Bio-based water-soluble film including starch, carrageenan and pullulan

Abstract

Disclosed herein is a water-soluble film including a plasticizer and a film-forming resin comprising starch, carrageenan, and pullulan. Starch is present in the film in an amount in a range of about 50 wt.% to about 90 wt.% or in a range of about 1 wt.% to about 30 wt.%, based on the total weight of starch, carrageenan, and pullulan; carrageenan is present in the film in an amount in a range of about 5 wt.% to about 14 wt.%, based on the total weight of the starch, carrageenan, and pullulan. The ratio of starch to the sum of carrageenan and pullulan is in a range of from about 0.01 to about 0.43 or in a range from about 1 to about 9.

Description

BIO-BASED WATER-SOLUBLE FILM INCLUDING STARCH, CARRAGEENAN AND PULLULANCROSS REFERENCE TO RELATED APPLICATION

[0001] The benefit of priority to U.S. Provisional Application No. 63 / 657,424 filed June 07, 2024, is hereby claimed and the disclosure is incorporated herein by reference in its entirety.FIELD

[0002] The present disclosure relates to water soluble films and related articles. More particularly, the disclosure relates to water-soluble films comprising a plasticized mixture of starch, carrageenan, and pullulan.BACKGROUND

[0003] Water-soluble polymeric films are commonly used as packaging materials to simplify dispensing, pouring, dissolving, and dosing of a material to be delivered. A consumer can directly add the pouched composition to a mixing vessel, such as a bucket, sink, or washing machine. Advantageously, this provides for accurate dosing while eliminating the need for the consumer to measure the composition. Additionally, the water- soluble polymeric film packaging can separate otherwise strong chemistries from the consumer’s hand, protecting the consumer from coming in contact with harsh chemicals. The pouched composition may also reduce mess that would be associated with dispensing a similar composition from a vessel, such as pouring a composition from a bottle. In sum, soluble pre-measured polymeric film pouches provide for the convenience and safety of consumer use in a variety of applications. An important sector of these applications is the detergent market where many detergent formulations contain at least small amounts of water. This complicates the selection of materials that can perform acceptably and thus raising the need for polymers that are ultimately water soluble but capable of containing a composition that includes some water.SUMMARY

[0004] Water-soluble films according to the disclosure include a film-forming resin and a plasticizer, wherein the film-forming resin includes a mixture of starch, carrageenan, and pullulan; and starch is present in an amount in a range of about 50 wt.% to about 90 wt.%, based on the total weight of starch, carrageenan, and pullulan, and carrageenan is present in an amount in a range of about 5 wt.% to about 14 wt.%, based on the total weight of the starch, carrageenan, and pullulan. Optionally, a cross-linker may be added to the film.

[0005] The disclosure further provides water-soluble films including a film-forming resin and a plasticizer, wherein the film-forming resin includes a mixture of starch, carrageenan,and pullulan ; and starch is present in an amount in a range of about 1 wt.% to about 30 wt.%, based on the total weight of starch, carrageenan, and pullulan, and carrageenan is present in an amount in a range of about 5 wt.% to about 14 wt.%, based on the total weight of the starch, carrageenan, and pullulan. Optionally, a cross-linker may be added to the film.

[0006] The disclosure further provides water-soluble films comprising a film forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of starch, carrageenan, and pullulan in an amount of at least 50 wt.% based on the total weight of the film, and the ratio of starch to the sum of carrageenan and pullulan is in a range of from about 0.01 to about 0.43 or in a range from about 1 to about 9.

[0007] The disclosure further provides methods of decreasing blocking force of a water- soluble film according to the disclosure comprising including in the film a polyethylene glycol (PEG) having a molecular weight in a range of about 1000 Da to about 20,000 Da, or about 1000 Da to about 10,000 Da, or about 1000 Da to about 5000 Da, or about 1000 Da to about 4000 Da in an amount of a least about 1 wt.%, based on the total weight of the non-water parts of the film.

[0008] The disclosure further provides methods of increasing the strain at break of a water-soluble film according to the disclosure comprising including in the film a polyethylene glycol (PEG) having a molecular weight in a range of about 1000 Da to about 20,000 Da, or about 1000 Da to about 10,000 Da, or about 1000 Da to about 5000 Da, or about 1000 Da to about 4000 Da in an amount of at least about 1 wt.%, based on the total weight of the nonwater parts of the film.

[0009] The disclosure further provides methods of making and using water-soluble films according to the disclosure, and articles made from a water-soluble film according to the disclosure.

[0010] The disclosure further provides a water-soluble article in the form of a packet comprising a sealed compartment, the article comprising a water-soluble film according to the disclosure sealed to a second water-soluble film.

[0011] For the compositions and methods described herein, optional features, including but not limited to components and compositional ranges thereof, are contemplated to be selected from the various aspects, claims, and Examples provided herein. For example, formulation approaches described in the Examples can be combined with any of the additional features provided in the description and claims herein.

[0012] Further aspects and advantages will be apparent to those of ordinary skill in the art from a review of the following detailed description. While the film and article of the disclosurecan be implemented in various forms, the description hereafter includes specific example compositions with the understanding that the disclosure is illustrative and is not intended to limit the invention to the specific compositions described herein.DETAILED DESCRIPTION

[0013] Water-soluble polymeric films are commonly used as packaging materials to simplify dispensing, pouring, dissolving, and dosing of a material to be delivered. A consumer can directly add the pouched composition to a mixing vessel, such as a bucket, sink, or washing machine. Advantageously, this provides for accurate dosing while eliminating the need for the consumer to measure the composition. Additionally, the water- soluble polymeric film packaging can separate otherwise strong chemistries from the consumer’s hand, protecting the consumer from coming in contact with harsh chemicals. The pouched composition may also reduce mess that would be associated with dispensing a similar composition from a vessel, such as pouring a composition from a bottle. In sum, soluble pre-measured polymeric film pouches provide for the convenience and safety of consumer use in a variety of applications.

[0014] The films described herein can be designed to have a reduced carbon footprint by using raw materials from renewable sources. Conventional water-soluble films often include resins of petrochemical origin leading to a low renewable carbon index (RCI). In contrast, bio-based polymers have much higher renewable carbon indices, but their application has been limited because they can be stiff in nature and immiscible or not compatible with other components in conventional water-soluble films. The use of bio-based polymers in water- soluble films has generally been limited, due to a need to maintain mechanical properties suitable for conversion into and use as packages, such as a high level of elongation, deformation recovery, and strength properties.

[0015] “Bio-based” as used herein refers to materials for which at least a portion of the materials is derived from raw materials such as plants and other renewable agriculture, marine, and forestry materials. Bio-based materials can be naturally occurring or can be derivable from naturally occurring materials. Bio-based polymers include, but are not limited to, polysaccharides (including but not limited to pullulan, carrageenans, alginates, celluloses, starches, dextrins, maltodextrins, xanthan gum, guar gum, locust bean gum) and proteins and protein derivatives (e.g., gelatins, collagens, keratins). Bio-based molecules include, but are not limited to, sugar alcohols (including but not limited to sorbitol, xylitol, erythritol, mannitol, and isomalt) and other polyols (including but not limited to glycerol). The filmforming resins of the water-soluble films of the disclosure can comprise at least 95 wt.%, at least 96 wt.%, at least 97 wt.%, at least 98 wt.%, at least 99 wt.%, or 100 wt.% bio-basedmaterials, based on the total weight of the film-forming resin. The water-soluble films of the disclosure can comprise at least 95 wt%, at least 96 wt.%, at least 97 wt.%, at least 98 wt.%, at least 99 wt.%, or 100 wt.% bio-based materials, based on the total weight of the film.

[0016] Renewable Carbon Index (“RCI”) refers to the fraction (or percentage) of the carbon atoms in the average structure of a material which are derived from feedstocks other than petroleum or natural gas. Typically, and desirably, when components of water-soluble films are produced from natural materials or in a sustainable manner, the RCI will be in excess of 0.75 or 75%, due to the use of materials found in nature, or to the use of feedstocks derived from sustainable sources such as plants, fungi or algae, products of bacterial fermentation processes, or products of treatments of plant-, fungal- or algae- derived biomass. The major challenges in the formulation of water-soluble films with desirably high RCIs are the selection of a few suitable materials that are economically viable, while delivering performance that is as good as or better than the conventional products. The water-soluble films of the disclosure can have a renewable carbon index of at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, or 100%.

[0017] “Comprising” as used herein means that various components, ingredients or steps that can be conjointly employed in practicing the present disclosure. Accordingly, the term “comprising” encompasses the more restrictive terms “consisting essentially of” and “consisting of.” The present compositions can comprise, consist essentially of, or consist of any of the required and optional elements disclosed herein. For example, a thermoformed packet can “consist essentially of” a film described herein for use of its thermoforming characteristics, while including a non-thermoformed film (e.g., lid portion). The invention illustratively disclosed herein suitably may be practiced in the absence of any element or step which is not specifically disclosed herein.

[0018] Films, such as those made in accordance with the disclosure, are defined by the polymer industry (Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc., 1967, Vol. 6, page 764) as “shaped plastics that are comparatively thin in relation to their breadth and width and have a maximum thickness of 0.010 in.”

[0019] The water-soluble film can be a self-supporting film, i.e., one which does not require a substrate in order to maintain integrity of the film structure, and optionally can be free-standing, i.e., one which does not include such a substrate. Uniform films refer to those which are virtually free of breaks, tears, holes, bubbles, and striations.

[0020] All percentages, parts and ratios are based upon the total dry weight of the formed film composition and all measurements are made at about 25 °C, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level andtherefore do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.

[0021] All ranges set forth herein include all possible subsets of ranges and any combinations of such subset ranges. By default, ranges are inclusive of the stated endpoints, unless stated otherwise. Where a range of values is provided, it is understood that each intervening value between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also contemplated to be part of the disclosure.

[0022] The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to include both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “15 mm” is intended to include “about 15 mm,” and “about 15 mm” can include a range of from 14.5 mm to 15.4 mm, e.g., by numerical rounding.

[0023] As used herein and unless specified otherwise, the terms “wt.%” and “wt%” are intended to refer to the composition of the identified elements in “dry” (non-water) parts by weight of the entire film (when applicable) or parts by weight of the entire composition enclosed within a pouch (when applicable).

[0024] As used herein and unless specified otherwise, the term “PHR” or “phr” is intended to refer to the composition of the identified element in parts per one hundred parts water- soluble polymer or film-forming resin in the water-soluble film.

[0025] The film can be made by any suitable method, including a solution casting method. The film can be used to form a container (pouch) by any suitable process, including vertical form, fill, and sealing (VFFS), or thermoforming. The film can be sealed by any suitable process including, for example, solvent sealing or heat sealing of film layers, e.g., around a periphery of a container. The pouches can be used for dosing materials to be delivered into bulk water, for example.

[0026] The films, articles, pouches, and related methods of making and use are contemplated to include embodiments including any combination of one or more of the elements, features, and steps further described below (including those shown in the Examples and figures), unless stated otherwise.

[0027] As used herein, the terms packet(s) and pouch(es) should be considered interchangeable. In certain embodiments, the terms packet(s) and pouch(es), respectively, are used to refer to a container made using the film and a sealed container preferably having a material sealed therein, e.g., in the form of a measured dose delivery system. The sealed pouches can be made from any suitable method, including such processes and features such as heat sealing, solvent welding, and adhesive sealing (e.g., with use of a water- soluble adhesive).Water-soluble films

[0028] The film and related pouches described herein comprise a plasticized water- soluble film. The water-soluble film comprises a film-forming resin comprising starch, carrageenan and pullulan in the amounts described herein and a plasticizer as described herein.

[0029] The water-soluble film can have any suitable thickness, and film thicknesses of about 76 microns (pm) and about 88 pm are typical and particularly contemplated. For example, the film can have a thickness in a range of about 5 to about 200 pm, or in a range of about 20 to about 100 pm, or about 40 to about 90 pm, or about 50 to about 80 pm, or about 60 to about 65 pm, for example about 65 pm, 76 pm, or 88 pm.

[0030] The film can include any suitable amount of resin content; for example, an amount in a range of about 1 wt.% to about 99 wt.%, or about 35 wt.% to about 90 wt.% based on the total weight of the film, or in a range of about 55 to about 95%, or about 60% to 90%, or about 65% to about 85%, or at least 50%.Pullulan

[0031] Pullulan is a polysaccharide comprising repeating maltotriose units and is typically produced from starch by a fungus, Aureobasidium pullulans. Films containing pullulan as the primary or only film-forming resins are commonly used in edible applications, including edible films and coatings, owing their flexibility, clarity, low oxygen permeability and to being highly water soluble. Pullulan is commercially available from many sources.

[0032] The water-soluble film of the disclosure can include pullulan in any amount such that when combined with the amounts of other film-forming resins, e.g., starch and carrageenan, the total amount of film-forming resin adds up to 100%. For example, a filmforming resin can comprise about 20 wt.% starch, 7 wt.% carrageenan and 73 wt.% pullulan based on the weight percent of the film-forming resin, such that the total amount of filmforming resins is 100%. As another example, a film-forming resin can comprise 60 wt.% starch, 10 wt.% carrageenan and 30 wt.% pullulan. As another example, a film-forming resincan comprise 70 wt.% starch, 7 wt.% carrageenan and 23 wt.% pullulan. If pullulan is absent from the film-forming resin, the film can be insufficiently water-soluble and / or flexible for many water-soluble film applications, e.g., in packaging contents intended for release in a cold wash cycle.

[0033] The water-soluble film of the disclosure can comprise a mixture of starch, carrageenan, and pullulan, wherein starch is present in an amount in a range from about 50 wt.% to about 90 wt.%, the carrageenan is present in an amount in a range from about 5 wt.% to about 14 wt.% and pullulan is present in an amount such as the ratio of starch to the sum of carrageenan and pullulan ranges from about 1 to about 9, and the amounts of film-forming resins add up to 100%. For example, the starch to carrageenan + pullulan ratio of a water-soluble film containing 50 wt.% starch, 12 wt.% carrageenan and 38 wt.% pullulan, based on the total amount of film forming resin; equals 1 . As another example, the starch to carrageenan + pullulan ratio of a water-soluble film containing 90 wt.% starch, 5 wt.% carrageenan and 5 wt.% pullulan, based on the total amount of film forming resin; equals 9.

[0034] The water-soluble film of the disclosure can comprise a mixture of starch, carrageenan, and pullulan, wherein starch is present in an amount in a range from about 1 wt.% to about 30 wt.%, the carrageenan is present in an amount in a range from about 5 wt.% to about 14 wt.% and pullulan is present in an amount such as the ratio of starch to the sum of carrageenan and pullulan ranges from about 0.01 to about 0.43, and the amounts of film-forming resins add up to 100%. For example, the starch to carrageenan + pullulan ratio of a water-soluble film containing 30 wt.% starch, 12 wt.% carrageenan and 58 wt.% pullulan, based on the total amount of film forming resin; equals 0.43. As another example, the starch to carrageenan + pullulan ratio of a water-soluble film containing 1 wt.% starch, 12 wt.% carrageenan and 87 wt.% pullulan, based on the total amount of film forming resin; equals 0.01 . As another example, the starch to carrageenan + pullulan ratio of a water- soluble film containing 20 wt.% starch, 7 wt.% carrageenan and 73 wt.% pullulan, based on the total amount of film forming resin; equals 0.3.Starch

[0035] Starches are naturally occurring polysaccharides consisting of repeating glucose molecules. Starches can be modified to possess a positive charge (cationic starches) or can contain neutral groups or non-ionic groups.

[0036] According to the disclosure, the starch can comprise substantially gelatinized starch, unmodified starch, cationic starch, or a combination thereof.

[0037] Water-soluble films according to the disclosure can contain about 50 wt.% to about 90 wt.% starch, based on the total weight of the film-forming resin in the film. For example, the water-soluble film can contain, from about 50 wt.% to about 85 wt.%, or from about 60 wt.% to about 75 wt.%, or about 60 wt.%, or about 70 wt.%, or about 85 wt.% starch, based on the total weight of the film-forming resin, or any values therebetween or ranges defined by such values. If the amount of starch exceeds 90 wt.% of the film-forming resin in the film, the resulting film can be insufficiently water-soluble.

[0038] Water soluble films according to the disclosure can contain about 1 wt.% to about 30 wt.% starch, based on the total weight of the film-forming resin. For example, the water- soluble film can contain, from about 5 wt.% to about 30 wt.%, or about 10 wt.% to about 25 wt.%, or about 20 wt.%, or about 30 wt.%, or about 10 wt.%, or about 5 wt.% starch, or any values therebetween or ranges defined by such values, based on the total weight of the film-forming resins in the film. If the amount of starch is less than 1 wt.%, the economic benefits of including starch in the film-forming resin may not be realized.Carrageenan

[0039] Carrageenans are a family of naturally occurring polysaccharides consisting of sulfated disaccharide repeat units of galactose and 3,6-anhydrogalactose. Carrageenans are generally obtained by extraction from red seaweeds. Multiple types of carrageenans are known, distinguished in part by their sulfate group content. For instance, kappa-, iota-, and lambda-carrageenan include, on average, one, two, and three sulfate groups per disaccharide repeat unit, respectively. Some properties of carrageenans depend on sulfate group content. For instance, kappa-carrageenan generally forms rigid gels upon crosslinking, iota-carrageenan generally forms soft gels upon cross-linking, and lambda- carrageenan is generally soluble and does not readily form gels. Carrageenans are commercially available, for instance from CP Kelco.

[0040] Water-soluble films according to the disclosure can contain about 5 wt.% to about 14 wt.% carrageenan, based on the total weight of the film-forming resin. For example, the water-soluble film can contain, from about 5 wt.% to about 14 wt.%, or about 7 wt.% to about 12 wt.%, or about 6 wt.%, or about 7 wt.%, or about 8 wt.%, or about 9 wt.%, about 10 wt.%, about 11 wt.%, about 12 wt.%, about 13 wt.%, or about 14 wt.% carrageenan, or any values therebetween or ranges defined by such values, based on the total weight of the film-forming resins. If the amount of carrageenan exceeds about 14 wt.%, mechanical properties of the film, such as elongation at break, can be affected and the films can be insufficiently water- soluble. If the amount of carrageenan is less than about 5 wt.%, benefits to film propertiesthat can be derived from the addition of carrageenan, including but not limited to high mechanical strength under high-humidity conditions, may be limited.Other Resins

[0041] The water-soluble film can further include one or more additional bio-based or naturally occurring polymers, including, but not limited to, guar gum, gum Acacia, xanthan gum, locust bean gum, celluloses, cellulose ethers, cellulose esters, cellulose amides, methylcelluloses, carboxymethylcelluloses and salts thereof, ethylcelluloses, hydroxyethyl celluloses, hydroxypropyl methylcelluloses, polyaminoacids, gelatins, dextrins, maltodextrins, pea protein, casein protein, copolymers of the foregoing, and combinations of any of the foregoing. Such polymers are commercially available from a variety of sources. When present in the film, the one or more additional bio-based or naturally occurring polymers can be present in an amount of up to about 50 wt.%, or up to about 40 wt.%, or up to about 30 wt.%, or about 20 wt.%, or up to about 10 wt.%, or up to about 5 wt.%, based on the total weight of the film.

[0042] The water-soluble film can further include one or more synthetic (i.e., not naturally occurring) polymers, including, but not limited to, polyvinyl alcohol (PVOH) homopolymers, PVOH copolymers, polyacrylates, polymethacrylates, polyacrylic acids and salts thereof, polymethacrylic acids and salts thereof, water-soluble acrylate copolymers, polyvinyl pyrrolidone, and polyethyleneimine. Yet other synthetic water-soluble polymers can include polyalkylene oxides (for instance, polyethylene oxide, also referred to as polyethylene glycol (PEG)), polyacrylamides, polyvinyl acetates, polycarboxylic acids and salts thereof, polyamides, copolymers of any of the foregoing, and combinations of any of the foregoing. Such synthetic polymers are commercially available from a variety of sources. When present in the film, the one or more synthetic polymers can be present in an amount of up to about 20 wt.%, or up to about 10 wt.%, or up to about 5 wt.%, based on the total weight of the film.

[0043] The water-soluble film can include bio-based polyvinyl alcohol. Bio-based polyvinyl alcohol includes polyvinyl alcohol in which at least a portion of the carbon comprising the polyvinyl alcohol is derived from biomass. In particular, bio-based polyvinyl alcohol can include polyvinyl alcohol produced by hydrolysis or saponification of bio-based polyvinyl acetate or of a blend of polyvinyl acetates that includes a bio-based polyvinyl acetate. In turn, bio-based polyvinyl acetate can include polyvinyl acetate produced by polymerizing a bio-based vinyl acetate or a blend of vinyl acetates that includes a bio-based vinyl acetate. In general, bio-based vinyl acetate includes vinyl acetate for which at least a portion of the carbon comprising the vinyl acetate is derived from biomass. Vinyl acetatecan be obtained, for instance, by a gas phase reaction of ethylene, acetic acid, and oxygen; bio-based vinyl acetate can refer to vinyl acetate for which at least a portion of the ethylene and / or acetic acid is derived from biomass. For instance, bio-based vinyl acetate includes vinyl acetate obtained by a reaction of ethylene, acetic acid, and oxygen in which at least a portion of the ethylene and / or at least a portion of the acetic acid is bio-based. Accordingly, bio-based polyvinyl alcohol includes polyvinyl alcohol in which a portion of the carbon comprising the polyvinyl alcohol is derived from bio-based ethylene and / or bio-based acetic acid.

[0044] Plants that can be a source of bio-based ethylene and / or bio-based acetic acid include, but are not limited to, potato, sweet potato, sugar beet, rice, wheat, palm oil, algae, corn, sugar cane, sorghum, and cassava. Similarly, bio-based acetic acid can be produced by a bioethanol route.

[0045] Bio-based polyvinyl alcohol can be characterized by a carbon-14 (14C) content. In general, biomass-derived resources have a greater abundance of14C (i.e., the amount of14C as a percent of total carbon content) relative to petroleum-derived resources. In particular, bio-based ethylene and acetic acid generally have higher abundances of14C relative to petroleum-derived ethylene and acetic acid, and in turn bio-based polyvinyl alcohol generally has a higher abundance of14C relative to polyvinyl alcohol that is completely petroleum- derived. Accordingly, the abundance of14C in a polymer, such as a polyvinyl alcohol resin, can serve as a marker of the polymer’s bio-based content. A material’s14C content can be measured by known means, for instance, by mass spectrometric methods.

[0046] The films of the disclosure can include bio-based polyvinyl alcohol, as described in U.S. Patent Application Publication No. 2023 / 0257491 A1 , U.S. Patent Application Publication No. 2023 / 0070770A1 , and International Patent Application Publication WO 2022 / 034906A1 , which are hereby incorporated by reference in their entirety. The polyvinyl alcohol resin comprising a film of the disclosure can comprise only petroleum-derived polyvinyl alcohol, or only bio-based polyvinyl alcohol, or a blend of petroleum-derived polyvinyl alcohol and bio-based polyvinyl alcohol. For a film comprising a blend of petroleum-derived (i.e., non-bio-based) polyvinyl alcohol and bio-based polyvinyl alcohol, the ratio of the amounts (by weight) of bio-based polyvinyl alcohol to non-bio-based polyvinyl alcohol is not particularly limited and can be, for instance, in a range of about 99:1 to about 1 :99, or about 95:5 to about 5:99, or about 80:20 to about 20:80, or about 70:30 to about 30:70, or about 60:40 to about 40:60.Cross-linkers

[0047] In a general sense, a cross-linker for a polymer is an additive that can form covalent or non-covalent bonds (i.e., cross-links) between polymer chains. Incorporating cross-links into the polymer or polymers comprising a polymer-based film by addition of a cross-linker can increase the effective polymer molecular weight and can affect film properties, including but not limited to mechanical properties and solubility. Some carrageenans are known to form cross-linked gels upon addition of a sufficient amount of one or more cations as cross-linkers, including but not limited to ammonium, sodium, potassium, or calcium. The properties of cross-linked gels formed by addition of a cation cross-linker to carrageenan depend on the type of carrageenan and the selection of crosslinkers. For instance, kappa-carrageenan forms stronger gels with potassium ion compared to calcium ion, and kappa-carrageenan gels tend to be brittle; iota-carrageenan forms stronger gels with calcium ion compared to potassium ion, and iota-carrageenan gels tend to be soft and elastic; and lambda carrageenan generally does not form cross-linked gels.

[0048] Films according to the disclosure can further comprise a cross-linker. The crosslinker can comprise one or more cations. Cations that promote gelation of one or more carrageenans, including but not limited to ammonium, sodium, potassium, and calcium, are contemplated as cross-linkers. In particular, metal ions are contemplated as cross-linkers; calcium ion is particularly contemplated. The cross-linker can be provided to the water- soluble film by, for instance, including a salt containing the cross-linker in the preparation of the water-soluble film, such as by adding the salt to a resin solution from which the water- soluble film is cast. Calcium chloride is particularly contemplated as a source of cross-linker. Potassium acetate is particularly contemplated as a source of cross-linker. A combination of a kappa-carrageenan with a potassium or calcium cross-linker is contemplated, e.g., a calcium cross-linker. A combination of an iota-carrageenan with a potassium or calcium cross-linker is contemplated, e.g., a calcium cross-linker. The cross-linker can be present in the film in a range of from about 0.001 wt.% to about 5.0 wt.%, or 0.01 wt.% to about 1 .0 wt.%, or about 0.02 wt.% to about 0.5 wt.%, or about 0.03 wt.% to about 0.3 wt.%, or about 0.05 wt.% to about 0.2 wt.%, based on the total weight of the film. The cross-linker can be present in the film in a range of from 0.001 PHR to about 7.0 PHR, or 0.01 PHR to about 1 , or about 0.1 PHR to about 6 PHR, or about 1 PHR to about 4 PHR, or about 2 PHR to about 3 PHR, or about 0.001 PHR to about 2.75 PHR, or about 0.01 PHR to about 2.5 PHR, or about 0.1 PHR to about 2 PHR, or any values therebetween or ranges defined by such values.Plasticizers

[0049] A plasticizer is a liquid, solid, or semi-solid that is added to a material (usually a resin or elastomer) making that material softer, more flexible (by decreasing the glasstransition temperature of the polymer), or easier to process. A polymer can alternatively be internally plasticized by chemically modifying the polymer or monomer. In addition, or in the alternative, a polymer can be externally plasticized by the addition of a suitable plasticizing agent. Water is recognized as an efficient plasticizer for many polymers; including but not limited to water-soluble polymers, however, the volatility of water limits its utility since polymer films generally need to have at least some resistance (robustness) to a variety of ambient conditions including low and high relative humidity.

[0050] The water-soluble film of the disclosure further comprises one or more plasticizers. The plasticizer can include, but is not limited to, sugar alcohols, polyols, and combinations thereof. For instance, the plasticizer can comprise glycerol, diglycerin, sorbitol, maltitol, monosaccharides, oligosaccharides, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols up to 400 Da molecular weight, hexylene glycol, neopentyl glycol, trimethylolpropane, polyether polyols, polyether diol, polyether triol, xylitol, 2-methyl-1 ,3-propanediol (MPD; MPDiol®), ethanolamines, glycerol propylene oxide polymers (such as, for example, Voranol™ available from The Dow Chemical Company), or a mixture thereof. Renewable or bio-based plasticizers are contemplated. Sorbitol, glycerol, and combinations thereof are particularly contemplated as plasticizers.

[0051] The total amount of non-water plasticizer can be in a range of about 10 wt.% to about 45 wt.%, or about 15 wt.% to about 35 wt.%, or about 20 wt.% to about 30 wt.%, or about 20 wt.% to about 45 wt.%, for example about 25 wt.%, based on total film weight. The amount of plasticizer can also be characterized in terms of PHR, and the total amount of non-water plasticizer can be at least 20 PHR, or at least about 30 PHR, or at least about 40 PHR, or in a range of about 10 to about 75 PHR, or about 15 to about 60 PHR, or about 20 to about 50 PHR, or about 25 to about 45 PHR, or about 20 to about 40 PHR, or about 30 to about 40 PHR. Specific amounts of plasticizers can be selected in a particular embodiment based on factors described herein, including desired film flexibility and conversion features of the water-soluble film. At low plasticizer levels, films may become brittle, difficult to process, or prone to breaking. At elevated plasticizer levels, films may be too soft, weak, or difficult to process for a desired use.Moderate Molecular Weight Polyalkylene Oxide

[0052] The water-soluble film can optionally include a moderate molecular weight polyalkylene oxide. As used herein, a “moderate molecular weight polyalkylene oxide” refers to a polyalkylene oxide having a molecular weight in a range of about 1000 to 20,000 Da, for example, about 1000 to about 19,000 Da, about 1000 to about 18,000 Da, about 1000 toabout 17,000 Da, about 1000 to about 16,000 Da, about 1000 to about 15,000 Da, about 1000 to about 14,000 Da, about 1000 to about 13,000 Da, about 1000 to about 12,000 Da, about 1000 to about 11 ,000 Da about 1000 to about 10,000 Da, about 1000 to about 9,000 Da, about 1000 to about 8,000 Da, about 1000 to about 7,000 Da, about 1000 to about 6,000 Da about 1000 to about 5,000 Da, about 1000 to about 4,000 Da, about 1000 to about 3,000 Da, about 1000 to about 2000 Da, or about 1500 Da. The moderate molecular weight polyalkylene oxide can be included in the film in any amount suitable to reduce the maximum blocking force and / or increase the strain at break of the film, relative to an identical film that does not include any moderate molecular weight polyalkylene oxide. The moderate molecular weight polyalkylene oxide can be included in the film in an amount in a range of about 0.25 PHR to about 25 PHR, for example, about 0.5 PHR to about 22 PHR, about 0.7 PHR to about 20 PHR, about 1 PHR to about 15 PHR, about 1 PHR to about 14 PHR, about 1 PHR to about 13 PHR, about 1 PHR to about 12 PHR, about 2 PHR to about 10 PHR, about 2 PHR to about 6 PHR, or about 4 PHR. The polyalkylene oxide can be a polyethylene oxide, also referred to herein as polyethylene glycol (PEG). Renewable or biobased polyalkylene oxides are contemplated.Auxiliary Agents

[0053] The water-soluble film can optionally contain other auxiliary agents and processing agents, including, but not limited to, surfactants, lubricants, release agents, fillers, extenders, antiblocking agents, detackifying agents, anti-foams (defoamers), nanoparticles such as layered silicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfate, or others), aversive agents such as bitterants (e.g., denatonium salts such as denatonium benzoate, denatonium saccharide, and denatonium chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and naringenin; and quassinoids such as quassin and brucine) and pungents (e.g., capsaicin, piperine, allyl isothiocyanate, and resinferatoxin), and other functional ingredients, in amounts suitable for their intended purposes. For example, the film can include a filler, a surfactant, an anti-block agent, or a combination of any or all of the foregoing. Renewable or bio-based fillers, surfactants, and anti-block agents are contemplated.

[0054] Surfactants for use in water-soluble films are well known in the art. Optionally, surfactants are included to aid in the dispersion of the resin solution upon casting. Suitable surfactants for the film of the present disclosure include, but are not limited to, propylene glycols, diethylene glycols, monoethanolamine, polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides (nonionics), polyoxyethylenated amines, quaternary ammonium salts and quaternized polyoxyethylenated amines (cationics), alkali metal salts of higher fatty acidscontaining about 8 to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylate sulfates and alkylbenzene sulfonates (anionics), and amine oxides, N-alkylbetaines and sulfobetaines (zwitterionics), dialkyl sulfosuccinates, lactylated fatty acid esters of glycerol and propylene glycol, lactylic esters of fatty acids, sodium alkyl sulfates, polysorbate esters (e.g., Tween® surfactants), polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, sorbitan esters (e.g., Span™ surfactants), sorbitan monostearate, sorbitan tristearate, sorbitan monolaurate, alkyl polyethylene glycol ethers, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, sodium lauryl sulfate, acetylated esters of fatty acids, myristyl dimethylamine oxide, trimethyl tallow alkyl ammonium chloride, quaternary ammonium compounds, salts thereof and combinations of any of the foregoing.

[0055] The amount of surfactant in the water-soluble film can be in a range of about 0.1 wt.% to about 8.0 wt.%, or about 1 .0 wt.% to about 7.0 wt.%, or about 3.0 wt.% to about 7.0 wt.%, or about 5.0 wt.% to about 7.0 wt.%, or about 0.1 wt.% to 2.5 wt.%. Too little surfactant can sometimes result in a film having holes, whereas too much surfactant can result in the film having a greasy or oily feel from excess surfactant present on the surface of the film.

[0056] Defoamers can aid in coalescing of foam bubbles. Suitable defoamers for use in films according to the present disclosure include, but are not limited to, hydrophobic silicas, for example silicon dioxide or fumed silica in fine particle sizes, including Foam Blast® defoamers available from Emerald Performance Materials, including Foam Blast® 327, Foam Blast® UVD, Foam Blast® 163, Foam Blast® 269, Foam Blast® 338, Foam Blast® 290, Foam Blast® 332, Foam Blast® 349, Foam Blast® 550 and Foam Blast® 339, which are proprietary, non-mineral oil defoamers. Other suitable silicon-based defoamers include Foam-a-Tac® defoamers, available from Enterprise Specialty Products. Other suitable defoamers can include non-silicon-based defoamers, including but not limited to Antifoam HL23, Antifoam HL27, Antifoam HL36, Antifoam HL40, Antifoam HL52, and Antifoam HL550, available from Harcros Chemicals. Optionally, defoamers can be used in an amount of 0.5 PHR or less, or 0.5 PHR to 0.01 PHR, for example, 0.3 PHR, 0.2 PHR, 0.1 PHR, 0.05 PHR, 0.04 PHR, 0.03 PHR, 0.02 PHR, or 0.01 PHR.

[0057] Suitable fillers, extenders, and detackifying agents can include, but are not limited to, starches, modified starches, crosslinked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose, silica, metallic oxides, calcium carbonate, talc, mica, and stearic acid and metal salts thereof, for example, magnesium stearate. Particularly contemplated fillers include starches and modified starches (for example, high amylose starch, amorphous silica, hydroxyethylated starch), silica, talc, or a combination thereof.

[0058] Fillers comprising a water-soluble film of the disclosure can include one or more anti-block agents. Silica is particularly contemplated as an anti-block agent. Clays and clay minerals, such as kaolinite, are particularly contemplated as anti-block agents. An anti-block agent can be present in an amount sufficient to reduce the strength of adhesion between two film surfaces. Anti-block agents can be present in an amount of at least 0.1 PHR, or at least 0.5 PHR, or at least 1 PHR, or in a range of about 0.1 to about 8.0 PHR, or about 0.1 PHR to about 6.0 PHR, or about 0.1 to about 5.0 PHR, or about 0.1 to about 3.0 PHR, or about 0.4 to 1 .0 PHR, or about 0.5 to about 0.9 PHR, or about 0.5 to about 2 PHR, or about 0.5 to about 1 .5 PHR, or about 0.1 to about 1 .2 PHR, or about 0.1 to about 0.7 PHR, for example about 0.5 PHR, 0.6 PHR, 0.7 PHR, 0.8 PHR, or 0.9 PHR.

[0059] Aversive agents can be incorporated within the film or may be applied as a coating to the film. The aversive agent may be added in an amount to cause an aversive response, such as bitterness, diluted from its commercial form or otherwise mixed with a solvent for ease in mixing with other water-soluble film components or applying as a coating to the water-soluble film. Such solvents may be selected from water, low molecular weight alcohols such as methanol or ethanol, or plasticizers disclosed herein.

[0060] The anti-block agent can have a median size in a range of about 3 to about 35 microns, or about 3 to about 25 microns, or about 25 microns to about 35 microns, or about 3 to about 11 microns, or about 4 to about 8 microns, or about 5 to about 6 microns, for example 5, 6, 7, or 8 microns. A suitable silica is an untreated synthetic amorphous silica designed for use in aqueous systems.

[0061] Polyalkylene oxides and particularly, polyethylene glycols are also contemplated as anti-block agents. Polyethylene glycols having an average molecular weight of greater than about 1000 Da, or greater than about 1 ,500 Da, or greater than about 2,000 Da, are particularly contemplated, and up to about 10,000 Da, or 8,000 Da, or 6,000 Da, or 5,000 Da, or 4,000 Da, or 3,000 Da.Film Properties

[0062] The water-soluble film of the disclosure can be characterized by a disintegration time, as determined in accordance with MonoSol Test Method MSTM-205, as described herein. For example, the film, when provided at a thickness of about 88 microns, can have a disintegration time in a range of about 10 seconds to 150 seconds, or about 20 seconds to about 100 seconds, or about 30 seconds to 50 seconds.

[0063] The water-soluble film of the disclosure can further be characterized by a dissolution time, as determined in accordance with MonoSol Test Method MSTM-205, as described herein. For example, the film, when provided at a thickness of about 88 microns,can have a dissolution time in a range of about 10 to about 300 seconds, or about 10 to about 200 seconds, or about 10 to about 100 seconds.

[0064] The water-soluble film of the disclosure can further be characterized by a tensile strength, as determined according to the Tensile Strength Test described herein. For example, the film, after being conditioned for at least 18 hours at 28 °C / 50% relative humidity (RH), can have a tensile strength in a range of about 10 N / mm2(MPa) to about 50 N / mm2, or about 10 N / mm2to about 40 N / mm2, or about 15 N / mm2to about 30 N / mm2, or about 20 N / mm2to 30 N / mm2. Alternatively, the film, after being conditioned for at least 18 hours at 28 °C / 65% RH, can have a is tensile strength in a range of about 5 N / mm2to about 20 N / mm2, or about 5 N / mm2to 15 N / mm2, or about 10 N / mm2to about 15 N / mm2. Generally, higher tensile strength values are desirable because they correspond to stronger pouches with less tendency to rupture.

[0065] The water-soluble film of the disclosure can further be characterized by a Young’s modulus, as determined according to the Tensile Strength Test described herein. For example, the film, after being conditioned for at least 18 hours at 28<€ / 50% RH, can have a Young’s modulus in a range of about 20 N / mm2to about 300 N / mm2, or about 30 N / mm2to about 200 N / mm2, or about 50 N / mm2to about 100 N / mm2. Alternatively, the film, after being conditioned for at least 18 hours at 28qC / 65% RH, can have a Young’s modulus in a range of about 10 N / mm2to about 100 N / mm2, or about 20 N / mm2to about 50 N / mm2. Generally, Young’s modulus is a measure of the stiffness of the film, with higher Young’s modulus indicating increased stiffness.

[0066] The water-soluble film of the disclosure can be further characterized by an elongation at break (i.e., strain at break), as determined according to the Elongation at Break Test described herein. For example, the film, after being conditioned for at least 18 hours at 28qC / 50% RH, can have a strain at break in a range of about 50% to about 400%, or about 50% to about 300%, or about 80% to about 200%. Alternatively, the film, after being conditioned for at least 18 hours at 28 °C / 65% RH, can have a strain at break in a range of about 50% to about 500%, or about 80% to about 300%, or about 100% to about 250%, or about 125% to about 200%.

[0067] Generally, the tensile strength, break strain and Young’s modulus of a film can be adjusted by one or more of (1 ) modifying the absolute and / or relative amounts of the components of the film forming resin; (2) including one or more additional film-forming resins as described herein; (3) modifying the amount of plasticizers in the film; (4) modifying the type of plasticizers in the film; (5) modifying the water content of the film, and (6) modifying the thickness of the film.

[0068] The water-soluble film of the disclosure can further be characterized by a seal strength, as determined according to the Seal Strength Test described herein. For example, the film can have a seal strength of about 5 newtons (N) or more, or about 10 N or more, or about 12 N, or more, or about 15 N or more, or in a range of about 5 N to about 30 N, or about 10 N to about 25 N, or about 12 N to about 20 N, or about 15 N to about 20 N.

[0069] The water-soluble film of the disclosure can further be characterized by a blocking force, as determined according to the Blocking Test described herein. For example, the film can have a blocking force of less than about 30 N, or less than about 20 N, or less than about 12 N, or less than about 10 N, or less than about 5 N, or less than about 3 N, or less than about 1 N. Blocking behavior of water-soluble films according to the disclosure can be marked by blocking force values of less than about 10 N, or less than about 5 N, or less than about 3 N, or less than about 1 N, or less than about.Fibers

[0070] Compositions described herein for the films of the disclosure can be used as compositions of fibers.

[0071] Fibers having the same composition as films of the disclosure are also contemplated. Such fibers can comprise the film-forming material including pullulan and pectin, and a plasticizer, as described herein. The fibers can include any of the secondary ingredients disclosed herein for the films of the disclosure. For example, fibers can comprise surfactants, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, antifoams, nanoparticles such as layered silicate- type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite or others), aversive agents such as bitterants, pungents, or combinations of any of the foregoing, in amounts suitable for their intended purposes.

[0072] Methods of making fibers are known in the art. For instance, U.S. Patent Application Publication No. 2022 / 0228305A1 describes wet cooled gel spinning, thermoplastic fiber spinning, and melt spinning methods for preparing fibers containing a water-soluble polymer or blend of water-soluble polymers. Such methods are generally suitable for making fibers according to the disclosure.

[0073] Fibers of the disclosure can be used as components of a nonwoven web comprising a plurality of fibers. A nonwoven web generally refers to an arrangement of fibers bonded to one another, wherein the fibers are neither woven nor knitted. In general, the plurality of fibers can be arranged in any orientation. The plurality of fibers can be arranged randomly (i.e., without having an orientation). The plurality of fibers can be arranged in a unidirectional orientation. The plurality of fibers can be arranged in abidirectional orientation. The plurality of fibers can be multi-directional, having different arrangements in different areas of the nonwoven web.

[0074] The disclosure provides a unit dose article comprising at least one compartment and optionally a composition housed in the compartment, wherein at least one wall of the compartment comprises a non-woven web of the disclosure. The composition housed in the compartment can be any composition disclosed herein.Water-Soluble Articles

[0075] The water-soluble film disclosed herein is useful for creating a sealed article in the form of a pouch defining an interior pouch volume to contain a composition therein for release into an aqueous environment. A “sealed article” optionally encompasses sealed compartments having a vent hole, for example, in embodiments wherein the compartment encloses a solid that off-gasses, but more commonly will be a completely sealed compartment.

[0076] The pouch may comprise a single compartment or multiple compartments. A water-soluble pouch can be formed from two layers of water-soluble polymer film sealed at an interface, or by a single film that is folded upon itself and sealed. The film forms at least one side wall of the pouch, optionally the entire pouch, and preferably an outer surface of the at least one sidewall. In another type of embodiment, the film forms an inner wall of the packet, e.g., as a dividing wall between compartments.

[0077] The disclosure further provides a water-soluble article in the form of a packet comprising a sealed compartment, the article comprising a first water-soluble film and a second water-soluble film, wherein the first water-soluble film is a water-soluble film according to the disclosure and the first water-soluble film is sealed to the second water- soluble film to form the sealed compartment. The second water-soluble film can have the same composition as the first water-soluble film. The second water-soluble film can have a different composition as the first water-soluble film. The article can comprise a composition contained in the sealed compartment. The composition can comprise any composition disclosed herein. The composition can comprise a household care composition. The composition can comprise a non-household care composition.

[0078] The water-soluble films, nonwovens, and articles can comprise a printed area. The area of print can be achieved using standard techniques, e.g., flexographic printing or inkjet printing.Sealed Articles

[0079] The water-soluble unit dose article can be heat sealed or solution sealed by any suitable process and apparatus, such as those already well-known in the art for sealing other water-soluble films, or readily adapted therefrom with only routine experimentation. For example, the water-soluble unit dose articles can be heat sealed on three sides. For example, the water-soluble film can be folded over onto itself and sealed on the edge opposite the fold and along one of the two remaining open edges with a heat impulse sealer, to provide a pouch of desired dimensions. A liquid composition (e.g., a household care composition) can be filled into the pouch using an injection system such as a pump or a syringe. In other embodiments, the water-soluble film can be stretched over a cavity of a specified dimension, and heat and a vacuum can be applied to thermoform the film into the shape of the cavity. The cavity can be then filled with the desired composition (e.g., a household care composition). The filled pouch can then be sealed with a second film. The second film can be pulled over the top of the cavity, and the side of the second film facing the filled pouch can be wetted for solution sealing. The second film can have the same composition of the film from which the cavity is formed (i.e., the first film), or the second film can have a composition that differs from that of the first film. Pressure can be applied, and the filled pouch can be bonded to the second film around the shaped cavity to form an encapsulated composition in a water-soluble unit dose article. The solution sealing can be achieved using a Mespack-Cloud sample machine, or the like, for example.

[0080] Films of the disclosure can be heat-sealed, for instance, according to the following method:1 . Condition the film to be sealed at 28 °C,l5G° / o RH for 24 hrs.2. Using a TS-12 heat sealer (or equivalent), select the sealing temperature and sealing time and allow the heat sealer to reach the target temperature.3. Cut tensile strips from the film. Place two strips on top of one another.4. Place the strips on a rubber platform and insert them into the TS-12 heat sealer.5. Begin sealing the films by stepping on the pedal below the machine and hold for the designated sealing time.6. Remove the sealed strips from the machine and repeat as desired, for instance for at least three replicate samples.7. Allow the seal at least 10 minutes to cool down. Take notice of the seal area of the film. If the film has begun to bubble, the temperature may be too high, or the sealing time may be too long.

[0081] The composition enclosed in the pouch is not particularly limited, for example including any of the variety of compositions described herein. In embodiments comprising multiple compartments, each compartment may contain identical and / or different compositions. In turn, the compositions may take any suitable form including, but not limited to liquid, solid, gel, paste, mull, pressed solids (tablets) and combinations thereof (e.g., a solid suspended in a liquid). In embodiments, the pouches comprise a first, second, and third compartment, each of which respectively contains a different first, second, and third composition.Article and / or Pouch Contents

[0082] In any embodiment, the water-soluble pouch can contain (enclose) a composition. The composition can be selected from a liquid, solid, or combination thereof. As used herein, “liquid” includes free-flowing liquids, as well as pastes, gels, foams and mousses. Non-limiting examples of liquids include light duty and heavy duty liquid detergent compositions, fabric enhancers, detergent gels commonly used for laundry, bleach and laundry additives. Non-limiting examples of liquids include agricultural compositions, automotive compositions, aviation compositions, food and nutritive compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, mercantile compositions, military and quasi-military compositions, office compositions, and recreational and park compositions, pet compositions, water-treatment compositions, including cleaning and detergent compositions applicable to any such use. Gases, e.g., suspended bubbles, or solids, e.g., particles, may be included within the liquids. A “solid” as used herein includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include granules, micro-capsules, beads, noodles, and pearlized balls. Solid compositions may provide a technical benefit including, but not limited to, through-the-wash benefits, pre-treatment benefits, and / or aesthetic effects.

[0083] In embodiments, the water-soluble unit dose article can comprise a household care composition. The household care composition can be selected from light duty liquid detergent compositions, heavy duty liquid detergent compositions, hard surface cleaning compositions, laundry detergent gels, bleaching compositions, laundry additives, fabric enhancer compositions, shampoos, body washes, other personal care compositions, and combinations thereof, optionally a liquid laundry detergent composition.

[0084] In another aspect of the disclosure, the household care composition can be selected from the group of laundry and automatic dishwashing compositions, including liquid laundry detergent compositions.

[0085] In another aspect of the disclosure, the household care composition can be selected from non-laundry and non-automatic dishwashing compositions, e.g., selected from light duty liquid detergent compositions, heavy duty liquid detergent compositions, hard surface cleaning compositions, bleaching compositions, shampoos, body washes, other personal care compositions, and other compositions which are non-laundry and nonautomatic dishwashing compositions, or mixtures of any of the foregoing.

[0086] The term ‘liquid laundry detergent composition’ refers to any laundry detergent composition comprising a liquid capable of wetting and treating a fabric, and includes, but is not limited to, liquids, gels, pastes, dispersions and the like. The liquid composition can include solids or gases in suitably subdivided form, but the liquid composition excludes forms which are non-fluid overall, such as tablets or granules.

[0087] The liquid detergent composition can be used in a fabric hand wash operation or may be used in an automatic machine fabric wash operation.

[0088] The European Commission Regulation No. 1297 / 2014 of 5 December 2014 amended, for the purposes of its adaptation to technical and scientific progress, Regulation (EC) No. 1272 / 2008 of the European Parliament and of the Council on classification, labelling and packaging of substances and mixtures to require additional provisions for liquid consumer laundry detergent in dosages for single use contained in a soluble packaging. Among those provisions were the requirements that the soluble packaging shall retain its liquid content for at least 30 seconds when the soluble packaging is placed in water at 20 °C. Accordingly, a liquid laundry detergent pouch according to the disclosure herein optionally is designed to retain its liquid content for at least 30 seconds when the soluble packaging is placed in water at 20 °C and rapidly and completely dissolve thereafter.

[0089] In other aspects, the household care composition may be an automatic dish washing detergent composition comprising an ingredient selected from surfactant, builder, sulfonated / carboxylated polymer, silicone suds suppressor, silicate, metal and / or glass care agent, enzyme, bleach, bleach activator, bleach catalyst, source of alkalinity, perfume, dye, solvent, filler, and mixtures thereof.

[0090] In other embodiments, the water-soluble unit dose article can comprise a nonhousehold care composition. The 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-military compositions, office compositions, recreational and park compositions, pet compositions, a pool and / or water-treatmentcomposition, and a combination thereof. In embodiments, the non-household care composition is a pool and / or water-treatment composition.

[0091] The composition contained in the water-soluble pouch, whether a household care composition or a non-household care composition, can contain water. For example, the composition can contain water in an amount of about 1 wt.% to about 15 wt.%, or about 3 wt.% to about 15 wt.%, or about 5 wt.% to about 15 wt.%, or about 10 wt.% to about 15 wt.%, based on the total weight of the composition.

[0092] In embodiments, the water-soluble unit dose article can be provided in any dimension suitable to fit through the neck of a trigger spray bottle (e.g., a spray bottle with a screw top neck having about a 28 mm diameter). The water-soluble unit dose article optionally can have a length of about 250 mm or less, or in a range of about 5 mm to about 250 mm, about 10 mm to about 250 mm, about 25 mm to about 250 mm, about 50 mm to about 225 mm, about 100 mm to about 225 mm, about 150 to about 225 mm, about 175 mm to about 225 mm, or about 200 mm. The water-soluble unit dose article optionally can have a width of about 50 mm or less, or in a range of about 2 mm to about 50 mm, about 5 mm to about 45 mm, about 10 mm to about 40 mm, about 15 mm to about 35 mm, or about 20 mm to about 30 mm. The water-soluble unit dose article can have a length of about 175 mm to about 225 mm, or about 200 mm and a width of about 20 mm to about 30 mm, or about 25 mm. In embodiments wherein the water-soluble unit dose article is provided to fit through the neck of a trigger spray bottle, the water-soluble unit dose article optionally comprises a household care composition having a pH of less than or equal to 2.

[0093] Fabric and home care products are optionally used or consumed in the form in which they are sold and are for treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care including air fresheners and scent delivery systems, car care, dishwashing, fabric conditioning (including softening and / or freshening), laundry detergency, laundry and rinse additive and / or care, hard surface cleaning and / or treatment including floor and toilet bowl cleaners, and other cleaning for fabric or home use.

[0094] Cleaning and / or treatment compositions include, but are not limited to, products for treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care including air fresheners and scent delivery systems, car care, dishwashing, fabric conditioning (including softening and / or freshening), laundry detergency, laundry and rinse additive and / or care, hard surface cleaning and / or treatment including floor and toilet bowl cleaners, granular or powder-form all- purpose or "heavy-duty" washing agents, especially cleaning detergents; liquid, gel or paste- form all-purpose washing agents, especially the so-called heavy-duty liquid types; liquid fine-fabric detergents; handdishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents, including the various tablet, granular, liquid and rinse-aid types for fabric and household use: car or carpet shampoos, bathroom cleaners including toilet bowl cleaners; as well as cleaning auxiliaries such as bleach additives and "stain-stick" or pre-treat types, substrate-laden products such as dryer added sheets.

[0095] Fabric and / or hard surface cleaning and / or treatment compositions include, unless otherwise indicated, granular or powder-form all-purpose or "heavy-duty" washing agents, especially cleaning detergents; liquid, gel or paste-form all-purpose washing agents, especially the so- called heavy-duty liquid types; liquid fine-fabric detergents; hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents, including the various tablet, granular, liquid and rinse-aid types for household and institutional use; liquid cleaning and disinfecting agents, car or carpet shampoos, bathroom cleaners including toilet bowl cleaners; fabric conditioning products including softening and / or freshening that may be in liquid, solid and / or dryer sheet form; as well as cleaning auxiliaries such as bleach additives and "stain-stick" or pre-treat types, substrate-laden products such as dryer added sheets. All of such products which are applicable may be in standard, concentrated or even highly concentrated form even to the extent that such products may in certain aspects be non-aqueous.

[0096] Further provided herein is a water-soluble unit dose article comprising a packet comprising an outer wall, the outer wall having an exterior surface and an interior surface defining an interior pouch volume, the outer wall comprising a water-soluble film according to the disclosure herein and optionally a composition contained in the interior pouch volume.

[0097] Further provided herein is a process for dosing a composition of bulk water comprising the steps of contacting with bulk water a water-soluble unit dose article as described herein, thereby dissolving at least a portion of the water-soluble film, and releasing the composition to the bulk water.

[0098] In general, the bulk water can be any bulk water which requires or benefits from a household care or non-household care composition provided therein. For example, the bulk water can be a pool or a spa. In general, the temperature of the bulk water can be any temperature sufficient to dissolve or disintegrate at least a portion of the water-soluble film. In embodiments, the bulk water has a temperature of at least about 10 °C, for example, in a range of about 10 °C to about 100 °C, about 10 °C to about 70 °C, about 10 °C to about 60 °C, about 20 °C to about 50 °C, or about 20 °C to about 40 °C. In general, the bulk water can be characterized by any pH value. For example, the pH of the bulk water can be in a range of about 4 to about 10, about 5 to about 9, or about 6 to about 7.

[0099] Edible water-soluble films of the disclosure can be used for the packaging of food products and / or beverage components, including, but not limited to convenience foods, condiments, preservatives, food manufacturing ingredients, and the like. Edible water- soluble films can be in the form of a pouch or sachet defining an interior pouch volume. Food products and / or beverage components can be enclosed in the interior pouch volume of the pouch or sachet prepared from one or more water-soluble films of the disclosure.

[0100] Disclosed herein are packaged food products, including instant food products, and methods of preparing such products for human and / or animal consumption. In general, the packaged food products according to the present disclosure include a cooking container having a sealed interior volume and containing at least two food products capable of being sealed. One of the food products may be a dehydrated food product, such as instant noodles or instant rice, which can be regenerated relatively quickly (e.g., within a few minutes or seconds) by the addition of a fluid such as hot or boiling water or even cold or room temperature water. The other food product may be a flavoring agent, such as seasonings, that modifies the taste of the dehydrated food product and / or a cooking agent, such as oil or butter, that modifies the cooking properties of the dehydrated food product. To keep the food products separate from each other during storage and distribution, the flavoring and / or cooking agent may be encapsulated within a packet until the point of use. Another example could be in beverage segment, where the container / cup has packets or compartments of various ingredients like coffee, milk granules, flavoring agents, spices etc. The ingredient packets could be made from different water soluble films of different barrier properties. The hot or cold liquid (water or creams or milks) dispensed through this cup or container dissolves the packets, releases the contents and extracts the ingredients to dispense beverage that is ready to use or use with additional ingredients. The packet may be made of water-soluble material so that the packet dissolves and releases its contents when water is added to the cooking container. This alleviates the consumer from having to cut or tear open the packet, thereby improving convenience to the consumer and reducing the likelihood that the packet contents are spilled outside the packaged product. In addition to being water- soluble, the packet material may be edible, and even flavorless (at least to humans), so that the packet has little or no impact on the taste of the cooked food product. Furthermore, the packet may be positioned between the dehydrated food product and a bottom of the container so that the packet is obscured from view. Arranging the packet out of sight reduces the likelihood that consumers will attempt to unnecessarily tear or cut open the packet.

[0101] Food products and / or beverage components can include, but are not limited to, beverage mixes such as energy drink powders, hydration drink powders, sports drink powders / concentrates, protein powders, hot cocoa, tea concentrate, tea leaves, mocha, fruitdrink concentrate, and coffee, chicory, flavor and texture enhancers such as refresh concentrates (e.g., fruit tea), flavor boosters, color boosters, texture boosters, freeze dried fruit, and protein shakes, food supplements such as fiber supplements and natural food supplements, dairy products, (e.g., cream), deli products, meat products (e.g., sausage), convenience foods such as instant noodle spice packs, soup concentrates, bakery items, and candy, condiments and preservatives such as kimchi, pickles, salsa, tomato paste, various spices (e.g., taco powder, dry pepper, pepper paste, soybean paste), milk powder, broth (liquid or solid forms, and as concentrates), and food manufacturing ingredients such as basic ingredients (e.g., yeast, salt, spices, food coloring, texture modifiers, flour, sugar, milk powder), egg products (e.g., liquid eggs, egg whites, or egg yolks), and additional ingredients (e.g., cream, gelatin, fruit fillings, broth (liquid or solid), tomato paste, dry pepper, pepper paste, or soybean paste).

[0102] The water-soluble films and nonwovens of the disclosure can be used to form a laundry sheet. The laundry sheet can include one or more layers of water-soluble films or nonwovens of the disclosure. The laundry sheet can include one or more layers of water- soluble films or nonwovens of the disclosure and one or more layers of a known water- soluble or water-dispersible film or nonwoven. The laundry sheet can further include laundry additives, such as detergents, bleaches, bleach components, and the like as disclosed herein.

[0103] The water-soluble films and nonwovens of the disclosure can be used to form various cosmetics masks including, a facial mask, e.g., a sheet shaped to conform to a human face. The mask may contain various active formulations to moisturize, reduce wrinkles etc. The facial mask delivers the actives to target organs and may degrade and dissolve over time with use. Water may be applied to the facial mask prior to application to the face. The facial mask can include one or more personal care compositions.

[0104] The water-soluble films of the disclosure can be used for packaging of animal feed, animal nutraceuticals, and animal medicines. Such compositions can be packaged in a single or multicomponent package. For example, a multicomponent package can be used to separate different types of foods, nutraceuticals, and / or medicines that may benefit from being physically separated prior to the point of use, e.g., for stability purposes. The films used in such packages can optionally include taste enhancers (sugar, salt, etc.), as a part of the film itself or a coating thereon or may be provided in a second layer of film layered or coextruded with the film. Such packaging of animal feed, nutraceuticals, and / or medicines can allow dosed consumption of required actives.

[0105] The water-soluble films of the disclosure can also include an active agent. The active agent can be incorporated in the film, for example, as a formulation component within the film or by coating the film with an active composition, or coextrusion, forming a dual or multilayer film that includes the active within a film (having the same or different composition). For example, a film of the disclosure or a water-soluble packet formed from a film of the disclosure may be coated by a powder including a mixture of a powdered lubricant and an active agent. The active agent can be selected from the group consisting of enzymes, oils, flavors, colorants, odor absorbers, pesticides, fertilizers, activators, acid catalysts, metal catalysts, ion scavengers, bleaches, bleach components, fabric softeners, a fragrance, taste enhancers (sugar, spice, salt etc.), vitamins, nutraceuticals, medicines or a combination thereof. The active agent can be microencapsulated. The active agent can be provided as part of an active composition, including a mixture of the active agent and a powdered lubricant. Suitable active agents, materials for microcapsules, and powdered lubricants can be any of those disclosed in U.S. 11 ,753,222B2, herein incorporated by reference in the entirety.Method of Making Films

[0106] Processes for producing water-soluble films by solution casting are well-known in the art. Typically, polymers and secondary additives are dissolved in a solvent, typically water, and the solution is metered onto a casting surface and allowed to substantially dry, or force-dried with heated air, to form a cast film. The resulting cast film is removed from the casting surface and optionally wound onto a roller. The process can be performed batchwise and is more efficiently performed in a continuous process. The polymers and secondary additives dissolved in the solvent can be virgin materials, i.e., not previously used to prepare a water-soluble film, and / or trim materials. Trim materials refer to left over film material (“trim”) collected during the film making process and / or pouch making process, for example, material that is trimmed off a cast film to ensure consistent sizing for rolling and / or material that is trimmed off a pouch or packet after the pouch or packet has been sealed. Films can be prepared from trim materials, virgin materials, or a combination of trim and virgin materials.

[0107] In the formation of continuous film webs, it is the conventional practice to meter a solution of the resin and secondary components onto a moving casting surface, for example, a continuously moving metal drum or belt, then allowing, or causing the solvent to be substantially removed from the liquid, whereby a self-supporting cast film is formed, and then stripping the resulting cast film from the casting surface. The solution can optionally be metered or coated onto a carrier film, release liner, or removable backing, whereby after solvent removal, the resulting cast film or coating can be separated from the carrier film,release liner, or removable backing (for example, immediately upon drying or at a later point in time, e.g., prior to use) or remain attached to the carrier film, release liner, or removable backing. A film or coating prepared on a carrier film, release liner, or removable backing can be self-supporting or non-self-supporting. Such carrier films, release liners, and removable backings can be made from various materials as is known in the art, e.g., polyethylene, polyethylene oxides, polyethylene terephthalates, polyolefins, oriented polypropylene, polytetrafluoroethylene, polyvinyl chlorides, and crosslinked polyvinyl alcohols.

[0108] In general, the casting surface can be any suitable substrate for producing polymeric films known to one of skill in the art. In embodiments, the substrate can be a casting roller or drum, a casting belt, or a combination thereof. As used herein, the substrate is used for producing a polymer film from one or more polymer resins or polymer resin solutions. The substrate comprises a substrate surface and the substrate surface can be coated with a release coating. The polymer resin solutions can be cast onto a substrate while the substrate is moving, e.g., rotating. In embodiments, the substrate is a casting drum. In embodiments, the substrate is a casting belt. The substrate can comprise stainless steel and optionally can have a stainless-steel surface. The substrate can comprise stainless steel that is optionally plated, e.g., chrome plated, nickel plated, zinc plated or a combination thereof.

[0109] A film according to the disclosure herein can be produced using a solvent band casting system. The system can include tanks for mixing and / or storing a water-soluble resin solution, having optional secondary additives, for use with a band casting machine having at least a first and a second rotating drum about which a casting surface is tensioned to travel with the rotation of the drums. A drying chamber, enclosing at least a portion of the casting surface downline of the die, is used to remove solvent from the solution composition as it travels in a thin sheet on the casting surface.

[0110] In addition, a release coating can be applied to the casting surface to provide one or more advantages to the film and / or the process. For example, the release coating can substantially reduce or eliminate bubbles in the produced film, or the release coating can improve the ease of release of the produced film from the casting surface. A roll coater release coating applicator in communication with a supply of a release coating and a portion of the band can transfer fluid release coating to the casting surface prior to application of the resin solutions to the band. A suitable solvent band casting system and related materials are further described in U.S. Patent Application Publication Nos. 2006 / 0081176 A1 and 2007 / 0085234 A1 , the disclosures of which are incorporated herein by reference in their entireties.

[0111] In general, the release coating can comprise one or more surfactants and an optional carrier, e.g., water. The release coating can comprise one or more surfactants, e.g., selected from a fluorosurfactant, a non-fluorinated anionic surfactant, a non-fluorinated zwitterionic surfactant, salts thereof, or any combination thereof. In embodiments, the anionic or zwitterionic surfactant(s) can be non-fluorinated and comprise a C6-C30 phosphate ester, a C6-C30 phosphate diester, a C6-C30 carboxylate, a C6-C30 dicarboxylate, a C6-C30 sulfate, a C6-C30 disulfate, or salts thereof. In embodiments, the release coating comprises a non-fluorinated zwitterionic surfactant or salts thereof. In embodiments, the release coating comprises a non-fluorinated anionic surfactant or salts thereof. In embodiments, the non- fluorinated anionic surfactant comprises a C6-C30 phosphate ester, or a Cs-Ci6 phosphate ester, Ce-Ceo phosphate diester, C16-C32 phosphate diester, a C6-C30 carboxylate, a C6-C30 dicarboxylate, a C6-C30 sulfate, a C6-C30 disulfate, or salts thereof. In embodiments, the non- fluorinated anionic surfactant comprises a C6-C30 phosphate ester, or a Ce-C phosphate ester, Ce-Ceo phosphate diester, C18-C32 phosphate diester, or salts thereof. In embodiments, the anionic surfactant can be selected from one or more of a Ce-based ammonium fluoroaliphatic phosphate ester; tridecyl alcohol ethoxylate phosphate ester, POE-12; tridecyl alcohol ethoxylate phosphate ester, POE-3; laureth-11 carboxylic acid; crypto-anionic surfactant - laureth-6 carboxylic acid; or sodium lauryl ether sulfate, POE-4.

[0112] As used herein, the term “non-fluorinated” refers to a surfactant that has less than 0.01 wt% fluorine based on the total molecular weight of the compound, or less than 0.001 wt% fluorine based on the total molecular weight of the compound, or less than 0.0001 wt% fluorine based on the total molecular weight of the compound.

[0113] In embodiments, the release coating can include a fluorosurfactant, e.g., a perfluoroalkyl-containing compound. In embodiments, the fluorosurfactant can include a solution of ZONYL FSP surfactant (E.l. du Pont de Nemours and Company). A range of from about 0.05% by weight to about 5.0% by weight of surfactant in the release coating is contemplated. The amount of surfactant required to provide adequate wetting can vary depending on the film being coated on the band. Other products may require higher concentrations to improve release properties. Hard surface spreading wetting will be more efficient with higher surfactant concentrations until the surfactant solution reaches the critical micelle concentration (CMC). This concentration represents a threshold beyond which additional surfactant will not produce any further efficiency in spreading wetting. However, increasing the concentration beyond the CMC may improve wetting by the polymer solution and improve the release properties of some film formulations.

[0114] The release coating can be applied to the surface of a substrate and optionally subsequently dried prior to casting a polymer resin or polymer resin solution onto the surfacecoated substrate. In embodiments, the release coating can have a pH of about 1 to about 5 when applied to the surface of the substrate, prior to drying the release coating on the surface of the substrate. In embodiments wherein the surfactant comprises a non-fluorinated anionic surfactant, a non-fluorinated zwitterionic surfactant, salts thereof, and a combination thereof, the release coating can have a pH of about 1 to about 8 or a pH of about 1 to about 5 when applied to the surface of the substrate, prior to drying the release coating on the surface of the substrate. For example, the release coating, when applied to the surface of the substrate, can have a pH of about 1 , about 1 .5, about 2, about 2.5, about 3, about 3.5, about 4, about 5, about 6, about 7, or about 8. In embodiments, the release coating can have a pH of about 1 to about 7, or about 1 to about 6, or about 1 to about 4, or about 1 to about 3, or about 2 to about 7, or about 2 to about 6, or about 2 to about 5, or about 2 to about 4 , or about 2 to about 3, or about 3 to about 7, or about 3 to about 5, or about 1 .5 to about 3.5, or about 4 to about 7 when applied to the surface of the substrate, prior to drying the release coating on the surface of the substrate.

[0115] In general, the release coating can have a surfactant concentration in a range of about 0.001 wt% to about 100 wt%, based on the total weight of the release coating. In embodiments, the release coating can have a surfactant concentration in a range of about 0.001 wt% to about 20 wt% prior to drying the release coating on the surface of the substrate. For example, the release coating can have a surfactant concentration in a range of about 0.001 wt% to about 10 wt%, or about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 4 wt%, or about 0.01 wt% to about 3 wt%, or about 0.01 wt% to about 2 wt%, or about 0.05 wt% to about 2 wt%, or about 0.1 wt% to about 2 wt%, or about 0.5 wt% to about 2 wt%, prior to drying the release coating on the surface of the substrate. In embodiments, the release coating can have a surfactant concentration in a range of about 0.01 wt% to about 4.00 wt%, based on the total weight of the release coating prior to drying the release coating on the surface of the substrate. In embodiments, the release coating can have a surfactant concentration in a range of about 0.05 wt% to about 2.00 wt%, based on the total weight of the release coating prior to drying the release coating on the surface of the substrate. In embodiments, the release coating can have a surfactant concentration in a range of about 2.5 wt% to about 100 wt%, based on the total weight of the release coating, after drying the release coating on the surface of the substrate. For example, after drying the release coating on the surface of the substrate, the release coating can have a surfactant concentration in a range of about 3 wt% to about 100 wt%, or about 4 wt% to about 90 wt%, or about 4 wt% to about 80 wt%, or about 4 wt% to about 70 wt%, or about 4 wt% to about 50 wt%, or about 4 wt% to about 30 wt%, or about 4 wt% to about 20 wt%, or about 4.7 wt% to about 100 wt%, or about 5 wt% to about 90 wt%, based on the total weight of the releasecoating. In embodiments, the release coating can have a surfactant concentration in a range of about 4.7 wt% to about 100 wt%, based on the total weight of the release coating, after drying the release coating on the surface of the substrate. For example, the release coating can include an amount of ZONYL surfactant in a range of about 0.05% by weight to about 5.0% by weight, based on the total weight of the release coating.

[0116] In general, the release coating as described herein can have a hydrophilic- lipophilic balance in a range of about 1 to about 30. In embodiments, the release coating can have a hydrophilic-lipophilic balance in a range of about 1 to about 20, or about 1 to about 18, or about 1 to about 17, or about 1 to about 16, or about 1 to about 15, or about 2 to about 17, or about 3 to about 17, or about 4 to about 15, or about 5 to about 12, or about 8 to about 12. In embodiments, the release coating can have a hydrophilic-lipophilic balance in a range of about 1 to about 20. In embodiments, the release coating can have a hydrophilic-lipophilic balance in a range of about 3 to about 17.

[0117] In general, the release coating has a thickness of about 0.1 nm to about 100 nm on the surface of the substrate. In embodiments, the release coating has a thickness of about 0.1 nm to about 80 nm, or about 0.1 nm to about 60 nm, or about 0.1 nm to about 40 nm, or about 0.1 nm to about 40 nm, or about 0.1 nm to about 20 nm, or about 0.1 nm to about 10 nm, or about 1 nm to about 10 nm, or about 1 nm to about 5 nm, on the surface of the substrate. In embodiments, the release coating has a thickness of about 0.1 nm to about 40 nm on the surface of the substrate. In embodiments, the release coating has a thickness of about 0.1 nm to about 10 nm on the surface of the substrate.

[0118] The amount of water in the metered solutions of resins and / or secondary components for film casting can be selected such that when the solution is heated to the casting temperature, the solutions have the highest solids level below the viscosity inflection point. Methods of determining the amount of solids at the viscosity inflection point are known in the art. In general, the metered solutions can comprise between 60 to 85% water, or 60 to 75% water, to provide suitable solutions for casting. The viscosity of each casting solution at 175 °F (about 80 °C) can be, for example, at least about 5,000 cPs, or at least about 6,000 cPs, or at least about 7,000 cPs, or at least about 8,000 cPs, or at least about 9,000 cPs. The viscosity of each casting solution at 175 °C (about 80 °C) can be, for example, no greater than about 15,000 cPs, or no greater than 14,000 cPs, or no greater than about 13,000 cPs, or no greater than about 12,000 cPs, or no greater than about 11 ,000 cPs.

[0119] The solution can be cast at any suitable temperature such that the film optionally has a temperature in a range of about 50 °C to about 105 °C, during drying. Without intending to be bound by theory, it is believed that as the casting solution and filmtemperature decreases significantly below about 50 °C, the amount of time required to dry the film undesirably increases, and the length of the drying chamber needed to fully dry the cast solution undesirably increases. Further, without intending to be bound by theory, it is believed that as the solution and film temperature increases significantly above about 105 °C, the solvent may rapidly boil out of the film, resulting in defects in the film surface such as holes or blisters in the finished films and / or facilitate undesirable reactions between adjacent backbone chain units resulting in a film having reduced solubility.

[0120] In a continuous or semi-continuous casting process, the moving casting surface can have any desired line speed, e.g., in a range of about 5 m / min to about 50 m / min. The line speed can sometimes affect the properties of the resulting film, for example, physical properties, thickness, residual moisture content and film quality. In general, as the line speed decreases, the thickness of the resulting film will increase and as the line speed increases, the thickness of the resulting film will decrease, assuming the delivery rate of solution remains constant. In general, as the line speed increases the residence time of the film in a fixed-size dryer decreases, thereby requiring an increase in drying temperatures, which may result in drying defects or sticking at high enough temperatures. In contrast, as the line speed decreases, the residence time of the film in the dryer increases.Methods of Making Pouches

[0121] Methods of forming containers from films are known in the art. The film can be used to form a container (pouch) by any suitable process, including vertical form, fill, and sealing (VFFS), or thermoforming. The film can be sealed by any suitable process including, for example, solvent sealing or heat sealing of film layers, e.g., around a periphery of a container. The pouches can be used for dosing materials to be delivered into bulk water, for example.

[0122] Pouches and packets may be made using any suitable equipment and method. For example, single compartment pouches may be made using vertical form filling, horizontal form filling, or rotary drum filling techniques commonly known in the art. Such processes may be either continuous or intermittent. The film may be dampened, and / or heated to increase the malleability thereof. The method may also involve the use of a vacuum to draw the film into a suitable mold. The vacuum drawing the film into the mold can be applied for about 0.2 to about 5 seconds, or about 0.3 to about 3, or about 0.5 to about 1 .5 seconds, once the film is on the horizontal portion of the surface. This vacuum can be such that it provides an under-pressure in a range of 10 mbar to 1000 mbar, or in a range of 100 mbar to 600 mbar, for example.

[0123] The molds, in which packets may be made, can have any shape, length, width and depth, depending on the required dimensions of the pouches. The molds may also vary in size and shape from one to another, if desirable. For example, the volume of the final pouches may be about 5 mL to about 300 mL, or about 10 mL to 150 mL, or about 20 mL to about 100 mL, and that the mold sizes are adjusted accordingly.Thermoforming

[0124] A thermoformable film is one that can be shaped through the application of heat and a force. Thermoforming a film is the process of heating the film, shaping it (e.g., in a mold), and then allowing the film to cool, whereupon the film will hold its shape, e.g., the shape of the mold. The heat may be applied using any suitable means. For example, the film may be heated directly by passing it under a heating element or through hot air, prior to feeding it onto a surface or once on a surface. Alternatively, it may be heated indirectly, for example by heating the surface or applying a hot item onto the film. In embodiments, the film is heated using an infrared light. The film may be heated to a temperature in a range of about 50 °C to about 150 °C, about 50 °C to about 120 °C, about 60 °C to about 130 °C, about 70 °C to about 120 °C, or about 60 °C to about 90 °C. The film may be heated to a temperature in a range of about 30 °C to about 100 °C, or about 40 °C to about 100 °C, or about 50 °C to about 100 °C, or about 60 °C to about 100 °C, or about 30 °C to about 90 °C, or about 40 °C to about 90 °C, or about 50 °C to about 90 °C. The film may be heated to temperature in a range of about 30 °C to about 80 °C, or about 40 °C to about 80 °C, or about 50 °C to about 80 °C, or about 60 °C to about 80 °C, or about 30 °C to about 70 °C, or about 30 °C to about 60 °C, or about 30 °C to about 50 °C. Thermoforming can be performed by any one or more of the following processes: 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.

[0125] Alternatively, 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.

[0126] Once a film has been heated and / or wetted, it may be drawn into an appropriate mold, preferably using a vacuum. The filling of the molded film can be accomplished by utilizing any suitable means. In embodiments, the most preferred method will depend on theproduct form and required speed of filling. In embodiments, the molded film is filled by in-line filling techniques. The filled, open packets are then closed forming the pouches, 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, preferably water-soluble film, over and onto the open packets and then preferably sealing the first and second film together, typically in the area between the molds and thus between the packets.

[0127] In general, a thermoformed film may be characterized by a draw ratio, where the draw ratio is the ratio of the area of the mold surface to the area of the film prior to drawing. A thermoformed film according to the disclosure, or an article comprising a thermoformed film according to the disclosure, can be characterized by a draw ratio of at least 2.0, or at least 2.5, or at least 2.6, or at least, 3.0, or at least 3.5.

[0128] Suitable behavior of water-soluble films according to the disclosure, following conditioning at for 18 to 24 hours 25 °C / 50% RH, is marked by tensile strength values of at least about 10 N / mm2, or at least 15 N / mm2, or in a range of about 5 N / mm2to about 30 N / mm2, or about 10 N / mm2to about 25 N / mm2, or about 15 N / mm2to about 20 N / mm2, as measured by the Tensile Strength Test described herein. Suitable behavior of water-soluble films according to the disclosure, following conditioning for 18 to 24 hours at 25 °C / 65% RH, is marked by tensile strength values of at least about 5 N / mm2, or at least about 10 N / mm2, or at least 15 N / mm2, or in a range of about 5 N / mm2to about 30 N / mm2, or about 10 N / mm2to about 25 N / mm2, or about 15 N / mm2to about 20 N / mm2, as measured by the Tensile Strength Test described herein. Generally, higher tensile strength values are desirable because they correspond to stronger pouch seals when the film is the limiting or weakest element of a seal.

[0129] Suitable behavior of water-soluble films according to the disclosure, following conditioning for 18 to 24 hours at 25 750% RH, is marked by Young’s modulus values of at least about 20, 25, 27, 30, 35, 40, or 45 N / mm2and / or up to about 300, 200, 150, 130, 120, 1 10, 100, 90, 80, 70, 60, 50, 40, or 30 N / mm2, or about 20 N / mm2to about 300 N / mm2, or about 20 N / mm2to about 200 N / mm2, or about 40 N / mm2to about 100 N / mm2. Suitable behavior of water-soluble films according to the disclosure, following conditioning for 18 to 24 hours at 25 65% RH, is marked by Young’s modulus values of at least about 5, 10, 15, or 20 N / mm2, and / or up to about 100, 90, 80, 70, 60, or 50 N / mm2.Test MethodsDissolution and Disintegration Test (MSTM-205)

[0130] 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. See, for example, U.S. Patent No. 7,022,656.

[0131] Apparatus and Materials:

[0132] 600 mL Beaker

[0133] Magnetic Stirrer (Labline Model No. 1250 or equivalent)

[0134] Magnetic Stirring Rod (5 cm)

[0135] Thermometer (0 to 100 °C ± 1 °C)

[0136] Template, Stainless Steel (3.8 cm x 3.2 cm)

[0137] Timer (0 - 300 seconds, accurate to the nearest second)

[0138] Polaroid 35 mm slide Mount (or equivalent)

[0139] MonoSol 35 mm Slide Mount Holder (or equivalent)

[0140] Distilled water

[0141] For each film to be tested, three test specimens are cut from a film sample that is a 3.8 cm x 3.2 cm specimen. If cut from a film web, specimens should be cut from areas of web evenly spaced along the traverse direction of the web. Each test specimen is then analyzed using the following procedure.

[0142] Lock each specimen in a separate 35 mm slide mount.

[0143] Fill beaker with 500 mL of distilled water. Measure water temperature with thermometer and, if necessary, heat or cool water to maintain temperature at 20 °C (about 68 °F).

[0144] Mark height of column of water. Place magnetic stirrer on base of holder. Place beaker on magnetic stirrer, add magnetic stirring rod to beaker, turn on stirrer, and adjust stir speed until a vortex develops which is approximately one-fifth the height of the water column. Mark depth of vortex.

[0145] Secure the 35 mm slide mount in the alligator clamp of the 35 mm slide mount holder such that the long end of the slide mount is parallel to the water surface. The depth adjuster of the holder should be set so that when dropped, the end of the clamp will be 0.6 cm below the surface of the water. One of the short sides of the slide mount should be next to the side of the beaker with the other positioned directly over the center of the stirring rod such that the film surface is perpendicular to the flow of the water.

[0146] In one motion, drop the secured slide and clamp into the water and start the timer. Disintegration occurs when the film breaks apart. When all visible film is released from the slide mount, raise the slide out of the water while continuing to monitor the solution for undissolved film fragments. Dissolution occurs when all film fragments are no longer visible, and the solution becomes clear.

[0147] After 300 seconds, if any film residue remained in the frame, the percent of surface area of the film remaining was estimated by visual inspection.

[0148] The results should include the following: complete sample identification; individual and average disintegration and dissolution times; and water temperature at which the samples were tested.

[0149] Film disintegration times (I) and film dissolution times (S) can be corrected to a standard or reference film thickness using the exponential algorithms shown below in Equation 1 and Equation 2, respectively.Corrected = Measured x (reference thickness / measured thickness)1 93[1]Scorrected = Smeasured x (reference thickness / measured thickness)1 83[2]Tensile Strength Test

[0150] A water-soluble film characterized by or to be tested for tensile strength according to the Tensile Strength (TS) Test is analyzed as follows. The procedure includes the determination of tensile strength according to ASTM D 882-97 (“Standard Test Method for Tensile Properties of Thin Plastic Sheeting”) or equivalent. An INSTRON tensile testing apparatus (Model 5544 Tensile Tester or equivalent) is used for the collection of film data. A minimum of three test specimens, each cut with reliable cutting tools to ensure dimensional stability and reproducibility, are tested in the machine direction (MD) (where applicable) for each measurement. Film specimens are conditioned for at least 18 hours at 23 °C / 35% RH, or 28 ‘0 / 50% RH, or 28 0 / 65% RH prior to measurement. Tests are conducted in the standard laboratory atmosphere of 23±2.0 and 35±5% RH. For tensile strength, 1”-wide (2.54 cm) samples of a single film sheet having a thickness of 88 pm are prepared. The sample is then transferred to the INSTRON tensile testing machine to proceed with testing while minimizing exposure in the 35% relative humidity environment. The tensile testing machine is prepared according to manufacturer instructions, equipped with a 500 N load cell, and calibrated. The correct grips and faces are fitted (INSTRON grips having model number 2702-032 faces, which are rubber coated and 25 mm wide, or equivalent). The samples are mounted into the tensile testing machine and analyzed to determine the tensile strength (i.e., stress required to break the film).

[0151] Young’s modulus is determined as the slope of a linear fit of stress-strain data. For films described herein, Young’s modulus was determined as the slope of a linear fit of stress-strain data over the range of 0.1-3% strain unless otherwise noted. For some films, Young’s modulus was determined as the slope of a linear fit of stress-strain data over the range of 1-20% strain, as noted herein.Elongation at Break Test

[0152] The procedure includes the determination of elongation at break (i.e., strain at break) based on ASTM D 882-97 (“Standard Test Method for Tensile Properties of Thin Plastic Sheeting”) or equivalent. An INSTRON® tensile testing apparatus (Model 5544 Tensile Tester or equivalent) is used for the collection of film data. A minimum of three test specimens, each cut with reliable cutting tools to ensure dimensional stability and reproducibility, are tested in the machine direction (MD) (where applicable) for each measurement. Film specimens are conditioned for at least 18 hours at 23 °C / 35% RH, or 28 °C / 50% RH, or 28 °C / 65% RH prior to measurement. Tests are conducted in the standard laboratory atmosphere of 23±2.0°C and 35±5% RH. For elongation at break determination, 1”-wide (2.54 cm) samples of a single film sheet having a thickness of 1.4 ± 0.15 mil (about 35.6 ± 3.8 pm) are prepared. The sample is then transferred to the INSTRON® tensile testing machine to proceed with testing while minimizing exposure in the 35% relative humidity environment. The tensile testing machine is prepared according to manufacturer instructions, equipped with a 500 N load cell, and calibrated. The correct grips and faces are fitted (INSTRON® grips having model number 2702-032 faces, which are rubber coated and 25 mm wide, or equivalent). The samples are mounted into the tensile testing machine and analyzed to determine the elongation at break (i.e., where Young’s modulus applies).Seal Strength Test

[0153] The Seal Strength Test measures the strength of the seal between two sealed film surfaces. The sealed film surfaces can be the surfaces of two different films sealed to each other, or the surfaces of two films having the same composition, or the sealed film surfaces can be surfaces of a single film sealed to itself.

[0154] An INSTRON tensile testing apparatus (Model 5544 Tensile Tester or equivalent) is used for the collection of film data. Films can be sealed to each other by any suitable means, including heat-sealing or water-sealing methods known in the art. For example, an ESIPROOF proofing apparatus or equivalent with an anilox roller 140 / 10 can be used for sealing two sheets of film with water. Alternatively, two sheets of film can be heat-sealed. The seal strength of the seal between two sealed film surfaces can accordingly be characterized as a water seal strength or a heat seal strength. A minimum of three testspecimens, each cut with reliable cutting tools to ensure dimensional stability and reproducibility, are tested in the machine direction (MD) (where applicable) for each measurement. Films are conditioned for 18 to 24 hours at 28<C / 35% RH prior to testing, and tests are conducted in the standard laboratory atmosphere of 23±2.0 °C and 35±5% RH.

[0155] Samples for measuring water seal strength can be prepared as follows. Prepare the test specimens by cutting four 100 mm x 300 mm film sheets with the 300 mm dimension in the machine direction (MD). For two sheets, tape the four corners of one sheet to a surface. Overlay the other sheet on top of the taped sheet so the appropriate surfaces are in contact. On top of the other taped sheet, place the remaining sheet on top so that the two surfaces to be sealed are contacted with each other. Tape one 100 mm end of each top sheet to secure to the bottom sheet. Thread the loose end of each top sheet through the ESIPROOF proofing roller using the 140 / 10 anilox roller. Apply 0.5 mL of water to the doctor blade. Pull the roller at a constant speed (75 mm per second) to coat the upper film and secure to the lower sheet. Allow the film to weld for 10-15 minutes. Using a strip punch or sample cutter, cut 25.4 mm wide samples in the transverse direction (TD).

[0156] The water-sealed or heat-sealed sample is transferred to the INSTRON testing machine to proceed with testing while minimizing exposure to environment. For the seal strength test, there is a 0.50" (1 .27 cm) separation between the rubber grips, all four of which are flat and square. Three (or more) 1"-wide (2.54 cm) samples are cut in the machine direction (MD). Place the unsealed flaps of a specimen in the grips of the testing machine, taking care to ensure the specimen is aligned with the grips and parallel to them, and that the specimen is not pulled too tightly in the tester's jaws. The load is balanced, and the test is initiated according to the instructions of the equipment manufacturer. At the end of the test, the tensile force (in N) required to tear or separate the layers is recorded as the seal strength.

[0157] The manner in which the sealed sample tears or separates at the end of the Seal Strength Test can provide information about the quality of the seal. Seal quality can be reported as “pass” or “fail.” In general, if the sealed sample breaks in the Seal Strength Test by delamination (peeling) of the films at the seal, then the seal is considered a weak point of the sealed sample (fail), while if the sealed sample breaks in the Seal Strength Test by tearing or breaking of one or both of the films, then the seal is not considered a weak point of the sealed sample (pass).Blocking Test

[0158] Blocking refers to the force required to separate one film layer from another film layer on a roll. In general, as blocking decreases, a film can more easily be unrolled withoutimparting strain or stretching to the film or producing tension in a converting process.Blocking force generally tends to increase as the level of plasticizer in a film increases. The blocking test measures the blocking force between layers of film on a roll. The blocking force measurement does not contain any friction force from the outer surface of the roll as it is being unwound.

[0159] Films of the disclosure characterized by or tested in accordance with the Blocking Test can be analyzed as follows.1 . Cast a sheet of the film approximately 4.5 inches x 3 feet (about 11 .4 cm x 91 .4 cm) using BYK Draw squares or doctor blade at an appropriate gauge.2. Using a constant adjustable torque rewinder or equivalent, load a roll core 3 inches in diameter x 10 feet long (about 7.5 cm diameter x 3.05 m long) and secure to the winder.3. Secure the film to the roll core using tape.4. Using approximately 50% torque in the settings, wind film into roll core, ensuring film is layered over itself and wrinkles are smoothed out.5. Using a thin absorbent wipe (e.g., Kimwipe® or equivalent), secure approximately 0.5 inch (about 1 .3 cm) between the top layer of film and the rest of the core to ensure the top layer section will not stick to the rest of the core.6. Condition the roll at 50% RH for 24 hours.7. Cut the film from the roll to obtain a flat sheet with a few layers and remove the wipe.8. Using a sample cutter, cut 3 strips approximately 6” (about 15 cm) long.9. Using a tensile testing apparatus (e.g., INSTRON Model 5544 Tensile Tester or equivalent) equipped with a 50 N load cell at a half inch gap, load in the MonoSol Peel Test Method. Load the 2 loose ends into a T-shape.10. Run the Peel Test and note the failure mode (Break, Tear, or Peel). The Peel Test records tensile force (in N) as the films are displaced from one another.11 . Optionally, repeat the test on 2 more replicate samples.Data Interpretation1 . Peak / maximum Force required to delaminate the two films is recorded.2. Higher force required to delaminate the films indicates higher blocking. A film with high blocking force typically tears or breaks during the test (i.e., failure mode is noted as “tear” or “break”).3. Lower force required to delaminate the films indicates lower blocking. A film low blocking force typically peels during the test (i.e., failure mode is noted as “peel”).

[0160] A block failure mode can be determined based on the manner in which the films separate from each other during the blocking test. For instance, the block failure mode can be assigned as “peel” if the films separate by peeling or delaminating from each other such that the films maintain their individual integrity, or “break” if separating the films results in tearing or breaking of one or both films.Water-seal Test

[0161] The water-seal test determines the compressive force needed for a singlecompartment pouch to burst. The pouch is made of two films that have been sealed to contain a liquid composition. The pouches are made by any suitable means known in the art as long as at least one seal is made by water- sealing.

[0162] The test is conducted in triplicate using an Instron mechanical tester or equivalent capable of operating in compression mode as indicated in ASTM method D695-15.

[0163] Prior to testing, the pouches are inspected for leaks and conditioned at 28 °C and 50% RH for 24hr. After conditioning, each pouch is sealed in a zippered bag containing the least amount of air possible and labeled with a unique identifier.To begin the test, the sample is placed between the two plates of the tester ensuring that the pouch is far from the edges of the zippered bag, and that the pouch is on the center of the bottom plate. The plates are set to compress the pouch, and the force at which the pouch bursts is recorded.EXAMPLES

[0164] The following examples are provided for illustration and are not intended to limit the scope of the invention. In general, resin solutions were prepared by mixing water and the components listed in the examples, and films were prepared by solution casting of the resin solutions and allowing the cast films to dry, and then removing the dried film from the casting substrate to result in a freestanding film. Amounts of each component are shown as weight % of the total non-water components of the film. Comparative examples (i.e., examples not according to the invention) are indicated with a C’ prefix.Example 1

[0165] Example films CX1-CX6 were prepared according to the film-forming resin formulations listed in Table 1 below by solution casting to result in a dry film thickness ofabout 88 pm. Amounts are shown as weight percents based on the total weight of non-water components.Table 1.

[0166] Films CX1 - CX4 were cast from solutions containing a single component film forming resin. Films containing only cationic starch (CX1 ) were not water soluble while compositions containing non-ionic starch could not be cast into films due to low viscosity of the film casting solution. Films containing only carrageenan (CX3) had unacceptable dissolution times (e.g., longer than 300 s which represents water solubility that is generally too low for water-soluble articles), while films containing pullulan only lacked mechanical stability as manifested by a break strain larger than 400% (i.e., excessive break strains are undesirable as articles of these films can exhibit excessive deformation due to the weight of the composition inside the article or the weight of surrounding articles).

[0167] Films CX5 and CX6 are examples of carrageenan-pullulan combinations that result in good mechanical properties and acceptable disintegration and dissolution times.Example 2

[0168] Example films X7-X11 were prepared according to the film-forming resin formulations listed in Table 2 below by solution casting to result in a dry film thickness of about 88 pm. Amounts are shown as weight percents based on the total weight of non-water components.Table 2.

[0169] Example films (X7 - X11 ) according to the disclosure show good mechanical properties as their tensile strength is at least 10 MPa and their strain at break between 50% and 400%; i.e., the films show enough strength to hold their shape and integrity when formed into objects and loaded with a composition, while maintaining flexibility for formability and conversion into articles / pouches. These films were also water-soluble, which is essential for the many applications for which these films may be used.Example 3

[0170] Example films CX12 - CX20 were prepared according to the film-forming resin formulations listed in Tables 3 and 4 by solution casting to result in a dry film thickness ofabout 88 pm. Amounts are shown as weight percents based on the total weight of non-water components.Table 3.Table 4.

[0171] Films CX12 - CX20 contained different combinations of carrageenan and two types of starch but lacked pullulan. The omission of pullulan resulted in limited solubility as in films CX12- CX15, or inadequate mechanical properties, having low tensile strength (e.g., tensile strength of less than 10MPa) or low flexibility (e.g., strain at break lower than 50%) that can cause conversion issues and limit the shelf life of articles due to brittleness or not enough strength to hold a composition enclosed in a package made therefrom.Example 4

[0172] Example films X21 - X30 were prepared according to the film-forming resin formulations listed in Tables 5 and 6 by solution casting to result in a dry film thickness of about 88 pm. Amounts are shown as weight percents based on the total weight of non-water components.Table 5.Table 6.

[0173] Films X21 - X25 and X30 contained carrageenan, pullulan, and a cationic starch; films X27 - X29 contained carrageenan, pullulan, and a non-ionic starch. Both types of starches provided the films with adequate mechanical properties and water-solubility, e.g., tensile strength of at least 10 MPa, break strain at 50%RH between 50% and 400% and dissolution times between 10 seconds and 300 seconds. These films are believed to have enough strength to hold compositions without tearing, excessive deformation or formabilityproblems and they are water-soluble thus the articles can release the composition when contacted with water.Table 7.Table 8.

[0174] Blocking results are shown in table 8.

[0175] Films CX1 , CX12, CX13, CX16, CX17 and CX18, having a high starch content and including carrageenan had acceptable blocking forces shown by their ability to peel rather than to tear when tested according to the blocking test described herein. However, these films show poor to no water solubility, low tensile strength, and / or low strain at break, due to their lack of pullulan (tables 1 , 3, 4, and 5) thus these films are not suitable for making of water-soluble articles.

[0176] Pullulan containing films X23 and X25 have improved tensile strength and are water soluble (Table 5). Film X23 contained, in addition, a moderate molecular weight polyethylene glycol (PEG) (about 1000 to about 20000 Da), which contributed to lowering the blocking force while maintaining the strength of the film and improving the strain at break, low blocking force is shown as the films peeling rather than tearing when tested according to the blocking test, which can be useful when unwinding a roll of film to be formed into articles described herein.

[0177] Film X31 containing a moderate molecular weight PEG also shows a lower blocking force than a film of similar composition but without the PEG (film X32, table 7). The addition of PEG did not negatively affect the strength or the flexibility of the film.

Claims

What is claimed is:1 . A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of starch, carrageenan and pullulan, wherein starch is present in an amount in a range of about 50 wt.% to about 90 wt.%, based on the total weight of starch, carrageenan, and pullulan; carrageenan is present in an amount in a range of about 5 wt.% to about 14 wt.%, based on the total weight of the starch, carrageenan, and pullulan.

2. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of starch, carrageenan and pullulan, wherein starch is present in an amount in a range of about 1 wt.% to about 30 wt.%, based on the total weight of starch, carrageenan, and pullulan; carrageenan is present in an amount in a range of about 5 wt.% to about14 wt.%, based on the total weight of starch, carrageenan, and pullulan.

3. The water-soluble films of claim 1 or claim 2, wherein the film-forming resin consists of the starch, carrageenan, and pullulan.

4. The water soluble-film of any one of the preceding claims, wherein the film further comprises a cross-linker.

5. The water-soluble film of claim 4, wherein the cross-linker comprises a metal ion.

6. The water-soluble film of claim 4 or 5, wherein the cross-linker comprises a calcium ion, a magnesium ion, or a potassium ion.

7. The water-soluble film of claim 6, wherein the cross-linker comprises a calcium ion.

8. The water-soluble film of claim 7, wherein the film comprises calcium chloride to provide the calcium ion.

9. The water-soluble film of claim 6, wherein the film comprises potassium acetate to provide the potassium ion.

10. The water-soluble film of any one of the preceding claims, wherein the plasticizer is selected from polyols, sugar alcohols, glycerol, diglycerin, sorbitol, maltitol, monosaccharides, oligosaccharides, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols up to 400 Da molecular weight, hexylene glycol, neopentyl glycol, trimethylolpropane, polyether polyols,polyether diol, polyether triol, xylitol, 2-methyl-1 ,3-propanediol, ethanolamines, glycerol propylene oxide polymers, and mixtures thereof.11 . The water-soluble film of claim 10, wherein the plasticizer is selected from polyols, sugar alcohols, and mixtures thereof.

12. The water-soluble film of any one of the preceding claims, wherein the plasticizer is present in an amount in a range of about 20 PHR to about 50 PHR, or about 20 PHR to about 40 PHR, or greater than about 20 PHR and less than about 50 PHR, or greater than about 20 PHR and less than 40 PHR.

13. The water-soluble film of any one of the preceding claims, wherein the film comprises one or more auxiliary agents selected from fillers, surfactants, anti-block agents, antioxidants, antifoams, bleaching agents, aversive agents, and pungents.

14. The water-soluble film of any one of the preceding claims, wherein the filmforming resin further comprises one or more bio-based resins selected from guar gum, gum Acacia, xanthan gum, locust bean gum, starch, modified starches, celluloses, cellulose ethers, cellulose esters, cellulose amides, methylcelluloses, carboxymethylcelluloses and salts thereof, ethylcelluloses, hydroxyethyl celluloses, hydroxypropyl methylcelluloses, polyaminoacids, gelatins, dextrins, maltodextrins, pea proteins, casein proteins, copolymers of the foregoing, and a combination of any of the foregoing.

15. The water-soluble film of any one of the preceding claims, further comprising a polyalkylene oxide.

16. The water-soluble film of claim 15, wherein the polyalkylene oxide comprises polyethylene oxide.

17. The water-soluble film of claim 15 or claim 16, wherein the polyalkylene oxide is present in an amount in a range of 0.25 parts per hundred parts film-forming resin (PHR) to about 25 PHR, for example, about 0.5 PHR to about 22 PHR, about 0.7 PHR to about 20 PHR, about 1 PHR to about 15 PHR, about 1 PHR to about 14 PHR, about 1 PHR to about 13 PHR, about 1 PHR to about 12 PHR, about 2 PHR to about 10 PHR, about 2 PHR to about 6 PHR, or about 4 PHR.

18. The water-soluble film of any one of claims 15 to 17, wherein the polyalkylene oxide has a weight-average molecular weight in a range of about 1000 Da to about 20,000 Da, or about 1 ,000 Da to about 10,000 Da, or about 1 ,000 Da to about 5,000 Da, or about1 ,000 to about 4,000Da19. The water-soluble film of any one of the preceding claims, wherein the film comprises at least 95 wt.% bio-based materials.

20. The water-soluble film of claim 19, wherein the film comprises at least 99 wt.% bio-based materials.21 . The water-soluble film of claim 19, wherein the film has a Renewable Carbon Index of 100 wt.%.

22. The water-soluble film of any one of the preceding claims, wherein the film, when provided at a thickness of 88 pm, has a disintegration time in a range of about 10 to about 150 seconds, as measured according to MSTM-205.

23. The water-soluble film of any one of the preceding claims, wherein the film, when provided at a thickness of 88 pm, has a dissolution time in a range of about 10 to about 300 seconds, or about 10 to about 200 seconds, or about 10 to about 100 seconds, as measured according to MSTM-205.

24. The water-soluble film of any one of the preceding claims, wherein the film has a strain at break in a range of about 50% to about 400%, or about 50% to about 300%, or about 100% to about 200%, after being conditioned for at least 18 hours at 28 °C / 50% RH, as measured according to the Elongation at Break Test.

25. The water-soluble film of any one of the preceding claims, wherein the film has a tensile strength of at least 10 N / mm2(MPa), or in a range of about 5 N / mm2(MPa) to about 50 N / mm2, or about 10 N / mm2to about 40 N / mm2, or about 20 N / mm2to about 30 N / mm2, or about 20 N / mm2to 25 N / mm2, after being conditioned for at least 18 hours at 28 °C / 50% RH, as measured according to the Tensile Strength Test.

26. The water-soluble film of any one of the preceding claims, wherein the film, when sealed to itself by a first portion of a surface of the film being sealed to a second portion of a surface of the film, has a seal strength of about 5 N or more, or about 10 N or more, or about 12 N or more, or about 15 N or more, or in a range of about 5 N to about 30 N, or about 10 N to about 25 N, or about 12 N to about 20 N, or about 15 N to about 20 N, as measured according to the Seal Strength Test.

27. The water-soluble film of any of the preceding claims, wherein the film is characterized by having a blocking force of no greater than 10 N, or no greater than 5 N, or no greater than 1 N, as measured according to the Blocking Test.

28. A method of increasing the strain at break of a water-soluble film according to any one of claims 1 to 21 , comprising; including in the film a polyethylene glycol (PEG) having a molecular weight in a range of about 1000 Da to about 20,000 Da, or about 1000 Da to about 10,000 Da, or about1000 Da to about 5000 Da, or about 1000 Da to about 4000 Da in an amount of at least about 1 wt.%, based on the total weight of the non-water parts of the film.

29. The method of claim 28, wherein the PEG is provided in an amount of about 0.1 wt.% to about 5 wt.%, or about 0.5 wt.% to about 4 wt.%, or about 0.5 wt.% to about3 wt.% and the PEG has a molecular weight of about 1000 Da to about 2000 Da, or about 1250 Da to about 1750 Da, or about 1300 Da to about 1500 Da.

30. A method of decreasing blocking force of a water-soluble film according to any one of claims 1 to 21 comprising including in the film a polyethylene glycol (PEG) having a molecular weight in a range of about 1000 Da to about 20,000 Da, or about 1000 Da to about 10,000 Da, or about 1000 Da to about 5000 Da, or about 1000 Da to about 4000 Da in an amount of at least about 1 wt.%, based on the total weight of the non-water parts of the film.31 . The method of claim 30, wherein the PEG is provided in an amount of about 0.1 wt.% to about 5 wt.%, or about 0.5 wt.% to about 4 wt.%, or about 0.5 wt.% to about3 wt.% and the PEG has a molecular weight of about 1000 Da to about 2000 Da, or about 1250 Da to about 1750 Da, or about 1300 Da to about 1500 Da.

32. A water-soluble article in the form of a packet comprising a sealed compartment, the article comprising a first water-soluble film and a second water-soluble film, wherein the first water-soluble film is a water-soluble film according to any one of the preceding claims, and wherein the first water-soluble film is sealed to the second water-soluble film to form the sealed compartment.

33. The water-soluble article of claim 32, wherein the article comprises a composition contained in the sealed compartment.

34. The water-soluble article of claim 33, wherein the composition comprises a household care composition.

35. The water-soluble article of claim 34, wherein the household care composition is selected from light duty liquid detergent compositions, heavy duty liquid detergent compositions, hard surface cleaning compositions, laundry detergent gels, bleaching compositions, laundry additives, fabric enhancer compositions, shampoos, body washes, other personal care compositions, and combinations thereof,36. The water-soluble article of claim 34 or claim 35, wherein the household care composition comprises water in an amount in a range of from about 1 wt.% to about 15 wt.%, based on the weight of the household care composition.

37. The water-soluble article of claim 36, wherein the household care composition comprises water in an amount in a range of from about 10 wt.% to about 15 wt.%, based on the weight of the household care composition.

38. The water-soluble article of claim 33, wherein the composition comprises a non-household care composition.

39. The water-soluble article of any one of claims 32 to 38, wherein the first water-soluble film is a thermoformed film.

40. The water-soluble article of any one of claims 32 to 39, wherein the second water-soluble film has the same composition as the first water-soluble film.41 . The water-soluble article of any one of claims 32 to 40, wherein the first water-soluble film, when sealed to itself by a first portion of a surface of the first water- soluble film being sealed to a second portion of a surface of the first water-soluble film, has a seal strength of about 5 N or more, about 10 N or more, or about 12 N or more, or about 15 N or more, or in a range of about 5 N to about 30 N, or about 10 N to about 25 N, or about 12 N to about 20 N, or about 15 N to about 20 N, as determined by the Seal Strength Test.

42. The water-soluble article of claim 32, wherein the first and second water- soluble films are edible.

43. The water-soluble article of claim 42, wherein the article comprises a composition contained in the sealed compartment.

44. The water-soluble article of claim 43, wherein the composition comprises an instant food product and / or beverage component.

45. A water-soluble film comprising a film forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of starch, carrageenan and pullulan in an amount of at least 50 wt.% based on the total weight of the film, wherein the ratio of starch to the sum of carrageenan and pullulan is in a range of from about 0.01 to about 0.43 or in a range from about 1 to about 9.

46. A water-soluble article in the form of a sheet comprising a first water-soluble film, wherein the first water-soluble film is a water-soluble film according to any one of claims 1 to 27, the sheet further comprising one or more laundry additives or one or more personal care compositions.

47. The water-soluble article of claim 46, wherein the sheet is a laundry sheet and comprises one or more laundry additives.

48. The water-soluble article of claim 47, wherein the sheet is a facial mask shaped to conform to a human face, the sheet comprising one or more personal care compositions.

Images