple extractions on the same seaweed sample for a given solvent or H2O2.

[0114] A further series of extractions were undertaken by first extracting the dry seaweed, followed by two further extractions on the wet solid mass with a fresh 10% (v / v) solution for each extraction. The resulting 10% (w / v) seaweed pigment extracts were rich dark green-brown solutions with high concentration of seaweed-derived pigments. The results are provided in Table 3.

[0115] The extracts for each solvent and H2O2 were combined, and the combination measured for OD. The results are shown in Table 4.

[0116] The H2O2 oxidizing agent acts as a decolouring agent oxidizing the pigments present in the extract. The resulting combined extract from the H2O2 solution, presents a lower normalized OD of 2.3, compared to the ethanol and methanol extracts with OD of 4.6 and 4.4, respectively.

[0117] These results suggest that ethanol and methanol are stronger pigment extractors with higher extraction efficiency than H2O2, although the 10% v / v solutions used for pre-treat the raw seaweed is a very low concentration. Even though the H2O2 pretreatment appears to show a low extraction efficiency the later produced polysaccharide extract solution showed lower OD values compared to the ethanol and methanol equivalents, resulting in a much lighter coloured polysaccharide extract.

[0118] Example 2 - Pre-extraction, Extraction Residue and Unrefined Polysaccharide Sugars

[0119] Analysis Method

[0120] 2.1 Gas Chromatography - Mass spectrometry (GC-MS) testing

[0121] Samples were frozen at -20°C. 1 ml of each of the extraction liquid fractions were dried down in a speed- vacuum concentrator (SpeedVac, Eppendorf Concentrator Plus) to obtain about 20 mg of dried material.

[0122] Samples were hydrolysed in 4 ml of 4 M HC1 at 80 °C for 10 h. After samples had cooled to room temperature 20 pl of the hydrolysate was dried in the SpeedVac. A set of standards containing alginic acid and fucoidan was prepared, dried and derivatised as for the liquid extraction samples to enable calibration.

[0123] Hydrolysed samples and standards were derivatized by adding 20 pl of methoxymation solution (20mg / ml methoxyamine hydrochloride, (Fluka®), in dry pyridine, (Fluka®). After shaking at 30 °C for 90 min (BenchMark Multi Therm) 40 pl of MSTFA (Macherey -Nagel) was added to complete derivatization in the thermomixer at 37 °C for 30 min. Derivatised samples were immediately transferred into 200 pl glass micro-vials, crimp capped and analysed using GC-MS. 1 pl of each sample and standard was injected onto a 30 m DB5-MS column at a split-ratio of 2: 1 (Trace-GC, Thermo Scientific®) coupled to an ISQ7000 mass spectrometer (Thermo Scientific®). Mass spectra were collected in the m / z range 54-500 at ion source and transfer-line temperatures of 230 °C and 250 °C, respectively. Helium carrier gas flow was ramped from 2.2 ml min-1 for 10 min up to 2.6 ml min-1 in one minute and held for further 2 min. The temperature programme started at 80 °C, held for 1 min, ramped at 10 °C min-1 to 90 °C; then 30 °C °C min-1 till 330 °C and held for 3 min before cooling. Fucose, mannuronic acid, glucose and mannitol were quantified using five calibration standards in the range of between 0.5 mg / ml and 1 pg / ml with these used to determine sample concentrations.

[0124] A further set of analyses were undertaken using IMS (Industrial MethylatedSpirit) in the pre-treatment extraction process. Raw Asco seaweed (washed and processed to 1-4 mm particle size) was pre-treated with 10% v / v, 20% v / v and 40% v / v industrial methylated spirit in water. The extracts were analysed on a dry matter basis (mg / g DW) afteracid hydrolysis and the results are provided in Table 6 and Figure 2. The is date shows that both mannuronic acid and guluronic acid (both markers for alginate) and fucose (marker for fucoidan) were detected at relatively low levels, whereas mannitol and glucose (probably derived from laminarin and other polysaccharides) were much higher. At these levels the pigment extract solution is substantially free of fucoidan and alginate, whilst having much higher levels of mannitol and glucose. This would suggest that the amount of fucoidan and alginate polysaccharide extraction is minimal with this extraction stage, but that other sugars and polysaccharides may be extracted at higher levels. This means that the mixture of polysaccharides sugars in the residual seaweed will be different in proportion compared to the untreated seaweed. The residual seaweed will have proportionally higher levels of fucoidan and alginate and proportionately less mannitol and glucose producing polysaccharides compared to the untreated seaweed, which is beneficial for the following basic extraction stage. It is preferred that the pigment extract provides on hydrolysis less than 0.3 mg.g’1DW of each of mannuronic acid, guluronic acid and fucose and most preferably less than 0.25 mg.g’1DW of each of these. It is preferred that the pigment extract provides on hydrolysis greater than 2 mg.g’1DW of glucose, preferably greater than 2.4 mg.g’1DW of glucose. It is preferred that the pigment extract provides on hydrolysis greater than 3 mg.g’1DW of mannitol, preferably greater than 4 mg.g’1DW of mannitol and most preferably greater than 4.5 mg.g’1DW of mannitol. The residual solid seaweed material for each of the samples extracted for 90 minutes were analysed for their composition before base extraction and the results are provided in Figure 3 and |Table 7 as SI 0, S20, S40. It can be seen for each of these samples that the level of fucose is 14 mg.g’1DW or higher and significantly higher than the level of mannuronic acid between 5.24 and 8.25 mg.g’1DW, glucose and mannitol are at comparable or slightly lower levels than the mannuronic acid. This would suggest that the pre-treatment solid has high levels of fucoidan compared to the other polysaccharides.

[0125] A sample of brown seaweed was pre-treated using 10% v / v industrial methylated spirits in water to provide a pre-treated residual solid seaweed broadly corresponding to S10 Solid in Table 7. This pre-treated solid was divided into three parts, and each part was base extracted with a 1% Na2COs aqueous solution at room temperature, 50°C and 60°C for 90 mins. Samples for analysis were taken at 30, 60 and 90 mins. The results of the testing of the solid reside samples after extraction are shown in Table 7 and Figure 3. It can be seen that the room temperature residual solid after extraction still retains relatively high levels of fucose and mannuronic acid in its hydrolysate with relatively low levels of glucose and mannitol. This is in contrast with the extractions at 50°C and 60°C where it can be seen that there is a significant drop in fucose and mannuronic acid as the temperatureincreases with the lowest levels being with the 60°C extraction. The analysis of the hydrolysed liquid samples corresponding to the desirable aqueous polysaccharide extract solutions are shown in Table 8 and Figure 4. It can be seen that as the extraction temperature increases and the time of extraction increases the levels of fucose and mannuronic acid increase in the liquid extract. Glucose and mannitol are also extracted. The resultant aqueous polysaccharide extract solutions contain a mixture of fucoidan, alginate, mannitol and glucose. Although not directly detected the high levels of glucose in both the pre-extract and unrefined polysaccharide extract imply the presence of laminarian in both the pre-extract and the unrefined polysaccharide extract as laminarian is hydrolysed in the test to produce glucose. The exact level of laminarian in both extracts may be determined by known analysis techniques.

[0126] Example 3 - Alkaline extracts of various seaweed species and their blend

[0127] Wet solid seaweed, after been extracted in cold (15-18 C) with either ethanol or H2O2, were extracted at 65°C for 90min. The pH and the total dissolved solids (TDS, mg / 1) were measured once the extract was completed and filtered. The filtered liquid extracts were analyzed for sugar content, oligomer content and BRIX. The results are shown in Table 9.

[0128] Extracts of different species pretreated with different solvents, ethanol and H2O2, respectively, performed at the same extraction conditions, showed comparable total dissolved solutes (TDS). Only Fucus spiralis extracted after H2O2 pretreated, showed higher TDS than the ethanol extracts, overall the blends showed comparable TDS levels.

[0129] Overall total oligomer content of the extracts showed higher values in H2O2 pretreated seaweed species as well as in their blend, when compared with those seaweeds pretreated with ethanol (610.6 vs. 206.4, respectively). Similarly, the species, Ascophyllum nodosum and Fucus vesiculosus showed the higher total sugar content and oligomer content that other species especially with the H2O2 pretreated samples.

[0130] Example 5 - Biopolymer film manufacture.

[0131] The liquid extracts of Example 3 were employed in biopolymer film production.

[0132] To each of the extracts of Example 3 when below 50°C, was added 2.00 wt% starch, 0.50 wt% carrageenan, 1.20 wt% glycerol, 0.60wt% sorbitol and 0.00124 wt%Bittrex (based on a solution with a 94-96% water content). After mixing and conditioning these formulations were used to slip cast using a conventional slip casting die and conditions to provide biopolymer films. Typical properties of the biopolymer films made were measured, including tensile strength data, water content, area density and thickness. The results are shown in Table 10. These results show that all of the biopolymer films, which contained the unrefined mixed polysaccharide extracts exhibited acceptable physical and mechanical properties with low water content.

[0133] Example 5 - Manufacture of Unit Dose Pods

[0134] The biopolymer films of Example 5 were used to make encapsulated pods via vacuum forming and heat sealing. All of these films provided intact vacuum formed pods with heat sealing from two biopolymer films encapsulating a liquid. The results are provided in Table 10, where it can be seen that each pod passed the vacuum forming and capsule production tests. In addition, the water-soluble capsules comprising the unrefined biopolymer extracts were found to resist initial dissolution in water for 30 seconds or more and exhibited a resistance to 300 newtons of applied pressure indicating that they met regulatory requirements for laundry pod use.

[0135] Example 6 - Extraction time v Temperature

[0136] A series of pre-extracted seaweed samples were subjected to basic extraction with 1,0 wt% Na2CO3 solution. The pre-extracted seaweed samples are shown in Table 11.

[0137] Three basic extraction times were tested (30min, 60min, 90min) over three temperatures (40degrees, 50degrees, 60degrees). A sample of wet pre-treated seaweed was heated at either 40, 50, 60 degrees for either 30min, 60min or 90min. Following extraction, the solid was filtered and the basic liquid extract was collected, and TDS, DM, pH, and Brix were recorded. The results are shown in Table 12.

[0138] Example 7- Biopolymer Film Formation

[0139] Various film formulations were prepared using various polysaccharide extract solutions from the basic extraction process as described in preceding examples and with various pre-extraction processes. The concentration of material in the unrefined polysaccharide extract will vary. Typically, the raw extract will be diluted at a 5X dilution with water, and this may provide anywhere between 0.1 and 0.8 wt.% DM (dry mass). Formulated solutions may be cast at a water content of 50-96 wt.% to make biopolymer films.

[0140] Typical formulation ranges showing the lower and upper values (DM= Dry Mass) are as illustrated in Table 13 for the unrefined polysaccharide based formulations and the resultant films. The films have been case to a water content of 20 wt.%.Atypical formulation comprising unrefined polysaccharide extract (PS Extract) used for casting and evaluation is as follows.Typical variants of this formulation suitable for and evaluated for biopolymer film forming are as follows and % are wt.% DM with the balance being water:

[0141] PS.1~ a film formulation comprising unrefined seaweed-derived extract (0.1- 0.8%) and organic plasticizers including potato starch (0.5- 2%), carrageenan (0.25-0.75%) and glycerol (1.2 - 3%).

[0142] PS 2- a film formulation comprising unrefined seaweed-derived extract (0.1- 0.8% DM%) and organic plasticizers including potato starch (0.5-2%), carrageenan (0.25- 0.75%) and sorbitol (1.2 - 3%)

[0143] PS3 - a film formulation comprising unrefined seaweed-derived extract (0.1- 0.8%) and organic plasticizers including potato starch (0.5-2%), carrageenan (0.25-0.75%) and Propanediol (1-1.8%)

[0144] PS5- a film formulation comprising unrefined seaweed-derived extract (0.1- 0.8%) and organic plasticizers including potato starch (0.5-2%), carrageenan (0.25-0.75%), glycerol (0.8 - 1.4%) and sorbitol (0.4-1%)

[0145] PS.Flexi. series - a film formulation comprising unrefined seaweed-derived extract and organic plasticizers including potato starch (0.5%), carrageenan (0.5-1.5%), glycerol (1.8%)

[0146] The properties of various films were measured and are provided in Table 14. Pretreatment method is described as either ethanol or H2O2. Both pre-treatments were undertaken at 10% concentration applied to 10% w / v seaweed.

[0147] These biopolymer films exhibited good properties and could be easily vacuum formed and used to manufacture water-soluble capsules comprising laundry detergents meeting the regulatory requirements for laundry capsules, where no liquid product is released up to a compression of 300 Newtons.

[0148] Example 8 - Film Solution Composition Processing Rheology

[0149] Film composition rheology was evaluated. A film formulation was prepared by adding the plasticizers to the clarified unrefined polysaccharide seaweed extract while mixing at room temperature and then heated up to 60C for enhancing homogeneity of final solution. The solution turned into a gel after cooling down to below 50C.

[0150] The viscosity (MPas) was measured every hour while mixing at constant temperature for 7 hours. The data is provided in Table 15. As shown in the table, a significant change of viscosity occurred when the solution was heated up at temperature of 70 or above. Continuous stirring at 80C led to a decline in viscosity compared to when the same solution was mixed at 70C - this may indicate that 70 is the maximum / optimal temperature to stir the solution over time.

[0151] The overall increase of viscosity of the solution may be related to increases of polymerization or increases of intermolecular forces regulated by the time of stirring at constant temperature. The decline observed at higher temperatures could indicate a reversal of these reactions, a break-down, or transformation.

[0152] The same solution prepared at 60C and heated at 50C was cooled down into a gel form and re-heated to 60C and 70C. Similarly, the same solution prepared at 60C and heated at 70C was cooled into a gel form and re-heated to 60C and 70C. The results are shown in Table 16. The heat and re-heat processes are also referred to first and second heating cycle, respectively. For example, a solution prepared at 60C is heated at 50C, cooled to room temperature and re-heated at 70C (also referred to 60C / 50C / 70C.TABLE 16

[0153] Results showed significant increase of viscosity after a second heating cycle at 60C with viscosity values higher than those recorded at first heating cycle at 50C. Similarly, after a second heating cycle at 70C. Likewise, a further increase in viscosity was recorded on a solution subjected to a first heating cycle at 70C and reheated at 50C and 70C. Results may suggest the role of temperature over time and how a further heating cycles within 50C and 70C may increase the viscosity.

[0154] While exemplary embodiments incorporating the principles of the present disclosure have been described herein, the present disclosure is not limited to such embodiments. Instead, this application is intended to cover any combinations of the individual features of the exemplary embodiments described herein and the principles described herein and to cover any variations, uses, or adaptations of the disclosure using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this disclosure pertains. It is also to be understood that any aspects described as such, and their features are not mutually exclusive from any other aspect and its features in this disclosure and this disclosure should not be interpreted as such. Any individual features of any two or more aspects may be combined with each other.

Claims

CLAIMS1. A water-soluble capsule comprising a sealed compartment containing a composition, the capsule walls comprising a first water soluble biopolymer film and a second water soluble biopolymer film, the first water soluble biopolymer film being sealed to the second water soluble film to form the sealed compartment, wherein the biopolymer film comprises an unrefined polysaccharide extract of seaweed.

2. A water-soluble capsule as claimed in claim 1, wherein the unrefined polysaccharide extract comprises a mixture of unrefined polysaccharides.

3. A water-soluble capsule as claimed in claim 2, wherein the mixture of unrefined polysaccharides comprises two or more of unrefined alginate, unrefined fucoidan, unrefined laminarin and unrefined mannitol.

4. A water-soluble capsule as claimed in claim 2 or 3, wherein the mixture of unrefined polysaccharides comprises unrefined glucose.

5. A water-soluble capsule as claimed in claim 1, wherein the unrefined polysaccharide extract comprises unrefined carrageenan or unrefined agar or unrefined cellulose or mixtures of two or more of these polysaccharides.

6. A water-soluble capsule as claimed in claim 1, wherein the unrefined polysaccharide extract comprises unrefined starch or unrefined hemicellulose or unrefined cellulose or unrefined ulvan or mixtures of two or more of these polysaccharides.

7. A water-soluble capsule as claimed in claim 1, wherein the unrefined polysaccharides extract comprises two or more unrefined polysaccharides from one or more different seaweeds.

8. A water-soluble capsule as claimed in claim 7, wherein the one or more different seaweeds are from the same taxonomical seaweed group.

9. A water-soluble capsule as claimed in claim 7, wherein the one or more different seaweeds are from different taxonomical seaweed groups.

10. A water-soluble capsule as claimed in claim 1, wherein the seaweed is brown seaweed.

11. A water-soluble capsule as claimed in claim 1, wherein the seaweed is red seaweed.

12. A water-soluble capsule as claimed in claim 1, wherein the seaweed is green seaweed.

13. A water-soluble capsule as claimed in claim 1, wherein the biopolymer film comprises further materials and additives to provide a formulation and the formulation having been homogenized.

14. A water-soluble capsule as claimed in claim 1, wherein the unrefined polysaccharide extract solution has been pre-conditioned before addition to a biopolymer film formulation used to make the biopolymer film.

15. A water-soluble capsule as claimed in claim 13, wherein the unrefined polysaccharide extract solution is pre-conditioned during or after the formulation homogenization process.

16. A water-soluble capsule as claimed in claim 1, wherein the comprising plant-based plasticisers.

17. A water-soluble capsule as claimed in claim 16, wherein the plasticizer is selected from the group consisting of glycerine, trimethylol propane, sorbitol, and combinations thereof.

18. A water-soluble capsule as claimed in claim 1, wherein the capsule is soluble in water at ambient or elevated temperatures.

19. A water-soluble capsule as claimed in any one of claims claim 1 to 18, wherein the composition in the sealed compartment comprises a non-household care composition.

20. A water-soluble capsule as claimed in any one of claims claim 1 to 18, wherein the composition in the sealed compartment comprises a household care composition.

21. A water-soluble capsule as claimed claim 20, wherein the composition in the sealed compartment comprises a liquid detergent.

22. A water-soluble capsule as claimed claim 20, wherein the composition in the sealed compartment comprises a laundry cleaning composition.

23. A water-soluble capsule as claimed claim 20, wherein the composition in the sealed compartment comprises a dishwasher detergent.

24. A water-soluble capsule as claimed claim 19, wherein the composition in the sealed compartment comprises an edible food composition or water or a beverage or a fertiliser composition or a cosmetic or a personal care composition or a pharmaceutical composition suitable for oral administration.

25. A water-soluble capsule as claimed in any one of claims claim 1 to 18, wherein the composition in the sealed compartment is aqueous.

26. A water-soluble capsule as claimed in any one of claims claim 1 to 18, wherein the composition in the sealed compartment is a solid, powder, gel or liquid.

27. A water-soluble capsule as claimed in any one of claims claim 1 to 18, wherein the composition in the sealed compartment is edible.

28. A water-soluble capsule as claimed in any one of the claims claim 1 to 18, wherein the capsule resists disintegration and product release for a minimum of 30 seconds.

29. A water-soluble capsule as claimed in any one of the claims claim 1 to 18, wherein the capsule can resist a compression force of up to 300N, where no liquid product is released up to 300N.

30. A method of making a water-soluble capsule as claimed in any one of claims 1 to 29, wherein the compartment is provided by a vacuum formed first biopolymer film and which compartment is filled with a composition and which composition is sealed within the compartment by the sealing of a second biopolymer film to the vacuum formed first biopolymer film.

31. A method as claimed in claim 30, wherein the first biopolymer film is vacuum formed without heating.

32. A method as claimed in claim 30 or 31, wherein the second biopolymer film is sealed to the first biopolymer with heating.

33. A method as claimed in claim 30 to 32, wherein the second biopolymer film is sealed to the first biopolymer with an aqueous solution.

34. A method as claimed in claim 33, wherein the aqueous solution comprises a mixture of one or more of starch, glycerol, CaCh, tannic acid or NaCCh.

35. A method as claimed in claim 33, wherein the aqueous solution comprises a mixture of starch, glycerol, CaCh, tannic acid or Na2COs.

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