Water-soluble films and deep-drawn articles made therefrom

Abstract

When provided as a pouch or packet enclosing a liquid composition, water-soluble films and deep-draw articles made therefrom are provided that exhibit desirable delayed liquid release and low residue values ​​from the pouch or packet. [Solution] A thermoformed article comprising a film thermoformed into the form of a pouch defining an internal pouch volume, wherein the film comprises a mixture of polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 30 parts by weight based on 100 parts by weight of the total polyvinyl alcohol resin, the thermoformed film in the form of a pouch defining an internal pouch volume being characterized by a draw ratio ranging from about 2.3 to about 2.9, the article being characterized by a release time of at least 30 seconds when formed into a sealed packet and tested according to a Liquid Release Test, and the article being characterized by a residue value of at most 9% when determined by a Residue Test.

Description

[Technical field]

[0001] The present disclosure relates generally to water-soluble films and related articles. More specifically, the present disclosure relates to water-soluble films suitable for thermoforming deep-drawn profiles, and thermoformed articles comprising the same, which, when provided as a pouch or packet enclosing a liquid composition, exhibit desirable delayed liquid release and low residue values ​​from the pouch or packet. [Background technology]

[0002] Water-soluble polymeric films are commonly used as packaging materials to simplify the dispersion, injection, dissolution and administration of materials to be delivered.For example, pouches made from water-soluble films are commonly used to package household care compositions, such as laundry detergents and dishwashing detergents.Consumers can add the pouched composition directly to a mixing container, such as a bucket, sink, or washing machine.Advantageously, this eliminates the need for consumers to measure the composition while providing accurate dosing.The pouched composition can also reduce the mess associated with dispensing similar compositions from a container, such as pouring liquid laundry detergent from a bottle.In short, the soluble pre-measured polymeric film pouch provides convenience for consumers to use in a variety of applications.

[0003] Soluble unit doses (SUDS) can be designed to contain multiple cavities, with each cavity having a unique shape and size. Some commercially available water-soluble films perform poorly in more complex unit dose designs, such as unit doses with deep box-like cavities. In addition, some commercially available water-soluble films exhibit excellent cold water solubility, but perform poorly to prevent premature release of liquid contents, which is currently required by some regulatory agencies to prevent immediate release of liquid materials, for example, when a child places a soluble unit dose in their mouth. Furthermore, while some commercially available water-soluble films may exhibit suitable delay of liquid release to meet regulatory requirements, these films often exhibit poor solubility, such that unacceptable film residue remains after the unit dose is used and its contents are released. Thus, a need exists in the art for a water-soluble film suitable for thermoforming deep-draw profiles, for example, for use in water-soluble single dose packaging, which can be formed into a package for holding liquid detergent, and which, when formed into a package, retains the liquid contents for at least 30 seconds and does not leave an unacceptable level of residue when the soluble package is placed in water at 20°C. Summary of the Invention

[0004] One aspect of the present disclosure provides a thermoformed article comprising a film thermoformed into the form of a pouch defining an internal pouch volume, wherein the film comprises a mixture of a polyvinyl alcohol resin and a plasticizer, wherein the plasticizer is provided in an amount ranging from about 5 to about 30 parts by weight based on 100 parts by weight of the total polyvinyl alcohol resin, wherein the thermoformed film in the form of the pouch defining the internal pouch volume is characterized by a draw ratio ranging from about 2.3 to about 2.9, and wherein the article, when formed into a sealed packet and tested according to the Liquid Release Test, is characterized by a release time of at least 30 seconds, and a residue value of at most 9% when determined by the Residue Test.

[0005] Another aspect of the present disclosure is a unit dose article comprising a sealed compartment and a composition contained within the sealed compartment, the unit dose article comprising: (a) a first film thermoformed in the form of a pouch defining an interior pouch volume, the pouch having an opening; and (b) a second film sealed to the first film at the opening to create the sealed compartment, the first film comprising a mixture of polyvinyl alcohol resin and a plasticizer, the plasticizer comprising a total polyvinyl alcohol resin and a plasticizer. A unit dose article is provided, wherein a first film is provided in an amount ranging from about 5 to about 30 parts by weight based on 100 parts by weight of the alcohol resin and thermoformed into a pouch defining an internal pouch volume, the first film being characterized by a stretch ratio ranging from about 2.3 to about 2.9, the first film being characterized by a release time of at least 30 seconds when formed into a sealed packet and tested according to a Liquid Release Test, and the first film being characterized by a residue value of at most 9% when determined by a Residue Test.

[0006] Another aspect of the present disclosure provides a method of improving the liquid release time of a thermoformed film, comprising contacting a thermoformed film having a stretch ratio in the range of 2.3 to 3.1 with a liquid detergent or solvent for at least 2 days, wherein the film comprises a polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount in the range of about 5 to about 30 parts by weight (phr) based on 100 parts by weight of the total polyvinyl alcohol resin, and the liquid detergent or solvent comprises about 10% to about 30% water, based on the total weight of the detergent or solvent.

[0007] For the compositions and methods described herein, it is contemplated that optional features, including but not limited to components, compositional ranges thereof, substituents, conditions, and steps, may be selected from the various aspects, embodiments, and examples provided herein.

[0008] Further aspects and advantages will become apparent to those skilled in the art from consideration of the following detailed description in conjunction with the drawings. While the films, articles, pouches, and methods of making and using them are susceptible to embodiments in various forms, the following description 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]

[0009] To further facilitate understanding of the present invention, four drawings are attached hereto.

[0010] [Figure 1-1] 1 shows a dynamic mechanical analysis (DMA) thermogram of Film A according to the present disclosure, which shows the appearance of a second order glass transition temperature when thermoformed to a stretch ratio of 2.6 or greater. [Figure 1-2] 1 shows a dynamic mechanical analysis (DMA) thermogram of Film A according to the present disclosure, which shows the appearance of a second order glass transition temperature when thermoformed to a stretch ratio of 2.6 or greater. [Figure 2-1] 1 shows a DMA thermogram of Film B according to the present disclosure, showing the appearance of a second order glass transition temperature when thermoformed to a stretch ratio of 2.6 or greater. [Figure 2-2] 1 shows a DMA thermogram of Film B according to the present disclosure, showing the appearance of a second order glass transition temperature when thermoformed to a stretch ratio of 2.6 or greater. [Figure 3-1] 1 shows a DMA thermogram of Film C not according to the present disclosure, which shows no appearance of a secondary glass transition temperature when thermoformed to stretch ratios of 2.6 or greater. [Figure 3-2] 1 shows a DMA thermogram of Film C not according to the present disclosure, which shows no appearance of a secondary glass transition temperature when thermoformed to stretch ratios of 2.6 or greater. [Figure 4A] One setup for liquid release testing is shown, which uses a beaker and a plastic grid to help keep the buoyant pouch completely submerged in water. [Figure 4B] 1 shows the liquid release test setup in use. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] One aspect of the present disclosure provides a thermoformed article comprising a film thermoformed into the form of a pouch defining an internal pouch volume, wherein the film comprises a mixture of a polyvinyl alcohol resin and a plasticizer, wherein the plasticizer is provided in an amount ranging from about 5 to about 25 parts by weight based on 100 parts by weight of the total polyvinyl alcohol resin, wherein the thermoformed film in the form of the pouch defining the internal pouch volume is characterized by a stretch ratio ranging from about 2.3 to about 2.9, and wherein the article, when formed into a sealed packet and tested according to the Liquid Release Test, is characterized by a release time of at least 30 seconds, and a residue value of at most 9% when determined by the Residue Test.

[0012] Generally, thermoforming of a film results in a thinning of the film as it is drawn into a cavity or mold, compared to the thickness of the film prior to thermoforming. Thus, as the stretch ratio of the film increases, the thickness of the film is expected to decrease. Such thinning of the film is expected to result in faster release of the composition contained within the thermoformed film at a given temperature, since there is less film material between the water and the encapsulated composition. Furthermore, without intending to be bound by theory, it is believed that thermoforming promotes alignment of the polymer chains and introduces stress within the polymer matrix, which may result in a decreased collapse time of the film, and a decreased time for the film to contain any encapsulated composition when the film comes into contact with water (i.e., exhibiting a decreased liquid release time) compared to the same film that has not been thermoformed. Advantageously, it has been found that for articles of the present disclosure prepared from thermoformed films containing plasticizer in an amount of about 5 to about 25 phr, the stress from thermoforming may be relieved by contacting the film with a liquid detergent composition or solvent containing about 10 to about 30% by weight of water. Such stress relaxation of the polymer chains correlates with improved liquid release times compared to films that are thermoformed and not contacted with such liquid detergents or solvents, or compared to thermoformed films with high initial plasticizer content (greater than 40 phr). As used herein, "polyvinyl alcohol-co-[monomer] polymers" includes partially hydrolyzed polyvinyl acetate copolymers (i.e., terpolymers containing vinyl acetate monomer units, vinyl alcohol monomer units, and comonomer (e.g., maleate) units) and fully hydrolyzed polyvinyl acetate copolymers (i.e., true copolymers containing vinyl alcohol monomer units and comonomer (e.g., maleate) units).

[0013] "Comprising" as used herein means various components, ingredients, or steps that may be used in combination in the practice of the present disclosure. Thus, the term "comprising" encompasses the more restrictive terms "consisting essentially of" and "consisting of". The composition may include, consist essentially of, or consist of any of the required and optional elements disclosed herein. For example, a thermoformed packet may "consist essentially of" a film as described herein due to the use of the thermoforming properties of the film, while including a non-thermoformable film (e.g., a lid portion), and optional markings on the film, for example, by inkjet printing. The inventions illustratively disclosed herein may be suitably practiced in the absence of any element or step not specifically disclosed herein.

[0014] Films, such as those made in accordance with the present disclosure, are defined by the polymer industry (Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc., 1967, Vol. 6, page 764) as "molded plastics that are relatively thin for their breadth and width, having a maximum thickness of 0.010 inches."

[0015] A self-supporting film is one that is capable of supporting its own weight. A uniform film refers to a film that is virtually free of breaks, tears, holes, bubbles, and streaks.

[0016] To be considered a water-soluble film according to the present disclosure, the film is about 1.5 mils (about 0.038 mm) thick and dissolves in water at a temperature of 20° C. (68° F.) in 300 seconds or less according to MonoSol Test Method MSTM-205.

[0017] As used herein, the terms packet and pouch should be considered interchangeable. In certain embodiments, the terms packet and pouch are used to refer to a container made using a film and preferably a sealed container that seals a material therein, for example in the form of a metered dose delivery system, respectively. Sealed pouches can be made by any suitable method, including processes and features such as heat sealing, solvent bonding, and adhesive sealing (e.g., with a water-soluble adhesive).

[0018] Unless otherwise specified, all percentages, parts and ratios are based on 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.

[0019] All ranges described herein include all possible subset ranges and any combination of such subset ranges. By default, ranges include the endpoints described unless otherwise stated. When a range of values ​​is provided, it is understood that each intervening value between the upper and lower limits of the range, and any other stated or intervening value within the described range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may be independently included within the smaller ranges, and are also encompassed within the disclosure, subject to any specifically excluded limit in the described range. When a described range includes one or both of these limits, ranges excluding either or both of these included limits are also considered to be part of the disclosure.

[0020] The dimensions and values ​​disclosed herein should not 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," which may include a range from 14.5 mm to 15.4 mm, for example, by numerical rounding.

[0021] As used herein, and unless otherwise specified, the terms "weight percent (wt.%)" and "weight percent (wt%)" are intended to refer to the composition of the specified element in "dry" (non-aqueous) parts by weight of the total film (if applicable), or parts by weight of the total composition enclosed in the pouch (if applicable). As used herein, and unless otherwise specified, the term "PHR" is intended to refer to parts of the composition of the specified element per 100 parts of water-soluble polymer (or resin, whether polyvinyl alcohol) in the water-soluble film.

[0022] As described below, the films and pouches prepared therefrom surprisingly provide one or more benefits, including, but not limited to, (a) superior ability of the film to be converted into a deep-draw pouch or article having a stretch ratio of at least about 2.6 using automated equipment (formability), (b) pouches having a passing grade when tested according to the Liquid Release Test disclosed herein, and / or (c) a residue value of less than 9% when tested according to the Residue Test disclosed herein, and / or (d) maintaining transparency in the stretched state, as indicated by a change in transmittance of the stretched film of less than 5% compared to the film in the unstretched state. In embodiments, the films and pouches prepared therefrom of the present disclosure exhibit at least two benefits selected from (a), (b), (c), and (d) above. In some embodiments, the films and pouches prepared therefrom of the present disclosure exhibit a passing grade when tested according to the Liquid Release Test (b) and exhibit at least one benefit selected from (a) and (c). In some embodiments, the films of the present disclosure and pouches prepared therefrom exhibit a passing grade when tested according to Liquid Release Test (b) and exhibit excellent conversion to deep draw pouches (a). In some embodiments, the films of the present disclosure and pouches prepared therefrom exhibit a passing grade when tested according to Liquid Release Test (b) and exhibit residue values ​​of less than 9% when tested according to Residue Test (c) disclosed herein. In some embodiments, the films of the present disclosure and pouches prepared therefrom exhibit a passing grade when tested according to Liquid Release Test (b) and maintain transparency in the stretched state (d). In embodiments, the films of the present disclosure and pouches prepared therefrom exhibit each of (a), (b), (c), and (d).

[0023] As used herein, unless otherwise specified, a "deep draw" profile refers to a profile having a stretch ratio of at least 2.6. Good film formability can be determined by visual inspection, where the film smoothly and uniformly follows the shape of the cavity (e.g., walls, corners, and bottom of the cavity) and the thermoformed article area (e.g., walls, corners, and bottom of the thermoformed shape) is free of or minimizes defects (e.g., no creases or wrinkles in areas that are intended to be smooth surfaces in the thermoformed shape). In an embodiment, a "deep draw" profile refers to a profile having a stretch ratio of at least 2.9.

[0024] The film can be made by a solvent casting process. The film can be used to form an article or pouch by any suitable process, including thermoforming of the film layer around the article, and, for example, solvent sealing or heat sealing. The pouch can be used, for example, to deposit materials that are delivered to the bulk water.

[0025] The films, articles, pouches, or related methods of making and using 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 drawings), unless otherwise noted.

[0026] Water-soluble film Unit dose designs, including the number of cavities and the shape and size of the cavities, can be used to differentiate and benefit from commercially available single use dosages (SUDS). Formability of the film used to prepare SUDS becomes more important as the cavity depth increases, the number of cavities increases, and the shape of the cavities becomes more box-like and less oval. The films of the present disclosure can be designed to perform in complex unit dose designs and can have one or more advantages, such as formability into deep-draw and / or box-like profiles. The films and related articles and pouches described herein can include plasticized solution-cast water-soluble films. The films can optionally further include one or more additives selected from fillers, surfactants, antiblocking agents, antioxidants, defoamers, bleaching agents, aversive agents, irritants, other functional ingredients, and combinations of the foregoing. In one aspect, the water-soluble films can include at least about 50% by weight of PVOH resins, including one or more PVOH polymers, in total.

[0027] Without wishing to be bound by theory, it is believed that a resin with a moderately low viscosity, as described below, allows for easier flow of the polymer molecules at thermoforming temperatures and faster solubility at lower temperatures (e.g., 12 cP to 28 cP, or about 14 cP to about 26 cP, or about 18 cP to about 24 cP). However, the viscosity of the resin must not be so low that it does not have enough viscosity to create physical strength and robust soluble unit doses.

[0028] The film may have any suitable thickness, with film thicknesses of about 76 microns (μm) or 88 microns being typical and specifically contemplated. Other values ​​and ranges contemplated include a range of about 5 to about 200 μm, or a range of about 20 to about 100 μm, or about 60 to about 120 μm, or about 70 to about 100 μm, or about 40 to about 90 μm, or about 50 to about 80 μm, or about 60 to about 65 μm, e.g., values ​​of 65 μm, 76 μm, 88 μm, or 90 μm.

[0029] PVOH resin The films described herein include one or more polyvinyl alcohol (PVOH) polymers to make up the PVOH resin content of the film, and may include PVOH copolymer resins.

[0030] Polyvinyl alcohol is a synthetic resin that is generally prepared by alcoholysis of polyvinyl acetate, commonly referred to as hydrolysis or saponification. Fully hydrolyzed PVOH, in which substantially all of the acetate groups have been converted to alcohol groups, is a strongly hydrogen-bonded, highly crystalline polymer that is soluble only in hot water above about 140°F (about 60°C). If a sufficient number of acetate groups remain after hydrolysis of polyvinyl acetate, i.e., the PVOH polymer is partially hydrolyzed, the polymer is less hydrogen-bonded, less crystalline, and generally soluble in cold water below about 50°F (about 10°C). Thus, the partially hydrolyzed polymer is a vinyl alcohol-vinyl acetate copolymer, generally referred to as homopolymer PVOH, although it is a PVOH copolymer.

[0031] Specifically, the PVOH resin may comprise a partially or fully hydrolyzed PVOH copolymer comprising anionic monomer units, vinyl alcohol monomer units, and optionally vinyl acetate monomer units. In various embodiments, the anionic monomer units are vinyl acetate, alkyl acrylates, maleic acid, monoalkyl maleates, dialkyl maleates, monomethyl maleates, dimethyl maleates, maleic anhydride, fumaric acid, monoalkyl fumarates, dialkyl fumarates, monomethyl fumarate, dimethyl fumarate, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid, monoalkyl citraconic acid, dialkyl citraconic acid, citraconic anhydride, mesaconic acid, monoalkyl mesaconic acid, dialkyl mesaconic acid, glutaconic acid, monoalkyl glutaconic acid, dialkyl glutaconic acid, glutaconic anhydride, The anionic monomer may be one or more of lutaconic acid, vinylsulfonic acid, alkylsulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-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). For example, the anionic monomer may include one or more of monomethyl maleate and its alkali metal salts (e.g., sodium salt).

[0032] In one class of embodiments, the PVOH is a carboxyl-modified copolymer. In another aspect, the PVOH can be modified with dicarboxyl-type monomers. In one class of these embodiments, the alpha carbon of the carbonyl is in contact with an unsaturated bond (e.g., maleic acid, fumaric acid). In another class of these embodiments, the alpha carbon of the carbonyl is in contact with an unsaturated bond with a methyl branch (e.g., citraconic acid, mesaconic acid). In another class of these embodiments, the beta carbon of the carbonyl is in contact with an unsaturated bond (e.g., itaconic acid, cis-glutaconic acid, trans-glutaconic acid). Monomers that provide alkyl carboxyl groups are contemplated. Maleate-type (e.g., dialkyl maleate, including monoalkyl maleate) or itaconate-type (i.e., itaconic acid) comonomers are specifically contemplated.

[0033] In certain carboxylate-containing PVOH copolymers, when the carboxylate units are converted to carboxylic acid groups, they can easily form stable γ-lactone ring moieties by cyclization with adjacent hydroxyl groups. Specifically, such γ-lactone ring formation occurs when the carboxylate-containing PVOH copolymers are in contact with liquid laundry detergent formulations. The chemical incompatibility comes from the acid-base equilibrium present in the liquid laundry detergent formulation, usually in the form of an amine-fatty acid equilibrium and / or an amine-anionic surfactant acid equilibrium. Even when the detergent formulation is at an alkaline pH due to the presence of a molar excess of amine, exchangeable hydrogen ions are still available to react with the carboxylate groups of the PVOH copolymer. When this occurs, a carboxylic acid group is formed, and if the lactone has a stable five-membered (γ) ring structure, the carboxylic acid group can then easily react with adjacent hydroxyl groups to form an intramolecular lactone. There may be many similar chemical incompatibilities for other liquid products, too numerous to mention. The solubility of the polymer, and therefore the film, is significantly affected by this reaction to form lactones, and complete insolubility may in some cases result in deposition of polymer residues on objects dispersed in liquids with the polymer / film (e.g., on clothes at the end of a wash cycle using detergent pouches made from such films). In contrast, other carboxylate-containing PVOH copolymers may potentially form lactone ring moieties with fewer or more than five members. However, these lactone moieties are unstable due to steric and / or entropic effects, and therefore such copolymers do not show the same change in solubility in the presence of laundry detergent as carboxylate-containing PVOH copolymers that may form γ-lactone ring moieties.

[0034] In an embodiment, the polyvinyl alcohol resin comprises a polyvinyl alcohol-co-maleate polymer. In a refinement of the above embodiment, the polyvinyl alcohol-co-maleate polymer may comprise one or more monomer units selected from maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and alkali metal salts thereof. The polyvinyl alcohol-co-maleate polymer may be a partially or fully hydrolyzed copolymer of polyvinyl acetate and maleic anhydride. In embodiments, the polyvinyl alcohol-co-maleate can include at least 1 mol% maleate modified and up to about 8 mol% maleate modified, such as about 1.5 mol%, about 1.75 mol%, about 2 mol%, about 2.4 mol%, about 2.5 mol%, about 2.8 mol%, about 3 mol%, about 3.2 mol%, about 3.5 mol%, about 3.8 mol%, about 4 mol%, about 4.2 mol%, about 4.5 mol%, about 5 mol%, about 6 mol%, about 7 mol%, or about 8 mol%.

[0035] In embodiments where the polyvinyl alcohol resin comprises a blend of polyvinyl alcohol polymers or copolymers, at least one of the polyvinyl alcohol polymers may comprise a first polyvinyl alcohol-co-maleate polymer. In embodiments, the blend of polyvinyl alcohol polymers may further comprise a second polyvinyl alcohol-co-maleate polymer. The first and second polyvinyl alcohol-co-maleate polymers may differ in viscosity, degree of modification, degree of hydrolysis, or combinations of the foregoing. In embodiments, the first polyvinyl alcohol-co-maleate polymer comprises maleate monomer units derived from a member selected from the group of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof. In embodiments, the second polyvinyl alcohol-co-maleate polymer comprises maleate monomer units derived from a member selected from the group of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof. As used herein, and unless otherwise specified, a monomeric unit of a polymer is "derived from" a monomer to the extent that the monomer has undergone polymerization and is present in the polymer.

[0036] In embodiments, the first polyvinyl alcohol-co-maleate polymer may contain from about 1 mol % to about 3 mol % maleate modification, based on the total moles of monomer units. In embodiments, the second polyvinyl alcohol-co-maleate polymer may contain from about 3 mol % to about 5 mol % maleate modification, based on the total moles of monomer units. In embodiments, the first polyvinyl alcohol-co-maleate polymer may contain from about 1 to less than 3 mol % maleate modification and the second polyvinyl alcohol-co-maleate polymer may contain from greater than 3 mol % to up to about 5 mol % maleate modification, based on the total moles of monomer units. In embodiments where the polyvinyl alcohol resin comprises a blend of PVOH polymers including polyvinyl alcohol-co-maleate copolymers, the PVOH resin blend may have an arithmetic weighted average amount of maleate groups ranging from at least about 2 mol% maleate modified up to about 8 mol% maleate modified, e.g., about 2.1 mol%, about 2.2 mol%, about 2.3 mol%, about 2.5 mol%, about 2.6 mol%, about 2.7 mol%, about 3 mol%, about 3.2 mol%, about 3.5 mol%, about 3.8 mol%, about 4 mol%, about 4.5 mol%, about 5 mol%, about 6 mol%, about 7 mol%, or about 8 mol%. Arithmetic Weighted Average of Modifications

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[0037] Without wishing to be bound by theory, it is believed that a film comprising two polyvinyl alcohol-co-maleate polymers differing in viscosity, degree of modification, degree of hydrolysis, or a combination thereof, may be less susceptible to the formation of ordered domains within the film upon thermoforming compared to a film comprising only one type of polyvinyl alcohol polymer, leading to improved liquid release times due to reduced stresses within the thermoformed film.

[0038] The amount of PVOH resin in the film can range, for example, from about 55 to about 95% by weight, or from about 60 to about 90% by weight, or from about 65 to about 85% by weight, based on the total weight of the film. In embodiments including a blend of PVOH polymers, the first polyvinyl alcohol-co-maleate polymer can be provided in an amount ranging from about 50% to about 90% by weight, e.g., from about 60% to about 80% by weight, or about 70% by weight, based on the total weight of the polyvinyl alcohol polymers. In embodiments including a blend of PVOH polymers, the second polyvinyl alcohol-co-maleate polymer can be provided in an amount ranging from about 10% to about 50% by weight, e.g., from about 20% to about 40% by weight, or about 30% by weight, based on the total weight of the polyvinyl alcohol polymers. In embodiments, the PVOH resin comprises a first polyvinyl alcohol-co-maleate polymer and a second polyvinyl alcohol-co-maleate polymer, the first polyvinyl alcohol-co-maleate polymer being provided in an amount within the range of about 50% to about 90%, about 55% to about 85%, about 60% to about 80%, about 65% to about 75%, or about 70% by weight, based on the total weight of the PVOH polymer, with the remainder being comprised of the second polyvinyl alcohol-co-maleate polymer.

[0039] The total PVOH resin content in the film may have a degree of hydrolysis (DH or DH) of at least 80%, 84%, or 85%, and up to about 99.7%, 98%, or 96%, e.g., in the range of about 84% to about 90%, or 85% to 88% or 86.5%, or in the range of 88% to 95%, about 89% to 93%, or 89.5% to 92%, e.g., about 89%, about 90%, about 92%, about 93%, about 94%, about 95%, or about 96%. As used herein, the degree of hydrolysis is expressed as the mole percentage of vinyl acetate units converted to vinyl alcohol units.

[0040] The degree of hydrolysis of the resin blend is also defined as the arithmetically weighted average degree of hydrolysis.

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[0041] The viscosity (μ) of the PVOH polymer is determined by measuring the freshly made solution using a Brookfield LV type viscometer with a UL adapter as described in the Brookfield test method of British Standard EN ISO 15023-2:2006 Annex E. It is international practice to state the viscosity of a 4% aqueous polyvinyl alcohol solution at 20° C. Unless otherwise stated, all viscosities specified herein in centipoise (cP) should be understood to refer to the viscosity of a 4% aqueous polyvinyl alcohol solution at 20° C. Similarly, when a resin is described as having (or not having) a particular viscosity, it is intended that the specified viscosity is the average viscosity of the resin essentially having the corresponding molecular weight distribution, unless otherwise stated.

[0042] Without being bound by theory, it is believed that the lower viscosity (molecular weight) of PVOH allows for easier molecular mobility at high temperatures, and therefore allows the film to flow more easily in deep cavities. Without being bound by theory, it is believed that the lower viscosity of PVOH resin allows for greater chain mobility at any given temperature, and upon cooling and stress relaxation after the thermoforming step, the lower molecular weight PVOH polymer can more easily migrate into favorable structures of packing and hydrogen bonding that result in higher mechanical strength. It is recognized that this trend cannot continue all the way to a "zero" viscosity, and thus the PVOH resin, or combination of one or more PVOH resins provided in the water-soluble film, can have an average viscosity of at least about 14 cP, or at least about 16 cP, or at least about 17 cP, or at least about 18 cP, or at least about 19 cP, or at least about 20 cP, and up to about 26 cP, or up to about 24 cP, or up to about 23 cP, or up to about 22 cP, or up to about 21 cP, or up to about 20 cP, e.g., in the range of about 12 cP to 28 cP, or about 14 cP to about 26 cP, or about 18 cP to about 24 cP. When the PVOH resin portion of the film is a combination of one or more resins, the combination can have an average viscosity corresponding to the values ​​and ranges described herein, e.g., by weight average of the viscosity values ​​of the individual components. In another type of embodiment, the combination of PVOH resins (in their intended proportions) can be made up as a 4% aqueous solution and the viscosity can be measured. Suitable PVOH resins for use individually or in combination can have a viscosity in the range of about 10 cP to about 40 cP, or about 5 cP to about 38 cP, or about 10 cP to about 36 cP, or about 10 cP to about 20 cP, or about 12 cP to about 20 cP, or about 14 cP to about 19 cP, or about 12 cP to about 34 cP, or about 14 cP to about 32 cP, or about 18 cP to about 30 cP, or about 20 cP to about 28 cP, or about 21 cP to about 26 cP, such as 32 cP, or 26 cP, or 23.5 cP, or 21 cP, or 19 cP, or 16.5 cP, or 14 cP. The viscosity of PVOH resin depends on the weight average molecular weight of the PVOH resin.

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[0043] In embodiments comprising a blend of PVOH polymers, including a first PVOH-co-maleate polymer and a second PVOH-co-maleate polymer, the first PVOH-co-maleate polymer can have a viscosity in the range of about 18 to about 30 cP, e.g., about 19 to about 28 cP, about 20 to about 26 cP, or about 21 to about 26 cP. In embodiments comprising a blend of PVOH polymers, including a first PVOH-co-maleate polymer and a second PVOH-co-maleate polymer, the second PVOH-co-maleate polymer can have a viscosity in the range of about 10 to about 20 cP, e.g., about 12 to about 19 cP, or about 14 to about 19 cP.

[0044] Other water soluble polymers for use in addition to the PVOH copolymers in the films can include, but are not limited to, vinyl alcohol-vinyl acetate copolymers, sometimes referred to as PVOH homopolymers, polyacrylates, water soluble acrylate copolymers, polyvinylpyrrolidone, polyethyleneimine, pullulan, water soluble natural polymers (including, but not limited to, guar gum, gum Acacia, xanthan gum, carrageenan, pectin, amylopectin, alginic acid and its salts, and starch), water soluble polymer derivatives (including, but not limited to, modified starches, ethoxylated starches, and hydroxypropylated starches), copolymers of the foregoing, and combinations of any of the foregoing. Still other water soluble polymers may include polyalkylene oxides, polyacrylamides, polyacrylic acids and their salts, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and their salts, polyamino acids, polyamides, gelatin, methylcellulose, carboxymethylcellulose and its salts, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and combinations of any of the foregoing. In embodiments, the film may include polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxides, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polyamides, gelatin, methylcellulose, carboxymethylcellulose, carboxymethylcellulose salts, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, starch, modified starch, guar gum, gum arabic, xanthan gum, carrageenan, polyacrylates, polyacrylate salts, and copolymers of any of the foregoing; such water soluble polymers, whether PVOH or not, are commercially available from a variety of sources.

[0045] Plasticizer A plasticizer is a liquid, solid, or semi-solid that is added to a material (usually a resin or elastomer) to make it softer, more flexible, and easier to process (by lowering the glass transition temperature of the polymer). At low plasticizer levels, the film may become brittle, difficult to process, or prone to breaking. At high plasticizer levels, the film may be too soft, weak, or difficult to process for the desired use. Water is recognized as a very efficient plasticizer for PVOH and other polymers, including but not limited to water-soluble polymers, but the volatility of water limits its usefulness, as polymer films need to have at least some resistance (robustness) to a variety of ambient conditions, including low and high relative humidity.

[0046] Plasticizers may include, but are not limited to, glycerol, diglycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol (DPG), tetraethylene glycol, propylene glycol, polyethylene glycols up to 400 MW, neopentyl glycol, trimethylolpropane (TMP), polyether polyols, 2-methyl-1,3-propanediol (e.g., MP Diol®), ethanolamine, and mixtures thereof. In some embodiments, the plasticizer is selected from glycerol, diglycerol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycols up to MW 400 (e.g., PEG 200), sorbitol, 2-methyl-1,3-propanediol, trimethylolpropane, polyether polyols, and combinations of the foregoing. In one class of embodiments, the plasticizer is selected from the group of sorbitol, glycerol, propylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, dipropylene glycol, and combinations thereof. In one class of embodiments, the plasticizer is selected from glycerol, propylene glycol, sorbitol, 2-methyl-1,3-propanediol, and combinations of the foregoing. In another class of embodiments, the plasticizer includes glycerol, sorbitol, or combinations of the foregoing.

[0047] The total amount of non-aqueous plasticizer can be in the range of about 5 to about 30 parts by weight per 100 parts PVOH resin (PHR), or about 5 to about 25 PHR, or about 10 to about 25 PHR, or about 15 to about 24 PHR, or about 18 to about 23 PHR, e.g., about 18 PHR, about 20 PHR, about 21 PHR, about 22 PHR, about 23 PHR, or about 24 PHR.

[0048] Auxiliary Film Component The water-soluble films may contain other auxiliary and processing aids in amounts suitable for their intended purpose, such as, but not limited to, surfactants, lubricants, release agents, fillers, extenders, crosslinkers, antiblocking agents, antioxidants, tack reducers, antifoaming agents (defoamers), nanoparticles such as layered silicate type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite, etc.), bittering agents (e.g., denatonium salts such as denatonium benzoate, denatonium saccharides, and denatonium chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and naringenin; and quassinoids such as quassin and brucine), and aversive agents such as irritants (e.g., capsaicin, piperine, allyl isothiocyanate, and resinferratoxin), and other functional ingredients. In embodiments, the water-soluble film may include surfactants, plasticizers compatibilizers, lubricants, release agents, fillers, extenders, crosslinkers, antiblocking agents, antioxidants, tack reducers, antifoaming agents, nanoparticles, bleaching agents, aversive agents, surfactants, and combinations thereof.

[0049] Suitable surfactants may include nonionic, cationic, anionic, and zwitterionic classes.Suitable surfactants include, but are not limited to, polyoxyethylene polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylene glycols, and alkanolamides (nonionic), polyoxyethylene amines, quaternary ammonium salts, and quaternized polyoxyethylene amines (cationic), as well as amine oxides, N-alkyl betaines, and sulfobetaines (zwitterionic).Other suitable surfactants include dioctyl sodium sulfosuccinate, lactylated fatty acid esters of glycerol and propylene glycol, lactyl esters of fatty acids, sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, and acetylated esters of fatty acids, and combinations thereof. In various embodiments, the amount of surfactant in the water-soluble film can range, for example, from about 0.1% to 4.0% by weight, or from about 1.0% to 3.0% by weight, or from about 1.5% to about 2.5% by weight, or from about 0.1 PHR to about 9 PHR, or from about 0.1 to about 8 PHR, or from about 0.1 to about 6 PHR, or from about 0.5 PHR to about 2.9 PHR, or from about 0.5 PHR to about 1.5 PHR, or from about 1 PHR to about 6 PHR, or from about 1.5 PHR to about 5 PHR, or from about 2 PHR to about 4 PHR.

[0050] Suitable fillers / bulking agents / antiblocking agents / stickiness reducers include, but are not limited to, starch, modified starch, crosslinked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, mica, stearic acid and its metal salts, such as magnesium stearate. Preferred materials are starch, modified starch, and silica. In one type of embodiment, the amount of filler / bulking agent / antiblocking agent / stickiness reducer in the water-soluble film can range, for example, from about 1% to about 6% by weight, or from about 1% to about 4% by weight, or from about 2% to about 4% by weight, or from about 1 PHR to about 6 PHR, or from about 1 PHR to about 4 PHR, or from about 2 PHR to about 4 PHR. In some embodiments, the film may be substantially free of silica. As used herein and unless otherwise stated, "substantially free of silica" refers to a film having silica present in an amount less than about 500 ppm. For example, less than about 400 ppm, less than about 300 ppm, less than about 200 ppm, or less than about 100 ppm.

[0051] The antiblocking agent (e.g., stearic acid), if present in the film, may be present in the film in an amount of at least 0.1 PHR, or at least 0.5 PHR, or at least 1 PHR, or from about 0.1 to 5.0 PHR, or from about 0.1 to about 3.0 PHR, or from about 0.4 to 1.0 PHR, or from about 0.5 to about 0.9 PHR, or from about 0.5 to about 2 PHR, or from about 0.5 to about 1.5 PHR, or from 0.1 to 1.2 PHR, or from 0.1 to 2.7 PHR, for example, 0.5 PHR, 0.6 PHR, 0.7 PHR, 0.8 PHR, or 0.9 PHR.

[0052] The water-soluble film of the present disclosure can be obtained by casting, blow molding, extrusion, or extrusion blow molding a mixture of polyvinyl alcohol, plasticizer, and any optional secondary or auxiliary additives. The process for solvent casting of PVOH is well known in the art. For example, in a film-forming process, polyvinyl alcohol resin and secondary additives are dissolved in a solvent, typically water, metered onto a surface, substantially dried (or forced dried) to form a cast film, and then the resulting cast film is removed from the casting surface. The process can be carried out in batches, or more efficiently in a continuous process.

[0053] In forming a continuous film of polyvinyl alcohol, it is conventional practice to meter a solution of the solution onto a moving casting surface, such as a continuously moving metal drum or belt, causing the solvent to be substantially removed from the liquid, thereby forming a self-supporting cast film, and then stripping the resulting cast film from the casting surface.

[0054] Optionally, the water-soluble film can be a self-supporting film consisting of one layer or multiple similar layers.

[0055] thermoformed articles The present disclosure provides a water-soluble unit dose article. The water-soluble unit dose article comprises at least a first thermoformed compartment and, optionally, a composition stored in the compartment. Suitable compositions are described in more detail below. The final water-soluble unit dose article comprises a water-soluble film that is thermoformed (formed) such that the unit dose article comprises at least one internal compartment surrounded by the water-soluble film. The intermediate structure considered as an embodiment of the disclosure herein may include an element of the article or a part of the article in an unsealed state, for example, to allow the intermediate structure to provide the composition before final filling. The water-soluble unit dose article is configured such that the composition does not leak out of the compartment during storage. However, when the water-soluble unit dose article comes into contact with water, the water-soluble film dissolves and releases the contents of the internal compartment, for example, into a washing solution, bulk water, or other environment (e.g., soil in the case of an agricultural composition).

[0056] Compartments of the final unit dose article, if present, should be understood to mean the closed internal space within the unit dose article that holds the composition. In reality, the compartments may be devoid of composition or devoid of solid or liquid type composition disposed therein, for example, containing only air to provide the article with buoyancy for a period of time before dissolving.

[0057] Thermoforming of a film is a process in which a film is heated, molded (e.g., into a mold), and then the film is cooled so that the film will retain its shape, e.g., the shape of the mold. Heat can be applied using any suitable means. For example, the film can be directly heated by passing it under a heating element or through hot air before or once it is applied onto the surface. Alternatively, the film can be indirectly heated, for example, by heating the surface or by applying a hot item onto the film. In some embodiments, the film is heated using infrared light. The film can be heated to a temperature in the range of about 50 to about 150°C, about 50 to about 120°C, about 60 to about 130°C, about 70 to about 120°C, or about 80 to about 100°C. The water-soluble film before thermoforming may have a thickness in the range of about 5 to about 200 μm, or in the range of about 20 to about 100 μm, or about 60 to about 120 μm, or about 70 to about 100 μm, or about 40 to about 90 μm, or about 50 to about 80 μm, or about 60 to about 65 μm, for example, 65 μm, 76 μm, 88 μm, or 90 μm.

[0058] Thermoforming can be performed by any suitable process, including vacuum thermoforming (by cavity or in a positive mold), pressure thermoforming (e.g., positive gas pressure, optionally vacuum assisted), and mechanical thermoforming (e.g., draped over a positive mold, optionally vacuum assisted). In one type of embodiment, the thermoforming is vacuum thermoforming. In another type of embodiment, the vacuum thermoforming is by use of a cavity mold. The cavity mold may have a single cavity or may contain two or more cavities. The vacuum that draws the film into the mold may be applied for about 0.2 to about 5 seconds, or about 0.3 to about 4, or about 0.5 to about 3 seconds, once the film is resting on the horizontal portion of the surface. The vacuum may be such as to provide a low pressure, for example, in the range of 10 mbar to 1000 mbar, or in the range of 100 mbar to 600 mbar.

[0059] The mold in which the article can be made can have any shape, length, width, and depth depending on the required dimensions. The molds can also differ from each other in size and shape, if desired. For example, the volume of the final article can be about 5 ml to about 300 ml, or about 10 to 150 ml, or about 20 to about 100 ml, and the size of the mold is adjusted accordingly. In some embodiments, the size of the mold can be selected so that the final article has a volume in the range of 25 mL or less, or 20 mL or less, or 15 mL or less, or 10 mL or less, or 5 mL or less, for example, about 5 mL to about 50 mL, or about 5 mL to about 30 mL.

[0060] Alternatively or additionally, the film may be moistened by any suitable means prior to or once it is applied to the surface, such as 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, or indirectly by moistening the surface or by applying a moistening item to the film.

[0061] Once the film has been heated and / or wetted on top of a mold in a first orientation, the film can be drawn into a suitable mold, preferably using a vacuum, into a second orientation.

[0062] The distance in the z-direction that the film travels from the first orientation to the second orientation is the stretch depth. Filling of the formed film can be accomplished by utilizing any suitable means. In some embodiments, the most preferred method will depend on the product form and the required filling speed. In some embodiments, the formed film is filled by in-line filling techniques with the product contained in the resulting pouch. The filled open packet is then sealed using a second film by any suitable method to form a pouch. This can be accomplished in a continuous constant motion while in a horizontal position. Sealing can be accomplished by continuously feeding a second film (which may be the same or different from the thermoforming film), preferably a water-soluble film, over and over the open packet, and then preferably sealing the first and second films together, typically in the area between the dies and therefore between the packets.

[0063] Any suitable method of sealing the packet and / or its individual compartments may be utilized. Non-limiting examples of such means include heat sealing, solvent welding, solvent or wet sealing, and combinations thereof. Typically, only the areas where the seal will be formed are treated with heat or solvent. Heat or solvent may be applied by any method, typically onto the sealing material, and typically only onto the areas where the seal will be formed. When solvent or wet sealing or welding is used, it may be preferred that heat is also applied. A preferred method of wet or solvent sealing / welding includes selectively applying solvent onto the areas between the forms or onto the sealing material, for example by spraying or printing the solvent onto these areas, and then applying pressure onto these areas to form the seal. For example, sealing rolls and sealing belts (optionally also providing heat), as described above, may be used.

[0064] In some embodiments, a thermoformed article comprising a water-soluble film of the present disclosure, where the film has an initial thickness in the range of 75-90 μm, may be characterized by a stretch depth (the distance in the z-direction that the film travels from a first orientation to a second orientation during the thermoforming step) of at least 15 mm, or at least 20 mm, or at least 25 mm. In some embodiments, a thermoformed article according to the present disclosure includes a thermoformed cavity that includes walls, corners, and a base, and may be characterized by a stretch depth of at least 25 mm.

[0065] In some embodiments, a thermoformed article comprising a water-soluble film of the present disclosure may be characterized by a stretch ratio of at least 2.5, or at least 2.6, or at least 2.7, or at least 2.8, or at least 2.9, or at least 3.0, or at least 2.7, or at least 3.5, or at least 4.0. The stretch ratio is the ratio of the area of ​​the mold surface to the area of ​​the film before drawing. In some embodiments, a thermoformed article according to the present disclosure may comprise a thermoformed cavity comprising walls, corners, and a bottom, and may be characterized by a stretch ratio of at least 2.6. In some embodiments, a thermoformed article according to the present disclosure may comprise a thermoformed cavity comprising walls, corners, and a bottom, and may be characterized by a stretch ratio of at least 3.0. In some embodiments, a thermoformed article according to the present disclosure may comprise a thermoformed cavity comprising walls, corners, and a bottom, and may be characterized by a stretch ratio of at least 3.6. The stretch ratio relative to the original film thickness is another parameter that describes the extent to which a film becomes thinner, for example, in terms of a thicker film being able to tolerate a higher stretch ratio. In some embodiments, thermoformed articles comprising the water-soluble films of the present disclosure can be characterized by the ratio of the initial film thickness to the depth of the stretch ratio, for example, the depth of the stretch ratio and film thickness described herein and in the examples.

[0066] A unit dose article of the present disclosure may include a sealed compartment and a composition stored within the sealed compartment, the unit dose article including: (a) a first film thermoformed in the form of a pouch defining an internal pouch volume, the pouch having an opening; and (b) a second film sealed to the first film at the opening to create the sealed compartment, the first film and the second film being selected from any water-soluble film disclosed herein, the first film thermoformed in the form of a pouch defining an internal pouch volume characterized by a stretch ratio in the range of about 2.3 to about 2.9, the first film formed into a sealed packet characterized by a release time of at least 30 seconds when tested according to a Liquid Release Test, and the first film characterized by a residue value of at most 9% when determined by a Residue Test. In an embodiment, the first film comprises a mixture of polyvinyl alcohol resin and plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 30 parts by weight based on 100 parts by weight of the total polyvinyl alcohol resin. In an embodiment, the first film and the second film are the same. In an embodiment, the first film and the second film are the same except that the second film is not thermoformed. In an embodiment, the first film and the second film are different and differ in the type of resin (e.g., modified or unmodified polyvinyl alcohol, PVOH of different viscosity, different degree of hydrolysis, etc.), amount of resin, type of plasticizer, amount of plasticizer, and / or type and amount of processing aid.

[0067] In an embodiment, the film comprises about 70 parts of a first polyvinyl alcohol-co-maleate copolymer, about 30 parts of a second polyvinyl alcohol-co-maleate copolymer, and about 20-25 parts of a plasticizer per 100 parts of polyvinyl alcohol polymer, and when thermoformed to a stretch ratio of 2.9, the film has a passing grade when evaluated by the Liquid Release Test after contact with liquid laundry detergent for 1 day, or 7 days, or 14 days. In an embodiment, the film comprises about 70 parts of a first polyvinyl alcohol-co-maleate copolymer, about 30 parts of a second polyvinyl alcohol-co-maleate copolymer, and about 20-25 parts of a plasticizer per 100 parts of polyvinyl alcohol polymer, and when thermoformed to a stretch ratio of 3.1, the film has a passing grade when evaluated by the Liquid Release Test after contact with liquid laundry detergent for 7 days, or 14 days. In an embodiment, the film comprises about 70 parts of a first polyvinyl alcohol-co-maleate copolymer, about 30 parts of a second polyvinyl alcohol-co-maleate copolymer, and about 40-45 parts of a plasticizer per 100 parts of polyvinyl alcohol, and when thermoformed to a stretch ratio of 2.9, the film has a passing grade when evaluated by the Liquid Release Test after contact with liquid laundry detergent for 1 day, or 7 days, or 14 days.

[0068] The thermoformed shape (e.g., as defined by the mold) may additionally or alternatively be characterized as being box-like (e.g., as compared to a more rounded shape). The boxiness of the mold and resulting thermoformed cavity is defined by the radii of curvature provided at the intersections of the walls, such as, for example, between the individual side walls and between the side walls and the bottom of the cavity. Thus, in one aspect, the mold may be characterized as having a radius of curvature at any intersection (i.e., the smallest radius of curvature throughout the mold) of 10 mm or less to be considered a more box-like profile. In other embodiments, the radius is, for example, 8 mm or less, or in the range of 0.1 mm to 5 mm.

[0069] The film is useful, for example, for creating articles and / or pouches for containing detergent compositions. The cleaning actives can be in any form, such as powder, gel, paste, liquid, tablet, or any combination thereof. The film is also useful in any other application where improved wet handling and low cold water residue are desired. The film forms at least one sidewall of the article and / or pouch, optionally the entire article and / or pouch, and preferably the outer wall of at least one sidewall.

[0070] The films described herein can also be used to make articles and / or pouches with two or more compartments, made from the same film or in combination with films of other polymeric materials. The additional films can be obtained, for example, by casting, blowing, extrusion, or extrusion blowing of the same or different polymeric materials known in the art. In one type of embodiment, the polymers, copolymers, or derivatives thereof suitable for use as the additional film are selected from polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxide, polyacrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamides, maleic acid / acrylic acid copolymers, polysaccharides including starch and gelatin, natural gums such as xanthan gum, and carrageenan. For example, the polymer may be selected from polyacrylates and water soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and combinations thereof, or may be selected from polyvinyl alcohol, polyvinyl alcohol copolymers and hydroxypropylmethylcellulose (HPMC), and combinations thereof. One contemplated embodiment is characterized by the polymer level in the packet material, for example, the PVOH copolymers mentioned above are at least 60% as mentioned above.

[0071] The article and / or pouch of the present disclosure may comprise at least one sealed compartment. Thus, the article and / or pouch may comprise a single compartment or multiple compartments. The water-soluble pouch or sachet may be formed from two layers of water-soluble polymeric film sealed at the interface or by a single film folded over and sealed on itself. One or both of the films may comprise the PVOH film described above. The film defines an internal article and / or pouch container volume that contains any desired composition for release into an aqueous environment.

[0072] The volume of the pouch container is not particularly limited. In one type of embodiment, the volume of the pouch container is 25 mL or less. In another embodiment, the volume is less than 25 mL. Another type of pouch container has a volume of less than 50 mL.

[0073] The compositions for use in the pouch are not particularly limited. In embodiments with multiple compartments, each compartment may contain the same and / or different compositions. The compositions may thereby take any suitable form, including but not limited to liquids, solids, and combinations thereof (e.g., solids suspended in liquids). In some embodiments, the pouch comprises a first, second, and third compartment, each of which contains a different first, second, and third composition, respectively. Liquid detergents are specifically contemplated.

[0074] The compartments of the multi-compartment article and / or pouch may be of the same or different size and / or volume. The compartments of the multi-compartment article and / or pouch may be separated or joined in any suitable manner. In some embodiments, the second and / or third and / or subsequent compartments are superimposed on the first compartment. In one embodiment, the third compartment may be superimposed on the second compartment, which is then superimposed on the first compartment in a sandwich configuration. Alternatively, the second and third compartments may be superimposed on the first compartment. However, it is also envisioned that the first, second and optionally third and subsequent compartments may be attached in a side-by-side relationship to each other. The compartments may be packaged in a series, with each compartment being individually separable by a perforation. Thus, each compartment may be individually torn from the rest of the series by an end user, for example, to pre-treat or post-treat a fabric with a composition from one compartment. In some embodiments, the first compartment may be surrounded by at least a second compartment, for example, in a tire and rim configuration, or in a pouch within a pouch configuration.

[0075] The articles and / or pouches of the present disclosure may comprise one or more different films. For example, in single compartment embodiments, the packet may be made from one wall folded over on itself and sealed at the edges, or two walls sealed together at the edges. In multi-compartment embodiments, the articles and / or packets may be made from one or more films, such that any given packet compartment may comprise walls made from a single film or from multiple films having different compositions. In one embodiment, the multi-compartment article and / or pouch comprises at least three walls: an upper outer wall, a lower outer wall, and a partition wall. The upper and lower outer walls are generally opposite and form the exterior of the article and / or pouch. The partition wall is on the interior of the article and / or pouch and is secured to the generally opposite outer wall along the seal line. The partition wall separates the interior of the multi-compartment article and / or pouch into at least a first and a second compartment.

[0076] In one embodiment, the article and / or pouch comprises first and second sealed compartments, the second compartment being in a generally nested relationship with the first sealed compartment such that the second sealed compartment and the first sealed compartment share a partition wall within the article and / or pouch.

[0077] In one embodiment, the article and / or pouch comprising the first and second compartments further comprises a third sealed compartment in a generally superimposed relationship with the first sealed compartment such that the third sealed compartment and the first sealed compartment share a partition wall within the article and / or pouch.

[0078] In some embodiments, the first composition and the second composition are selected from one of the following combinations: liquid, liquid; liquid, powder; powder, powder; liquid, gel; liquid, paste; powder, gel; powder; paste; gel; paste; gel, gel; paste, paste.

[0079] In some embodiments, the first, second, and third compositions are selected from one of the following combinations: solid / liquid / liquid, and liquid / liquid / liquid. Other combinations may include gels or pastes of similar combinations.

[0080] In one embodiment, a single compartment or multiple sealed compartments contain a composition. The multiple compartments may each contain the same or different compositions. The composition is selected from a liquid, a powder, or a combination thereof.

[0081] In embodiments, the compositions may be selected from the group of liquid light duty and heavy duty liquid detergent compositions, powder detergent compositions, dish detergents for hand and / or machine washing; hard surface cleaning compositions, fabric enhancers, detergent gels commonly used in laundry, as well as bleaches and laundry additives, shampoos and body washes.

[0082] The formed article and / or pouch can then be cut by a cutting device. Cutting can be accomplished using any known method. It may also be preferred that cutting is done in a continuous manner, preferably at a constant speed, and preferably in a horizontal position. The cutting device may be, for example, a sharp article, or a hot article, or a laser, in the latter case, where the hot article or laser "burns" through the film / sealing area.

[0083] The different compartments of the multi-compartment pouch may be made together in a side-by-side fashion, and the resulting joined pouch may or may not be separated by cutting. Alternatively, the compartments may be made separately.

[0084] In some embodiments, the articles and / or pouches may be made according to a process that includes a) forming a first compartment (as described above), b) forming recesses in some or all of the sealed compartments formed in step (a) to produce a second molded compartment superimposed on the first compartment, c) filling and sealing the second compartment with a third film, d) sealing the first, second, and third films, and e) cutting the films to produce the multi-compartment article and / or pouch. The recesses formed in step (b) may be achieved by applying a vacuum to the compartments prepared in step (a).

[0085] In some embodiments, the second and / or third compartment may be made in separate steps and then combined with the first compartment, as described in European Patent Application No. 08101442.5, or WO 2009 / 152031.

[0086] In some embodiments, the articles and / or pouches may be made according to a process that includes a) forming a first compartment using a first film on a first forming machine, optionally using heat and / or vacuum; b) filling the first compartment with a first composition; c) deforming a second film on a second forming machine, optionally using heat and vacuum, to create a second and optionally a third shaped compartment; d) filling the second and optionally the third compartment; e) sealing the second and optionally the third compartment using a third film; f) placing the sealed second and optionally the third compartment onto the first compartment; g) sealing the first, second and optionally the third compartment; and h) cutting the film to produce a multi-compartment article and / or pouch.

[0087] The first and second forming machines may be selected based on their suitability for carrying out the above process. In some embodiments, the first forming machine is preferably a horizontal forming machine and the second forming machine is preferably a rotary drum former, preferably located above the first forming machine.

[0088] It should be appreciated that by using appropriate supply stations, it may be possible to produce multi-compartment articles and / or pouches incorporating a number of different or unique compositions and / or different or unique liquid, gel or paste compositions.

[0089] In some embodiments, the film and / or article and / or pouch is sprayed or dusted with a suitable material, such as an active agent, a lubricant, an aversive agent, or mixtures thereof, In some embodiments, the film and / or pouch is printed thereon, for example, with an ink and / or an active agent.

[0090] Contents of the article and / or pouch The article and / or pouch may contain various compositions, for example, household care compositions. A multi-compartment article and / or pouch may contain the same or different compositions in each separate compartment. The composition is proximal to the water-soluble film. The composition may be less than about 10 cm, or less than about 5 cm, or less than about 1 cm from the film. Typically, the composition is adjacent to or in contact with the film. The film may be in the form of a pouch or compartment that contains the composition therein.

[0091] Multi-compartment articles and / or pouches may be utilized to hold compositions containing incompatible ingredients (e.g., bleach and enzymes) that are physically separated or divided from one another. It is believed that such dividers may extend the useful life and / or reduce the physical instability of such ingredients. Additionally or alternatively, such dividers may provide aesthetic benefits, as described in European Patent Application No. 09161692.0.

[0092] Non-limiting examples of useful compositions (e.g., household care compositions) include light-duty and heavy-duty liquid detergent compositions, hard surface cleaning compositions, detergent gels commonly used in laundry, bleaches and laundry additives, fabric enhancer compositions (such as fabric softeners), shampoos, body washes, and other personal care compositions. The compositions used in the present articles and / or pouches may be in the form of liquids, solids, or powders. Liquid compositions may include solids. Solids may include powders or agglomerates such as microcapsules, beads, noodles, or one or more pearl-sized balls, or mixtures thereof. Such solid elements may provide technical benefits through cleaning or as pre-treatment, delayed, or continuous release components, and may additionally or alternatively provide aesthetic benefits.

[0093] In embodiments where the composition stored in the sealed compartment comprises a liquid composition, the liquid composition may comprise 10-30% water, e.g., 10-25% water, 10-20% water, 10-18% water, 10-17% water, or 10-16% water. In embodiments, the liquid composition stored in the sealed compartment may comprise 10-18% water. In embodiments, the liquid composition stored in the sealed compartment may comprise 12-16% water.

[0094] In the case of an article containing a liquid composition adjacent to or in contact with the film that constitutes the article, the components of the liquid composition may migrate into the film, or the components of the film may migrate into the liquid composition, or both. This migration of components may affect the composition of the film and therefore the physical properties of the film. Without intending to be bound by theory, it is believed that the amount of water provided in the liquid composition that contacts the film affects the migration of components between the film and the liquid composition. In the case of a composition that contains a low amount of water, for example less than 10% by weight, the migration of components may be reduced so that the physical properties of the film are not significantly affected. In the case of a composition that contains a high amount of water, for example more than 30% by weight, the physical integrity of the film may be affected due to the increased solubility of the film in the liquid composition.

[0095] The present disclosure further provides a method of improving the liquid release time of a thermoformed film of the present disclosure, comprising contacting a thermoformed film having a stretch ratio of 2.3 to 3.1 with a liquid detergent or solvent for at least 2 days, wherein the film comprises a polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 25 parts by weight based on 100 parts by weight of the total polyvinyl alcohol resin, and the liquid detergent or solvent comprises about 10% to about 30% water based on the total weight of the detergent or solvent.

[0096] The detergent or solvent is not particularly limited, so long as the water content is in the range of about 10 to about 30% by weight, for example, about 10 to 25% by weight, about 10 to 20% by weight, about 10 to 18% by weight, about 10 to 17% by weight, about 10 to 16% by weight, about 12 to 18% by weight, or about 12 to 16% by weight, based on the total weight of the detergent or solvent. The remainder of the composition may include any liquid detergent ingredient disclosed herein, plasticizers, or other solvents. In embodiments, the detergent or solvent composition may include glycerin, propylene glycol, amines, alkyl ethers, alkyl ethoxylates, fatty acids, fatty alcohols, alkyl sulfonic acids, and combinations thereof.

[0097] Test Liquid Laundry Detergent 1 (LLD1) Suitable liquid laundry detergents for use as compositions contained within pouches or packets of the films disclosed herein for testing have the following formulas: LLD1 contains approximately 10% total moisture, including water added to the formulation and water contained in other ingredients. [Table 1]

[0098] Test Liquid Laundry Detergent 2 (LLD2) Another suitable liquid laundry detergent for use as the composition contained within a pouch or packet of the films disclosed herein for testing has the following formula: LLD2 contains approximately 14% total moisture, including water added to the formula and water contained in other ingredients. [Table 2]

[0099] Test Liquid Laundry Detergent 2 (LLD3) Another suitable liquid laundry detergent for use as the composition contained within a pouch or packet of the films disclosed herein for testing has the following formulation: LLD3 contains approximately 4% total moisture, including the water contained in the raw materials that make up the film. [Table 3]

[0100] Liquid Release Test Water-soluble films and / or pouches characterized or tested for delayed dissolution according to the Liquid Release Test are analyzed as follows, using the following materials: 2 L beaker and 1.2 L deionized (DI) water The test water-soluble pouch contains the liquid composition (typically 20-30 mL, recorded volume) and the pouch is preconditioned for at least 24 hours at 23±1°C and 50±4% relative humidity (RH), or 38±1°C and 80±4% relative humidity (RH). ●Capsule / frame stand ●Thermometer Alligator clips or plastic grid Timer

[0101] Before performing the experiment, ensure that enough DI water is available to repeat the experiment five times and that the beaker is clean and dry. This method is generally consistent with ASTM D4332-13 (Standard Practice for Conditioning Containers, Packages or Packaging Components for Testing), however, this test method does not maintain control of 50±2% RH.

[0102] To set up for testing, carefully attach the water soluble pouch to an alligator clip attached to a frame stand. If a plastic grid is used, the water soluble pouch is placed in an empty beaker and the grid is placed over the beaker as shown in Figure 4A. The orientation of the pouch within the beaker should be such that the natural buoyancy of the pouch, if any, is allowed for (i.e., the side of the pouch that will float to the top should be placed towards the top). If the pouch is symmetrical, the orientation of the pouch will generally not be important.

[0103] Next, fill a 2L beaker with 1200 milliliters of DI water at 20° C. If using the alligator clip setup, lower the pouch into the water.

[0104] Make sure the pouch is completely underwater on all sides. As soon as the pouch is lowered into the water start a timer or, if using a plastic grid setting, add water to the beaker.

[0105] Release of liquid contents is defined as the first visible evidence of liquid exiting the pouch underwater.

[0106] A timer is used to record when the liquid contents are released into the surrounding water at the 45 second stop point (release time).

[0107] A pass or fail grade will be given to each pouch. A pass grade is given if the soluble pouch retains its liquid for at least 30 seconds. A fail grade is given if the soluble pouch does not retain its liquid for at least 30 seconds.

[0108] This process is repeated five times with fresh DI water and a new water-soluble pouch for each film tested. In line with the general principles of testing and safety related regulations, the test is successful if at least 85% of the pouches tested do not release their contents within a minimum of 30 seconds, with a 90% confidence level.

[0109] Unless otherwise reported, a total of at least 15 pouches are tested for each film sample type. For each sample, the conditioning conditions (e.g., days after pouch formation) and thickness of the film tested are reported.

[0110] Air Release Test Water-soluble films and / or pouches characterized or tested for delayed dissolution according to the Air Release Test are analyzed as follows, using the following materials: 2 L beaker and 1.2 L deionized (DI) water The test water-soluble pouches contain air and the pouches are preconditioned for at least 24 hours at 23±1°C and 50±4% relative humidity (RH), or 38±1°C and 80±4% relative humidity (RH). ●Capsule / frame stand ●Thermometer Alligator clips or plastic grid Timer

[0111] Prior to performing the experiment, ensure that enough DI water is available to repeat the experiment five times and ensure that the beakers are clean and dry.

[0112] To set up for testing, carefully attach the water soluble pouch to an alligator clip attached to a frame stand. If a plastic grid is used, the water soluble pouch is placed in an empty beaker and the grid is placed over the beaker as shown in Figure 4A. The orientation of the pouch within the beaker should be such that the natural buoyancy of the pouch, if any, is allowed for (i.e., the side of the pouch that will float to the top should be placed towards the top). If the pouch is symmetrical, the orientation of the pouch will generally not be important.

[0113] Next, fill a 2L beaker with 1200 milliliters of DI water at 20° C. If using the alligator clip setup, lower the pouch into the water.

[0114] Make sure the pouch is completely underwater on all sides. As soon as the pouch is lowered into the water start a timer or, if using a plastic grid setting, add water to the beaker.

[0115] Air content release is defined as the first visible evidence of air exiting the pouch underwater.

[0116] A timer is used to record when the air is released into the surrounding water at the 45 second stop point (release time).

[0117] A pass or fail grade will be given to each pouch. A pass grade is obtained if no air bubbles are visible for 30 seconds or more. A fail grade is obtained if air bubbles are visible within 30 seconds. As described herein, the liquid release time of a thermoformed film can be improved by exposing the thermoformed film to a water-containing detergent or solvent. Liquid release time is generally measured at a time T=24 hours or more. Thus, air release time (ART) can be considered as the release time of the pouch at T=0, before the liquid composition of the pouch acts on the thermoformed film.

[0118] This process is repeated five times with fresh DI water and a new water-soluble pouch for each film tested. In line with the general principles of testing and safety related regulations, the test is successful if at least 85% of the pouches tested do not release their contents within a minimum of 30 seconds, with a 90% confidence level.

[0119] References herein to liquid release times measured "according to the Liquid Release Test" are tested with an LLD2 having approximately 14% water by weight, unless otherwise indicated.

[0120] Residue Testing This method can be used to quantitatively evaluate film residue. Pouches containing liquid compositions such as liquid laundry detergent (LLD) are collected from a conditioning environment (38° C., 80% relative humidity (RH)) after a given storage time. Pouches described herein were conditioned in contact with LLD3 (LLD of 4% water) for 63 days. The pouches are cut open and the LLD is drained into a waste container. The detergent is completely removed from the film by wiping with a Kimwipe. ATR spectra (n=3) of the inside of the capsule are collected. Each sample will be tested using a weigh boat and espresso brown cotton fabric cut into a 54 mm circle. The weigh boat is weighed and recorded, the washed film is weighed and recorded, and the dry weight of the fabric circle is measured and recorded. A 1000 mL beaker is filled with 800 mL of tap water at 10° C.±1° C., a stir bar is added, and the beaker is placed on a hot plate. The RPM of the hot plate is set at 550. The pouch is cut into approximately four equal strips. All four strips are dropped into the beaker and a timer is started as soon as the pouch strips touch the water.

[0121] The vacuum flask is fitted with a rubber collar, a Büchner funnel, and a vacuum pump. The fabric circle is placed inside the Büchner funnel so that all holes in the funnel are covered. DI water is used to wet and stabilize the edges of the fabric. After the pouch strip has been in the water for approximately 14 minutes and 45 seconds, the vacuum pump is started. When the timer reaches 15 minutes, the stirring is stopped and liquid is poured from the beaker directly into the fabric and center of the funnel at a rate that will not displace the fabric. After all the liquid has been filtered, the beaker and stir bar are inspected for visible residue. The sides of the beaker and stir bar are sprayed with DI water from a squirt bottle, the beaker is rotated several times, and the water is poured into the Büchner funnel. The vacuum pump is turned on to draw out as much water as possible. Once the vacuum pump is off, tweezers are used to pull up one edge of the fabric, followed by the other edge. The two edges are pinched together with the tweezers and the fabric is transferred to a weigh boat. Allow the samples to dry for at least a minimum of 6 hours. After the samples are dry, take the weight of the weigh boat, fabric, and film as the final weight and subtract the original weight of the weigh boat and fabric from the final weight to get the weight of the film residue. The percent residue is calculated as follows: Residue % = (residue weight / initial film weight) * 100. A correction factor of 0.02 is added to the residue result to account for the loss of fabric during the filtration process.

[0122] A pass or fail grade is given to each pouch. Unless otherwise defined, reference to the results of the residue test is the % residue after 63 days of storage in contact with LLD3. For pouches described herein, a pass grade is given if the % residue after 63 days of storage in contact with LLD3 is less than 9%, and a fail grade is given if the % residue after 63 days of storage in contact with LLD3 is at least 9%. In an embodiment, a film according to the present disclosure has a residue of 10% or less after 84 days of storage in contact with LLD3.

[0123] Transmittance Test This test method may measure the transmission, haze, and clarity of films using a BYK Haze-Gard I or equivalent and BYK SmartChart software. The absorption and scattering behavior of a film specimen will determine how much light is transmitted and how objects are seen through a transparent product.

[0124] Total transmittance is the ratio of transmitted light to incident light. It is affected by absorption and reflection properties. Depending on the angular distribution of the diffuse portion, the transparent film will look different. Haze is the percentage of light that passes through that deviates from the incident beam by more than 2.5 degrees on average. Contrast is lost. Transparency is the see-through quality determined in an angular range of less than 2.5 degrees.

[0125] If calibration is required, BYK Calibration Standard Serial Number 1306881 is used. The film may be, but does not need to be, conditioned. If the film is conditioned, the conditioning parameters are recorded. Identify the test area of ​​the film sample and remove any kind of dirt, fingerprints, and scratches. The film sample is placed on the smaller tapered ring of the holder. The larger ring is then placed on the outside of the smaller ring until the film is wrinkle-free and smooth for a haze reading. Film imperfections should be minimized as they can affect how light transmits through the sample.

[0126] Place the film specimen in the appropriate port. If either measurement mode is Transmission or Haze, start with the Haze port. To read transparency only, start with the Transparency port only. Do not move or shift the sample while the measure button is pressed and the indicator light is flashing. Haze readings are distance dependent and the film must be flush against the haze port opening.

[0127] At least three measurements are taken for each sample, with the sample moving in the film holder before each reading. The film may be uniaxially stretched before testing. The films of the present disclosure advantageously exhibit a change in transmission value of less than 20%, less than 15%, less than 10%, or less than 5% after stretching by a stretch factor of 3 (i.e., 3 times its original length) compared to the transmission of the film in its unstretched state.

[0128] dynamic mechanical analysis DMA was performed using a Discover DMA 850 or equivalent with TIROS v 5.4 software. The water-soluble films tested can be flat non-thermoformed films, thermoformed films not exposed to liquid laundry detergent, and thermoformed films after exposure to liquid laundry detergent. The films are conditioned and / or stored in contact with liquid laundry detergent for at least 24 hours at 23° C., 50% RH or 38° C., 80% RH.

[0129] Experiment 1: Standard temperature ramp under constant frequency and amplitude. Starting from -50°C, the temperature was increased to 140°C at a rate of 5°C / min. A frequency of 10hz and an amplitude of 10μm were used with a preload force of 0.1N.

[0130] Experiment 2: Stress Relaxation Analysis. Temperature is equilibrated to 22° C. The film is strained to 200% elongation and held for 5 minutes. The initial stress and post-relaxation stress are monitored. The stress is released and the film is monitored for recovery for 15 minutes.

[0131] DMA thermograms were collected showing storage modulus, loss modulus, loss factor (tan delta), length, and glass transition temperature.

[0132] Various aspects of the articles and methods are described below using numbered paragraphs.

[0133] Aspect A A1. A thermoformed article comprising a film thermoformed into the form of a pouch defining an interior pouch volume, the film comprising a mixture of polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 30 parts by weight (PHR) based on 100 parts by weight of the total polyvinyl alcohol resin; 1. A thermoformed article, wherein a thermoformed film in the form of a pouch defining an interior pouch volume is characterized by a stretch ratio in the range of about 2.3 to about 2.9, wherein the article, when formed into a sealed packet and tested according to a Liquid Release Test, is characterized by a release time of at least 30 seconds, and wherein the article, when determined by a Residue Test, is characterized by a residue value of at most 9%.

[0134] A2. Polyvinyl alcohol resin, a first polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 50% to about 90% by weight based on the total weight of the polyvinyl alcohol polymer; a second polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 10% to about 50% by weight, based on the total weight of the polyvinyl alcohol polymer; The article of A1, wherein the first and second polyvinyl alcohol-co-maleate copolymers differ in degree of maleate modification, viscosity, degree of hydrolysis, or a combination thereof.

[0135] A3. The article of A2, wherein the first polyvinyl alcohol-co-maleate polymer comprises maleate monomer units derived from a member selected from the group of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof.

[0136] A4. The article of A3, wherein the maleate monomer units are provided in the first polyvinyl alcohol-co-maleate polymer in an amount ranging from about 1 mol % to about 3 mol %, based on the total moles of monomer units.

[0137] A5. The article of any one of claims A2-A4, wherein the first polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 18 to about 30 cP as determined by measuring a freshly made solution of 4% polyvinyl alcohol in water at 20° C. using a Brookfield LV type viscometer with a UL adapter as described in the Brookfield test method of British Standard EN ISO 15023-2:2006 Annex E.

[0138] A6. The article of any one of claims A2-A5, wherein the second polyvinyl alcohol-co-maleate polymer comprises maleate monomer units derived from a member selected from the group of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof.

[0139] A7. The article of A6, wherein the maleate monomer units are provided in the second polyvinyl alcohol-co-maleate polymer in an amount ranging from about 3 mol % to about 5 mol %, based on the total moles of monomer units.

[0140] A8. The article of any one of A2-A7, wherein the second polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 10 to about 20 cP as determined by measuring a freshly made solution of 4% polyvinyl alcohol in water at 20°C using a Brookfield LV type viscometer with a UL adapter as described in the Brookfield test method of British Standard EN ISO 15023-2:2006 Annex E.

[0141] A9. The article of any one of A1-A8, wherein the plasticizer is selected from the group consisting of sorbitol, glycerol, propylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, dipropylene glycol, and combinations thereof.

[0142] A10. The article of A9, wherein the plasticizer comprises sorbitol and glycerol.

[0143] A11. The article of any one of A2-A10, wherein the first polyvinyl alcohol-co-maleate polymer is provided in an amount ranging from about 60% to about 80% by weight, based on the total weight of the polyvinyl alcohol polymer, and the second polyvinyl alcohol-co-maleate polymer constitutes the remainder of the polyvinyl alcohol polymer.

[0144] A12. The article of any one of A1-A11, wherein the mixture further comprises a polyvinyl alcohol polymer selected from a polyvinyl alcohol homopolymer, a polyvinyl alcohol copolymer, and combinations thereof.

[0145] A13. The article of any one of A1-A12, wherein the mixture further comprises a polymer selected from polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxide, polyacrylamide, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polyamide, gelatin, methylcellulose, carboxymethylcellulose, carboxymethylcellulose salts, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, starch, modified starch, guar gum, gum arabic, xanthan gum, carrageenan, polyacrylates, polyacrylate salts, and copolymers of any of the foregoing.

[0146] A14. The article of any one of A1-A13, wherein the mixture further comprises one or more components selected from surfactants, plasticizer compatibilizers, lubricants, release agents, fillers, extenders, crosslinkers, antiblocking agents, antioxidants, tack reducers, defoamers, nanoparticles, bleaching agents, aversive agents, surface active agents, and combinations thereof.

[0147] A15. The article of any one of A1-A14, wherein the plasticizer is provided in an amount ranging from about 5 to about 25 PHR, from about 10 to about 25 PHR, from about 15 to about 25 PHR, or from about 18 to about 23 PHR.

[0148] Aspect B B1. A unit dose article comprising a sealed compartment and a composition contained in the sealed compartment, the unit dose article comprising: (a) a first film thermoformed in the form of a pouch defining an interior pouch volume, the pouch having an opening; (b) a second film sealed to the first film at the opening to create a sealed compartment; the first film comprises a mixture of a polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 30 parts by weight based on 100 parts by weight of the total polyvinyl alcohol resin; A unit dose article, wherein a first film thermoformed into a pouch defining an interior pouch volume is characterized by a stretch ratio in the range of about 2.3 to about 3.1, wherein the first film is characterized by a release time of at least 30 seconds when formed into a sealed packet and tested according to a Liquid Release Test, and wherein the first film is characterized by a residue value of at most 9% when determined by a Residue Test.

[0149] B2. The unit dose article of B1, wherein the second film comprises a mixture of polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 50 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol resin.

[0150] B3. The polyvinyl alcohol resin of the first film and the second film comprises a mixture of a first polyvinyl alcohol-co-maleate polymer and a second polyvinyl alcohol-co-maleate polymer; the first polyvinyl alcohol-co-maleate polymer is provided in an amount ranging from about 50% to about 90% by weight, based on the total weight of the polyvinyl alcohol polymers in the film, and the second polyvinyl alcohol-co-maleate polymer is provided in an amount ranging from about 10% to about 50% by weight, based on the total weight of the polyvinyl alcohol polymers in the film; The unit dose article of any one of B1 to B2, wherein the first and second polyvinyl alcohol-co-maleate copolymers differ in degree of maleate modification, viscosity, degree of hydrolysis, or a combination thereof.

[0151] B4. The unit dose article of any one of B1-B3, wherein the composition contained in the sealed compartment comprises a liquid composition.

[0152] B5. The unit dose article of B4, wherein the liquid composition comprises 10-30% water, about 10-25% water, about 10-20% water, about 10-18% water, about 10-17% water, or about 10-16% water, based on the total weight of the liquid composition.

[0153] B6. The unit dose article of any one of B1-B5, wherein the second film comprises a polyvinyl alcohol homopolymer, an anionic polyvinyl alcohol copolymer, or a combination thereof.

[0154] B7. The unit dose article of B6, wherein the anionic polyvinyl alcohol copolymer is selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers.

[0155] B8. The unit dose article of B7, wherein the carboxylated anionic polyvinyl alcohol copolymer comprises carboxylate monomer units derived from monomers selected from acrylates, methacrylates, maleates, and mixtures thereof.

[0156] B9. The unit dose article of any one of B1-B8, wherein the plasticizer is provided in the first film in an amount ranging from about 5 to about 25 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol polymer in the first film.

[0157] B10. The unit dose article of any one of B1-B9, wherein the plasticizer is provided in the second film in an amount ranging from about 5 to about 30 or from about 5 to about 25 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol polymer in the second film.

[0158] B11. The unit dose article of any one of B1-B9, wherein the plasticizer is provided in the second film in an amount ranging from about 25 to about 50 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol polymer in the second film.

[0159] B12. The unit dose article of any one of B3-B11, wherein the first polyvinyl alcohol-co-maleate polymer comprises maleate monomer units derived from a member selected from the group consisting of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof.

[0160] B13. The unit dose article of B12, wherein the maleate monomer units are provided in the first polyvinyl alcohol-co-maleate polymer in an amount ranging from about 1 mol % to about 3 mol %, based on the total moles of monomer units.

[0161] B14. The unit dose article of any one of B3-B13, wherein the first polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 18 to about 30 cP as determined by measuring a freshly made solution of 4% polyvinyl alcohol in water at 20° C. using a Brookfield LV type viscometer with a UL adapter as described in the Brookfield test method of British Standard EN ISO 15023-2:2006 Annex E.

[0162] B15. The unit dose article of any one of B3-B14, wherein the second polyvinyl alcohol-co-maleate polymer comprises maleate monomer units derived from a member selected from the group of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof.

[0163] B16. The unit dose article of B15, wherein the maleate monomer units are provided in the second polyvinyl alcohol-co-maleate polymer in an amount ranging from about 3 mol % to about 5 mol %, based on the total moles of monomer units.

[0164] B17. The unit dose article of any one of B3-B16, wherein the second polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 10 to about 20 cP as determined by measuring a freshly made solution of 4% polyvinyl alcohol in water at 20° C. using a Brookfield LV type viscometer with a UL adapter as described in the Brookfield test method of British Standard EN ISO 15023-2:2006 Annex E.

[0165] B18. The unit dose article of any one of B1-B17, wherein the plasticizer is provided in an amount ranging from about 10 to about 30 parts by weight, or from about 10 to about 25 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol polymer.

[0166] B19. The unit dose article of any one of B1-B18, wherein the plasticizer is selected from sorbitol, glycerol, propylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, dipropylene glycol, and combinations thereof.

[0167] B20. The unit dose article of B19, wherein the plasticizer comprises sorbitol and glycerol.

[0168] B21. The unit dose article of any one of B3-B20, wherein the first polyvinyl alcohol-co-maleate polymer is provided in an amount ranging from about 60% to about 80% by weight, based on the total weight of the polyvinyl alcohol polymer, and the second polyvinyl alcohol-co-maleate polymer constitutes the remainder of the polyvinyl alcohol polymer.

[0169] B22. The unit dose article of any one of B1-B21, wherein the first film, the second film, or both, further comprises a polymer selected from polyvinyl alcohol, anionic polyvinyl alcohol copolymers, polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxides, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polyamides, gelatin, methylcellulose, carboxymethylcellulose, carboxymethylcellulose salts, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, starch, modified starch, guar gum, gum arabic, xanthan gum, carrageenan, polyacrylates, polyacrylate salts, and copolymers of any of the foregoing.

[0170] B23. The unit dose article of any one of B1-B22, wherein the first film, the second film, or both, further comprises one or more components selected from the group consisting of surfactants, plasticizer compatibilizers, lubricants, release agents, fillers, extenders, crosslinkers, antiblocking agents, antioxidants, tack reducers, antifoaming agents, nanoparticles, bleaching agents, aversive agents, surface active agents, and combinations thereof.

[0171] B24. A unit dose article according to any one of B3-B23, wherein the first film comprises a first polyvinyl alcohol-co-maleate polymer in an amount of about 70% by weight, based on the total weight of the polyvinyl alcohol polymer, the first polyvinyl alcohol-co-maleate polymer comprises maleate monomer units in an amount ranging from about 1.5 mol% to about 2.0 mol%, based on the total monomer units, and the first polyvinyl alcohol-co-maleate polymer has a viscosity ranging from about 21 cP to about 26 cP.

[0172] B25. The unit dose article of any one of B3-B24, wherein the first film comprises a second polyvinyl alcohol-co-maleate polymer in an amount of about 30% by weight, based on the total weight of the polyvinyl alcohol polymer, the second polyvinyl alcohol-co-maleate polymer comprises maleate monomer units in an amount ranging from about 3.8 mol% to about 4.2 mol%, based on the total monomer units, and the second polyvinyl alcohol-co-maleate polymer has a viscosity ranging from about 14 cP to about 19 cP.

[0173] B26, (a) a first film; a first polyvinyl alcohol-co-maleate polymer in an amount of about 70% by weight, based on the total weight of the polyvinyl alcohol polymer, the first polyvinyl alcohol-co-maleate polymer comprising maleate monomer units in an amount ranging from about 1.5 mol % to about 2.0 mol %, based on the total monomer units, the first polyvinyl alcohol-co-maleate polymer having a viscosity ranging from about 21 cP to about 26 cP; a second polyvinyl alcohol-co-maleate polymer in an amount of about 30% by weight, based on the total weight of the polyvinyl alcohol polymer, the second polyvinyl alcohol-co-maleate polymer comprising maleate monomer units in an amount ranging from about 3.8 mol % to about 4.2 mol %, based on the total monomer units, the second polyvinyl alcohol-co-maleate polymer having a viscosity ranging from about 14 cP to about 19 cP; a plasticizer provided in an amount ranging from about 18 to about 23 parts by weight based on 100 parts by weight of the total polyvinyl alcohol polymer in the first film, the plasticizer consisting of sorbitol and glycerin; (b) a second film; an anionic polyvinyl alcohol copolymer, the anionic polyvinyl alcohol copolymer being a carboxylated anionic polyvinyl alcohol copolymer, the carboxylate groups of the carboxylated anionic polyvinyl alcohol copolymer comprising methyl acrylate; a plasticizer provided in an amount ranging from about 35 to about 45 parts by weight based on 100 parts by weight of the total polyvinyl alcohol in the second film; (c) the unit dose article comprises a liquid laundry detergent contained in a sealed compartment; (d) The unit dose article of any one of claims B3-B25, wherein the unit dose article is characterized by a stretch ratio of at least 2.3, a release time of at least 30 seconds when tested according to a Liquid Release Test, and a residue value of at most 9% when determined by a Residue Test.

[0174] Aspect C C1. A method for improving the liquid release time of a thermoformed film, comprising: The method includes contacting a thermoformed film having a stretch ratio of 2.3 to 3.1 with a liquid detergent or solvent for at least 2 days; the film comprises a polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 30 parts by weight based on 100 parts by weight of the total polyvinyl alcohol resin; The method wherein the liquid detergent or solvent comprises about 10% to about 30% water, based on the total weight of the detergent or solvent.

[0175] C2. Polyvinyl alcohol resin is a first polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 50% to about 90% by weight based on the total weight of the polyvinyl alcohol polymer; a second polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 10% to about 50% by weight, based on the total weight of the polyvinyl alcohol polymer; The method of C2, wherein the first and second polyvinyl alcohol-co-maleate copolymers differ in degree of maleate modification, viscosity, degree of hydrolysis, or a combination thereof.

[0176] C3. The method of C2, wherein the first polyvinyl alcohol-co-maleate polymer comprises maleate monomer units derived from a member selected from the group of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof.

[0177] C4. The method of C3, wherein the maleate monomer units are provided in the first polyvinyl alcohol-co-maleate polymer in an amount ranging from about 1 mol % to about 3 mol %, based on the total moles of monomer units.

[0178] C5. The method of any one of C2 to C4, wherein the first polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 18 to about 30 cP as determined by measuring a freshly made solution of 4% polyvinyl alcohol in water at 20° C. using a Brookfield LV type viscometer with a UL adapter as described in the Brookfield test method of British Standard EN ISO 15023-2:2006 Annex E.

[0179] C6. The method of any one of C2-C5, wherein the second polyvinyl alcohol-co-maleate polymer comprises maleate monomer units derived from a member selected from the group of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof.

[0180] C7. The method of C6, wherein the maleate monomer units are provided in the second polyvinyl alcohol-co-maleate polymer in an amount ranging from about 3 mol % to about 5 mol %, based on the total moles of monomer units.

[0181] C8. The method of any one of C2 to C7, wherein the second polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 10 to about 20 cP as determined by measuring a freshly made solution of 4% polyvinyl alcohol in water at 20° C. using a Brookfield LV type viscometer equipped with a UL adapter as described in the Brookfield test method of British Standard EN ISO 15023-2:2006 Annex E.

[0182] C9. The method of any one of C1-C8, wherein the plasticizer is selected from the group of sorbitol, glycerol, propylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, dipropylene glycol, and combinations thereof.

[0183] C10. The method of C9, wherein the plasticizer comprises sorbitol and glycerol.

[0184] C11. The method of any one of C2-C10, wherein the first polyvinyl alcohol-co-maleate polymer is provided in an amount ranging from about 60% to about 80% by weight, based on the total weight of the polyvinyl alcohol polymer, and the second polyvinyl alcohol-co-maleate polymer constitutes the remainder of the polyvinyl alcohol polymer.

[0185] C12. The method of any one of C1-C11, wherein the mixture further comprises a polyvinyl alcohol polymer selected from a polyvinyl alcohol homopolymer, a polyvinyl alcohol copolymer, and combinations thereof.

[0186] C13. The method of any one of C1-C12, wherein the mixture further comprises a polymer selected from polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxide, polyacrylamide, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polyamide, gelatin, methylcellulose, carboxymethylcellulose, carboxymethylcellulose salts, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, starch, modified starch, guar gum, gum arabic, xanthan gum, carrageenan, polyacrylates, polyacrylate salts, and copolymers of any of the foregoing.

[0187] C14. The method of any one of C1-C13, wherein the mixture further comprises one or more components selected from surfactants, plasticizer compatibilizers, lubricants, release agents, fillers, extenders, crosslinkers, antiblocking agents, antioxidants, tack reducers, antifoaming agents, nanoparticles, bleaching agents, aversive agents, surface active agents, and combinations thereof.

[0188] C15. The method of any one of C1 to C14, wherein the plasticizer is provided in an amount ranging from about 5 to about 25 parts by weight, about 10 to about 25 parts by weight, about 15 to about 25 parts by weight, or about 18 to about 23 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol resin.

[0189] C16. The method of any one of claims C1-C15, wherein the liquid detergent or solvent comprises, based on the total weight of the detergent or solvent, about 10% to about 25% water, about 10% to about 20% water, about 10% to about 18% water, about 10% to about 17% water, or about 10% to about 16% water. EXAMPLES

[0190] The water-soluble films were thermoformed into pouches enclosing liquid laundry detergent, conditioned at 23° C., 50% RH, or 38° C., 80% RH, and tested for liquid release, residue, DMA, and / or permeability according to the test methods described herein. Films A-F were prepared according to the formulations shown in the table below. [Table 4]

[0191] The films were thermoformed into pouches with stretch ratios of 2.1 to 3.6. The pouches were filled with liquid laundry detergent and characterized by DMA and tested for liquid release time and / or residue according to the test methods described herein. The films were also uniaxially stretched up to 3x and the permeability of the films was tested according to the Permeability Test.

[0192] FIG. 1 shows the DMA thermograms of Film A (flat film) before thermoforming at stretch ratios of 2.6, 2.0, and 3.6. The DMA thermogram of Film A shows the appearance of a second order glass transition temperature after thermoforming to a stretch ratio of at least 2.6. Without intending to be bound by theory, it is believed that the appearance of a second order glass transition temperature indicates that there is an order in the film upon thermoforming, but no crystalline phase is formed. When this film was exposed to liquid laundry detergent for one week, the DMA thermogram (not shown) contained only one glass transition temperature, which is consistent with the thermogram of the initial, flat, non-thermoformed film. Without intending to be bound by theory, it is believed that plasticizers and / or organic solvents from the liquid laundry detergent were able to migrate into the film and relieve the stress in the ordered phase, converting the ordered phase back to an amorphous phase.

[0193] Figure 2 shows the DMA thermograms of Film B (flat film) before thermoforming at stretch ratios of 2.6, 2.0, and 3.6. The DMA thermogram of Film B shows the appearance of a second glass transition temperature after thermoforming to a stretch ratio of at least 2.6. When this film was exposed to liquid laundry detergent for one week, the DMA thermogram (not shown) contained only one glass transition temperature, consistent with the thermogram of the initial, flat, non-thermoformed film.

[0194] Figure 3 shows the DMA thermograms of Film C (flat film) before thermoforming at stretch ratios of 2.6, 2.0, and 3.6. The DMA thermogram of Film C did not show the appearance of a second order glass transition temperature after thermoforming to a stretch ratio of at least 2.6, but did show a shift in the glass transition temperature. Without wishing to be bound by theory, it is believed that the lack of appearance of a second order glass transition temperature is the result of the increased amount of plasticizer in the film (compared to Films A and B).

[0195] Table 1 below shows the transmittance data for various films at various stretch factors before exposure to liquid laundry detergent. [Table 5]

[0196] A second set of water-soluble films were thermoformed into pouches and tested for air outgrowth, liquid outgrowth, and residue according to the test methods described herein. Films A through D are as described above. Films G and H are described in the table below. [Table 6]

[0197] The films were converted into pouches and evaluated for air release. The films were thermoformed to stretch ratios of 2.3, 2.9, or 3.3 and sealed with a second film having the same composition as the thermoformed film to form empty (i.e., air-filled) pouches. The sealed pouches were stored at 23° C. / 50% RH or 38° C. / 80% RH for 1, 7, 14, or 28 days and evaluated according to the Air Release Test described herein. The test films were relatively fresh films, approximately one month old from the time of casting. The results are shown in Table 3. [Table 7]

[0198] In general, the air release performance of each film at each stretch ratio was maintained or improved during storage at 23°C / 50% RH or 38°C / 80% RH. Furthermore, storing the films at higher temperature and humidity conditions generally improved the air release performance. Specifically, films thermoformed to a stretch ratio of 2.9 had a fail grade for air release after 14 or 28 days storage at 23°C / 50% RH, but had a pass grade for air release after 14 or 28 days storage at 38°C / 80% RH. In addition, for films thermoformed to a stretch ratio of 3.3, films A, B, and C stored at 38°C / 80% RH for 28 days had a pass grade for air release, but all of the films stored at 23°C / 50% RH for 28 days had a fail grade for air release. Without wishing to be bound by theory, it is believed that storing thermoformed films under high humidity conditions increases the migration of water into the film, promoting polymer chain relaxation from the aligned and stressed condition caused by thermoforming, further plasticizing the films and improving their physical integrity. Thus, the ART data suggests that water is a necessary component to improve LRT behavior.

[0199] The films were also evaluated for liquid release after contact with LLD2 (a liquid laundry detergent at about 14% water). The films were thermoformed into pouches with stretch ratios of 2.3 to 3.1 and filled with LLD2. The pouches were sealed with a second film having the same composition as the film making up the pouch, and the sealed pouches were tested for liquid release 1, 7, or 14 days after contact with liquid laundry detergent while stored in a 23°C / 50% RH environment according to the Liquid Release Test described herein. These test films were not relatively fresh films, but were approximately 6.5 months old from the time of casting. The results are shown in Table 4. [Table 8]

[0200] The results in Table 4 show that all films thermoformed to stretch ratios between 2.3 and 2.6 passed the liquid release test after only one day of contact with LLD3 (a liquid laundry detergent containing approximately 14% water). Additionally, for films thermoformed to a stretch ratio of 2.9, all films except Film H had a passing grade for liquid release after 7 and 14 days of contact with an LLD of 14% water, and all films except Films B and H had a passing grade for liquid release after only one day of contact with an LLD of 14% water.

[0201] The results in Tables 3 and 4 show the effect of contacting the thermoformed films with an LLD. When thermoformed to a stretch ratio of 2.9, none of the films had a passing grade for air release after up to 28 days of storage at 23° C. / 50% RH, but pouches containing Films A, C, D, and G stored at 23° C. / 50% RH that were thermoformed to a stretch ratio of 2.9 and contacted with an LLD of 14% water for only 1 day had a passing grade for liquid release.

[0202] The films were also evaluated for liquid release after contact with LLD2 (liquid laundry detergent containing about 4% water). The films were thermoformed into pouches with stretch ratios of 2.3 to 3.3 and filled with LLD2. The pouches were sealed with a second film having the same composition as the film making up the pouch, and the sealed pouches were tested for liquid release 1, 7, 14, or 28 days after contact with liquid laundry detergent while stored in a 23°C / 50% RH environment according to the Liquid Release Test described herein. These test films were relatively fresh films, approximately one month old from the time of casting. The results are shown in Table 5. [Table 9]

[0203] The results in Table 5 show that the effect of contact with an LLD containing about 4% water is less pronounced than the effect of contact with an LLD containing 14% water. Specifically, a film thermoformed to a stretch ratio of 2.9 required at least 14 days of contact with an LLD of 4% water at 23° C. / 50% RH to achieve a passing grade for liquid release, while the same film required no more than 7 days of contact with an LLD of 14% water under the same storage conditions to achieve a passing grade.

[0204] The films were also tested for residues after extended contact with liquid laundry detergent. The films were thermoformed into pouches, the pouches were filled with LLD2 (a liquid laundry detergent containing about 4% water), sealed with a second film having the same composition as the film making up the pouch, and tested according to the residue test described herein. At the time of initial pouch formation, these test films were relatively fresh, approximately one month after casting. The results of the residue test are shown in Table 6.

[0205] Table 6 also includes measurements of the sorbitol content of the films after contact with liquid laundry detergent. Films A, B, C, D, and G, containing sorbitol as a plasticizer, were all thermoformed into pouches, which were filled with LLD2 and sealed with a second film. After 7 days of contact with liquid laundry detergent, the pouches were opened, the detergent was removed, and the sorbitol content of each film was measured by liquid chromatography. Table 6 lists the relative change in sorbitol content compared to the initial sorbitol content of each film after 7 days of contact with liquid laundry detergent. [Table 10]

[0206] The results in Table 6 show that the films of the present disclosure, Films A and B, exhibit good residue values ​​(less than 9%) at 63 days. Importantly, Film B, which contains about 20-25 parts of plasticizer per 100 parts of polyvinyl alcohol polymer in the film, showed significantly better residue performance after 84 days of contact with liquid laundry detergent compared to Films A, C, and D. Film G, which contains silica but is otherwise identical to Film B, showed the best residue values ​​in each measurement. Table 4 also shows a significant reduction in the sorbitol content of each film after 7 days of contact with liquid laundry detergent. Without wishing to be bound by theory, it is believed that components of the thermoformed film may migrate into the liquid composition contained in the pouch and vice versa, and that the presence of water in the liquid composition may facilitate this migration of components.

[0207] Because various modifications and alterations to adapt to particular operating requirements and environments will be apparent to those skilled in the art, this disclosure is not to be deemed limited to the embodiments selected for illustrative purposes, but rather covers all changes and alterations that do not constitute a departure from the true spirit and scope of the disclosure.

[0208] Accordingly, the foregoing description is merely set forth for clarity of understanding, and no unnecessary limitations should be understood therefrom, since modifications within the scope of the disclosure may be apparent to those skilled in the art.

[0209] All patents, patent applications, and literature references cited herein are hereby incorporated by reference in their entirety. In the event of a conflict, the present description, including definitions, will control.

[0210] Throughout this specification, when compounds, compositions, articles, methods, and processes are described as comprising components, steps, or materials, it is contemplated that the composition, process, or apparatus can also comprise, consist essentially of, or consist of any combination of the listed components or materials, unless otherwise specified.

Claims

1. 1. A thermoformed article comprising a film thermoformed into the form of a pouch defining an interior pouch volume, the film comprising a mixture of a polyvinyl alcohol resin and a plasticizer; The polyvinyl alcohol resin is a first polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 50% to about 90% by weight, or from about 60% to about 80% by weight, based on the total weight of the polyvinyl alcohol polymer; a second polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 10% to about 50% by weight, based on said total weight of polyvinyl alcohol polymer, optionally said second polyvinyl alcohol-co-maleate polymer comprising the remainder of the polyvinyl alcohol polymer; the first and second polyvinyl alcohol-co-maleate polymers independently comprise maleate monomer units derived from a member selected from the group consisting of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof; the first and second polyvinyl alcohol-co-maleate copolymers differ in degree of maleate modification, viscosity, degree of hydrolysis, or a combination thereof; the plasticizer is provided in an amount ranging from about 5 to about 30 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol resin; 1. A thermoformed article, wherein the thermoformed film in the form of a pouch defining an interior pouch volume is characterized by a stretch ratio in the range of about 2.3 to about 2.9, wherein the article, when formed into a sealed packet and tested according to a Liquid Release Test, is characterized by a release time of at least 30 seconds, and wherein the article, when determined by a Residue Test, is characterized by a residue value of at most 9%.

2. The article of claim 1, wherein the maleate monomer units in the first polyvinyl alcohol-co-maleate polymer are provided in an amount ranging from about 1 mol% to about 3 mol%, based on the total moles of the monomer units in the first polyvinyl alcohol-co-maleate polymer, and optionally, the maleate monomer units in the second polyvinyl alcohol-co-maleate polymer are provided in an amount ranging from about 3 mol% to about 5 mol%, based on the total moles of the monomer units in the second polyvinyl alcohol-co-maleate polymer.

3. 3. The article of claim 1 or 2, wherein the first polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 18 to about 30 cP, and optionally the second polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 10 to about 20 cP, as determined by measuring a freshly made solution of 4% polyvinyl alcohol in water at 20°C using a Brookfield LV type viscometer equipped with a UL adapter as described in the Brookfield test methods of British Standard EN ISO 15023-2:2006 Annex E.

4. 3. The article of claim 1 or 2, wherein the plasticizer is selected from the group of sorbitol, glycerol, propylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, dipropylene glycol, and combinations thereof, optionally wherein the plasticizer comprises sorbitol and glycerol.

5. 3. The article of claim 1 or 2, wherein the mixture further comprises a polymer selected from polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxide, polyacrylamide, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polyamide, gelatin, methylcellulose, carboxymethylcellulose, carboxymethylcellulose salts, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, starch, modified starch, guar gum, gum acacia, xanthan gum, carrageenan, polyacrylate, polyacrylate salt, and copolymers of any of the foregoing.

6. 3. The article of claim 1 or 2, wherein the mixture further comprises one or more components selected from surfactants, plasticizer compatibilizers, lubricants, release agents, fillers, extenders, crosslinkers, antiblocking agents, antioxidants, tack reducers, antifoaming agents, nanoparticles, bleaching agents, aversive agents, and combinations thereof.

7. A unit dose article comprising a sealed compartment and a composition contained in said sealed compartment, said unit dose article comprising: (a) a first film thermoformed into the form of a pouch defining an interior pouch volume, the pouch having an opening; (b) a second film sealed to the first film at the opening to create the sealed compartment; the first film comprises a mixture of a polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 30 parts by weight, optionally in an amount ranging from about 5 to about 25 parts by weight, or in an amount ranging from about 10 to about 30 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol resin in the first film; the second film comprises a mixture of polyvinyl alcohol resin and a plasticizer, and the plasticizer is provided in an amount ranging from about 5 to about 50 parts by weight, optionally in an amount ranging from about 5 to about 30 parts by weight, or in an amount ranging from about 5 to about 25 parts by weight, or in an amount ranging from about 25 to about 50 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol resin of the second film; 1. A unit dose article, wherein the first film, thermoformed into the form of a pouch defining an interior pouch volume, is characterized by a stretch ratio in the range of about 2.3 to about 2.9, the first film, when formed into a sealed packet and tested according to a Liquid Release Test, is characterized by a release time of at least 30 seconds, and the first film, when determined by a Residue Test, is characterized by a residue value of at most 9%.

8. the polyvinyl alcohol resin of the first film and the polyvinyl alcohol resin of the second film independently comprise a mixture of a first polyvinyl alcohol-co-maleate polymer and a second polyvinyl alcohol-co-maleate polymer; the first polyvinyl alcohol-co-maleate polymer is provided in an amount ranging from about 50% to about 90% by weight, optionally in an amount ranging from about 60% to about 80% by weight, based on the total weight of polyvinyl alcohol polymers in the film, and the second polyvinyl alcohol-co-maleate polymer is provided in an amount ranging from about 10% to about 50% by weight, based on the total weight of polyvinyl alcohol polymers in the film; the first and second polyvinyl alcohol-co-maleate polymers of the first and second films respectively comprise maleate monomer units derived from a member selected from the group consisting of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof; 8. The unit dose article of claim 7, wherein the first and second polyvinyl alcohol-co-maleate copolymers differ in degree of maleate modification, viscosity, degree of hydrolysis, or a combination thereof.

9. 9. The unit dose article of claim 7 or 8, wherein the composition contained in the sealed compartment comprises a liquid composition, optionally wherein the liquid composition comprises 10 to 30% water, based on the total weight of the liquid composition.

10. The unit dose article of claim 8, wherein the maleate monomer units in the first polyvinyl alcohol-co-maleate polymer are provided in an amount ranging from about 1 mol % to about 3 mol %, based on the total moles of the monomer units in the first polyvinyl alcohol-co-maleate polymer, and optionally, the maleate monomer units in the second polyvinyl alcohol-co-maleate polymer are provided in an amount ranging from about 3 mol % to about 5 mol %, based on the total moles of the monomer units in the second polyvinyl alcohol-co-maleate polymer.

11. 9. The unit dose article of claim 8, wherein the first polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 18 to about 30 cP, and optionally the second polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 10 to about 20 cP, as determined by measuring a freshly made solution of 4% polyvinyl alcohol in water at 20°C using a Brookfield LV type viscometer with a UL adapter as described in the Brookfield test method of British Standard EN ISO 15023-2:2006 Annex E.

12. A unit dose article as described in claim 7 or 8, wherein the plasticizer in the first film is selected from sorbitol, glycerol, propylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, dipropylene glycol, and combinations thereof, and optionally, the plasticizer includes sorbitol and glycerol.

13. 9. The unit dose article of claim 8, wherein the first film comprises the first polyvinyl alcohol-co-maleate polymer in an amount of about 70 wt %, based on the total weight of the polyvinyl alcohol polymer, the first polyvinyl alcohol-co-maleate polymer comprising maleate monomer units in an amount ranging from about 1.5 mol % to about 2.0 mol %, based on total monomer units, and the first polyvinyl alcohol-co-maleate polymer has a viscosity ranging from about 21 cP to about 26 cP; and optionally the first film comprises the second polyvinyl alcohol-co-maleate polymer in an amount of about 30 wt %, based on the total weight of the polyvinyl alcohol polymer, the second polyvinyl alcohol-co-maleate polymer comprising maleate monomer units in an amount ranging from about 3.8 mol % to about 4.2 mol %, based on the total monomer units, and the second polyvinyl alcohol-co-maleate polymer has a viscosity ranging from about 14 cP to about 19 cP.

14. (a) the first film is the first polyvinyl alcohol-co-maleate polymer in an amount of about 70 wt %, based on the total weight of the polyvinyl alcohol polymer, the first polyvinyl alcohol-co-maleate polymer comprising maleate monomer units in an amount ranging from about 1.5 mol % to about 2.0 mol %, based on the total monomer units, and the first polyvinyl alcohol-co-maleate polymer having a viscosity ranging from about 21 cP to about 26 cP; the second polyvinyl alcohol-co-maleate polymer in an amount of about 30 wt %, based on the total weight of the polyvinyl alcohol polymer, the second polyvinyl alcohol-co-maleate polymer comprising maleate monomer units in an amount ranging from about 3.8 mol % to about 4.2 mol %, based on the total monomer units, and the second polyvinyl alcohol-co-maleate polymer having a viscosity ranging from about 14 cP to about 19 cP; a plasticizer provided in an amount ranging from about 18 to about 23 parts by weight based on 100 parts by weight of the total polyvinyl alcohol polymer in the first film, the plasticizer consisting of sorbitol and glycerin; (b) the second film is an anionic polyvinyl alcohol copolymer, wherein the anionic polyvinyl alcohol copolymer is a carboxylated anionic polyvinyl alcohol copolymer, and the carboxylate groups comprising the carboxylated anionic polyvinyl alcohol copolymer comprise methyl acrylate; a plasticizer provided in an amount ranging from about 35 to about 45 parts by weight based on 100 parts by weight of the total polyvinyl alcohol in said second film; (c) the unit dose article comprises a liquid laundry detergent contained in the sealed compartment; (d) the unit dose article of claim 8, wherein the unit dose article is characterized by a stretch ratio of at least 2.3, a release time of at least 30 seconds when tested according to a Liquid Release Test, and a residue value of at most 9% when determined by a Residue Test.

15. 1. A method for improving the liquid release time of a thermoformed film, comprising: contacting a thermoformed film having a stretch ratio of 2.3 to 3.1 with a liquid detergent or solvent for at least two days; the film comprises a polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 30 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol resin; the liquid detergent or solvent comprises about 10% to about 30% water, based on the total weight of the liquid detergent or solvent; The method wherein the liquid release time of the thermoformed film and the liquid release time of the thermoformed film after the contacting step are tested according to the Liquid Release Test described herein.

16. The polyvinyl alcohol resin is a first polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 50% to about 90% by weight, based on the total weight of the polyvinyl alcohol polymer; a second polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 10% to about 50% by weight, based on said total weight of the polyvinyl alcohol polymer; 16. The method of claim 15, wherein the first and second polyvinyl alcohol-co-maleate copolymers differ in degree of maleate modification, viscosity, degree of hydrolysis, or a combination thereof.

17. A thermoformed film in the form of a pouch defining an interior pouch volume, said thermoformed film being prepared by thermoforming the film to a stretch ratio in the range of about 2.3 to about 2.9; the film comprises a mixture of a polyvinyl alcohol resin and a plasticizer, the plasticizer being provided in an amount ranging from about 5 to about 30 parts by weight, based on 100 parts by weight of the total polyvinyl alcohol resin; The polyvinyl alcohol resin is a first polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 50% to about 90% by weight, based on the total weight of the polyvinyl alcohol polymer; a second polyvinyl alcohol-co-maleate polymer provided in an amount ranging from about 10% to about 50% by weight, based on said total weight of the polyvinyl alcohol polymer; Optionally, the first and second polyvinyl alcohol-co-maleate polymers each comprise maleate monomer units derived from a member selected from the group consisting of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and combinations thereof; A thermoformable film wherein the first and second polyvinyl alcohol-co-maleate polymers differ in degree of maleate modification, viscosity, degree of hydrolysis, or a combination thereof.

18. The method of claim 17, wherein the maleate monomer units in the first polyvinyl alcohol-co-maleate polymer are provided in an amount ranging from about 1 mol % to about 3 mol %, based on the total number of moles of monomer units in the first polyvinyl alcohol-co-maleate polymer; 20. The thermoformable film of claim 17, wherein optionally, the maleate monomer units in the second polyvinyl alcohol-co-maleate polymer are provided in an amount ranging from about 3 mole % to about 5 mole %, based on the total number of moles of the monomer units in the second polyvinyl alcohol-co-maleate polymer.

19. The method of claim 19, wherein the first polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 18 to about 30 cP as determined by measuring a freshly made solution of a 4% aqueous polyvinyl alcohol solution at 20°C using a Brookfield LV type viscometer equipped with a UL adapter as described in the Brookfield test method of British Standard EN ISO 15023-2:2006 Annex E; Optionally, the thermoformable film of claim 17 or 18, wherein the second polyvinyl alcohol-co-maleate polymer has a viscosity in the range of about 10 to about 20 cP.

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