Water-soluble films with polyvinyl alcohol (PVOH) and natural polymer blends

Abstract

Water-soluble films comprising: a film-forming resin; and optionally, a plasticizer; wherein: the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a biopolymer (or natural polymer); the PVOH is present in an amount up to about 40 wt.%, based on the total weight of the film-forming resin; and the biopolymer is present in an amount of at least about 60 wt.%, based on the total weight of the film-forming resin; with the provisos that: (a) when the biopolymer comprises pullulan, pullulan is not the sole biopolymer in the film; and (b) when the biopolymer comprises starch, starch is not the sole biopolymer in the film. Multiple combinations of biopolymers are contemplated.

Description

Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATIONWATER-SOLUBLE FILMS WITH POLYVINYL ALCOHOL (PVOH) AND NATURAL POLYMER BLENDSCROSS REFERENCE TO RELATED APPLICATION

[0001] The benefit of priority to U.S. Provisional Application No. 63 / 709,013 filed October 18, 2024, is hereby claimed and the disclosure is incorporated herein by reference in its entirety.SUMMARY

[0002] The disclosure provides a water-soluble film including: a film-forming resin; and optionally, a plasticizer (e.g., a plasticizer can be present in or absent from the film); wherein: the film-forming resin includes a mixture of a water-soluble polyvinyl alcohol (PVOH) and a biopolymer (or natural polymer) (e.g., at least one PVOH polymer and at least one biopolymer in admixture); the PVOH is present in an amount up to about 40 wt.%, based on the total weight of the film-forming resin; and the biopolymer is present in an amount of at least about 60 wt.%, based on the total weight of the film-forming resin; with the provisos that: (a) when the biopolymer includes pullulan, pullulan is not the sole biopolymer in the film; and (b) when the biopolymer includes starch, starch is not the sole biopolymer in the film.

[0003] The disclosure further provides a water-soluble film including a film-forming resin and a plasticizer, the film-forming resin includes a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; the PVOH is a PVOH homopolymer and is present in an amount of about 10 to about 20 wt.%, based on the total weight of the filmforming resin and the water-soluble biopolymer includes carrageenan and pullulan, the carrageenan is present in an amount of about 5 to about 20 wt.%, based on the total weight of the film-forming resin, and the remainder of the film-forming resin includes pullulan.

[0004] The disclosure further provides a water-soluble film including a film-forming resin and a plasticizer, the film-forming resin includes a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is an anionic group-modified PVOH and is present in an amount of about 10 to about 35 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer includes carrageenan and pullulan, the carrageenan is present in an amount of about 5 to about 20 wt.%, based on the total weight of the film-forming resin, and the remainder of the film-forming resin is pullulan.

[0005] The disclosure further provides a water-soluble film including a film-forming resin and a plasticizer, the film-forming resin includes a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; PVOH is a PVOH homopolymer or anAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION anionic group-modified PVOH and is present in an amount of about 10 to about 40 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer includes pullulan and tamarind gum, the pullulan is present in an amount of about 15 to about 40 wt.%, based on the total weight of the film-forming resin, and the remainder of the filmforming resin is tamarind gum provided that tamarind gum is provided in an amount equal to or less than 50 wt.%, based on the total weight of the film-forming resin.

[0006] The disclosure further provides a water-soluble film including a film-forming resin and a plasticizer, the film-forming resin includes a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; PVOH is an anionic group-modified PVOH and is present in an amount from about 8 to about 15 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer includes pullulan, starch, and carrageenan, wherein the starch is present in an amount of about 10 to about 30 wt.% (about 20 wt.%), based on the total weight of the film-forming resin, carrageenan is present in an amount of about 5 to about 20 wt.% (about 10 wt.%), based on the total weight of the film-forming resin, and pullulan is provided in an amount in a range of about 45 to about 75 wt.%, based on the total weight of the film-forming resin, and each component is selected such that the sum of PVOH, pullulan, starch and carrageenan is 100 wt.%.

[0007] 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.

[0008] The disclosure further provides methods of making and using water-soluble film according to the disclosure, and articles made from a water-soluble film according to the disclosure.

[0009] 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, embodiments, claims, and Examples provided herein. For example, features of the embodiments and formulation approaches described in Examples 1 to 4 can be combined with any of the additional features provided in the description and claims herein.

[0010] 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 disclosure are susceptible of embodiments in various forms, the description hereafter includes specific embodiments with the understanding that the disclosure is illustrative and is not intended to limit the invention to the specific embodiments described herein.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0011] The film, pouches, and related methods of use are contemplated to include embodiments including any combination of one or more of the additional optional elements, features, and steps further described below, unless stated otherwise.DETAILED DESCRIPTION

[0012] Packaging material made from natural polymers is attractive due to its environmental sustainability. Alone, natural polymers such as starch, modified starch, pullulan, seaweeds, carrageenans, pectin, alginate, caseinate, cellulose based modified and non-modified polymers and pea protein do not provide the necessary properties required for packaging materials such as strength and stability in high moisture conditions. Polyvinyl alcohol (PVOH) is a water-soluble polymer that is used in packaging laundry detergent as single-unit doses due to its high tensile strength. As described herein, blending a natural polymer with a limited amount of PVOH can be utilized to improve the strength and water resistance of the natural polymer to improve film strength and water resistance while still maintaining a high content of natural polymer in the blend system.

[0013] The disclosure generally provides water-soluble films comprising a film-forming resin and optionally a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a biopolymer (or natural polymer) (e.g., at least one PVOH polymer and at least one biopolymer in the mixture), wherein the PVOH is present in an amount up to about 40 wt.%, based on the weight of the film-forming resin and the biopolymer is present in an amount of at least about 60 wt.%, based on the total weight of the film-forming resin, with the provisos that (a) when the biopolymer comprises pullulan, pullulan is not the sole biopolymer in the film; and (b) when the biopolymer comprises starch, starch is not the sole biopolymer in the film.Water Soluble Film

[0014] As used herein, a film is “water-soluble” when the film, at a thickness of about 1 .5 mil (about 0.038 mm), dissolves in 300 seconds or less in water at a temperature of 20 °C (68 °F) in accordance with MonoSol Test Method MSTM-205.

[0015] As used herein, the term “natural polymer” refers to a polymer produced by or extracted from living organisms. The terms “natural polymer” and “biopolymer” are used interchangeably herein.

[0016] The film and related pouches described herein comprise a plasticized water- soluble film. The water-soluble film comprises a film-forming resin comprising at least one biopolymer (i.e., natural polymer) and PVOH.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0017] 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, or any values therebetween or ranges defined by such values.

[0018] 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%, based on the total weight of the film. The combination of polyvinyl alcohol and biopolymer can be provided in an amount of at least about 50 wt.%, based on the total weight of the film.

[0019] The films described herein can be designed to be environmentally friendly or renewable products, for process sustainability and reduced environmental impact. Conventional water-soluble films are often not environmentally friendly and can have a low renewable carbon index (RCI), due to high content of petroleum-based raw materials. The water-soluble films of the disclosure can include at least 99 wt.% bio-based materials, or at least 98, 96, 95, 94, 92, or 90 wt.% bio-based materials. The water-soluble films can have a Renewable Carbon Index of about 100 wt.%, or about 99, 98, 95, 94, 92, or about 90 wt.%.PVOH resins

[0020] The water-soluble film may include one or more polyvinyl alcohol (PVOH) resins disclosed herein to make up the PVOH resin content of the film and can include a PVOH copolymer or homopolymer.

[0021] Polyvinyl alcohol is a synthetic resin generally prepared by the alcoholysis, usually termed hydrolysis or saponification, of polyvinyl acetate. Fully hydrolyzed PVOH, where virtually all the acetate groups have been converted to alcohol groups, is a strongly hydrogen-bonded, highly crystalline polymer which dissolves only in hot water- greater than about 140°F (about 60°C). If a sufficient number of acetate groups are allowed to remain after the hydrolysis of polyvinyl acetate, that is, the PVOH polymer is partially hydrolyzed, then the polymer is more weakly hydrogen-bonded, less crystalline, and is generally soluble in cold water - less than about 50°F (about 10°C). As such, the partially hydrolyzed polymer is a vinyl alcohol-vinyl acetate copolymer that is a PVOH copolymer but it is more commonly referred to as homopolymer PVOH.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0022] The term PVOH copolymer is generally used to describe polymers that are derived by the hydrolysis of a copolymer of a vinyl ester, typically vinyl acetate, and another monomer. PVOH copolymers can be tailored to desired film characteristics by varying the kind and quantity of copolymerized monomers. Examples of copolymerizations are those of vinyl acetate with a carboxylic acid or with an ester of a carboxylic acid. Again, if the hydrolysis of acetate groups in these copolymers is only partial, then the resulting polymer could be described as a PVOH terpolymer — having vinyl acetate, vinyl alcohol, and carboxylic acid groups — although it is commonly referred to as a PVOH copolymer.

[0023] The PVOH resin can include an unmodified polyvinyl alcohol (PVOH homopolymer), an anionic group-modified polyvinyl alcohol, a cationic group-modified polyvinyl alcohol, or a combination thereof.

[0024] The PVOH resin may include a partially or fully hydrolyzed PVOH copolymer that includes an anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate monomer unit. The anionic monomer can be one or more of vinyl acetic acid, alkyl acrylates, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconic anhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1 -methyl propane sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the foregoing (e.g., sodium, potassium, or other alkali metal salts), esters of the foregoing (e.g., methyl, ethyl, or other C1-C4 or C6 alkyl esters), and combinations of the foregoing (e.g., multiple types of anionic monomers or equivalent forms of the same anionic monomer). The anionic group-modified polyvinyl alcohol can be a polyvinyl alcohol modified with itaconic acid, monomethyl maleate (MMM), methyl acrylate (MA), aminopropyl sulfonate, maleic acid, maleic anhydride, n-vinylpyrrolidone, n-vinylcaprolactam, a derivative of any of the foregoing, or a combination thereof. For example, the anionic group-modified polyvinyl alcohol can include polyvinyl alcohol modified with monomethyl maleate, methyl acrylate, or a combination thereof.

[0025] The total PVOH resin content of the film can have a degree of hydrolysis (D.H. or DH) of at least 80%, 84%, or 85% and at most about 99.7%, 98%, or 96%, for example in aAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION range of about 84% to about 90%, or 85% to 88%, or 86.5%, or in a range of 85% to 99.7%, about 88% to 98%, or 90% to 96%, for example, 91%, 92%, 93%, 94%, 95%, or 96%. As used herein, the degree of hydrolysis is expressed as a mole percentage of vinyl acetate units converted to vinyl alcohol units.

[0026] The degree of hydrolysis, while specifically is a measure of the amount of acetates removed from the polyvinyl acetate polymer (e.g. via hydrolysis, saponification), it is most commonly used to understand the amount of acetate remaining on the PVOH polymer or copolymer. The acetate groups form the amorphous or non-crystalline regions of the PVOH copolymer. Therefore, it can be stated as an approximation, the higher the degree of hydrolysis, the relatively higher is the crystallinity of the PVOH copolymer or blends of the PVOH copolymer. When a PVOH resin is described as having (or not having) a particular degree of hydrolysis, unless specified otherwise, it is intended that the specified degree of hydrolysis is the average degree of hydrolysis for the PVOH resin.

[0027] The level of incorporation of the one or more anionic monomer units in the PVOH copolymers can be in a range of about 0.1 mol.% to about 10 mol.%, or about 1 mol.% to about 5 mol.%. For example, at least about 0.1 , 0.5, 1 .0, 1 .5, 2.0, 2.5, 3.0, 3.5, or 4.0 mol.% and / or up to about 3.0, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5 or 10 mol.%.

[0028] The anionic group-modified polyvinyl alcohol can include at least about 0.5 mol.% anionic group modification. The anionic group-modified polyvinyl alcohol can include about 1 .0 mol.% to about 5.0 mol.% anionic group modification. The anionic group-modified polyvinyl alcohol can include about 1 .0 mol.% to about 3.5 mol.% anionic group modification.

[0029] The viscosity of a PVOH polymer (p) is determined by measuring a freshly made solution using a Brookfield LV type viscometer with UL adapter as described in British Standard ENISO 15023-2:2006 Annex E Brookfield Test method. It is international practice to state the viscosity of 4% (w / v) aqueous polyvinyl alcohol solutions at 20°C. All viscosities specified herein in Centipoise (cP) should be understood to refer to the viscosity of 4% (w / v) aqueous polyvinyl alcohol solution at 20°C, unless specified otherwise. Similarly, when a resin is described as having (or not having) a particular viscosity, unless specified otherwise, it is intended that the specified viscosity is the average viscosity for the resin, which inherently has a corresponding molecular weight distribution.

[0030] It is well known in the art that the viscosity of PVOH is correlated with the weight average molecular weight {MW) of the PVOH resin, and often the viscosity is used as a proxy for the weight average molecular weight. Suitable PVOH resins, for use individually orAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION in combinations, can have viscosities in a range of about 1 cP to about 40 cP, or about 5 cP to about 38 cP, or about 10 cP to about 36 cP, or about 12 cP to about 34 cP, or about 14 cP to about 32 cP, for example 32 cP, 23 cP, or 20 cP, or 16.5 cP.

[0031] PVOH can be present in the film in an amount of up to about 40 wt.% based on the total weight of the film forming resin, or from about 5 to about 40 wt.%, or from about 10 to about 20 wt.%, or from about 10 to about 35 wt.%, or from about 10 to about 40 wt.%, or from about 8 to about 15 wt.%, based on the total weight of the film forming resin. When more than one type of PVOH is used in a film-forming resin, the amount of PVOH refers to the total amount of PVOH, i.e., the sum of the total amount of any PVOH homopolymers and any PVOH anionic group-modified copolymers. The amount of PVOH can be, for example, about 10 to about 40 wt.%, or about 10 wt.% to about 35 wt.%, or about 10 wt.% to about 30 wt.%, or about 12 wt.% to about 28 wt.%, or about 12 wt.% to 25 wt.%, or about 14 wt.% to about 22 wt.%, based on the total weight of the film-forming resin. For example, a filmforming resin can include PVOH in amounts of at least 0.01 , 0.1 , 0.5, 1 , 2, 3, 4, 5, 7, 10, 15, 20, 30, or 40 wt.% and / or up to 1 , 2, 3, 4, 5, 7, 10, 15, 20, 30, 40, or 50 wt.%, based on the weight of the film-forming resin.

[0032] The polyvinyl alcohol can be a 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 acetate can 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.

[0033] 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,Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION corn, sugar cane, sorghum, and cassava. Similarly, bio-based acetic acid can be produced by a bioethanol route.

[0034] 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.

[0035] 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 provided in 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.

[0036] In general, lower amounts of PVOH limit the benefits rendered by PVOH, for example increased tensile strength relative to an otherwise identical film without PVOH. Higher amounts of PVOH can lead to miscibility problems and phase separation with some combinations of biopolymers. Higher amounts of PVOH can also lead to films with lower RCI values, when the PVOH included in the film is not a bio-based PVOH.Biopolymer Resins

[0037] Water soluble films of the disclosure can include one or more biopolymers in an amount in a range of about 60 wt.% to about 99.99 wt.% e.g., complementary to the amount of PVOH to add to a total 100% of the weight of the film- forming resin. For example, the film can contain at least 60, 70, 80, 90, 95, 96, 97, 98, or 99 wt.% and / or up to 60, 70, 80, 90, 95,Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION96, 97, 98, 99, 99.9, or 99.99 wt.% of biopolymer, based on the total weight of the filmforming resin.

[0038] The biopolymer can be a water-soluble biopolymer.

[0039] The biopolymer can be selected from the group consisting of polysaccharides (e.g., plant, seaweed, fungal, and / or fermentation based, and / or algae-based polysaccharides), proteins (e.g., plant, animal, and / or animal-based (such as milk) proteins, lignins, and combinations thereof. The biopolymer can be selected from the group consisting of starches, pullulan, fermentation-based biopolymers, seaweed-based biopolymers, carrageenans, pectin, alginate, caseinate, celluloses (e.g., modified and nonmodified cellulose polymers), pea protein, chitin, chitosan, lignin, agar, polysaccharide gums (e.g., gum Arabic, guar gum, locust bean gum, fenugreek gum) and combinations thereof. The biopolymer can be an algae-derived biopolymer. The biopolymer can be an algae- derived biopolymer comprising carrageenan, alginate, agar, or a combination thereof. The biopolymer can be a fermentation-derived biopolymer. For example, a fungal-assisted fermentation can form pullulan from a polysaccharide such as starch. The biopolymer can be a fermentation-derived biopolymer comprising pullulan.

[0040] The biopolymer can comprise 1 , 2, 3, or 4 different biopolymers, e.g., 0, 1 , 2, 3, or 4 different polysaccharides and / or 0, 1 , 2, 3, or 4 different proteins.

[0041] The biopolymer can comprise a first biopolymer and a second biopolymer, wherein the first biopolymer is present in an amount of about 3 wt.% to about 97 wt.%, relative to the total weight of the biopolymers, and the second biopolymer can be present in an amount in a range of about 3 wt.% to about 97 wt.%, based on the total weight of the biopolymers. The first biopolymer can be present in an amount in a range of about 3 wt.% to about 87 wt.%, based on the total weight of the biopolymer, for example, at least 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.%. The second biopolymer can be present in an amount in a range of about 3 wt.% to about 87 wt.%, based on the total weight of the biopolymer, for example, at least 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.%.

[0042] The biopolymer can comprise a first biopolymer, a second biopolymer, and a third biopolymer, wherein the first biopolymer can be present in an amount of about 1 .5 wt.% to 97 wt.%, based on the total weight of the biopolymers, the second biopolymer can be present in an amount of about 1 .5 wt.% to 97 wt.%, based on the total weight of theAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION biopolymers, and the third biopolymer can be present in an amount of about 1 .5 wt.% to about 97 wt.%, based on the total weight of the biopolymers. The first biopolymer can be present in an amount in a range of about 1 .5 wt.% to about 97 wt.%, based on the total weight of the biopolymers, for example, at least 1 .5, 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.%. The second biopolymer can be present in an amount in a range of about 1 .5 wt.% to about 97 wt.%, based on the total weight of the biopolymers, for example, at least 1.5, 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.%. The third biopolymer can be present in an amount in a range of about 1 .5 wt.% to about 97 wt.%, based on the total weight of the biopolymers, for example, at least 1.5, 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.%.

[0043] The biopolymer can comprise a first biopolymer, a second biopolymer, a third biopolymer, and a fourth biopolymer, wherein the first biopolymer can be present in an amount of about 1 wt.% to 97 wt.%, based on the total weight of the biopolymers, the second biopolymer can be present in an amount of about 1 wt.% to 97 wt.%, based on the total weight of the biopolymers, and the third biopolymer can be present in an amount of about 1 wt.% to about 97 wt.%, based on the total weight of the biopolymers. The first biopolymer can be present in an amount of about 1 wt.% to 97 wt.%, based on the total weight of the biopolymer, for example, at least 1 , 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.%. The second biopolymer can be present in an amount of about 1 wt.% to 97 wt.%, based on the total weight of the biopolymer, for example, at least 1 , 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.%. The third biopolymer can be present in an amount of about 1 wt.% to 97 wt.%, based on the total weight of the biopolymer, for example, at least 1 , 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 3, 5, 7, 10, 15, 20, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.%. The fourth biopolymer can be present in an amount of about 1 wt.% to 97 wt.%, based on the total weight of the biopolymer, for example, at least 1 , 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85,90, 95, or 97 wt.%.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATIONPullulan

[0044] 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 to their generally high water solubility, flexibility, clarity, and low oxygen permeability. Pullulan is commercially available from many sources.

[0045] According to the disclosure, pullulan is generally included in water soluble films in combination with at least one more biopolymer, i.e., pullulan is not included as the sole biopolymer in the water-soluble film. For example, pullulan can be included in combination with carrageenan, starch, tamarind gum, or combinations thereof. Films containing pullulan as the sole biopolymer can lack water resistance required in films to be used for single unit dose packaging to be safely handled as some of the compositions encapsulated in single unit dose packages can include water.

[0046] When pullulan is included in a water-soluble film, it can be included in an amount in a range of about 25 wt.% to about 90 wt.%, about 35 wt.% to about 85 wt.%, about 45 wt.% to about 75 wt.%, about 50 wt.% to about 75 wt.%, about 55 wt.% to about 75 wt.%, about 60 wt.% to about 75 wt.%, about 70 wt.% to about 75 wt.%, about 80 to about 85 wt.%, or about 25 wt.% to about 25 wt.%, based on the total weight of film-forming resin.Carrageenan

[0047] 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. The water-soluble films of the disclosure can include kappa-carrageenan. The water-soluble films of the disclosure can include iota-carrageenan. The water-soluble films of the disclosure can include lambda- carrageenan.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0048] When carrageenan is included in a water-soluble film, it can be included in an amount in a range of about 5 wt.% to about 20 wt.%, about 9 wt.% to about 15 wt.%, or about 5, 9, 10,11 , 12, 13, 15, or about 20 wt.%, based on the total weight of the film-forming resin.Tamarind Gum

[0049] Tamarind seed gum or tamarind gum is a naturally occurring biopolymer rich in xyloglucan, a hemicellulose that occurs in the primary cell wall of vascular plants, including tamarind (Tamarindus Indica L). Films comprising tamarind gum as the sole or primary filmforming resin are usually not water or heat sealable and / or may lack enough flexibility needed for thermoforming, which limits the applications of such films in packaging applications. Therefore, tamarind gum films can benefit from blending the tamarind gum with PVOH and / or with other biopolymers to provide better flexibility (e.g., larger strain at break values than otherwise identical films including tamarind gum only) and better sealability.

[0050] When tamarind gum is included in a water-soluble film, it can be included in an amount in a range of about 20 wt.% to about 85 wt.%, or from about 20 wt.% to about 65 wt.%, about 20 to about 50 wt.%, about 50 to about 65 wt.%, about 50, 55, 62, or about 65 wt.%. The film-forming resin can include tamarind gum in an amount of equal to or less than 50 wt.%, based on the total weight of the film-forming resin. The film-forming resin can include tamarind gum in an amount of greater than 50 wt.%, based on the total weight of the film forming resin.Starch

[0051] Starches are naturally derived polysaccharides consisting of anhydroglucose units with 1 -4a and 1-6a glycoside bonds, having linear or branched chains. Linear chains are known as amylose and branched chains are known as amylopectin. Starches can be obtained from multiple plant sources including but not limited to corn, potato, tapioca, rice, and wheat. Starch can be made water soluble by a gelatinization process. Gelatinization includes swelling of the starch granules and breaking of intermolecular bonds to disrupt the semicrystalline region of the starch. Generally, starches with lower molecular weight, lower amounts of amylose, and which have modifications are more easily gelatinized. Starch molecular weight can be reduced through acid hydrolysis, which increases the maximum cook %. Chemical or enzymatic modifications to starch can increase water solubility, inhibit retrogradation, and reduce starch solution viscosity. Chemical modifications can be located at the 2nd and 3rd carbon of the glucose unit via reactions with the secondary alcohols atAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION those sites. Chemical and / or enzymatic modifications can include nonionic (e.g., hydroxyethyl, hydroxypropyl), anionic (e.g., carboxyl), cationic (e.g., trimethyl ammonium).

[0052] The water-soluble film can include a water-soluble starch comprising a substantially gelatinized starch. Any source of starch can be used, e.g., from corn, potato, tapioca, rice, or wheat. The water-soluble film can include a non-gelatinized starch.

[0053] The water-soluble starch can have an average molecular weight in a range of about 103-107g / mol, or about 103-106g / mol or about 104-105g / mol.

[0054] The water-soluble starch can comprise an unmodified starch, a neutral group or non-ionic group-modified starch, a cationic group-modified starch, and combinations thereof.

[0055] In general, when starch is included in the water-soluble films of the disclosure, starch is included in combination with other biopolymers (i.e., starch is not the sole biopolymer). The addition of starch with a corresponding decrease in PVOH can produce films with mechanical properties comparable to the analogous films without starch with the additional benefit of an increased bio-based content (when non-biobased PVOH is used) and / or lower costs as starch is generally less expensive than PVOH.

[0056] When starch is included in a water-soluble film, it can be included in an amount in a range of about 10 wt.% to about 40 wt.%, about 10 wt.% to about 30 wt.%, about 10 wt.% to about 20 wt.%, or about 10, 12, 15, 20 25, 30, 35, or about 40 wt.%Pectin

[0057] Pectins are a family of hetero-polysaccharides consisting mainly of partially methoxylated polygalacturonic acids. Pectins occur naturally in terrestrial plants and are predominantly found in the rinds of citrus fruits and apple pomace from where it is most commonly extracted. Pectins are readily soluble in water and have been used as viscosity modifiers and gel forming agents. Pectins are commercially available, for instance from CP Kelco.

[0058] In some water-soluble films, when the biopolymer comprises pectin, pectin is not the sole biopolymer in the film. In some water-soluble films, when the biopolymer comprises pectin, pectin is the sole biopolymer in the film.Alginate

[0059] Alginates are salt derivatives of alginic acid, a linear copolymer of -D- mannuronate (M) and a-L- guluronate (G) residues covalently linked together in differentAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION sequences. Alginates are commercially extracted form brown seaweeds like giant kelp Macrocystis pyrifera, Ascophyllum nodosum, and types of Laminaria

[0060] The biopolymer can comprise pullulan and at least one of carrageenan, starch, and tamarind gum. The biopolymer can comprise pullulan and carrageenan and the water- soluble film can include carrageenan in an amount in a range of about 5 wt.% to about 20 wt.%, about 6 wt.% to about 18 wt.%, about 7 wt.% to about 16 wt.%, or about 8 wt.% to about 14 wt.%, based on the total weight of the film-forming resin and pullulan can make up the balance of the biopolymer. The biopolymer can comprise pullulan, carrageenan, and starch and the water-soluble film can include carrageenan in an amount in a range of about 5 wt.% to about 20 wt.%, about 6 wt.% to about 18 wt.%, about 7 wt.% to about 16 wt.%, about 8 wt.% to about 14 wt.%, or about 9 wt.% to about 12 wt.%, or about 10 wt.% based on the total weight of the film-forming resin, starch in an amount in a range of about 10 wt% to about 30 wt.%, about 12 wt.% to about 28 wt.%, about 14 wt.% to about 26 wt%, about 16 wt.% to about 24 wt.%, about 18 wt.% to about 22 wt.%, or about 20 wt.%, based on the total weight of the film-forming resin, and the pullulan can make up the balance of the biopolymer.

[0061] The biopolymer can comprise tamarind gum and pullulan and the water-soluble film can include pullulan in an amount in a range of about 15 wt.% to about 40 wt.%, about 20 wt.% to about 35 wt.%, or about 25 wt.% to about 30 wt.%, based on the total weight of film-forming resin and the tamarind gum can make up the balance of the biopolymer.

[0062] The biopolymer can comprise starch, pullulan, and at least one of chitin and chitosan. The biopolymer can comprise at least two biopolymers selected from the group consisting of pullulan, starch, carrageenan, pectin, and alginate. The biopolymer can comprise a native starch, a modified starch, or a combination thereof. The biopolymer can comprise about 5 wt.% to about 20 wt.% carrageenan and about 10 wt.% to about 30 wt.% starch.

[0063] A film-forming resin according to the disclosure can contain about 10 to about 20 wt.% of a PVOH homopolymer and a biopolymer including about 5 to about 20 wt.% carrageenan, and the remainder of pullulan based on the total weight of the film-forming resin. For example, a film-forming resin can contain about 7 wt.% PVOH homopolymer, about 10 wt.% carrageenan, and about 83 wt.% pullulan. For example, a film-forming resin can contain about 11 wt.% PVOH, about 10 wt.% carrageenan, and about 79 wt.% pullulan. As demonstrated in the Examples, below, a water-soluble film including such a blend of PVOH homopolymer and biopolymer including carrageenan and pullulan canAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION advantageously provide a film that has good compatibility (i.e., no phase separation of different polymer types), and water resistance relative to an otherwise identical film including pullulan alone, as indicated by tensile strength and Young’s modulus values higher than those of the otherwise identical film including pullulan alone.

[0064] A film-forming resin according to the disclosure can contain about 10 to about 35 wt.% of an anionic group-modified PVOH and a biopolymer including about 5 to about 20 wt.% carrageenan, and the remainder of pullulan based on the total weight of the filmforming resin. For example, a film-forming resin can contain about 14 wt.% of anionic group- modified PVOH, about 10 wt.% carrageenan, and about 76 wt.% pullulan. For example, a film-forming resin can contain about 28 wt.% of anionic group-modified PVOH, about 10 wt.% carrageenan, and about 62 wt.% pullulan. For example, a film-forming resin can contain about 29 wt.% of anionic group-modified PVOH, about 14 wt.% carrageenan, and about 57 wt.% pullulan. As demonstrated in the Examples, below, a water-soluble film including such a blend of an anionic group-modified PVOH and biopolymer including carrageenan and pullulan can advantageously provide a film that has good compatibility (i.e., no phase separation of different polymer types), and water resistance relative to an otherwise identical film including pullulan alone, as indicated by tensile strength and Young’s modulus values higher than those of the otherwise identical film including pullulan alone.

[0065] A film-forming resin according to the disclosure can contain about 10 to about 40 wt.% of a PVOH and about 60 to about 90 wt.% of a biopolymer comprising tamarind gum. The PVOH can include a PVOH homopolymer, an anionic group-modified PVOH, or a combination thereof.

[0066] A film-forming resin according to the disclosure can contain about 10 to about 40 wt.% of a PVOH and about 60 to about 90 wt.% of a biopolymer. The PVOH can include a PVOH homopolymer, an anionic group-modified PVOH, or a combination thereof. The biopolymer can include about 15 to about 40 wt.% pullulan, and the remainder of tamarind gum, based on the total weight of the film-forming resin. For example, a film-forming resin can contain about 7 wt.% of PVOH homopolymer, about 29 wt.% pullulan, and about 64 wt.% tamarind gum. For example, a film-forming resin can contain about 14 wt.% of a PVOH homopolymer, about 29 wt.% pullulan, and about 57 wt.% tamarind gum. For example, a film-forming resin can contain about 21 wt.% of a PVOH homopolymer, about 29 wt.% pullulan, and about 50 wt.% tamarind gum. The film-forming resin can include tamarind gum in an amount of equal to or less than 50 wt.%, based on the total weight of the film-forming resin. The film-forming resin can include tamarind gum in an amount of greater than 50Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION wt.%, based on the total weight of the film forming resin. As demonstrated in the Examples below, it was surprisingly found that the addition of PVOH to tamarind gum only films did not provide an increase to the mechanical properties of the resulting films (i.e., the films including a blend of PVOH and tamarind gum had similar properties to an otherwise identical film including only tamarind gum). Advantageously, the addition of PVOH to a blend of pullulan and tamarind gum resulted in an increase to the tensile strength of films conditioned at high humidity (i.e., 65% RH), relative to an otherwise identical film including only pullulan and tamarind gum. Further surprisingly, it was observed that the addition of pullulan to a blend of PVOH and tamarind gum resulted in improved strain at break values, compared to films that only included a blend of PVOH and tamarind gum, particularly in view of the showing that pullulan and PVOH are not miscible under all circumstances.

[0067] A film-forming resin according to the disclosure can contain about 8 to about 15 wt.% of an anionic group-modified PVOH and a biopolymer including about 45 to about 75 wt.% pullulan, about 10 to about 30 wt.% of starch, and about 5 to about 20 wt.% carrageenan, based on the total weight of the film-forming resin. For example, a film-forming resin can contain about 10 wt.% of anionic group-modified PVOH, about 60 wt.% pullulan, about 10 wt.% carrageenan, and about 20 wt.% starch. As demonstrated in the Examples, below.

[0068] The film-forming resin in the water-soluble film can contain at least about 90 wt.%, or at least 92, 94, 96, 98, or 99 wt.% and / or up to about 100 wt.% of a combination of PVOH and biopolymer. Alternatively, the film-forming resin may contain no more than 1 , 2, 4, 6, 8, or 10 w.% of components or resins other than PVOH and biopolymers.

[0069] For example, a water-soluble film containing up to 45% pullulan, 40% starch, and 15% PVOH as the film-forming ingredient can have higher mechanical and water resistance than a film made from a blend of pullulan and starch.

[0070] In another example, a water-soluble film can be made by blending up to 50% starch, 20% carrageenan, and 30% PVOH to achieve better mechanicals and water resistance.

[0071] In another example, a water-soluble film can be made by blending up to 30% starch, 20% pullulan, 20% carrageenan, and 30% PVOH to achieve better mechanical and water resistance.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0072] In another example, a water-soluble film can be made by blending up to 65% pullulan, 15% pectin, and 20% PVOH to improve mechanical and water resistance properties.

[0073] In another example, a water-soluble film can be made by blending up to 50% starch, 20% alginate and 30% PVOH.

[0074] In another example, a water-soluble film can be made by blending up to 30% starch, 20% pullulan, 20% alginate, and 30% PVOH to achieve better mechanical and water resistance.

[0075] In another example, a water-soluble film can be made by blending up to 70% pullulan, 10% Carrageenan and 10% PVOH to achieve higher strength and water resistance.

[0076] In another example, a water-soluble film can be made by blending up to 60% pullulan, 20% starch, 10% carrageenan, and 10% PVOH.

[0077] In another example, a water-soluble film can be made by blending up to 30% pullulan, 40% starch, 10% carrageenan, and 20% PVOH.

[0078] In another example, a water-soluble film can be made by blending up to 70% pullulan, 20% Carrageenan, and 5% PVOH to achieve higher strength and water resistance.

[0079] In another example, a water-soluble film can be made by blending up to 70% pullulan, 25% Carrageenan, and 1% PVOH to achieve higher strength and water resistance.Other Resins

[0080] 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.

[0081] 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,Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATIONPVOH 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 10 wt.%, or up to about 5 wt.%, or up to about 2.5 wt.%, based on the total weight of the film.Plasticizers

[0082] 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 glass transition 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.

[0083] 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.

[0084] 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. TheAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION amount of plasticizer can also be characterized in terms of parts per 100 parts film-forming resin (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, some biopolymer combinations may produce films that 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.Auxiliary Agents

[0085] 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.

[0086] 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 acids containing 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®Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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-blockAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0091] 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.

[0092] 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.

[0093] 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

[0094] 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.

[0095] 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,Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION can have a dissolution time in a range of about 10 to about 500 seconds, or about 10 to about 300 seconds, or about 10 to about 200 seconds, or about 10 to about 100 seconds.

[0096] The water-soluble film of the disclosure can further be characterized by a tensile strength, as determined according to the Tensile Properties 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 tensile strength in a range of about 5 N / mm2to about 40 N / mm2, or 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 can be desirable because they generally correspond to stronger pouches with less tendency to rupture.

[0097] The water-soluble film of the disclosure can further be characterized by a Young’s modulus, as determined according to the Tensile Properties Test described herein. For example, the film, after being conditioned for at least 18 hours at 28 °C / 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 28 °C / 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.

[0098] The water-soluble film of the disclosure can be further characterized by strain at break, as determined according to the Tensile Properties Test described herein. For example, the film, after being conditioned for at least 18 hours at 28 °C / 50% RH, can have a strain at break in a range of about 80% to about 500%, or about 50% to about 400%, or about 50% to about 300%, or about 80% to about 200%, or about 120% to about 300%, or about 100% to about 200%, or about 100% to about 250%. 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 100% to about 700%, or about 80% to about 300%, or about 100% to about 250%, or about 125% to about 200%, about 250% to about 700%, or about 500% to about 650%, or about 500% to about 600%.

[0099] Generally, the tensile strength, strain at break 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 resinsAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0100] 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 4 Newtons (N) or more, or 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.

[0101] 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.

[0102] 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 5 N, or less than about 10 N, or less than about 7 N, or less than about 3 N, or less than about 1 N

[0103] “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.

[0104] 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.”Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0105] 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.

[0106] 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 and therefore do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.

[0107] 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.

[0108] 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.

[0109] 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).

[0110] 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 of film-forming resin in the water-soluble film.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0111] 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.

[0112] 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.

[0113] 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).

[0114] “Bio-based” as used herein refers to materials for which at least a portion of the materials is derived from living or once-living matter. 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).

[0115] 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 withAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.Water-soluble films of the disclosure can have RCI values of at least about 80%, 90%, 95%, or up to 90%, 95%, 98%, 99%, or up to about 100%.Fibers

[0116] Compositions described herein for the films of the disclosure can be used as compositions of fibers.

[0117] 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.

[0118] 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.

[0119] 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 a bidirectional orientation. The plurality of fibers can be multi-directional, having different arrangements in different areas of the nonwoven web.

[0120] 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATIONWater-Soluble Articles

[0121] The water-soluble film disclosed herein is useful for creating a sealed article in the form of a pouch or a packet 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.

[0122] The pouch may comprise a single compartment or multiple compartments. A water-soluble pouch can be formed from a first and a second water-soluble films according to the disclosure, the two water-soluble films 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.

[0123] 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.

[0124] 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

[0125] 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 edgeAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0126] 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 / 50% 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.

[0127] 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 limitedAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0128] According to the disclosure, water-soluble articles can include a first water- soluble film 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. The first water-soluble film sealed to itself can be characterized by a seal strength of about 4 N or more, or about 8 N or more, or about 10 N or more, or in a range of about 4 N to about 30 N, or about 5 N to about 25 N, or about 8 N to about 20 N, or about 10 N to about 20 N, as determined by the Seal Strength Test.Article and / or Pouch Contents

[0129] In any embodiment, the water-soluble pouch can contain (enclose) a composition, for example, a household care 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.

[0130] 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0131] The household care composition can optionally contain ingredients intended to discourage ingestion including 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] The liquid detergent composition can be used in a fabric hand wash operation or may be used in an automatic machine fabric wash operation.

[0136] 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0137] In other aspects, the household care composition may be an automatic dish washing detergent composition comprising an ingredient selected from surfactant, builder, sulfonated I 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.

[0138] 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-treatment composition, and a combination thereof. In embodiments, the non-household care composition is a pool and / or water-treatment composition.

[0139] 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.

[0140] 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.

[0141] 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 theAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0142] 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; 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 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.

[0143] 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.

[0144] 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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. TheAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0149] 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, fruit drink 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).

[0150] 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0151] 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.

[0152] 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.

[0153] 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

[0154] 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, orAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0155] 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.

[0156] 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0157] 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.

[0158] 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.

[0159] 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0160] 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.

[0161] 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.

[0162] 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 surface coated 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.

[0163] 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. InAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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 release coating. 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.

[0164] 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.

[0165] 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 ofAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0166] 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.

[0167] 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 film temperature 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.

[0168] 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 aAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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

[0169] 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.

[0170] 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.

[0171] 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

[0172] 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 filmAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0173] 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.

[0174] 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 the product 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.

[0175] 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0176] According to the disclosure, the first and second water-soluble films in a water- soluble article can be one or both thermoformed films.Dissolution and Disintegration Test (MSTM-205)

[0177] 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.

[0178] Apparatus and Materials:

[0179] 600 mL Beaker

[0180] Magnetic Stirrer (Labline Model No. 1250 or equivalent)

[0181] Magnetic Stirring Rod (5 cm)

[0182] Thermometer (0 to 100 °C ± 1 °C)

[0183] Template, Stainless Steel (3.8 cm x 3.2 cm)

[0184] Timer (0 - 300 seconds, accurate to the nearest second)

[0185] Polaroid 35 mm slide Mount (or equivalent)

[0186] MonoSol 35 mm Slide Mount Holder (or equivalent)

[0187] Distilled water

[0188] 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.

[0189] Lock each specimen in a separate 35 mm slide mount.

[0190] 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).

[0191] 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.

[0192] 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 depthAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.Icorrected = Imeasured x (reference thickness / measured thickness)1 93[1]Scorrected = Smeasured x (reference thickness / measured thickness)1 83[2]Tensile Properties Test

[0197] A water-soluble film characterized by or to be tested for tensile strength, Young’s modulus and break strain according to the Tensile Properties 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 film type. Samples of a single film sheet having a thickness of about 88 pm are cut T’-wide (2.54 cm) and about 5 inches long.

[0198] Film specimens are conditioned for at least 18 hours at 28 °C / 50% RH, or 28 °C / 65% RH prior to measurement. Tests are conducted in the standard laboratoryAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION atmosphere of 23±2.0°C and 35±5% RH in a manner that minimizes exposure to the laboratory standard conditions.

[0199] The tensile testing machine equipped with a 500 N load cell is prepared and calibrated according to the manufacturer instructions. 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 testing machine and the test is run at a strain rate of 508 mm / min until the film breaks.

[0200]

[0201] The 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 2-5% 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. The Young’s modulus for a particular film composition is the average of the Young’s modulus values of all the specimens tested.

[0202] The tensile strength of the film is defined as the force required to break the film divided by the cross-sectional area of the film. The tensile strength of a particular film composition is the average of the tensile strength values of all the specimens tested.

[0203] The elongation at break or strain at break is the maximum length of the film measured before it breaks. The break strain of a particular film composition is the average of the break strain values of all the specimens tested.Seal Strength Test

[0204] 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.

[0205] 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 test specimens, each cut with reliable cutting tools to ensure dimensional stability andAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0206] 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).

[0207] 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.

[0208] 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

[0209] 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 withoutAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION imparting 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.

[0210] 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION2. 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”).

[0211] 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.

[0212] The aspects described in the following numbered paragraphs are particularly contemplated:

[0213] 1 . A water-soluble film comprising a film-forming resin and optionally, a plasticizer(e.g., a plasticizer can be present in or absent from the film); wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a biopolymer (or natural polymer) (e.g., at least one PVOH polymer and at least one biopolymer in admixture); the PVOH is present in an amount up to about 50 wt.%, based on the total weight of the film-forming resin; and the biopolymer is present in an amount of at least about 50 wt.%, based on the total weight of the film-forming resin.

[0214] 2. The water-soluble film of paragraph 1 , wherein the water-soluble polyvinyl alcohol comprises an unmodified polyvinyl alcohol (e.g., PVOH homopolymer), an anionic group-modified polyvinyl alcohol, a cationic group-modified polyvinyl alcohol, or a combination thereof.

[0215] 3. The water-soluble film of paragraph 1 or paragraph 2, wherein the polyvinyl alcohol comprises an anionic group-modified polyvinyl alcohol having a degree of modification in a range of about 0.1-10 mol.%.

[0216] 4. The water-soluble film of paragraph 3, wherein the anionic group-modified polyvinyl alcohol has a degree of modification in a range of about 1 .0-5.0 mol.%.

[0217] 5. The water-soluble film of paragraph 4, wherein the anionic group-modified polyvinyl alcohol comprises a polyvinyl alcohol modified with itaconic acid, monomethyl maleate (MMM), methyl acrylate (MA), aminopropyl sulfonate, maleic acid, maleic anhydride, n-vinylpyrrolidone, n-vinylcaprolactam, a derivative of any of the foregoing, or a combination thereof.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0218] 6. The water-soluble film of paragraph 5, wherein the anionic group-modified polyvinyl alcohol comprises the polyvinyl alcohol modified with monomethyl maleate, methyl acrylate, or a combination thereof.

[0219] 7. The water-soluble film of any of paragraphs 1-6, wherein the PVOH is present in an amount in a range of about 0.01 wt.% to about 50 wt.%, or about 1 wt.% to about 20 wt.%, or about 1 wt.% to about 10 wt.%, or about 2 wt.% to about 7 wt.%, or about 1 wt.% to 5 wt.%, or about 0.5 wt.% to about 3 wt.%, based on the total weight of the film-forming resin (e.g., at least 0.01 , 0.1 , 0.5, 1 , 2, 3, 4, 5, 7, 10, 15, 20, 30, or 40 wt.% and / or up to 1 , 2, 3, 4, 5, 7, 10, 15, 20, 30, 40, or 50 wt.%).

[0220] 8. The water-soluble film of any of paragraphs 1-6, wherein the biopolymer is present in an amount in a range of about 50 wt.% to about 99.99 wt.% (e.g., complementary to any of the above PVOH ranges), based on the total weight of the film-forming resin (e.g., at least 50, 60, 70, 80, 90, 95, 96, 97, 98, or 99 wt.% and / or up to 60, 70, 80, 90, 95, 96, 97, 98, 99, 99.9, or 99.99 wt.%).

[0221] 9. The water-soluble film of any of paragraphs 1-6, wherein a combined amount of the PVOH and the biopolymer is at least 90 wt.%, based on the total weight of the filmforming resin (e.g., at least 90, 92, 94, 96, 98, or 99 wt.% and / or up to 100 wt.%; alternatively not more than 1 , 2, 4, 6, 8, or 10 wt.% of components other than PVOH and biopolymers in the film-forming resin).

[0222] 10. The water-soluble film of any of paragraphs 1 -6, wherein the biopolymer is selected from the group consisting of polysaccharides (e.g., plant, seaweed, fungal and / or fermentation-based, and / or algae-based polysaccharides), proteins (e.g., plant, animal, and / or animal-based (such as milk) proteins), lignins, and combinations thereof.

[0223] 11 . The water-soluble film of any of paragraphs 1-6, wherein the biopolymer is selected from the group consisting of starches (e.g., native starch and / or modified starch), pullulan, fermentation-based biopolymers, seaweed-based biopolymers, carrageenans, pectin (e.g., unmodified or modified pectin, such as high methoxy- or low methoxy-pectin), alginate, caseinate, celluloses (e.g., modified and non-modified cellulose polymers), pea protein, chitin, chitosan, lignin, agar, polysaccharide gums (e.g., gum arabic, guar gum, locust bean gum, fenugreek gum) and combinations thereof.

[0224] 12. The water-soluble film of any of paragraphs 1-6, wherein the biopolymer comprises (or contains) 1 , 2, 3, or 4 different biopolymers (e.g., 0, 1 , 2, 3, or 4 different polysaccharides and / or 0, 1 , 2, 3, or 4 different proteins).Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0225] 13. The water-soluble film of paragraph 12, wherein: the biopolymer comprises a first biopolymer and a second biopolymer; the first biopolymer is present in an amount of about 3 wt.% to 97 wt.% relative to total biopolymers; and the second biopolymer is present in an amount of about 3 wt.% to 97 wt.% relative to total biopolymers (e.g., at Ieast 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.% independently selected for each of the first and second biopolymers).

[0226] 14. The water-soluble film of paragraph 12, wherein: the biopolymer comprises a first biopolymer, a second biopolymer, and a third biopolymer; the first biopolymer is present in an amount of about 1 .5 wt.% to 97 wt.% relative to total biopolymers; the second biopolymer is present in an amount of about 1 .5 wt.% to 97 wt.% relative to total biopolymers; and the third biopolymer is present in an amount of about 1 .5 wt.% to 97 wt.% relative to total biopolymers (e.g., at least 1.5, 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.% independently selected for each of the first, second, and third biopolymers).

[0227] 15. The water-soluble film of paragraph 12, wherein: the biopolymer comprises a first biopolymer, a second biopolymer, a third biopolymer, and a fourth biopolymer; the first biopolymer is present in an amount of about 1 wt.% to 97 wt.% relative to total biopolymers; the second biopolymer is present in an amount of about 1 wt.% to 97 wt.% relative to total biopolymers; the third biopolymer is present in an amount of about 1 wt.% to 97 wt.% relative to total biopolymers; and the fourth biopolymer is present in an amount of about 1 wt.% to 97 wt.% relative to total biopolymers; (e.g., at least 1 , 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.% independently selected for each of the first, second, third, and fourth biopolymers).Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0228] 16. The water-soluble film of any of paragraphs 1-15, wherein the biopolymer is a water-soluble biopolymer.

[0229] 17. The water-soluble film of any of paragraphs 1-15, wherein the biopolymer comprises an algae-derived biopolymer.

[0230] 18. The water-soluble film of paragraph 17, wherein the algae derived biopolymer comprises carrageenan, alginate, agar, or combinations thereof.

[0231] 19. The water-soluble film of any of paragraphs 1-15, wherein the biopolymer comprises a fermentation-derived biopolymer (e.g., fungal-assisted fermentation of a polysaccharide such as starch to form pullulan).

[0232] 20. The water-soluble film of paragraph 19, where the fermentation-derived biopolymer comprises pullulan.

[0233] 21 . The water-soluble film of any of paragraphs 1-15, wherein the biopolymer comprises starch, pullulan, and at least one of chitin and chitosan.

[0234] 22. The water-soluble film of any of paragraphs 1 -15, wherein the biopolymer comprises at least two biopolymers selected from the group consisting of pullulans, starches, carrageenans, pectins, and alginates.

[0235] 23. The water-soluble film of any of paragraphs 1-15, wherein the biopolymer comprises a native starch, a modified starch or a combination thereof.

[0236] 24. The water-soluble film of paragraph 1 , wherein the film-forming resin comprises no more than 10 wt.% PVOH.

[0237] 25. The water-soluble film of paragraph 1 , wherein the film-forming resin comprises a mixture of water-soluble polyvinyl alcohol (PVOH) and water-soluble biopolymer in an amount of at least 50 wt.% based on the total weight of the film.

[0238] 26. The water-soluble film of any one of the preceding paragraphs, wherein the plasticizer is selected from the group of 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 a combination thereof.

[0239] 27. The water-soluble film of any one of the preceding paragraphs, wherein the plasticizer is present in an amount in a range of about 5 wt.% to 45 wt.%, about 10 wt.% toAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION45 wt.%, or about 10 wt.% to about 30 wt.%, or about 15 wt.% to about 35 wt.%, or about 20 wt.% to about 20 wt.%, based on the total weight of the non-water components of the film.

[0240] 28. The water-soluble film of any one of the preceding paragraphs, wherein the plasticizer is present in an amount in a range of about 10 PHR to about 85 PHR, or about 15 PHR to about 75 PHR, or about 20 PHR to about 50 PHR, or about 25 PHR to about 45 PHR, or about 30 PHR to about 40 PHR.

[0241] 29. The water-soluble film of any one of the preceding paragraphs, wherein the film comprises one or more auxiliary agents selected from fillers, surfactants, anti-block agents, antioxidants, antifoams, bleaching agents, aversive agents, and pungents.

[0242] 30. The water-soluble film of any one of the preceding paragraphs, 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.

[0243] 31 . The water-soluble film of any one of the preceding paragraphs, wherein the film, when provided at a thickness of 88 pm, has a dissolution time in a range of about 10 to about 500 seconds, or about 10 to about 300 seconds, or about 10 to about 150 seconds, as measured according to MSTM-205.

[0244] 32. The water-soluble film of any one of the preceding paragraphs, wherein the film has a strain at break in a range of about 80% to about 500%, 100% to about 500%, or about 120% to about 300%, or about 100% to about 200%, or about 100% to about 250%, after being conditioned for at least 18 hours at 28 °C / 50% RH, as measured according to the Elongation at Break Test.

[0245] 33. The water-soluble film of any one of the preceding paragraphs, wherein the film has a strain at break in a range of about 250% to about 700%, or about 500% to about 650%, or about 500% to about 600%, after being conditioned for at least 18 hours at 28 °C / 65% RH, as measured according to the Elongation at Break Test.

[0246] 34. The water-soluble film of any one of the preceding paragraphs, wherein the film has a tensile strength in a range of about 5 N / mm2(MPa) to about 50 N / mm2, or about 5 N / mm2to about 40 N / mm2, or about 5 N / mm2to about 30 N / mm2, or about 5 N / mm2to about 25 N / mm2, or about 5 N / mm2to about 20 N / mm2, or about 5 N / mm2to 15 N / mm2after being conditioned for at least 18 hours at 28 °C / 50% RH, as measured according to the Tensile Properties Test.

[0247] 35. The water-soluble film of any one of the preceding paragraphs, wherein the film has a tensile strength in a range of about 5 N / mm2(MPa) to about 40 N / mm2, or about 5Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATIONN / mm2to about 30 N / mm2, or about 5 N / mm2to about 20 N / mm2, or about 5 N / mm2to about 15 N / mm2, or about 5 N / mm2to about 10 N / mm2after being conditioned for at least 18 hours at 28 °C / 65% RH, as measured according to the Tensile Properties Test.

[0248] 36. The water-soluble film of any one of the preceding paragraphs, 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 4 N or more, or about 8 N or more, or about 10 N or more, or in a range of about 4 N to about 30 N, or about 5 N to about 25 N, or about 8 N to about 20 N, or about 10 N to about 20 N, as measured according to the Seal Strength Test.

[0249] 37. The water-soluble film of any one of the preceding paragraphs, wherein the biopolymer is 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 protein, casein protein, copolymers of the foregoing, and a combination of any of the foregoing.

[0250] 38. The water-soluble film of any one of the preceding paragraphs, wherein the PVOH comprises a bio-based PVOH.

[0251] 39. The water-soluble film of paragraph 47, wherein the PVOH consists of a biobased PVOH.

[0252] 40. The water-soluble film of any one of the preceding paragraphs, wherein the film comprises at least 95 wt.% bio-based materials.

[0253] 41 . The water-soluble film of paragraph 47, wherein the film comprises at least 99 wt.% bio-based materials.

[0254] 42. The water-soluble film of paragraph 47, wherein the film has a Renewable Carbon Index of 100 wt.%.

[0255] 43. The water-soluble film of any one of the preceding paragraphs, wherein the film is characterized by having a blocking force of no greater than 5 N, or no greater than 3 N, or no greater than 1 N, as measured according to the Blocking Test.

[0256] 44. 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,Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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.

[0257] 45. The water-soluble article of paragraph 53, wherein the article comprises a composition contained in the sealed compartment.

[0258] 46. The water-soluble article of paragraph 54, wherein the composition comprises a household care composition.

[0259] 47. The water-soluble article of paragraph 55, 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.

[0260] 48. The water-soluble article of paragraph 55 or paragraph 56, 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.

[0261] 49. The water-soluble article of paragraph 57, 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.

[0262] 50. The water-soluble article of paragraph 54, wherein the composition comprises a non-household care composition.

[0263] 51 . The water-soluble article of any one of paragraphs 53 to 59, wherein the first water-soluble film is a thermoformed film.

[0264] 52. The water-soluble article of any one of paragraphs 53 to 60, wherein the second water-soluble film has the same composition as the first water-soluble film.

[0265] 53. The water-soluble article of any one of paragraphs 53 to 61 , 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 4 N or more, or about 8 N or more, or about 10 N or more, or in a range of about 4 N to about 30 N, or about 5 N to about 25 N, or about 8 N to about 20 N, or about 10 N to about 20 N, as determined by the Seal Strength Test.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0266] 54. The water-soluble article of paragraph 53, wherein the first and second water- soluble films are edible.

[0267] 55. The water-soluble article of paragraph 63, wherein the article comprises a composition contained in the sealed compartment.

[0268] 56. The water-soluble article of paragraph 64, wherein the composition comprises an instant food product and / or beverage component.

[0269] 57. 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 paragraphs 1 to 28, the sheet further comprising one or more laundry additives or one or more personal care compositions.

[0270] 58. The water-soluble article of paragraph 66, wherein the sheet is a laundry sheet and comprises one or more laundry additives.

[0271] 59. The water-soluble article of paragraph 66, wherein the sheet is a facial mask shaped to conform to a human face, the sheet comprising one or more personal care compositions.

[0272] 60. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is present in an amount of about 15 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer comprises pullulan in an amount of about 45 wt.% and starch in an amount of about 40 wt%, based on the total weight of the film-forming resin.

[0273] 61 . A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is present in an amount of about 30 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer comprises carrageenan in an amount of about 20 wt.% and starch in an amount of about 50 wt%, based on the total weight of the film-forming resin.

[0274] 62. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is present in an amount of about 30 wt.%, based on the total weightAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION of the film-forming resin and the water-soluble biopolymer comprises carrageenan in an amount of about 20 wt.%, pullulan is present in an amount of about 20 wt.%, and starch in an amount of about 30 wt.%, based on the total weight of the film-forming resin.

[0275] 63. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is present in an amount of about 20 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer comprises pullulan in an amount of about 65 wt.% and pectin in an amount of about 15 wt%, based on the total weight of the film-forming resin.

[0276] 64. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is present in an amount of about 30 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer comprises alginate in an amount of about 20 wt.% and starch in an amount of about 50 wt%, based on the total weight of the film-forming resin.

[0277] 65. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is present in an amount of about 30 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer comprises pullulan in an amount of about 20 wt.%, alginate in an amount of about 20 wt.%, and starch in an amount of about 30 wt.%, based on the total weight of the film-forming resin.

[0278] 66. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is present in an amount of about 10 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer comprises pullulan in an amount of about 70 wt.%, and carrageenan in an amount of about 10 wt.%, based on the total weight of the film-forming resin.

[0279] 67. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer;Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION wherein PVOH is present in an amount of about 10 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer comprises pullulan in an amount of about 60 wt.%, starch in an amount of about 20 wt.%, and carrageenan in an amount of about 10 wt.%, based on the total weight of the film-forming resin.

[0280] 68. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is present in an amount of about 20 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer comprises pullulan in an amount of about 30 wt.%, carrageenan in an amount of about 10 wt.%, and starch in an amount of about 40 wt.%, based on the total weight of the film-forming resin.EXAMPLES

[0281] 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, 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 casting solution.Example 1

[0282] Films 1 A-1 L were prepared according to the formulations listed in Tables 1 and 2 by solution casting. A polyvinyl alcohol (PVOH) homopolymer with a degree of hydrolysis between 86.7 and 88.7 mol% and a viscosity of about 16.5-19.8 cP was used in these films.

[0283] Comparative example film 1 A containing pullulan as the only biopolymer and no PVOH had low tensile strength (i.e., tensile strength <5 MPa at 50%RH). Films 1 B - 1 D generally exhibited incompatibility leading to microphase separation and low tensile strength. Films having tensile strengths lower than e.g., 5 MPa can break during conversion into articles or lead to articles that may break prematurely, for example during shipping and handling. Films 1 E and 1 F, containing higher amounts of PVOH and pullulan as the sole biopolymer presented macroscopic phase separation, these films had higher strength than films with lower PVOH content, however the phase separation lead to formation of PVOH domains and potential defects at the boundaries of these domains. Without intending to be bound by theory, it is believed that films containing PVOH in combination with pullulan as theAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION only biopolymer, are more likely to suffer from phase miscibility problems which are detrimental to mechanical behavior.Table 1.

[0284] Comparative example film 1G containing pullulan, carrageenan and no PVOH had a low tensile strength at 65%RH compared to films containing PVOH. Films 1 K and 1 L presented microphase separation and strain at break values at 50%RH lower than 100%. In general, low strain at break values lead to films not being stretchy enough to be formed into articles, such films may tear during thermoforming. Films 1 H and 1 J containing pullulan, carrageenan and PVOH in amounts of 7 and 11 wt.% with respect to the total weight of the film forming resin, presented good compatibility (i.e., no phase separation) and waterAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION resistance as indicated by tensile strength and Young’s modulus that were higher than the tensile strengths and Young’s modulus of the films without PVOH (1 A and 1 G).Table 2.Example 2

[0285] Films 2A-2D were prepared according to the formulations listed in Table 3 by solution casting. A monomethyl maleate modified PVOH with a degree of modification between 1 .5-2.0 mol% and a degree of hydrolysis between 89 and 93 mol% was used in these films. Films contained two biopolymers: pullulan and carrageenan and varied amounts of PVOH.

[0286] Comparative film 2C, with a weight % of PVOH relative to total resin weight of 43%, showed microphase separation which can lead to film defects and long-term instabilityAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION as the PVOH segregates into PVOH rich domains. Films 2A, 2B and 2D all presented good phase miscibility (i.e., no separation), low blocking force, and better tensile strength and higher Young’s modulus than similar films that did not contain PVOH (1 A, 1G).Table 3.Example 3

[0287] Films 3A-3H were prepared according to the formulations listed in Tables 4 and 5 by solution casting. A polyvinyl alcohol (PVOH) homopolymer with a degree of hydrolysis between 86.7 and 88.7 mol% and a viscosity of about 16.5-19.8 cP was used in these films.

[0288] Tamarind gum was the only biopolymer in formulations 3A - 3D. All the compositions showed complete miscibility.Table 4.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0289] Formulations 3E - 3H contained 20 wt.% pullulan (based on the total weight of the non-water film components) combined with tamarind gum and various amounts of PVOH homopolymer, except for composition 3E which contained no PVOH. All formulations showed good compatibility (i.e., no phase separation) (Table 5).

[0290] Surprisingly, the addition of PVOH to tamarind gum only compositions were not observed to increase mechanical properties of the resulting films. Advantageously, the addition of PVOH to pullulan-tamarind gum compositions was observed to increase the tensile strength of films conditioned at high humidity (i.e., 65% RH), compared to films containing no PVOH. High strength at high humidity is believed to be a measure of waterAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION resistance and an indicator of high performance in humid conditions (less tendency for films to break in humid conditions). Surprisingly, the addition of pullulan to PVOH-tamarind gum compositions was observed to result in films with improved strain at break values, compared to films that contain tamarind gum and PVOH only. This was particularly surprisingly in view of the showing in Example 1 that PVOH and pullulan are not miscible under all circumstances.Table 5.Example 4

[0291] Formulations 4A-4D were prepared according to the compositions listed in Table 6 by solution casting. Film compositions contained a ternary mixture of biopolymers: carrageenan, modified starch, and pullulan; and one of two types of PVOH.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0292] Formulations 4A and 4B contained a polyvinyl alcohol homopolymer with a degree of hydrolysis between 86.7 and 88.7 mol% and a viscosity of about 16.5-19.8 cP.

[0293] Formulations 4C and 4D contained a monomethyl maleate modified PVOH with a degree of modification between 1 .5-2.0 mol% and a degree of hydrolysis between 89 and 93 mol%.Table 6.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION

[0294] Of the ternary biopolymer blend films, only formulation 4A was cast into films and measured. Formulations 4B, 4C, and 4D presented phase separation that prevented them from being cast into films.

[0295] Film 4A was not only miscible but it also had comparable mechanical properties to other films containing blends of biopolymers and PVOH, e.g., film 2B, even when more than half of the PVOH was replaced by starch, increasing the biopolymer content of the film.

Claims

Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATIONWhat is claimed is:1 . A water-soluble film comprising: a film-forming resin; and optionally, a plasticizer (e.g., a plasticizer can be present in or absent from the film); wherein: the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a biopolymer (or natural polymer) (e.g., at least one PVOH polymer and at least one biopolymer in admixture); the PVOH is present in an amount up to about 40 wt.%, based on the total weight of the film-forming resin; and the biopolymer is present in an amount of at least about 60 wt.%, based on the total weight of the film-forming resin; with the provisos that:(a) when the biopolymer comprises pullulan, pullulan is not the sole biopolymer in the film; and(b) when the biopolymer comprises starch, starch is not the sole biopolymer in the film.

2. The water-soluble film of claim 1 , wherein the water-soluble polyvinyl alcohol comprises an unmodified polyvinyl alcohol (e.g., PVOH homopolymer), an anionic group- modified polyvinyl alcohol, a cationic group-modified polyvinyl alcohol, or a combination thereof.

3. The water-soluble film of claim 1 or claim 2, wherein the polyvinyl alcohol comprises an anionic group-modified polyvinyl alcohol having a degree of modification in a range of about 0.1-10 mol.%.

4. The water-soluble film of claim 3, wherein the anionic group-modified polyvinyl alcohol has a degree of modification in a range of about 1 .0-5.0 mol.%.

5. The water-soluble film of claim 4, wherein the anionic group-modified polyvinyl alcohol comprises a polyvinyl alcohol modified with itaconic acid, monomethyl maleate (MMM), methyl acrylate (MA), aminopropyl sulfonate, maleic acid, maleic anhydride, n-vinylpyrrolidone, n-vinylcaprolactam, a derivative of any of the foregoing, or a combination thereof.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION6. The water-soluble film of claim 5, wherein the anionic group-modified polyvinyl alcohol comprises the polyvinyl alcohol modified with monomethyl maleate, methyl acrylate, or a combination thereof.

7. The water-soluble film of any of claims 1 -6, wherein the PVOH is present in an amount in a range of about 10 wt.% to about 40 wt.%, or about 10 wt.% to about 35 wt.%, or about 10 wt.% to about 30 wt.%, or about 12 wt.% to about 28 wt.%, or about 12 wt.% to 25 wt.%, or about 14 wt.% to about 22 wt.%, based on the total weight of the film-forming resin (e.g., at least 0.01 , 0.1 , 0.5, 1 , 2, 3, 4, 5, 7, 10, 15, 20, 30, or 40 wt.% and / or up to 1 , 2, 3, 4, 5, 7, 10, 15, 20, 30, 40, or 50 wt.%).

8. The water-soluble film of any one of claims 1 or 2, wherein the PVOH is a homopolymer and is present in an amount in a range of about 10 wt.% to about 40 wt.%, about 10 wt.% to about 30 wt.%, about 10 wt.% to about 25 wt%, or about 12 wt.% to about 22 wt.%, based on the total weight of the film-forming resin.

9. The water-soluble film of any one of claims 1 -7, wherein the PVOH is an anionic group-modified PVOH and is present in an amount in a range of about 10 wt.% to about 40 wt.%, about 10 wt.% to about 35 wt.%, or about 10 wt.% to about 30 wt%, based on the total weight of the film-forming resin.

10. The water-soluble film of any of claims 1 -8, wherein the biopolymer is present in an amount in a range of about 60 wt.% to about 99.99 wt.% (e.g., complementary to any of the above PVOH ranges), based on the total weight of the film-forming resin (e.g., at least 60, 70, 80, 90, 95, 96, 97, 98, or 99 wt.% and / or up to 60, 70, 80, 90, 95, 96, 97, 98, 99, 99.9, or 99.99 wt.%).11 . The water-soluble film of any of claims 1 -8, wherein a combined amount of the PVOH and the biopolymer is at least 90 wt.%, based on the total weight of the filmforming resin (e.g., at least 90, 92, 94, 96, 98, or 99 wt.% and / or up to 100 wt.%; alternatively not more than 1 , 2, 4, 6, 8, or 10 wt.% of components other than PVOH and biopolymers in the film-forming resin).

12. The water-soluble film of any of claims 1 -8, wherein the biopolymer is selected from the group consisting of polysaccharides (e.g., plant, seaweed, fungal and / or fermentation-based, and / or algae-based polysaccharides), proteins (e.g., plant, animal, and / or animal-based (such as milk) proteins), lignins, and combinations thereof.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION13. The water-soluble film of any of claims 1-8, wherein the biopolymer is selected from the group consisting of starches (e.g., native starch and / or modified starch), pullulan, fermentation-based biopolymers, seaweed-based biopolymers, carrageenans, pectin (e.g., unmodified or modified pectin, such as high methoxy- or low methoxy-pectin), alginate, caseinate, celluloses (e.g., modified and non-modified cellulose polymers), pea protein, chitin, chitosan, lignin, agar, polysaccharide gums (e.g., gum arabic, guar gum, locust bean gum, fenugreek gum) and combinations thereof.

14. The water-soluble film of any of claims 1-8, wherein the biopolymer comprises (or contains) 1 , 2, 3, or 4 different biopolymers (e.g., 0, 1 , 2, 3, or 4 different polysaccharides and / or 0, 1 , 2, 3, or 4 different proteins).

15. The water-soluble film of claim 14, wherein : the biopolymer comprises a first biopolymer and a second biopolymer; the first biopolymer is present in an amount of about 3 wt.% to 97 wt.% relative to total biopolymers; and the second biopolymer is present in an amount of about 3 wt.% to 97 wt.% relative to total biopolymers (e.g., at Ieast 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.% independently selected for each of the first and second biopolymers).

16. The water-soluble film of claim 14, wherein : the biopolymer comprises a first biopolymer, a second biopolymer, and a third biopolymer; the first biopolymer is present in an amount of about 1 .5 wt.% to 97 wt.% relative to total biopolymers; the second biopolymer is present in an amount of about 1 .5 wt.% to 97 wt.% relative to total biopolymers; and the third biopolymer is present in an amount of about 1 .5 wt.% to 97 wt.% relative to total biopolymers (e.g., at least 1.5, 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.% independently selected for each of the first, second, and third biopolymers).

17. The water-soluble film of claim 14, wherein : the biopolymer comprises a first biopolymer, a second biopolymer, a thirdAtty. Docket No. 30658 / 70816A / PC PATENT APPLICATION biopolymer, and a fourth biopolymer; the first biopolymer is present in an amount of about 1 wt.% to 97 wt.% relative to total biopolymers; the second biopolymer is present in an amount of about 1 wt.% to 97 wt.% relative to total biopolymers; the third biopolymer is present in an amount of about 1 wt.% to 97 wt.% relative to total biopolymers; and the fourth biopolymer is present in an amount of about 1 wt.% to 97 wt.% relative to total biopolymers; (e.g., at least 1 , 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% and / or up to 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 97 wt.% independently selected for each of the first, second, third, and fourth biopolymers).

18. The water-soluble film of any of claims 1 -17, wherein the biopolymer is a water-soluble biopolymer.

19. The water-soluble film of any of claims 1 -17, wherein the biopolymer comprises an algae-derived biopolymer.

20. The water-soluble film of claim 19, wherein the algae derived biopolymer comprises carrageenan, alginate, agar, or combinations thereof.21 . The water-soluble film of any of claims 1 -17, wherein the biopolymer comprises a fermentation-derived biopolymer (e.g., fungal-assisted fermentation of a polysaccharide such as starch to form pullulan).

22. The water-soluble film of claim 21 , where the fermentation-derived biopolymer comprises pullulan.

23. The water-soluble film of any one of claims 1-17, wherein the biopolymer comprises pullulan and at least one of carrageenan, starch, and tamarind gum.

24. The water-soluble film of claim 23, wherein the biopolymer comprises pullulan and carrageenan.

25. The water-soluble film of claim 24, wherein the carrageenan is provided in an amount in a range of about 5 wt.% to about 20 wt.%, about 6 wt% to about 18 wt.%, about 7Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION wt.% to about 16 wt.%, or about 8 wt.% to about 14 wt.%, based on the total weight of the film-forming resin and the pullulan makes up the balance of the biopolymer.

26. The water-soluble film of claim 23, wherein the biopolymer comprises pullulan, carrageenan, and starch.

27. The water-soluble film of claim 26, wherein the carrageenan is provided in an amount in a range of about 5 wt.% to about 20 wt.%, based on the total weight of the filmforming resin, the starch is provided in an amount in a range of 10 wt.% to about 30 wt.%, based on the total weight of the film-forming resin, and the pullulan makes up the balance of the biopolymer.

28. The water-soluble film of any one of claims 1-17, wherein the biopolymer comprises tamarind gum and pullulan.

29. The water-soluble film of claim 28, wherein the pullulan is provided in an amount in a range of about 15 wt.% to about 40 wt.%, about 20 wt.% to about 35 wt.%, or about 25 wt.% to about 30 wt.%, based on the total weight of film-forming resin and the tamarind gum makes up the balance of the biopolymer.

30. The water-soluble film of claim 29, wherein the tamarind gum is provided in an amount of about 50 wt.% or less, based on the total weight of the film-forming resin.31 . The water-soluble film of any of claims 1 -17, wherein the biopolymer comprises starch, pullulan, and at least one of chitin and chitosan.

32. The water-soluble film of any of claims 1 -17, wherein the biopolymer comprises at least two biopolymers selected from the group consisting of pullulans, starches, carrageenans, pectins, and alginates.

33. The water-soluble film of any of claims 1 -17, or 24 wherein the biopolymer comprises a native starch, a modified starch or a combination thereof.

34. The water-soluble film of claim 1 , wherein the film-forming resin comprises a mixture of water-soluble polyvinyl alcohol (PVOH) and water-soluble biopolymer in an amount of at least 50 wt.% based on the total weight of the film.

35. The water-soluble film of any one of the preceding claims, wherein the plasticizer is selected from the group of polyols, sugar alcohols, glycerol, diglycerin, sorbitol,Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION 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 a combination thereof.

36. The water-soluble film of any one of the preceding claims, wherein the plasticizer is present in an amount in a range of about 5 wt.% to 45 wt.%, about 10 wt.% to 45 wt.%, or about 10 wt.% to about 30 wt.%, or about 15 wt.% to about 35 wt.%, or about 20 wt.% to about 30 wt.%, based on the total weight of the non-water components of the film.

37. The water-soluble film of any one of the preceding claims, wherein the plasticizer is present in an amount in a range of about 10 PHR to about 85 PHR, or about 15 PHR to about 75 PHR, or about 20 PHR to about 50 PHR, or about 25 PHR to about 45 PHR, or about 30 PHR to about 40 PHR.

38. 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.

39. 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.

40. 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 500 seconds, or about 10 to about 300 seconds, or about 10 to about 150 seconds, as measured according to MSTM-205.41 . The water-soluble film of any one of the preceding claims, wherein the film has a strain at break in a range of about 80% to about 500%, 100% to about 500%, or about 120% to about 300%, or about 100% to about 200%, or about 100% to about 250%, after being conditioned for at least 18 hours at 28 °C / 50% RH, as measured according to the Elongation at Break Test.

42. The water-soluble film of any one of the preceding claims, wherein the film has a strain at break in a range of about 100% to about 700%, about 250% to about 700%,Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION or about 500% to about 650%, or about 500% to about 600%, after being conditioned for at least 18 hours at 28 °C / 65% RH, as measured according to the Elongation at Break Test.

43. The water-soluble film of any one of the preceding claims, wherein the film has a tensile strength in a range of about 5 N / mm2(MPa) to about 50 N / mm2, or about 5 N / mm2to about 40 N / mm2, or about 5 N / mm2to about 30 N / mm2, or about 5 N / mm2to about 25 N / mm2, or about 5 N / mm2to about 20 N / mm2, or about 5 N / mm2to 15 N / mm2after being conditioned for at least 18 hours at 28 °C / 50% RH, as measured according to the Tensile Properties Test.

44. The water-soluble film of any one of the preceding claims, wherein the film has a tensile strength in a range of about 5 N / mm2(MPa) to about 40 N / mm2, or about 5 N / mm2to about 30 N / mm2, or about 5 N / mm2to about 20 N / mm2, or about 5 N / mm2to about 15 N / mm2, or about 5 N / mm2to about 10 N / mm2after being conditioned for at least 18 hours at 28 °C / 65% RH, as measured according to the Tensile Properties Test.

45. 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 4 N or more, or about 8 N or more, or about 10 N or more, or in a range of about 4 N to about 30 N, or about 5 N to about 25 N, or about 8 N to about 20 N, or about 10 N to about 20 N, as measured according to the Seal Strength Test.

46. The water-soluble film of any one of the preceding claims, wherein the biopolymer is 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 protein, casein protein, copolymers of the foregoing, and a combination of any of the foregoing.

47. The water-soluble film of any one of the preceding claims, wherein the PVOH comprises a bio-based PVOH.

48. The water-soluble film of claim 47, wherein the PVOH consists of a bio-basedPVOH.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION49. The water-soluble film of any one of the preceding claims, wherein the film comprises at least 95 wt.% bio-based materials.

50. The water-soluble film of claim 47, wherein the film comprises at least 99 wt.% bio-based materials.51 . The water-soluble film of claim 47, wherein the film has a Renewable Carbon Index of 100 wt.%.

52. The water-soluble film of any one of the preceding claims, wherein the film is characterized by having a blocking force of no greater than 5 N or no greater than 4 N, as measured according to the Blocking Test.

53. 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.

54. The water-soluble article of claim 53, wherein the article comprises a composition contained in the sealed compartment.

55. The water-soluble article of claim 54, wherein the composition comprises a household care composition.

56. The water-soluble article of claim 55, 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,57. The water-soluble article of claim 55 or claim 56, 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.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION58. The water-soluble article of claim 57, 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.

59. The water-soluble article of claim 54, wherein the composition comprises a non-household care composition.

60. The water-soluble article of any one of claims 53 to 59, wherein the first water-soluble film is a thermoformed film.61 . The water-soluble article of any one of claims 53 to 60, wherein the second water-soluble film has the same composition as the first water-soluble film.

62. The water-soluble article of any one of claims 53 to 61 , 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 4 N or more, or about 8 N or more, or about 10 N or more, or in a range of about 4 N to about 30 N, or about 5 N to about 25 N, or about 8 N to about 20 N, or about 10 N to about 20 N, as determined by the Seal Strength Test.

63. The water-soluble article of claim 53, wherein the first and second water- soluble films are edible.

64. The water-soluble article of claim 63, wherein the article comprises a composition contained in the sealed compartment.

65. The water-soluble article of claim 64, wherein the composition comprises an instant food product and / or beverage component.

66. 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 52, the sheet further comprising one or more laundry additives or one or more personal care compositions.

67. The water-soluble article of claim 66, wherein the sheet is a laundry sheet and comprises one or more laundry additives.Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION68. The water-soluble article of claim 66, wherein the sheet is a facial mask shaped to conform to a human face, the sheet comprising one or more personal care compositions.

69. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein the PVOH is a PVOH homopolymer and is present in an amount of about 10 to about 20 wt.%, based on the total weight of the film-forming resin and the water-soluble biopolymer comprises carrageenan and pullulan, wherein the carrageenan is present in an amount of about 5 to about 20 wt.%, based on the total weight of the film-forming resin, and the remainder of the film-forming resin comprises pullulan.

70. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is an anionic group-modified PVOH and is present in an amount of about 10 to about 35 wt.%, based on the total weight of the film-forming resin and the water- soluble biopolymer comprises carrageenan and pullulan, wherein the carrageenan is present in an amount of about 5 to about 20 wt.%, based on the total weight of the film-forming resin, and the remainder of the film-forming resin is pullulan.71 . A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is a PVOH homopolymer or an anionic group-modified PVOH and is present in an amount of about 10 to about 40 wt.%, based on the total weight of the filmforming resin and the water-soluble biopolymer comprises pullulan and tamarind gum, wherein the pullulan is present in an amount of about 15 to about 40 wt.%, based on the total weight of the film-forming resin, and the remainder of the film-forming resin is tamarind gum, based on the total weight of the film-forming resin.

72. A water-soluble film comprising a film-forming resin and a plasticizer, wherein the film-forming resin comprises a mixture of a water-soluble polyvinyl alcohol (PVOH) and a water soluble biopolymer; wherein PVOH is an anionic group-modified PVOH and is present in an amount of about 8 to about 15 wt.%, based on the total weight of the film-forming resin and the water-Atty. Docket No. 30658 / 70816A / PC PATENT APPLICATION soluble biopolymer comprises pullulan, starch, and carrageenan, wherein the starch is present in an amount of about 10 to about 30 wt.% (about 20 wt.%), based on the total weight of the film-forming resin, carrageenan is present in an amount of about 5 to about 20 wt.% (about 10 wt.%), based on the total weight of the film-forming resin, and pullulan is provided in an amount in a range of about 45 to about 75 wt.%, based on the total weight of the film-forming resin, and wherein each component is selected such that the sum of PVOH, pullulan, starch and carrageenan is 100 wt.%.

Images