Water-soluble film with resistance to cold temperature

Abstract

A water-soluble film may include a mixture of a polyvinyl alcohol and a plasticizer; the water-soluble film is characterized by a glass transition temperature (Tg) of about -16 °C or lower and a Young's modulus sufficient to prevent excessive deformation at room temperature; for example, a Young's modulus of about 37 MPa or higher.

Description

Docket No. 30658 / 70518WATER-SOLUBLE FILM WITH RESISTANCE TO COLD TEMPERATURECROSS REFERENCE TO RELATED APPLICATION

[0001] The benefit of priority to U.S. Provisional Application No. 63 / 700,881 filed September 30, 2024, is hereby claimed and the disclosure is incorporated herein by reference in its entirety.FIELD

[0002] The present disclosure relates generally to water-soluble films and related articles. More particularly, the disclosure relates to water-soluble films having resistance to cold temperature.BACKGROUND

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

[0004] This complicates the selection of materials that can perform acceptably and thus raising the need for polymers that are ultimately water soluble but capable of containing a composition that includes some water for a length of time without embrittlement.

[0005] Low temperatures and shaking and rubbing movements that can occur during transportation and storage can aggravate failure in films, thus water-soluble films that are not subjected to embrittlement and remain water soluble over time are an outstanding need.SUMMARY

[0006] The disclosure provides a water-soluble film, including a water-soluble mixture of a polyvinyl alcohol (PVOH) and a plasticizer; wherein the water-soluble film is characterized by at least one of a glass transition temperature (Tg) of about -16 °C or lower and a Young's modulus of about 37 MPa or higher.Docket No. 30658 / 70518

[0007] Another aspect of the disclosure provides an article comprising a pouch or packet made of the water-soluble film of the disclosure defining an interior pouch volume. The article may further comprise a consumer or chemical composition contained in the interior pouch volume and enclosed inside the pouch.

[0008] For the compositions and methods described herein, optional features, including but not limited to components, compositional ranges thereof, substituents, conditions, and steps are contemplated to be selected from the various aspects, embodiments, and examples provided herein.

[0009] 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, article, pouch, and their methods of making and use are capable of taking on 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.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The following drawing figures are appended hereto for further facilitating the understanding of the present invention.

[0011] Fig. 1 A is a graph of glass transition temperature (Tg) vs. total amount of plasticizer.

[0012] Fig. 1 B is a graph of glass transition temperature (Tg) vs. percent of MPD in total amount of plasticizer.

[0013] Fig. 1C is a graph of blocking force vs. percent of MPD in total amount of plasticizer.

[0014] Fig. 2A is a picture of a broken end of a brittle film after being tested for cold crack resistance.

[0015] Fig. 2B is a picture of a broken end of a film having low ductility after being tested for cold crack resistance.

[0016] Fig. 2C is a picture of a broken end of a ductile film after being tested for cold crack resistance.

[0017] Fig. 2D is a picture of a film that did not fail after being tested for cold crack resistance.

[0018] Fig. 3 is a graph of cold crack stress and cold crack strain versus temperature.Docket No. 30658 / 70518DETAILED DESCRIPTION

[0019] Water-soluble materials containing polyvinyl alcohol can be brittle and therefore usually require plasticization in order to be made into films and subsequently into single dose pouches. Some plasticizers have been found to provide acceptable mechanical properties for some polyvinyl alcohol and modified polyvinyl alcohol resins. However, inclusion of such plasticizers can also result in an increase in blocking force or blocking strength making these films of limited commercial use.

[0020] “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.

[0021] 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.”

[0022] 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.

[0023] 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.

[0024] 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 smallerDocket No. 30658 / 70518 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.

[0025] 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.

[0026] 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).

[0027] As used herein and unless specified otherwise, the term “PHR” or “phr” is intended to refer to the composition of the identified element in parts per one hundred parts water- soluble polymer or film-forming resin in the water-soluble film.

[0028] 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.

[0029] 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.

[0030] 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).Docket No. 30658 / 70518

[0031] As used herein, the term "between" in the context of a range is inclusive of the two ends of the range, unless specified otherwise.

[0032] The abbreviation, "e.g." is used herein to indicate a non-limiting example. Thus, the abbreviation "e.g." is synonymous with the term "for example." Where used herein, the terms "example" and "such as," particularly when followed by a listing of terms, are merely exemplary and illustrative and should not be deemed to be exclusive or comprehensive.

[0033] The foregoing description is given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, as modifications within the scope of the disclosure may be apparent to those having ordinary skill in the art.

[0034] All patents, publications and references cited herein are hereby fully incorporated by reference. In case of conflict between the present disclosure and incorporated patents, publications and references, the present disclosure should control.

[0035] As used herein, the term “room temperature” is intendent to refer to a temperature between about 20 °C (68 °F) to about 25 °C (77 °F).

[0036] To be considered a water-soluble film according to the present disclosure, 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.

[0037] The films described herein can be designed to have a glass transition temperature (Tg) of about -16 °C or about -20 °C or lower, and a Young’s modulus sufficient to prevent excessive deformation at room temperature; for example, a Young’s modulus of about 37 MPa or higher. In particular, films of the disclosure having a Tgof about -16 °C, about -18 °C, about -20° C, or lower can be designed to resist embrittlement and cracking at temperatures below room temperature and down to their Tg.

[0038] Films of the disclosure can be characterized by a Tgin a range of about -50 °C to about -16 °C, about -40 °C to about -16 °C, or about -30 °C to about -16 °C, as determined according to the Glass Transition Temperature Test described herein. For example, the film can have a Tgof about -50 °C, about -45 °C, about -40 °C, about -35 °C, about -30 °C, about -25 °C, about -22 °C, about -20 °C, about -18 °C, about -16 °C, or any values therebetween or ranges defined by such values. In general, as the Tgincreases, for example, above -16 °C, the film or articles made using the film can become more brittle and more likely to crack at temperatures below room temperature, for example, after exposure to household compositions. In general, as the Tgdecreases, for example, below about -50 °C, the film can become difficult to convert or shape by conventional processes used in the art to make films into articles.Docket No. 30658 / 70518

[0039] The water-soluble film of the disclosure can be characterized by a Young’s modulus of about 34 MPa or higher, about 37 MPa or higher, about 40 MPa or higher, or in a range of about 37 MPa to about 150 MPa, as determined according to the Tensile Properties Test described herein. For example, the film, after being conditioned for about 24 hours at 25qC / 35% RH, can have a Young’s modulus determined from the slope of a stress-strain curve between 2% and 5% strain, in a range of about 37 MPa to about 150 MPa, about 37 MPa to about 120 MPa, about 40 MPa to about 100 MPa, about 50 MPa to about 75 MPa, about 40 MPa to about 60 MPa, about 40 MPa to about 75 MPa, about 37 MPa, about 40 MPa, about 50 MPa, about 60 MPa, about 75 MPa, about 80 MPa, about 100 MPa, about 125 MPa, about 150 MPa or any values therebetween or ranges defined by such values. Generally, Young’s modulus is a measure of the stiffness of the film, with higher Young’s modulus indicating increased stiffness. As the Young’s modulus of a film decreases, e.g., below about 37 MPa, the stiffness of the film and any article manufactured with such film can decrease, such that a pouch made with such film can become misshapen or deformed during transport or room temperature storage by the weight of other pouches stored in the same secondary packaging. As the Young’s modulus of a film increases, e.g., above about 150 MPa, the film can become too stiff and difficult to convert or shape by conventional processes used in the art to make films into articles.

[0040] The water-soluble film of the disclosure can be characterized by a cold crack strain of at least about 150% at -10 °C, at least 160%, at least about 170%, at least about 200%, or between about 250% to about 400%, or between about 160% to about 400% at -10 °C, as determined according to the Cold Crack Resistance Test described herein, performed at -10 °C. For example, the film, after being tested at a constant temperature of -10 °C, can have a cold crack strain of about 150%, about 160%, about 170%, about 175%, about 200%, about 250%, about 275%, about 300%, about 325%, about 350%, about 375%, about 400%, or in a range of about 150% to about 400%, about 160% to about 400%, about 200% to about 300%, about 250% to about 400%, about 250% to about 350%, about 250% to about 300%, or any values therebetween or ranges defined by such values. In general, as the cold crack strain at -10 °C decreases, e.g., below 150%, the film can lack flexibility and the film, and any article made with such film can crack more easily, particularly at temperatures below room temperature. In general, as the cold crack strain at -10 °C increases, e.g., above 400%, the film can lack stiffness at room temperature and the film, or an article made with such film can become easy to deform.

[0041] The water-soluble film of the disclosure can be characterized by a cold crack stress and / or a ductile cold failure mode. The water-soluble film can be characterized by a cold crack stress of at least about 1 MPa at -10 °C, at least about 5 MPa, at least aboutDocket No. 30658 / 7051810 MPa, at least about 15 MPa, or between about 5 MPa to about 30 MPa at -10 °C, as determined according to the Cold Crack Resistance Test described herein. For example, a film, after being tested at a constant temperature of -10 °C, can have a cold crack stress of about 1 MPa, about 3 MPa, about 5 MPa, about 7.5 MPa, about 10 MPa, about 12 MPa, about 15 MPa, or in a range between about 5 MPa to about 30 MPa, about 15 MPa to about 25 MPa, about 5 MPa to about 20 MPa, about 9 MPa to about 12mPa, or any values therebetween or ranges defined by such values. Generally, higher cold crack stress values can be desirable because they correspond to stronger pouches with less tendency to rupture. In general, as the cold crack stress at -10 °C decreases, e.g., below 1 MPa, the film and any article made with such film can rupture more easily, for example under the weight or pressure of other similar articles stored tightly or in the same secondary packaging or due to transportation movement. Without intending to be bound by theory, it is believed that for some films, cold crack stress values higher than 30 MPa may not be achievable without simultaneously reducing the strain at break of the film to values below 150% at -10 °C.

[0042] The water-soluble film of the disclosure can be characterized by a ductile cold failure mode. As disclosed in the Cold Crack Resistance Test, herein, a film is subjected to a DMA instrument operating in a stress sweep mode at a frequency of 60 Hz and a constant temperature, having a maximum travel length of 25mm, wherein the oscillation stress gradually increases during the test until the film breaks. The broken ends of the films are inspected and the cold failure mode recorded on a scale of (i) to (iv), wherein a failure mode of (i) represents brittle failure, when the film breaks without stretching and cracks perpendicular to the fracture surface are usually observed and a failure mode of (iv) represents no failure at the given specimen length (about 8mm) and maximum travel distance (about 25mm), this indicating superior cold-cracked resistance.

[0043] Generally, the cold crack stress, cold crack strain, and Young’s modulus of a film can be adjusted by one or more of (1) modifying the absolute and / or relative amounts of the resin; (2) including one or more additional resins; (3) modifying the amount of plasticizers in the film as described herein; (4) modifying the type of plasticizers in the film; and (5) modifying the water content of the film.

[0044] The water-soluble film of the disclosure can be characterized by a blocking force in a range of about 0.01 N to 10 N, or a blocking strength in a range of about 0.01 to 30.3 mN / mm as determined by the Blocking test described herein. For example, a water-soluble film according to the disclosure can have a blocking force of about 0.01 N, about 0.05 N, about 1 N, about 2 N, about 5 N, about 7 N, about 10 N or any values therebetween or ranges defined by such values. For example, a water-soluble film according to the disclosure can have a blocking strength of about 0.01 mN / mm, about 5 mN / mm, about 10 mN / mm,Docket No. 30658 / 70518 about 20 mN / mm, about 25 mN / mm, about 30.3 mN / mm or any values therebetween or ranges defined by such values. In general, as the blocking force or blocking strength increases, e.g., above 10 N or above 30.3 mN / mm, the film can strongly stick to itself, for example when in a roll, which can lead to film tearing during further processing.Polyvinyl Alcohol (PVOH)

[0045] The film and related pouches described herein comprise a plasticized, water- soluble film. The water-soluble film can comprise a total of at least about 50 wt% of a PVOH resin comprising one or more PVOH polymers that optionally includes a PVOH copolymer. The film can have any suitable thickness, and a film thickness of about 76 microns (pm) is typical and particularly contemplated. Other values and ranges contemplated include values in a range of about 5 to about 200 pm, or in a range of about 20 to about 100 pm, about 40 to about 90pm, about 50 to 80 pm, or about 60 to 65 pm for example 50 pm, 65 pm, 76 pm, or 88 pm.

[0046] The amount of PVOH resin in the film can be in a range of at least about 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, or 90 wt.% and / or up to about 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.%, 95 wt.%, or 99 wt.%. The amount of PVOH resin in the film can be in a range of about 65 wt.% to about 80 wt.% PVOH, for example 67 wt.%, 68 wt.%, 69 wt.%, 7 wt.0%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, or 75 wt.%.

[0047] Polyvinyl alcohol is a synthetic polymer 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 is commonly referred to as homopolymer PVOH or an unmodified polyvinyl alcohol (PVOH). As used herein, the terms “unmodified polyvinyl alcohol” and “polyvinyl alcohol homopolymer” refer to a PVOH that is a fully or partially hydrolyzed polyvinyl acetate and have a vinyl alcohol monomer unit and optionally a vinyl acetate monomer unit (when partially hydrolyzed) without any third monomer unit.

[0048] The polyvinyl alcohol resin can include a modified polyvinyl alcohol and / or an unmodified polyvinyl alcohol. As used herein, the term “modified polyvinyl alcohol” refers to a polyvinyl alcohol chemically modified by a chemical group and can include a co-polymer orDocket No. 30658 / 70518 higher polymer (e.g., ter-polymer) including one or more monomers in addition to the vinyl acetate / vinyl alcohol groups. The modification can be neutral, e.g., provided by an ethylene, propylene, N-vinylpyrrolidone or other non-charged monomer species. The modification can be a cationic modification, e.g., provided by a positively charged monomer species. The modification can be an anionic modification, e.g., provided by a negatively charged monomer species.

[0049] As used herein, the term “a cationic group-modified polyvinyl alcohol” refers to a polyvinyl alcohol resin chemically modified by a cationic group and can include a partially or fully hydrolyzed PVOH copolymer that includes a cationic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate monomer unit (i.e., when not completely hydrolyzed). Examples of cationic polyvinyl alcohols include glycidyl-trimethylammonium chloride modified polyvinyl alcohols, and those derived from cationic monomers of acrylamide and methacrylamide derivatives such as N-(1 ,1 -dimethyl-dimethylaminopropyl) acrylamide and N-(dimethyl aminopropyl) methacrylamide and their quaternary ammonium salts.

[0050] The polyvinyl alcohol resin can include an anionic modified polyvinyl alcohol. As used herein, the term “anionic group-modified polyvinyl alcohol” or “anionic modified polyvinyl alcohol” refers to a polyvinyl alcohol resin chemically modified by an anionic group and can 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 (i.e., when not completely hydrolyzed). The PVOH copolymer can include two or more types of anionic monomer units. General classes of anionic monomer units which can be used for the PVOH copolymer include the vinyl polymerization units corresponding to sulfonic acid vinyl monomers and their esters, monocarboxylic acid vinyl monomers, their esters and anhydrides, dicarboxylic monomers having a polymerizable double bond, their esters and anhydrides, and alkali metal salts of any of the foregoing. Examples of suitable anionic monomer units include the vinyl polymerization units corresponding to vinyl anionic monomers including vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate (MMM), maleic anhydride, dimethyl maleate, methyl acrylate (MA), fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, itaconic acid, monoalkyl itaconate, dialkyl itaconate, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, carboxylic acid, aminopropyl sulfonate, n- vinylpyrrolidone, n-vinyl-caprolactam, citraconic acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, alkyl acrylates, (alkyl)acrylates, vinyl sulfonic acid, allyl sulfonic acid, ethyleneDocket No. 30658 / 70518 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).

[0051] The modified polyvinyl alcohol can include an anionic modified polyvinyl alcohol (PVOH) copolymer modified with an anionic group selected from the group of an itaconic acid, a monomethyl maleate (MMM), a maleic anhydride, a methyl acrylate (MA), an aminopropyl sulfonate, a maleic acid, a n-vinylpyrrolidone, a n-vinylcaprolactam, a derivative of any of the foregoing, or a combination of any of the foregoing. The anionic modified PVOH copolymer can be modified with an anionic group selected from the group of maleic acid, a monomethyl maleate, a maleic anhydride, a methyl acrylate, or a combination thereof. The anionic modified PVOH copolymer can be modified with an anionic group selected from the group of maleic acid, a monomethyl maleate, a maleic anhydride, or a combination thereof. The degree of modification of the PVOH can be about 0.5 mol% to about 10 mol.%, or about 1 .0 mol% to about 8.0 mol%, or about 1 .5 mol% to about 5 mol%, or about 1 .5 mol% to about 2%, about 3% to about 5%, or about 2.5 mol% to about 4.0 mol% (e.g., at least 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, 6.0, 8.0, or 10 mol.%) or any values therebetween or ranges defined by such values.

[0052] Generally, as the amount of modification increases, the water solubility increases, thus sufficient modification can inhibit hydrogen bonding and crystallinity, enabling solubility in cold water.

[0053] The degree of hydrolysis (DH) of the PVOH homopolymers and modified PVOH copolymers included in the water-soluble films of the present disclosure can be in a range of about 60% to about 99% ,or about 70% to about 99%, or about 74% to about 99% (e.g., about 74% to about 91 %, about 79% to about 92%, about 80% to about 90%, about 88% to 92%, about 89% to about 93%, or about 88%, 90% or 97% such as for cold-water soluble compositions; about 90% to about 99%, about 92% to about 99%, about 95% to about 99%, about 98% to about 99%, about 98% to about 99.9%, about 96%, about 98%, about 99%, or greater than 99% such as for hot-water soluble compositions. As the degree of hydrolysis is reduced, a water-soluble film made from the polymer will have reduced mechanical strength but faster solubility at temperatures below about 20eC. As the degree of hydrolysis increases, a water-soluble film made from the polymer will tend to be mechanically stronger but slower solubility at temperatures below about 20eC. The degree of hydrolysis of the PVOH can be chosen such that the water-solubility of the polymer is temperatureDocket No. 30658 / 70518 dependent, and thus the solubility of a film made from the polymer and additional ingredients is also influenced. In one option the film is cold water-soluble. For a co-poly(vinyl acetate vinyl alcohol) polymer that does not include any other monomers (e.g., a homopolymer not copolymerized with an anionic monomer) a cold water-soluble film, soluble in water at a temperature of less than 10eC, can include PVOH with a degree of hydrolysis in a range of about 74% to about 91%, or in a range of about 80% to about 90%, or in a range of about 85% to about 90%. In another option the film is hot water-soluble. For a co-poly(vinyl acetate vinyl alcohol) polymer that does not include any other monomers (e.g., a homopolymer not copolymerized with an anionic monomer) a hot water-soluble film, soluble in water at a temperature of at least about 60eC, can include PVOH with a degree of hydrolysis of at least about 98%.

[0054] When a PVOH polymer is referred to as having a specific degree of hydrolysis, the PVOH polymer will be understood to be a single polyvinyl alcohol polymer having the specified degree of hydrolysis and a blend of polyvinyl alcohol polymers having an average degree of hydrolysis as specified will generally be referred to by an average (e.g., weight average) degree of hydrolysis.

[0055] 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 BS EN ISO 15023-2:2006 Annex E Brookfield Test method. It is international practice to state the viscosity of 4% aqueous polyvinyl alcohol solutions at 20 °C. All viscosities specified herein in Centipoise (cP) should be understood to refer to the viscosity of 4% aqueous polyvinyl alcohol solution at 20 °C, unless specified otherwise. Similarly, when a polymer 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 polymer, which inherently has a corresponding molecular weight distribution. Additionally, when a resin includes a blend of one or more PVOH polymers and the resin / blend is described as having (or not having) a particular viscosity, unless specified otherwise, it is intended that the specified viscosity is the weighted average viscosity for the resin / blend, which inherently has a corresponding weighted average molecular weight distribution.

[0056] The PVOH in the water-soluble film can have a viscosity average of at least about 4 cP, about 5 cP, about 6 cP, about 8 cP, about 10 cP, about 12 cP, about 13 cP, about 13.5 cP, about 14 cP, about 15 cP, about 16 cP, about 17 cP, about 18 cP, about 19 cP, or about 20 cP and at most about 32 cP, about 28 cP, about 27 cP, about 26 cP, about 24 cP, about 22 cP, about 20 cP, about 19 cP, about 18 cP, or about 17.5 cP, for example in a range of about 10 cP to about 32 cP, about 13 cP to about 27 cP, about 13.5 cP to about 20 cP, about 16 cP to about 20 cP, about 18 cP to about 22 cP, about 21 cP to about 26 cP, aboutDocket No. 30658 / 7051831 cP to about 18 cP, or about 26 cP. It is well known in the art that the viscosity of PVOH polymers is correlated with the weight average molecular weight of the PVOH polymer, and often the viscosity is used as a proxy for the weight average molecular weight.

[0057] The water-soluble film of the disclosure can include a monomethyl maleate modified PVOH with a degree of modification in a range of about 1 .5 mol% to about 5 mol%, for example about 1 .5 mol% to about 2.5 mol%, about 3% to about 5%, about 1 .75 mol%, or about 4 mol%. The monomethyl maleate modified PVOH can have a degree of hydrolysis in a range of about 89% to about 93% and a viscosity in a range of about 18 cP to about 26 cP. For example, a water-soluble film can include a monomethyl maleate modified PVOH with a degree of modification of about 1 .5 mol% to about 2.5 mol%, a viscosity of about 21 cP to 26 cP, and a degree of hydrolysis of about 89% to 93% or at least about 96%. For example, a water-soluble film can include a monomethyl maleate modified PVOH with a degree of modification of about 3 mol% to about 5 mol%, a degree of hydrolysis of about 88 to about 92% and a viscosity of about 16 cP to about 20 cP.

[0058] “Bio-based” as used herein refers to materials for which at least a portion of the materials is derived from raw materials such as plants and other renewable agriculture, marine, and forestry materials. Bio-based materials can be naturally occurring or can be derivable from naturally occurring materials. The PVOH can include bio-based polyvinyl alcohol. Bio-based polyvinyl alcohol includes polyvinyl alcohol in which at least a portion of the carbon comprising the polyvinyl alcohol is derived from biomass. In particular, bio-based polyvinyl alcohol can include polyvinyl alcohol produced by hydrolysis or saponification of bio-based polyvinyl acetate or of a blend of polyvinyl acetates that includes a bio-based polyvinyl acetate. In turn, bio-based polyvinyl acetate can include polyvinyl acetate produced by polymerizing a bio-based vinyl acetate or a blend of vinyl acetates that includes a bio-based vinyl acetate. In general, bio-based vinyl acetate includes vinyl acetate for which at least a portion of the carbon comprising the vinyl acetate is derived from biomass. Vinyl 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 biobased. 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 biobased acetic acid.

[0059] 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,Docket No. 30658 / 70518 corn, sugar cane, sorghum, and cassava. Similarly, bio-based acetic acid can be produced by a bioethanol route.

[0060] 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.

[0061] 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 water- soluble films of the disclosure can comprise a PVOH comprising 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.Other resins

[0062] The water-soluble film can further include one or more additional water-soluble biobased 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.Docket No. 30658 / 70518

[0063] The water-soluble film can further include one or more synthetic (i.e., not naturally occurring) polymers, including, but not limited to, polyacrylates, polymethacrylates, polyacrylic acids and salts thereof, polymethacrylic acids and salts thereof, water-soluble acrylate copolymers, polyvinyl pyrrolidone, and polyethyleneimine. Yet other synthetic water-soluble polymers can include polyalkylene oxides (for instance, polyethylene oxide, also referred to as polyethylene glycol (PEG)), polyacrylamides, polyvinyl acetates, polycarboxylic acids and salts thereof, polyamides, copolymers of any of the foregoing, and combinations of any of the foregoing. Such synthetic polymers are commercially available from a variety of sources. When present in the film, the one or more synthetic polymers can be present in an amount of up to about 20 wt.%, or up to about 10 wt.%, or up to about 5 wt.%, based on the total weight of the film.Plasticizers

[0064] 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. As used herein, and unless specified otherwise, the term “plasticizer” does not encompass water.

[0065] The water-soluble film of the disclosure further comprises one or more plasticizers. The plasticizer can include, but is not limited to, polyols, sugar alcohols, glycerol, diglycerol, sorbitol, 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 combination thereof. Renewable or bio-based plasticizers are contemplated.

[0066] The total amount of non-water plasticizer can be in a range of about 10 wt.% to about 45 wt.%, about 10 wt.% to about 30 wt.%, 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. The amount of plasticizer can also be characterized in terms of PHR, and the totalDocket No. 30658 / 70518 amount of non-water plasticizer can be in a range of about 10 PHR to about 50 PHR, about 15 PHR to about 45 PHR, about 20 PHR to about 40 PHR, about 25 PHR to about 40 PHR, about 29 PHR to about 37 PHR. For example, the amount of non-water plasticizer can be about 20 PHR, about 29 PHR, about 31 PHR, about 35 PHR, about 38 PHR, about 42 PHR, about 50 PHR, or any values therebetween or ranges defined by such values.

[0067] Specific amounts of plasticizers can be selected in particular compositions based on factors described herein, including desired film flexibility and conversion features of the water-soluble film. At low plasticizer levels, e.g., below about 10 PHR, films may become brittle, difficult to process, prone to breaking, or have Tgvalues higher than -20 °C. At elevated plasticizer levels, e.g., above about 50 PHR, films may be too soft, weak, or difficult to process for a desired use.

[0068] The water-soluble film of the disclosure can include glycerol. The water-soluble film of the disclosure can include glycerol, sorbitol, or a combination thereof. The water- soluble film of the disclosure can include glycerol and one or more of sorbitol, a polyethylene glycol, and 2-methyl-1 ,3-propanediol (MPD; MPDiol®). The water-soluble film of the disclosure can include glycerol, sorbitol, a polyethylene glycol (e.g., PEG 300), 2-methyl-1 ,3- propanediol, or a mixture thereof.

[0069] When the water-soluble film of the disclosure includes 2-methyl-1 ,3-propanediol, the MPD can be included in an amount in a range of about 0.1 wt.% to about 20 wt.%, about 0.1 wt.% to about 18 wt.%, about 0.1 wt.% to about 16 wt.%, about 0.1 wt.% to about 14%, or about 0.1 wt.% to about 12 wt.%, based on the total weight of the plasticizer. For example, the amount of MPD to total weight of the plasticizer can be about 0.1 wt.%, about 0.5 wt.%, about 1 wt.%, about 2 wt.%, about 3 wt.%, about 4 wt.%, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 8 wt.%, about 9 wt.%, about 10 wt.%, about 12 wt.%, about 14 wt.%, about 16 wt.%, about 18 wt.%, about 20 wt.%, or any values therebetween or ranges defined by such values. For example, a film can contain 2.6 wt.% of MPD and 20.7 wt.% of a combination of glycerol, sorbitol, and PEG-300; for an amount of MPD to total weight of the plasticizer of about 11 wt.%. In general, as the amount of MPD to total weight of the plasticizer increases, e.g., above 25 wt.%, the blocking force of the film tends to increase (i.e., the film can be too sticky) and be difficult to unroll and process without the risk of tearing.Auxiliary Agents and Additives

[0070] The water-soluble film can optionally contain other auxiliary agents, additives and processing agents, including, but not limited to, surfactants, lubricants, release agents, fillers, extenders, antioxidants, antiblocking agents, detackifying agents, anti-foamsDocket No. 30658 / 70518(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.

[0071] 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® 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.

[0072] The amount of surfactant in the water-soluble film can be in a range of about 0.1 wt.% to about 8.0 wt.%, about 1 .0 wt.% to about 7.0 wt.%, about 3.0 wt.% to about 7.0 wt.%, about 5.0 wt.% to about 7.0 wt.%, 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.

[0073] 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,Docket No. 30658 / 70518Foam 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.

[0074] 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 native starches and modified starches (for example, high amylose starch, amorphous silica, hydroxyethylated starch), silica, talc, or a combination thereof.

[0075] Fillers 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. Native starches and modified starches can be used as anti-block agents. Non-limiting examples of modified starches include ethylated starch, hydroxyethylated starch, propylated starch, hydroxypropylated starch, and acetate modified starch.

[0076] The starch can have an amylose content of at least about 20%, about 23%, about 25%, about 30%, about 40%, about 50%, about 60%, about 65%, or about 75% and / or up to about 60%, about 70%, about 80%, about 85%, or about 95%, for example, in a range of about 65% to about 95%, or about 75% to about 85%, or about 20% to about 80%, or about 25% to about 70%, or about 30% to about 70%, or about 40% to about 60%, or about 23% to about 95%.

[0077] Sources of starch with an amylose content of between about 20% to about 80% include acorn, apple, arrowroot, barley, ester lily, elm tree, sapwood, iris tuber, maize, amylomaize, oat, pea, potato, sago and wheat. Sources of starch with an amylose content of between about 23% to about 95% include acorn, apple, ester lily, iris tuber, maize, amylomaize, oat, pea, sago and wheat.

[0078] Determination of amylose content can be accomplished by iodine complex formation as discussed in Amylose and Amylopectin Content of Starches Determined byDocket No. 30658 / 70518 their Iodine Complex Formation, F.L. Bates, D. French, and R.E. Rundle, J. Am. Chem. Soc., 1943, 65 (2), pp 142-148.

[0079] An anti-block agent can be present in an amount sufficient to reduce the strength of adhesion between two film surfaces. Anti-block agents can be present in an amount of at least 0.1 PHR, at least 0.5 PHR, at least 1 PHR, up to 2 PHR, up to 5 PHR, up to 8 PHR, or in a range of about 0.1 to about 8.0 PHR, about 0.1 PHR to about 6.0 PHR, about 0.1 to about 5.0 PHR, about 0.1 to about 3.0 PHR, about 0.4 to 1 .0 PHR, about 0.5 to about 0.9 PHR, about 0.5 to about 2 PHR, about 0.5 to about 1 .5 PHR, 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.

[0080] 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.

[0081] The anti-block agent can have a median size in a range of about 3 to about 35 microns, about 3 to about 25 microns, about 25 microns to about 35 microns, about 3 to about 11 microns, 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.

[0082] The water-soluble film disclosed herein can further include an antioxidant, for example, as a chloride scavenger. For example, suitable antioxidants / chloride scavengers include sulfite, bisulfite, thiosulfate, thiosulfate, iodide, nitrite, carbamate, ascorbate, and combinations thereof. In embodiments, the antioxidant is selected from propyl gallate (PGA), citric acid (CA), sodium metabisulfite (SMBS), carbamate, ascorbate, and combinations thereof. The antioxidant can be included in the film in an amount in a range of about 0.25 to about 1 .5 PHR, for example, about 0.25 PHR, about 0.30 PHR, about 0.35 PHR, about 0.40 PHR, about 0.45 PHR, about 0.5 PHR, about 0.75 PHR, about 1 .0 PHR, about 1 .25 PHR, or about 1 .5 PHR.

[0083] 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 20,000 Da, 10,000 Da, 6,000 Da, 5,000 Da, 4,000 Da, or 3,000 Da.Docket No. 30658 / 70518

[0084] For the compositions and methods described herein, optional features, including but not limited to components and compositional ranges thereof, are contemplated to be selected from the various aspects, claims, and Examples provided herein. For example, features and formulation approaches described in Example 1 can be combined with any of the additional features provided in the description and claims herein.

[0085] 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 feature combinations in various forms, the description hereafter includes specific combinations with the understanding that the disclosure is illustrative and is not intended to limit the invention to the specific combinations and examples described herein.

[0086] The film, pouches, and related methods of use are contemplated to include feature combinations including any combination of one or more of the additional optional elements, features, and steps further described below, unless stated otherwise.Methods of Making Films

[0087] Processes for producing water-soluble films by solution casting are well-known in the art. Typically, polymers and secondary additives are dissolved in a solvent, typically water, and the solution is metered onto a casting surface and allowed to substantially dry, or force-dried with heated air, to form a cast film. The resulting cast film is removed from the casting surface and optionally wound onto a roller. The process can be performed batchwise and is more efficiently performed in a continuous process. The polymers and secondary additives dissolved in the solvent can be virgin materials, i.e., not previously used to prepare a water-soluble film, and / or trim materials. Trim materials refer to left over film material (“trim”) collected during the film making process and / or pouch making process, for example, material that is trimmed off a cast film to ensure consistent sizing for rolling and / or material that is trimmed off a pouch or packet after the pouch or packet has been sealed. Films can be prepared from trim materials, virgin materials, or a combination of trim and virgin materials.

[0088] 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 pointDocket No. 30658 / 70518 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.

[0089] In general, the casting surface can be any suitable substrate for producing polymeric films known to one of skill in the art. 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. The substrate can be a casting drum. The substrate can be 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.

[0090] 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.

[0091] 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.

[0092] 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.,Docket No. 30658 / 70518 selected from a fluorosurfactant, a non-fluorinated anionic surfactant, a non-fluorinated zwitterionic surfactant, salts thereof, or any combination thereof. 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. The release coating can comprise a non-fluorinated zwitterionic surfactant or salts thereof. In embodiments, the release coating comprises a non-fluorinated anionic surfactant or salts thereof. The non-fluorinated anionic surfactant can comprise 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. The non-fluorinated anionic surfactant can comprise a C6-C30 phosphate ester, or a Ce-C phosphate ester, Ce-Ceo phosphate diester, C18-C32 phosphate diester, or salts thereof. 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.

[0093] 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, less than 0.001 wt% fluorine based on the total molecular weight of the compound, or less than 0.0001 wt%, or no measurable or detectable fluorine based on the total molecular weight of the compound.

[0094] The release coating can include a fluorosurfactant, e.g., a perfluoroalkyl-containing compound. 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.

[0095] 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. 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 theDocket No. 30658 / 70518 substrate. When the surfactant comprises a non-fluorinated anionic surfactant, a nonfluorinated 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. The release coating can have a pH of about 1 to about 7, about 1 to about 6, or about 1 to about 4, about 1 to about 3, about 2 to about 7, about 2 to about 6, about 2 to about 5, about 2 to about 4 , about 2 to about 3, about 3 to about 7, about 3 to about 5, 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.

[0096] 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. 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%, about 0.01 wt% to about 5 wt%, about 0.01 wt% to about 4 wt%, about 0.01 wt% to about 3 wt%, about 0.01 wt% to about 2 wt%, about 0.05 wt% to about 2 wt%, 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. 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. 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. 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%, about 4 wt% to about 90 wt%, about 4 wt% to about 80 wt%, about 4 wt% to about 70 wt%, about 4 wt% to about 50 wt%, about 4 wt% to about 30 wt%, about 4 wt% to about 20 wt%, 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. 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 aDocket No. 30658 / 70518 range of about 0.05% by weight to about 5.0% by weight, based on the total weight of the release coating.

[0097] In general, the release coating as described herein can have a hydrophilic- lipophilic balance in a range of about 1 to about 30. The release coating can have a hydrophilic-lipophilic balance in a range of about 1 to about 20, about 1 to about 18, about 1 to about 17, about 1 to about 16, about 1 to about 15, about 2 to about 17, about 3 to about 17, about 4 to about 15, about 5 to about 12, or about 8 to about 12. The release coating can have a hydrophilic-lipophilic balance in a range of about 1 to about 20. The release coating can have a hydrophilic-lipophilic balance in a range of about 3 to about 17.

[0098] In general, the release coating has a thickness of about 0.1 nm to about 100 nm on the surface of the substrate. The release coating can have a thickness of about 0.1 nm to about 80 nm, about 0.1 nm to about 60 nm, about 0.1 nm to about 40 nm, about 0.1 nm to about 40 nm, about 0.1 nm to about 20 nm, about 0.1 nm to about 10 nm, about 1 nm to about 10 nm, or about 1 nm to about 5 nm, on the surface of the substrate. The release coating can have a thickness of about 0.1 nm to about 40 nm on the surface of the substrate. The release coating can have a thickness of about 0.1 nm to about 10 nm on the surface of the substrate.

[0099] 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, at least about 6,000 cPs, at least about 7,000 cPs, at least about 8,000 cPs, 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, no greater than 14,000 cPs, no greater than about 13,000 cPs, no greater than about 12,000 cPs, or no greater than about 11 ,000 cPs.

[0100] 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 105Docket No. 30658 / 70518°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.

[0101] In a continuous or semi-continuous casting process, the moving casting surface can have any desired line speed, e.g., in a range of about 5 m / min to about 50 m / min. The line speed can sometimes affect the properties of the resulting film, for example, physical properties, thickness, residual moisture content and film quality. In general, as the line speed decreases, the thickness of the resulting film will increase and as the line speed increases, the thickness of the resulting film will decrease, assuming the delivery rate of solution remains constant. In general, as the line speed increases the residence time of the film in a fixed-size dryer decreases, thereby requiring an increase in drying temperatures, which may result in drying defects or sticking at high enough temperatures. In contrast, as the line speed decreases, the residence time of the film in the dryer increases.Water-Soluble Articles

[0102] The water-soluble film disclosed herein is useful for creating a sealed article in the form of a pouch defining an interior pouch volume to contain a composition therein for release into an aqueous environment. A “sealed article” optionally encompasses sealed compartments having a vent hole, for example, when the compartment encloses a solid that off-gasses, but more commonly will be a completely sealed compartment.

[0103] The pouch may comprise a single compartment or multiple compartments. A water-soluble pouch can be formed from two layers of water-soluble polymer film sealed at an interface, or by a single film that is folded upon itself and sealed. The film forms at least one side wall of the pouch, optionally the entire pouch, and preferably an outer surface of the at least one sidewall. In another type of embodiment, the film forms an inner wall of the packet, e.g., as a dividing wall between compartments.

[0104] The disclosure further provides a unit dose article in the form of a packet comprising a sealed compartment, the article comprising water-soluble film of the disclosure. 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 articles of the disclosure can comprise a composition contained in the sealed compartment. The composition can comprise any compositionDocket No. 30658 / 70518 disclosed herein. The composition can comprise a household care composition. The composition can comprise a non-household care composition.

[0105] The water-soluble films and articles can comprise a printed area. The area of print can be achieved using standard techniques, e.g., flexographic printing or inkjet printing.Methods of Making Articles and / or Pouches

[0106] 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, water 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.

[0107] 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, 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.

[0108] 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, about 10 mL to 150 mL, or about 20 mL to about 100 mL, and that the mold sizes are adjusted accordingly.Thermoforming

[0109] 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. The film can be heatedDocket No. 30658 / 70518 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, about 40 °C to about 100 °C, about 50 °C to about 100 °C, about 60 °C to about 100 °C, about 30 °C to about 90 °C, 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, about 40 °C to about 80 °C, about 50 °C to about 80 °C, about 60 °C to about 80 °C, about 30 °C to about 70 °C, 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 highspeed 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.

[0110] 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.

[0111] 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. The most preferred method will depend on the product form and required speed of filling. The molded film can be 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.

[0112] 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, at least 2.5, at least 2.6, at least, 3.0, or at least 3.5.Sealing ArticlesDocket No. 30658 / 70518

[0113] The water-soluble unit dose article can be heat sealed, water sealed, solvent welded, adhesive sealed, or solution sealed by any suitable process and apparatus, such as those already well-known in the art for sealing other water-soluble films, or readily adapted therefrom with only routine experimentation. For example, the water-soluble unit dose articles can be heat sealed on three sides. For example, the water-soluble film can be folded over onto itself and sealed on the edge opposite the fold and along one of the two remaining open edges with a heat impulse sealer, to provide a pouch of desired dimensions. A liquid composition (e.g., a household care composition) can be filled into the pouch using an injection system such as a pump or a syringe. Alternatively, 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 or water 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.

[0114] Films of the disclosure can be heat-sealed, for instance, according to the following method:1 . Condition the film to be sealed at 28 °C,l5G° / o RH for 24 hrs.2. Using a TS-12 heat sealer (or equivalent), select the sealing temperature and sealing time and allow the heat sealer to reach the target temperature.3. Cut tensile strips from the film. Place two strips on top of one another.4. Place the strips on a rubber platform and insert them into the TS-12 heat sealer.5. Begin sealing the films by stepping on the pedal below the machine and hold for the designated sealing time.6. Remove the sealed strips from the machine and repeat as desired, for instance for at least three replicate samples.7. Allow the seal at least 10 minutes to cool down. Take notice of the seal area of the film. If the film has begun to bubble, the temperature may be too high, or the sealing time may be too long.Docket No. 30658 / 70518

[0115] The composition enclosed in the pouch is not particularly limited, for example including any of the variety of compositions described herein. In articles / pouches comprising multiple compartments, each compartment may contain identical and / or different compositions. In turn, the compositions may take any suitable form including, but not limited to liquid, solid, gel, paste, mull, pressed solids (tablets) and combinations thereof (e.g., a solid suspended in a liquid). The pouches comprise a first, second, and third compartment, each of which respectively contains a different first, second, and third composition.Article and / or Pouch Contents

[0116] The water-soluble pouch can contain (enclose) a composition. The composition can be selected from a liquid, solid, or combination thereof. As used herein, “liquid” includes free-flowing liquids, as well as pastes, gels, foams, and mousses. Non-limiting examples of liquids include light duty and heavy-duty liquid detergent compositions, fabric enhancers, detergent gels commonly used for laundry, bleach, and laundry additives. Non-limiting examples of liquids include agricultural compositions, automotive compositions, aviation compositions, food and nutritive compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, mercantile compositions, military and quasi-military compositions, office compositions, and recreational and park compositions, pet compositions, water-treatment compositions, including cleaning and detergent compositions applicable to any such use. Gases, e.g., suspended bubbles, or solids, e.g., particles, may be included within the liquids. A “solid” as used herein includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include granules, micro-capsules, beads, noodles, and pearlized balls. Solid compositions may provide a technical benefit including, but not limited to, through-the-wash benefits, pre-treatment benefits, and / or aesthetic effects.

[0117] 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.

[0118] 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.

[0119] In another aspect of the disclosure, the household care composition can be selected from non-laundry and non-automatic dishwashing compositions, e.g., selected fromDocket No. 30658 / 70518 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.

[0120] 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.

[0121] The liquid detergent composition can be used in a fabric hand wash operation or may be used in an automatic machine fabric wash operation.

[0122] 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.

[0123] In other aspects, the household care composition may be an automatic dish washing detergent composition comprising an ingredient selected from surfactant, builder, sulfonated / carboxylated polymer, silicone suds suppressor, silicate, metal and / or glass care agent, enzyme, bleach, bleach activator, bleach catalyst, source of alkalinity, perfume, dye, solvent, filler, and mixtures thereof.

[0124] The water-soluble unit dose article can comprise a non-household 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. The non-household care composition is a pool and / or water-treatment composition.Docket No. 30658 / 70518

[0125] 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.%, about 3 wt.% to about 15 wt.%, about 5 wt.% to about 15 wt.%, or about 10 wt.% to about 15 wt.%, based on the total weight of the composition.

[0126] 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. When 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.

[0127] Fabric and home care products are optionally used or consumed in the form in which they are sold and are for treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care including air fresheners and scent delivery systems, car care, dishwashing, fabric conditioning (including softening and / or freshening), laundry detergency, laundry and rinse additive and / or care, hard surface cleaning and / or treatment including floor and toilet bowl cleaners, and other cleaning for fabric or home use.

[0128] 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 includingDocket No. 30658 / 70518 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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. 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.Docket No. 30658 / 70518Test MethodsTensile Properties Test

[0133] A water-soluble film characterized by or to be tested for tensile strength, Young’s modulus and break strain according to the Tensile Test is analyzed as follows. The procedure includes the determination of tensile strength according to ASTM D 882 (“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 five 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 1”-wide (2.54 cm) and about 5 inches long.

[0134] Film specimens are conditioned for at least 18 hours at 25 °C / 35% RH, or 25 °C / 50 RH%, or 28 °C / 50% RH, or 28 °C / 65% RH prior to measurement. Tests are conducted in the standard laboratory atmosphere of 23±2.0qC and 35±5% RH in a manner that minimizes exposure to the laboratory standard conditions.

[0135] 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 tensile testing machine and the test is run at a strain rate of 508 mm / min until the film breaks.

[0136] The Young’s modulus or elasticity modulus is 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 is 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.

[0137] 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.

[0138] 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.Blocking TestDocket No. 30658 / 70518

[0139] 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 without imparting strain or stretching to the film or producing tension in a converting process. Blocking force and strength generally tends to increase as the level of plasticizer in a film increases. The blocking test measures the blocking strength between layers of film on a roll. The blocking strength measurement does not contain any friction force from the outer surface of the roll as it is being unwound.

[0140] A water-soluble film characterized by or to be tested for Blocking strength is analyzed using a roll of the desired film and a force meter with a hook attached. The roll of film is wound and protected with a moisture barrier for at least one hour before testing with the roll sitting vertically. After the 1 -hr conditioning period, the roll is positioned on a horizontal surface such that the roll unwinds from underneath. Accordingly, blocking strength is calculated by dividing the blocking force by the roll width.

[0141] Rolls to be tested are typically about 330 mm wide. About 3 in (7.62 cm) of film are unrolled and the film fold over itself to create a 1-in (2.54 cm) wedge. A puncture is made at the mid-point of the wedge to accommodate the force meter hook. The force meter hook is attached to the hole on the folded film wedge. The force meter is placed on and affixed to height adjustable platform with the height of the platform adjusted to match the radius of the roll being tested, such that film releasing from the roll is parallel to the surface on which the roll is placed, ensuring the film exhibits a 90-degree angle at the point of release from the roll.

[0142] A measurement is taken by zeroing the force meter once attached to the roll and rotating the roll about 270saway from the force meter at a rate of 1 in per second (2.54 cm / s). The force reading is recorded, and two more measurements taken. Additional measurements can be taken at different roll depths by trimming down the roll to the desired depth, for example, half-way to the core, 1 in (2.54 cm) to the core and 1 / 8 in (0.3 cm) to the core.

[0143] The blocking force or blocking strenght is reported as the average of all measurements taken at the different roll depths.Glass Transition Temperature Test

[0144] The glass transition occurs when a flexible film changes into a hard and relatively brittle polymer film as temperature decreases. The glass transition occurs over a temperature range but is usually reported as a single value along an endothermic stepwiseDocket No. 30658 / 70518 change in a heat flow vs. Temperature curve. As used herein and unless specified otherwise, the term “glass transition temperature” is intended to refer to the mid-point temperature between the onset temperature where the heat flow changes (onset of the glass transition event) and the end of the detection of the glass transition event in a heat flow vs. temperature curve measured by differential scanning calorimetry (DSC) at a constant temperature change rate. Unless disclosed otherwise, reported glass transition temperatures represent the average midpoint temperature for 3 or more film samples.

[0145] A water-soluble film characterized by or to be tested for Glass Transition Temperature (Tg) is analyzed using a TA Instruments Q2000 differential scanning calorimeter (DSC) or equivalent.

[0146] Tests were performed using a with a 50 mL / min nitrogen purge and TZERO aluminum hermetic pans (available from TA Instruments) Film specimens to be tested are conditioned for at least 18 hr. at 25 °C / 35% RH prior to testing, and then cut in small pieces to provide about 3-5 mg total sample that fits into the pans (e.g., about 3 stacked, cut film pieces). The test is performed by equilibrating the sample at -80 °C, followed by heating the sample to 75 °C at a rate of 10 °C / min to begin generating a DSC heating curve. Upon generating the curves, the transition attributable to glass transition is identified and the Tgdetermined from the calorimetry curve as discussed above using the instrument software (TRIOS or equivalent).Cold Crack Resistance Test

[0147] Film resistance to cracking, particularly at temperatures below room temperature can be assessed using dynamic mechanical testing at the temperature of interest.

[0148] A water-soluble film characterized by or to be tested for cold crack stress and cold crack strain according to the Cold Crack Resistance Test is analyzed as follows. A Dynamic Mechanical Analyzer (DMA) apparatus with temperature control (DMA 850 by TA instruments or equivalent) is used for the collection of film data. A minimum of five test specimens, each cut with reliable cutting tools to ensure dimensional stability and reproducibility, are tested in the machine direction (where applicable) for each film type.Samples of a single film sheet having a thickness of about 88 pm are cut to a width of 6 mm and a length of about 25 mm.

[0149] Film specimens are conditioned for about 24 hours at 25 735% RH prior to measurement. Films are cooled in the DMA instrument to the starting temperature and allowed to reach the target temperature before applying any stress.Docket No. 30658 / 70518

[0150] The film’s cold crack stress and cold crack strain are measured with the DMA instrument operating in a stress sweep mode at a frequency of 60 Hz and a constant temperature. During the test, the oscillation stress gradually increases until the film breaks. The final stress at which the film fails is recorded as the failure stress, along with the initial and final lengths of the film.

[0151] The cold crack strain (i.e., failure strain) is then calculated using the formula: (final length - initial length) / final length x 100%.

[0152] As used herein, the term “necking” is intended to refer to a narrowing of a film subjected to mechanical strain. During testing, as the ends of a film specimen are pulled in opposite directions, the width of the film can decrease forming a section narrower than the initial width (i.e., “neck”) before breaking.

[0153] The broken ends of the films are visually inspected and compared to the standards shown in Figs. 2A-2D to determine the cold failure mode and the cold failure mode recorded according to the following criteria:(i) Brittle failure is said to occur when the film breaks without stretching. Brittle films may exhibit cracks perpendicular to the fracture surface and no necking. Fig. 2A shows an example of a film after brittle failure.(ii) Low ductility failure is said to occur when the film undergoes limited stretching before breaking, in these cases no substantial necking of the film is observed and no cracks perpendicular to the fracture surface are observed. Fig. 2B shows an example of a film after low ductility failure.(iii) Ductile failure is said to occur when the film exhibits a significant amount of stretch before breaking which is observed on the fractured specimens as necking of the film. Fig. 2C shows an example of a film after ductile failure.(iv) No failure is said to occur when the testing clamp reaches the travel limit before the specimen breaks, and it is an indication of superior cold-cracked resistance. Fig. 2D shows an example of a film having no failure. Under the testing conditions, using 8 mm long specimens and initial clamp to clamp distance of about 5.5 mm, specimens showing no failure are those able to stretch more than 25mm (maximum travel distance), which corresponds to a maximum strain of about 300-350%.

[0154] The cold crack stress and cold crack strain of a film composition at a given temperature is reported as the average of all the tested samples of such composition at the specific testing temperature.EXAMPLESDocket No. 30658 / 70518

[0155] The following examples are provided for illustration and are not intended to limit the scope of the invention. In general, resin solutions were prepared by mixing water and the components listed in the examples, and films were prepared by solution casting of the resin solutions and allowing the cast films to dry and then removing the dried film from the casting substrate to result in a freestanding film. Amounts of each component are shown as weight % of the total non-water components of the film casting solution.

[0156] Example 1

[0157] Films 1 A-1 L were prepared according to the formulations listed in Table 1 by solution casting. An MMM-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.Table 1.

[0158] The films contained different amounts of four plasticizers: glycerin, sorbitol, 2- methyl-1 ,3-propanediol (MPD), and PEG 300. PEG 300 denotes a polyethylene glycol having an average molecular weight of 300 Da. Amounts of each plasticizer and the % of MPD to total plasticizer is shown in table 2.Table 2.Docket No. 30658 / 70518

[0159] Component segregation and phase separation were observed in film 1 D; in view of this heterogeneity in the film, film 1 D was not further tested.

[0160] The Young’s modulus, Tgand blocking strength of the films were measured and are reported in Table 3. Tgwas measured within a month of film production to minimize the impact of physical aging; while aging does not significantly affect Tgin general, it was found that for film compositions that are sensitive to age, no appreciable change in Tgwas exhibited when tested within the first month following production.

[0161] Film processability was qualitatively assessed (Table 3) during film handling and ranked taking into consideration curling behavior, surface tackiness, and susceptibility to breakage during water sealing. A “++” grade was given to film compositions that showed very good processability, a “+” grade to films that had acceptable processability andgrade to films that were difficult to process and form into articles.

[0162] Table 3 also shows the cold failure modes of the films: (i) Brittle, (ii) Low ductility, (iii) Ductile, and (iv) no failure; and the overall assessment of their mechanical properties at low temperatures based on their strain at break, strength and failure modes: “+” = good; “0” = acceptable; = unacceptable.Table 3.Docket No. 30658 / 70518Refers to a prophetic / estimated result based on trends observed

[0163] The films of Example 1 contained blends of different plasticizers at varied levels and varied amounts of MPD as a weight percentage of total plasticizer. A linear relationship between Tgand total plasticizer content was observed (Fig. 1 A). Notably, the films of Example 1 exhibited a non-linear relationship between Tgvs. the % of MPD to total plasticizer content (Fig. 1 B) and blocking strength vs. the % of MPD to total plasticizer (Fig. 1C).

[0164] Films 1 A, 1 B, 1 C, 1 E, and 1 J had all Tglower than -16 °C and retained their mechanical properties at low temperatures, as shown by their cold crack stress and strain and their ductile behavior. These films presented no processability issues like curling or breaking during water sealing, and their Young’s modulus values indicated that they possess enough flexibility for being formed into articles. Additionally, films 1 A, 1 B, 1C, and 1 E wereDocket No. 30658 / 70518 characterized as self-blocking, i.e., presented a blocking strength <30.3 mN / m, without the addition of an antiblocking agent. Film 1 J had a blocking strength >30.3 mN / m, which was believed to be due to a higher MPD to total plasticizer amount (i.e., >30%), as MPD is expected to migrate to the surface and cause increased stickiness.

[0165] Films 1 F, 1 H, 1 K and 1 L having a Tghigher than -16 °C, showed good processability but unacceptable cold crack performance, suffering from brittle failure or low ductility at best, indicating that these films loose flexibility at low temperatures, which can lead to rupture of pouches or capsules made of these films and spillage of any composition contained herein. Film 1G presented a Young’s modulus at room temperature lower than 37MPa, which lead to poor processability.

[0166] Without intending to be bound by theory, it is believed that cold crack stress decreases monotonically as temperature increases. In contrast, cold crack strain is believed to first increase at temperatures lower than a transition temperature reaching a maximum value around the transition temperature (e.g., 10°C in the example shown in Fig. 3) and then decreases as temperature increases (Fig. 3).

[0167] Without intending to be bound by theory, it is believed that cold crack strain, or more broadly the failure mode, have a larger effect in material performance compared to cold crack stress. It is believed that cold crack strain increases as the glass transition temperature (Tg) decreases. Cold crack strain decreases continuously as the testing temperature increases reaching a value where the material becomes too soft for processing and pouches made from such a film can deform under the weight of adjacent pouches.

Claims

Docket No. 30658 / 70518What is claimed is:1 . A water-soluble film, comprising a water-soluble mixture of a polyvinyl alcohol (PVOH) and a plasticizer; wherein the water-soluble film is characterized by a glass transition temperature (Tg) of about -16 °C or lower and a Young’s modulus measured at 25 °C / 35% RH of about 37 MPa or higher.

2. The water-soluble film of claim 1 , characterized by a Tgin a range of about - 50 °C to about -16 °C, about -40 °C to about -16 °C, or about -30 °C to about -16 °C.

3. The water-soluble film of claim 1 or claim 2, characterized by a Young’s modulus in a range of about 37 MPa to about 150 MPa measured 25 ‘0 / 35% RH.

4. The water-soluble film of any one of the preceding claims, characterized by a cold crack strain of at least about 150% at -10 °C, at least about 200%, or between about 250% to about 400%.

5. The water-soluble film of any one of the preceding claims, characterized by a cold crack stress of at least about 1 MPa at -10 °C, at least about 5 MPa, at least about 10 MPa, at least about 15 MPa, or between about 15 MPa to about 30 MPa.

6. The water-soluble film of any one of the preceding claims, wherein the PVOH has a degree of hydrolysis in a range from about 65 mol% to about 99 mol%, about 70 mol% to about 99 mol%, about 74 mol% to about 99 mol%, about 80 mol% to about 95 mol%, or about 85 mol% to about 95 mol%.

7. The water-soluble film of any one of the preceding claims, wherein the polyvinyl alcohol comprises an anionic modified PVOH copolymer, a PVOH homopolymer, or a combination thereof.

8. The water-soluble film of any one of the preceding claims, wherein the polyvinyl alcohol comprises an anionic modified PVOH copolymer.

9. The water-soluble film of claim 8, wherein the anionic modified PVOH copolymer comprises an anionic group selected from maleic acid, monomethyl maleate, maleic anhydride, or a combination thereof.

10. The water-soluble film of any one of claims 7 to 9, wherein the anionic modified PVOH copolymer has a degree of modification in a range of about 0.5 mol% to about 10 mol%, about 1 mol% to about 8 mol%, or about 1 .5 mol% to about 5 mol%.Docket No. 30658 / 7051811 . The water-soluble film of any one of claims 7 to claim 10, wherein the anionic modified PVOH copolymer has a degree of modification in a range of about 1 .5 mol% to about 2.0 mol% or about 2.5 mol% to about 4.0 mol%.

12. The water-soluble film of any one of the preceding claims, wherein the PVOH comprises at least 95 wt.% bio-based PVOH.

13. 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 50 phr, about 15 phr to about 45 phr, about 20 phr to about 40 phr, or about 25 phr to about 40 phr, or about 29 phr to about 37 phr.

14. The water-soluble film of any one of the preceding claims, wherein the plasticizer comprises polyols, sugar alcohols, glycerol, diglycerol, sorbitol, 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, or a combination thereof.

15. The water-soluble film of any one of the preceding claims, wherein the plasticizer comprises glycerin.

16. The water-soluble film of any one of the preceding claims, wherein the plasticizer comprises glycerin and sorbitol.

17. The water-soluble film of any one of the preceding claims, wherein the plasticizer comprises 2-methyl-1 ,3-propanediol in an amount in a range of about 0.1 wt% to about 20 wt.%, about 0.1 wt% to about 18 wt%, about 0.1 wt% to about 16 wt%, about 0.1 wt% to about 14 wt%, or about 0.1 wt% to about 12 wt%, based on the total weight of the plasticizer.

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

19. The water-soluble film of claim 18, wherein the anti-blocking agent comprises starch.

20. The water-soluble film of claim 19, wherein the starch comprises native starch, modified starch, or a combination thereof.Docket No. 30658 / 7051821 . The water-soluble film of claim 19, wherein the starch is present in an amount up to about 5 PHR.

22. The water-soluble film of claim 19, wherein the starch is present in an amount up to about 2 PHR.

23. The water-soluble film of claim 19, wherein the starch has an amylose content in a range of about 20 wt.% to about 95 wt.%24. The water-soluble film of any one of the preceding claims, characterized by having a blocking strength in a range of about 0.01 mN / mm to 30.3 mN / mm.

25. The water-soluble film of any one of the preceding claims, wherein the PVOH is a monomethyl maleate modified PVOH, wherein the PVOH has a degree of modification in a range of about 1 .5 mol% to about 2.0 mol% and a degree of hydrolysis in a range of about 74 mol% to about 99 mol%; and the plasticizer is present in an amount in a range of about 29 phr to about 37 phr and comprises glycerin, sorbitol, PEG300, and 2-methyl-1 ,3-propanediol, and the 2-methyl-1 ,3- propanediol is included in an amount of less than about 20 wt% based on the total weight of the plasticizer.

26. A unit dose article in the form of a packet comprising a sealed compartment, the article comprising a water-soluble film of any one of the preceding claims.

27. The unit dose article of claim 26, comprising a composition housed in the sealed compartment.

28. The unit dose article of claim 27, wherein the composition is selected from the group consisting of light duty liquid detergent compositions, heavy duty liquid detergent compositions, hard surface cleaning compositions, bleaching compositions, shampoos, body washes, other personal care compositions, and mixtures thereof.

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