Highly transparent water-soluble films and methods for producing same

Abstract

The present disclosure provides a water-soluble film comprising a polyvinyl alcohol resin comprising a blend of a polyvinyl alcohol polymer, a starch, and a plasticizer, wherein the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) ranging from about 0.05 to about 3.0, and a haze at 100% strain ranging from about 0.5% to about 40%, as well as methods for preparing the same.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 267,587, filed February 4, 2022, the entire disclosure of which is incorporated herein by reference.

[0002] The present disclosure relates generally to water-soluble films and related articles. More specifically, the present disclosure relates to water-soluble films having high transparency. [Background technology]

[0003] Water-soluble polymeric films are commonly used as packaging materials to simplify the dispersion, injection, dissolution and administration of materials to be delivered. Advantageously, this eliminates the need for users to measure the composition, while providing accurate administration. The pouched composition can also reduce the confusion associated with dispensing similar compositions from containers, such as injecting compositions from bottles. In short, the pre-measured soluble polymeric film pouch provides convenience in a variety of applications.

[0004] Some commercially available water-soluble films may have a hazy appearance, especially after stretching, for example, after forming a pouch for enclosing unit dose composition. Such films with a hazy appearance may be viewed as undesirable by consumers. Current options for high transparency films generally include films that contain polyvinyl alcohol copolymer resins, which can increase the cost of making and using transparent films.Therefore, there is a need in the art to provide a cost-effective high transparency film. Summary of the Invention

[0005] One aspect of the present disclosure is a water-soluble film comprising a water-soluble mixture of polyvinyl alcohol resins including a first polyvinyl alcohol homopolymer having a viscosity in the range of about 16 cP to about 35 cP and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 15 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 60% to about 85% by weight, based on the total weight of the polyvinyl alcohol resin, and the second polyvinyl alcohol homopolymer is present in an amount in the range of about 50% to about 85% by weight, based on the total weight of the polyvinyl alcohol resin. the starch is present in an amount ranging from about 0.2 to about 3.0 parts by weight based on 100 parts polyvinyl alcohol resin (PHR); the plasticizer is present in an amount ranging from about 15 to about 35 PHR; and the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) ranging from about 0.05 to about 3.0, as determined according to the Coefficient of Friction Test, and a haze at 100% strain ranging from about 0.5% to about 70%, as determined according to the Haze Test.

[0006] Another aspect of the present disclosure provides a method of preparing a water-soluble film of the present disclosure, the method comprising the step of casting the water-soluble mixture of the present disclosure onto a surface, the surface being characterized by a gloss unit (GU) value at an angle of 60 degrees ranging from about 150 GU to about 550 GU.

[0007] Another aspect of the present disclosure provides a water-soluble film comprising a water-soluble mixture of polyvinyl alcohol resins including a polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 35 cP and a polyvinyl alcohol copolymer having anionic monomer units, wherein the polyvinyl alcohol homopolymer is present in an amount in the range of about 25% to about 75% by weight, based on the total weight of the polyvinyl alcohol resin, the polyvinyl alcohol copolymer is present in an amount in the range of about 75% to about 25% by weight, based on the total weight of the polyvinyl alcohol resin, the starch is present in an amount in the range of about 0.2 to about 6.0 parts by weight (PHR), based on 100 parts of the polyvinyl alcohol resin, and the plasticizer is present in an amount in the range of about 15 to about 35 PHR, wherein the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) in the range of about 0.05 to about 3.0, as determined according to the Coefficient of Friction Test, and a haze at 100% strain in the range of about 0.5% to about 40%, as determined according to the Haze Test.

[0008] The present disclosure further provides a water-soluble film comprising a water-soluble mixture of polyvinyl alcohol resins including a first polyvinyl alcohol copolymer having anionic monomer units selected from the group of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and alkali metal salts thereof, and a second polyvinyl alcohol copolymer having anionic monomer units selected from the group of alkyl acrylates, such as methyl acrylate, wherein the first polyvinyl alcohol copolymer is present in an amount ranging from about 1% by weight to about 50% by weight, based on the total weight of the polyvinyl alcohol resin; The second polyvinyl alcohol copolymer is present in an amount ranging from about 50% to about 99% by weight, based on the total weight of the polyvinyl alcohol resin; the starch is present in an amount ranging from about 0.2 to about 3.0 parts by weight, based on 100 parts of the polyvinyl alcohol resin (PHR); and the plasticizer is present in an amount ranging from about 15 to about 35 PHR, wherein the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) ranging from about 0.05 to about 3.0, as determined according to the Coefficient of Friction Test, and a haze at 100% strain ranging from about 0.5% to about 40%, as determined according to the Haze Test.

[0009] 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.

[0010] 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 may take a variety of forms, the following description includes specific embodiments, with the understanding that this disclosure is illustrative and is not intended to limit the invention to the specific embodiments described herein.

[0011] To further facilitate understanding of the present invention, two drawings are attached hereto. [Brief description of the drawings]

[0012] [Figure 1] An example of an apparatus for measuring the coefficient of friction of a film test piece is shown. [Figure 2A] 1 shows the transparency of transparent films of the present disclosure compared to a commercially available "transparent" film in the unstretched state. [Figure 2B] 1 shows the transparency of transparent films of the present disclosure compared to commercially available "transparent" films in the stretched state. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present disclosure provides water-soluble films that have high transparency and low tendency to "stick to themselves", for example, when provided as a roll of water-soluble film, or when the film is used to form a pouch containing the composition and packaged with other pouches in a secondary package. In general, transparency and tendency of a film to stick to itself are competing properties. Without intending to be bound by theory, it is believed that a smoother film surface makes the film less likely to scatter incident light, making the film more transparent / clear. In contrast, a film with less surface irregularities provides more surface area that can rub against another part of the film, which has the effect of sticking between the film surfaces. Antiblocking agents are typically included in the water-soluble film to reduce the possibility of the water-soluble film sticking to itself, whether rolled or otherwise. The films of the present disclosure can exhibit the beneficial properties of high transparency and low tendency to stick to themselves, while being substantially free of antiblocking agents, thereby providing a film with little or no inorganic components, reducing processing complexity. The present disclosure further provides a method of preparing a highly transparent film of the present disclosure, comprising solution casting the aqueous mixture onto a surface characterized by a gloss unit (GU) value at a 60° angle of at least about 150 GU to about 550 GU.

[0014] The water-soluble film of the present disclosure is advantageously a highly transparent film. As used herein, the term "transparency" generally refers to the overall visual appearance of a film. Generally, transparency and haze are inversely related, and as the haze value of a film decreases, the transparency of the film increases. As used herein, the term "haze" refers to the amount of light that is scattered when passing through a film.

[0015] The water-soluble films and pouches prepared therefrom surprisingly provide one or more benefits, including, but not limited to, (a) a haze value at 100% strain of about 40 or less, as determined by the haze test disclosed herein, and / or (b) a matte to gloss static coefficient of about 0.6 or less, as determined by the coefficient of friction test disclosed herein, and / or (c) a blocking value of about 3N or less, as determined for a whole film roll according to the blocking test disclosed herein, and / or (d) an elongation at break of at least 350%, as determined according to the elongation test disclosed herein, and / or (e) a tensile strength of at least about 40 MPa, as determined according to the tensile test disclosed herein. In embodiments, the films of the present disclosure and pouches prepared therefrom exhibit at least the benefit (a) described above. In some embodiments, the films of the present disclosure and pouches prepared therefrom exhibit at least the benefit (b) described above. In some embodiments, the films of the present disclosure and pouches prepared therefrom exhibit each of the benefits (a) and (b). In some embodiments, the films of the present disclosure and pouches prepared therefrom exhibit each of benefits (a), (b), and (c). In some embodiments, the films of the present disclosure and pouches prepared therefrom exhibit each of benefits (a), (b), (c), and (d). In some embodiments, the films of the present disclosure and pouches prepared therefrom exhibit each of benefits (a), (b), (c), (d), and (e).

[0016] The present disclosure provides a water-soluble film comprising a water-soluble mixture of polyvinyl alcohol resins including a first polyvinyl alcohol homopolymer having a viscosity in the range of about 16 cP to about 35 cP and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 15 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 60% to about 85% by weight, based on the total weight of the polyvinyl alcohol resin, and the second polyvinyl alcohol homopolymer is present in an amount in the range of about 60% to about 85% by weight, based on the total weight of the polyvinyl alcohol resin. the starch is present in an amount ranging from about 0.2 to about 6.0 parts by weight based on 100 parts polyvinyl alcohol resin (PHR), the plasticizer is present in an amount ranging from about 15 to about 35 PHR, and the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) ranging from about 0.05 to about 3.0, as determined according to the Coefficient of Friction Test, and a haze at 100% strain ranging from about 0.5% to about 40%, as determined according to the Haze Test.

[0017] "Comprising" as used herein means various components, ingredients, or steps that may be used together 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 packet may "consist essentially of" the film described herein, while including a secondary 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.

[0018] 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."

[0019] 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.

[0020] 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.

[0021] 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, e.g., 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 welding (sealing), and adhesive sealing (e.g., with a water-soluble adhesive).

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] The present disclosure further provides a water-soluble film comprising a water-soluble mixture of polyvinyl alcohol resins including a polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 35 cP and a polyvinyl alcohol copolymer having anionic monomer units, wherein the polyvinyl alcohol homopolymer is present in an amount in the range of about 25% to about 75% by weight, based on the total weight of the polyvinyl alcohol resin, the polyvinyl alcohol copolymer is present in an amount in the range of about 75% to about 25% by weight, based on the total weight of the polyvinyl alcohol resin, the starch is present in an amount in the range of about 0.2 to about 6.0 parts by weight (PHR), based on 100 parts of the polyvinyl alcohol resin, and the plasticizer is present in an amount in the range of about 15 to about 35 PHR, wherein the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) in the range of about 0.05 to about 3.0, as determined according to the Coefficient of Friction Test, and a haze at 100% strain in the range of about 0.5% to about 40%, as determined according to the Haze Test.

[0028] The present disclosure further provides a water-soluble film comprising a water-soluble mixture of polyvinyl alcohol resins including a first polyvinyl alcohol copolymer having anionic monomer units selected from the group of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, and alkali metal salts thereof, and a second polyvinyl alcohol copolymer having anionic monomer units selected from the group of alkyl acrylates, such as methyl acrylate, wherein the first polyvinyl alcohol copolymer is present in an amount ranging from about 1% by weight to about 50% by weight, based on the total weight of the polyvinyl alcohol resin; The second polyvinyl alcohol copolymer is present in an amount ranging from about 50% to about 99% by weight, based on the total weight of the polyvinyl alcohol resin; the starch is present in an amount ranging from about 0.2 to about 3.0 parts by weight, based on 100 parts of the polyvinyl alcohol resin (PHR); and the plasticizer is present in an amount ranging from about 15 to about 35 PHR, wherein the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) ranging from about 0.05 to about 3.0, as determined according to the Coefficient of Friction Test, and a haze at 100% strain ranging from about 0.5% to about 40%, as determined according to the Haze Test.

[0029] The films, articles, pouches, or related methods of making and using are considered 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.

[0030] Water-soluble film The films and related articles and pouches described herein may include a plasticized water-soluble film. The water-soluble film may be solvent cast. The film may optionally further include one or more additives selected from fillers, surfactants, antiblocking agents, antioxidants, antifoaming agents, bleaching agents, aversive agents, irritants, other functional ingredients, and combinations of the foregoing. In one embodiment, the water-soluble film may include at least about 50% by weight of polyvinyl alcohol (PVOH) resin, including one or more PVOH polymers. In embodiments, the water-soluble film may comprise a PVOH resin comprising one or more PVOH polymers in a total amount of at least about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95% by weight, for example, in a range of about 55% to about 95% by weight, about 60% to about 90% by weight, or about 65% to about 85% by weight, or about 70% to about 80% by weight, based on the total weight of the film.

[0031] 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 values ​​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, or about 20 to about 60 μm, or about 20 to about 50 μm, or about 30 to about 40 μm, such as values ​​of about 35 μm, about 36 μm, about 50 μm, about 65 μm, about 76 μm, about 88 μm, or about 90 μm.

[0032] PVOH resin The films described herein may include one or more polyvinyl alcohol (PVOH) polymers to make up the PVOH resin content of the film.

[0033] 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 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 PVOH copolymer, but is a vinyl alcohol-vinyl acetate copolymer, commonly referred to as one or more of homopolymer PVOH, PVOH homopolymer, or often simply PVOH, which may suggest the presence of an acetate component. As used herein and unless otherwise specified, "polyvinyl alcohol homopolymer" refers to a polyvinyl alcohol polymer that optionally contains vinyl acetate groups as a polymer component.

[0034] In an embodiment, the polyvinyl alcohol resin comprises a blend of at least two polyvinyl alcohol homopolymers differing in viscosity, degree of hydrolysis, or both. In an embodiment, the polyvinyl alcohol resin comprises a first polyvinyl alcohol homopolymer and a second polyvinyl alcohol homopolymer.

[0035] In some embodiments, 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).

[0036] 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.

[0037] 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.

[0038] 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%.

[0039] In an embodiment, the polyvinyl alcohol resin comprises polyvinyl alcohol-co-alkyl acrylate. In a refinement of the above embodiment, the polyvinyl alcohol-co-alkyl acrylate may comprise one or more methyl acrylate monomer units. The polyvinyl alcohol-co-alkyl acrylate polymer may be a partially or fully hydrolyzed copolymer of polyvinyl acetate and methyl acrylate. In an embodiment, the polyvinyl alcohol-co-alkyl acrylate may include at least 1 mol% alkyl acrylate modified up to about 8 mol% alkyl acrylate 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%. In embodiments, at least a portion of the acrylate modifications are not in the form of a lactone ring, for example, at least 25%, at least 50%, at least 75%, at least 80%, at least 85%, or at least 90% of the acrylate modifications are not in the form of a lactone ring.

[0040] 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% (w / v) 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% (w / v) 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.

[0041] Suitable PVOH resins for use individually or in combination have a viscosity of from about 5 cP to about 35 cP, or from about 5 cP to about 30 cP, or from about 5 cP to about 27 cP, or from about 5 cP to about 25 cP, or from about 5 cP to about 15 cP, or from about 5 cP to about 14 cP, or from about 5 cP to about 12 cP, or from about 5 cP to about 10 cP, or from about 5 cP to about 7 cP, or from about 5 cP to about 8 cP, or from about 10 cP to about 10 cP. The viscosity of the PVOH resin may be in the range of about 15 cP, or about 16 cP to about 35 cP, or about 18 cP to about 35 cP, or about 18 cP to about 30 cP, or about 18 cP to about 27 cP, or about 18 cP to about 25 cP, or about 20 cP to about 25 cP, for example, 32 cP, or 26 cP, or 23.5 cP, or 21 cP, or 19 cP, or 16.5 cP, or 14 cP, or 6 cP. The viscosity of the PVOH resin depends on the weight average molecular weight of the PVOH resin.

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[0042] In embodiments where the film comprises a blend of a first polyvinyl alcohol homopolymer and a second polyvinyl alcohol homopolymer, the first polyvinyl alcohol homopolymer may have a viscosity in the range of about 16 cP to about 35 cP, about 18 cP to about 35 cP, about 18 cP to about 30 cP, about 18 cP to about 27 cP, about 18 cP to about 25 cP, or about 20 cP to about 25 cP. In embodiments, the second polyvinyl alcohol homopolymer may have a viscosity in the range of about 5 cP to about 15 cP, about 5 cP to about 14 cP, about 5 cP to about 12 cP, about 5 cP to about 10 cP, about 5 cP to about 7 cP, about 5 cP to about 8 cP, or about 10 cP to about 15 cP. In an embodiment, the first polyvinyl alcohol homopolymer may have a viscosity in the range of about 16 cP to about 35 cP and the second polyvinyl alcohol homopolymer may have a viscosity in the range of about 5 cP to about 15 cP. In an embodiment, the first polyvinyl alcohol homopolymer may have a viscosity in the range of about 20 cP to about 25 cP and the second polyvinyl alcohol homopolymer may have a viscosity in the range of about 5 cP to about 7 cP.

[0043] In embodiments where the film comprises a blend of polyvinyl alcohol homopolymer and polyvinyl alcohol copolymer, the polyvinyl alcohol homopolymer may have a viscosity in the range of about 5 cP to about 35 cP, about 5 cP to about 15 cP, about 5 cP to about 7 cP, about 18 cP to about 27 cP, or about 20 cP to about 25 cP. In embodiments, the polyvinyl alcohol homopolymer may have a viscosity in the range of about 5 to about 7 cP. In embodiments, the polyvinyl alcohol copolymer may have a viscosity in the range of about 10 cP to about 30 cP, e.g., about 12 cP to about 28 cP, about 14 cP to about 26 cP, about 16 cP to about 24 cP, or about 18 cP to about 22 cP. In embodiments, the polyvinyl alcohol copolymer may have a viscosity in the range of about 18 cP to about 22 cP.

[0044] In embodiments where the film comprises a blend of a first polyvinyl alcohol copolymer and a second polyvinyl alcohol copolymer, the first polyvinyl alcohol copolymer may have a viscosity in the range of about 10 cP to about 30 cP, e.g., about 10 cP to about 20 cP, about 12 cP to about 19 cP, about 14 cP to about 19 cP, about 18 cP to about 30 cP, about 19 cP to about 28 cP, about 20 cP to about 26 cP, or about 21 cP to about 26 cP. In embodiments, the first polyvinyl alcohol copolymer may have a viscosity in the range of about 18 cP to about 30 cP, about 19 cP to about 28 cP, about 20 cP to about 26 cP, or about 21 cP to about 26 cP. In embodiments, the first polyvinyl alcohol copolymer may have a viscosity in the range of about 21 cP to about 26 cP. In embodiments, the second polyvinyl alcohol copolymer can have a viscosity in the range of about 10 cP to about 30 cP, e.g., about 12 cP to about 28 cP, about 14 cP to about 26 cP, about 16 cP to about 24 cP, or about 18 cP to about 22 cP. In embodiments, the polyvinyl alcohol copolymer can have a viscosity in the range of about 18 cP to about 22 cP.

[0045] In embodiments, the polyvinyl alcohol homopolymers and copolymers of the films of the present disclosure may have a degree of hydrolysis ranging from about 70% to about 99%. In embodiments, the first polyvinyl alcohol homopolymer, the second polyvinyl alcohol homopolymer, or both may have a degree of hydrolysis ranging from about 70% to about 99%, or from about 75% to about 95%, or from about 78% to about 90%, or from about 80% to about 90%, or from about 85% to about 90%. In embodiments, the first polyvinyl alcohol homopolymer, the second polyvinyl alcohol homopolymer, or both may have a degree of hydrolysis ranging from about 85% to about 90%, or from about 86% to about 89%.

[0046] The degree of hydrolysis of the resin blend is also defined as the arithmetically weighted average degree of hydrolysis.

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[0047] In an embodiment in which the water-soluble film comprises a first polyvinyl alcohol homopolymer and a second polyvinyl alcohol homopolymer, the first and second polyvinyl alcohol homopolymers can generally be included in the polyvinyl alcohol resin blend in any suitable ratio. In an embodiment, the first polyvinyl alcohol homopolymer can be included in the polyvinyl alcohol resin in an amount ranging from about 60% to about 85% by weight, for example, from about 65% to about 80% by weight, or from about 70% to about 80% by weight, for example, 60%, 65%, 70%, 75%, or 80% by weight, based on the total weight of the polyvinyl alcohol polymers in the resin. In an embodiment, the second polyvinyl alcohol homopolymer may be included in the polyvinyl alcohol resin in an amount ranging from about 15% to about 40% by weight, e.g., from about 15% to about 35% by weight, or from about 20% to about 30% by weight, e.g., 15%, 20%, 25%, 30%, 35%, or 40% by weight, based on the total weight of the polyvinyl alcohol polymer in the resin. In an embodiment, the first polyvinyl alcohol may be included in the polyvinyl alcohol resin in an amount ranging from about 65% to about 85% by weight, or from about 70% to about 80% by weight, based on the total weight of the polyvinyl alcohol polymer in the resin, and the second polyvinyl alcohol homopolymer may constitute the remainder of the polyvinyl alcohol polymer in the resin.

[0048] Without wishing to be bound by theory, it is believed that decreasing the relative amount of the second low viscosity polyvinyl alcohol homopolymer in the polyvinyl alcohol resin reduces the seal strength of the film by solvent sealing, and increasing the relative amount of the second polyvinyl alcohol homopolymer in the polyvinyl alcohol resin reduces the temperature window in which the film can be processed (e.g., by thermoforming).

[0049] In an embodiment in which the water-soluble film comprises a polyvinyl alcohol homopolymer and a polyvinyl alcohol copolymer, the polyvinyl alcohol homopolymer and copolymer can generally be included in the polyvinyl alcohol resin blend in any suitable ratio. In an embodiment, the polyvinyl alcohol homopolymer can be included in the polyvinyl alcohol resin in an amount ranging from about 25% by weight to about 75% by weight, for example, from about 30% by weight to about 70% by weight, from about 35% by weight to about 65% by weight, from about 40% by weight to about 60% by weight, or from about 45% by weight to about 55% by weight, for example, 30% by weight, 40% by weight, 50% by weight, 60% by weight, or 70% by weight, based on the total weight of the polyvinyl alcohol polymer in the resin. In an embodiment, the polyvinyl alcohol copolymer may be included in the polyvinyl alcohol resin in an amount ranging from about 75% to about 25% by weight, e.g., from about 30% to about 70% by weight, from about 35% to about 65% by weight, from about 40% to about 60% by weight, or from about 45% to about 55% by weight, e.g., 30%, 40%, 50%, 60%, or 70% by weight, based on the total weight of the polyvinyl alcohol polymer in the resin. In an embodiment, the polyvinyl alcohol homopolymer may be included in the polyvinyl alcohol resin in an amount ranging from about 40% to about 60% by weight, or from about 45% to about 55% by weight, based on the total weight of the polyvinyl alcohol polymer in the resin, and the polyvinyl alcohol copolymer may constitute the remainder of the polyvinyl alcohol polymer in the resin.

[0050] In an embodiment in which the water-soluble film comprises a first polyvinyl alcohol copolymer and a second polyvinyl alcohol copolymer, the first and second polyvinyl alcohol copolymers can generally be included in the polyvinyl alcohol resin blend in any suitable ratio. In an embodiment, the first polyvinyl alcohol copolymer can be included in the polyvinyl alcohol resin in an amount ranging from about 1% by weight to about 50% by weight, for example, from about 5% by weight to about 50% by weight, from about 10% by weight to about 50% by weight, from about 15% by weight to about 45% by weight, from about 20% by weight to about 40% by weight, from about 40% by weight to about 50% by weight, or from about 20% by weight to about 30% by weight, for example, 20% by weight, 25% by weight, 30% by weight, 40% by weight, or 50% by weight, based on the total weight of the polyvinyl alcohol polymer in the resin. In an embodiment, the second polyvinyl alcohol copolymer may be included in the polyvinyl alcohol resin in an amount ranging from about 50% to about 99% by weight, e.g., from about 50% to about 90% by weight, from about 50% to about 80% by weight, from about 50% to about 60% by weight, from about 60% to about 80% by weight, or from about 70% to about 80% by weight, e.g., 50%, 60%, 70%, 75%, or 80% by weight, based on the total weight of the polyvinyl alcohol polymer in the resin. In an embodiment, the first polyvinyl alcohol copolymer may be included in the polyvinyl alcohol resin in an amount ranging from about 40% to about 50% by weight, or from about 20% to about 30% by weight, based on the total weight of the polyvinyl alcohol polymer in the resin, and the polyvinyl alcohol copolymer may constitute the remainder of the polyvinyl alcohol polymer in the resin.

[0051] Plasticizer The water-soluble film of the present disclosure generally includes a plasticizer. A plasticizer is a liquid, solid, or semi-solid that is added to a material (usually a resin or elastomer) to make the material softer, more flexible, and easier to process (by lowering the glass transition temperature of the polymer). At low plasticizer levels, the film may be brittle, difficult to process, or prone to breakage. At high plasticizer levels, the film may be too soft, weak, or difficult to process for the desired use. Although water is recognized as a very efficient plasticizer for PVOH and other polymers, including but not limited to water-soluble polymers, the volatility of water limits its usefulness, since polymer films need to have at least some resistance (robustness) to a variety of ambient conditions, including low and high relative humidity.

[0052] The water-soluble film of the present disclosure further comprises a plasticizer. The plasticizer may include, but is not limited to, glycerol, diglycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 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, 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. In one class of embodiments, the plasticizer is selected from the group of triethylene glycol, sorbitol, glycerol, diglycerin, ethylene glycol, diethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols of molecular weight up to 400 Da, hexylene glycol, xylitol, 2-methyl-1,3,propanediol, ethanolamine, or combinations thereof. In one class of embodiments, the plasticizer comprises triethylene glycol, polyethylene glycol having a molecular weight of about 200 Da, sorbitol, glycerol, or a combination thereof.

[0053] The total amount of non-aqueous plasticizer can be in the range of about 10 to about 35 parts by weight per 100 parts PVOH resin (PHR), or about 15 to about 35 PHR, or about 15 to about 30 PHR, or about 15 to about 28 PHR, or about 17 PHR to about 25 PHR, or about 18 PHR to about 23 PHR, e.g., about 19 PHR, about 20 PHR, about 21 PHR, about 21 PHR, or about 23 PHR. In embodiments, the plasticizer can be provided in an amount ranging from about 15 to about 30 PHR, about 15 to about 28 PHR, about 18 to about 25 PHR, or about 18 to about 23 PHR. In embodiments, the plasticizer can include sorbitol, glycerol, or a combination thereof, and can be provided in the range of about 18 to about 23 PHR.

[0054] Surfactants Surfactants for use in the water-soluble film are known in the art. Optionally, a surfactant is included to aid in the dispersion of the resin solution during casting. Surfactants suitable for the water-soluble film of the present disclosure include, but are not limited to, dialkyl sulfosuccinates, 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, alkyl polyethylene glycol ethers, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, sodium lauryl sulfate, acetylated esters of fatty acids, myristyl dimethylamine oxide, trimethyl tallow alkyl ammonium chloride, quaternary ammonium compounds, alkali metal salts of higher fatty acids containing about 8 to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylate sulfates, alkyl benzene sulfonates, monoethanolamines, lauryl alcohol ethoxylates, propylene glycol, diethylene glycol, salts thereof, and combinations of any of the foregoing.

[0055] Suitable surfactants may include nonionic, cationic, anionic, and zwitterionic classes.Suitable surfactants include, but are not limited to, propylene glycol, diethylene glycol, monoethanolamine, polyoxyethylated polyoxypropylene glycol, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols, and alkanolamides (nonionic), polyoxyethylated amines, quaternary ammonium salts, and quaternized polyoxyethylated amines (cationic), alkali metal salts of higher fatty acids containing about 8 to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylate sulfates, and alkyl benzene sulfonates (anionic), and 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 ranges from about 0.1% to 2.5% by weight, optionally from about 1.0% to 2.0% by weight. In embodiments, the amount of surfactant in the water-soluble film, expressed in parts per 100 parts of total water-soluble polymer in the water-soluble film (phr), is present in the range of about 0.5 phr to about 4 phr, about 0.75 phr to about 3.0 phr, about 1.0 phr to about 2.5 phr, about 1.0 phr to about 2.0 phr, or about 1.5 phr.

[0056] Surfactants can be characterized in terms of hydrophilic / lipophilic balance (HLB). Griffin's method was described in 1954 (Griffin WC: "Calculation of HLB Values ​​of Non-Ionic Surfactants," Journal of the Society of Cosmetic Chemists 5(1954):259) and is used in the art to determine the HLB value of non-ionic surfactants as follows: HLB=20*Mh / M, where Mh is the molecular mass of the hydrophilic part of the molecule and M is the molecular mass of the entire molecule, giving an HLB value on a scale of 0 to 20. An HLB value of 0 corresponds to a completely lipophilic / hydrophobic molecule, and a value of 20 corresponds to a completely hydrophilic / lipophobic molecule.

[0057] The water-soluble films may contain other auxiliary and processing aids in amounts suitable for their intended purpose, such as, but not limited to, 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 quasin and brucine), and stimulants (e.g., capsaicin, piperine, allyl isothiocyanate, and resinferratoxin), as well as other functional ingredients.

[0058] Suitable fillers / bulking agents / anti-adhesive agents include, but are not limited to, starch, modified starch, cross-linked polyvinylpyrrolidone, cross-linked cellulose, and microcrystalline cellulose. Preferred materials are starch and modified starch. When included in the water-soluble film, the starch and / or modified starch can be provided in a range of about 0.2 PHR to about 6 PHR, about 0.2 PHR to about 5.0 PHR, about 0.2 PHR to about 4.0 PHR, about 0.2 PHR to about 3.0 PHR, about 0.2 PHR to about 1.0 PHR, or about 0.2 PHR to about 0.9 PHR, or about 0.2 PHR to about 0.8 PHR, or about 0.2 PHR to about 0.7 PHR, or about 0.4 PHR to about 0.7 PHR, or about 0.5 PHR to about 0.7 PHR, such as less than about 1 PHR, less than about 0.9 PHR, or less than about 0.7 PHR. Without wishing to be bound by theory, it is believed that the filler, such as starch, provided within the matrix of the polyvinyl alcohol polymer, strengthens the film and helps to maintain the plasticizer within the film matrix. Further, without wishing to be bound by theory, it is believed that as the amount of starch in a film decreases, the tendency of the plasticizer to migrate to the film surface increases, and as the amount of starch in a film increases, the tendency of the film to "stress whiten" or increase in opacity upon stretching the film increases.

[0059] Antiblocking agents (e.g., silicate-based materials such as fumed silica, SiO2, talc, and hydrosilicates), if present in the film, may be present in the film in a range of about 0.1 to 0.5 PHR, or about 0.1 to about 0.4 PHR, or about 0.1 to 0.3 PHR. In some embodiments, the film may be substantially free of antiblocking agents. In some embodiments, the film may be substantially free of silica, silicates, and / or SiO2. As used herein, and unless otherwise noted, "substantially free of antiblocking agents" refers to a film having antiblocking agents 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. As used herein, and unless otherwise stated, "substantially free of silica, silicates, and / or SiO2" refers to a film having silica, silicates, and / or SiO2 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. Without wishing to be bound by theory, it is believed that the antiblocking agent phase separates to the surface of the film, providing a rough surface and providing space between the layers of the film, allowing the layers of the film to slide over one another.

[0060] In a first aspect of the present disclosure, the water-soluble film of the present disclosure is a polyvinyl alcohol resin comprising a first polyvinyl alcohol homopolymer having a viscosity in the range of about 16 cP to about 35 cP, about 18 cP to about 27 cP, or about 20 cP to about 25 cP, and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 15 cP, about 10 cP to about 15 cP, or about 5 cP to about 7 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 60 wt% to about 85 wt%, about 65 wt% to about 85 wt%, or about 70 wt% to about 80 wt%, based on the total weight of the polyvinyl alcohol resin, and the second polyvinyl alcohol homopolymer is present in an amount in the range of about 60 wt% to about 85 wt%, about 65 wt% to about 85 wt%, or about 70 wt% to about 80 wt%, based on the total weight of the polyvinyl alcohol resin. and the water-soluble film may be characterized by a matte-to-gloss coefficient of friction of less than 3, e.g., less than 1.5, less than 1, or less than 0.6, and a haze at 100% strain in the range of 0.5 to 40%, 0.5 to 30%, or 0.5 to 20%, based on the total weight of the polyvinyl alcohol resin. In an embodiment of the first aspect, the water-soluble film of the present disclosure may include a polyvinyl alcohol resin comprising a first polyvinyl alcohol homopolymer having a viscosity in the range of about 20 cP to about 25 cP and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 7 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 70% by weight to about 80% by weight based on the total weight of the polyvinyl alcohol resin, the second polyvinyl alcohol homopolymer is present in an amount in the range of about 20% by weight to about 30% by weight based on the total weight of the polyvinyl alcohol resin, the plasticizer is present in an amount in the range of about 18 to about 23 PHR, and the starch is present in an amount in the range of about 0.5 to about 0.7 PHR.In an embodiment of the first aspect, the water-soluble film of the present disclosure may include a polyvinyl alcohol resin comprising a first polyvinyl alcohol homopolymer having a viscosity in the range of about 16 cP to about 35 cP and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 15 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 60% by weight to about 85% by weight based on the total weight of the polyvinyl alcohol resin, the second polyvinyl alcohol homopolymer is present in an amount in the range of about 15% by weight to about 40% by weight based on the total weight of the polyvinyl alcohol resin, the plasticizer is present in an amount in the range of about 15 to about 35 PHR, and the starch is present in an amount in the range of about 0.2 to about 1.0 PHR. In an embodiment of the first aspect, the water-soluble film of the present disclosure may comprise a polyvinyl alcohol resin comprising a first polyvinyl alcohol homopolymer having a viscosity in the range of about 20 cP to about 25 cP and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 7 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 70 wt% to about 80 wt%, based on the total weight of the polyvinyl alcohol resin, the second polyvinyl alcohol homopolymer is present in an amount in the range of about 20 wt% to about 30 wt%, based on the total weight of the polyvinyl alcohol resin, the plasticizer is present in an amount in the range of about 15 to about 35 PHR, and the starch is present in an amount in the range of about 0.2 to about 6.0 PHR, and the film may be characterized by a matte-to-gloss coefficient of friction of less than 0.6 and a haze at 100% strain in the range of 0.5 to 30%. In a refinement of the above embodiment, the water-soluble film may be further characterized by an elongation at break of from about 300% to about 350%.In an embodiment of a first aspect, the water-soluble film of the present disclosure may comprise a polyvinyl alcohol resin comprising a first polyvinyl alcohol homopolymer having a viscosity in the range of about 20 cP to about 25 cP and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 7 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 70 wt% to about 80 wt% based on the total weight of the polyvinyl alcohol resin, the second polyvinyl alcohol homopolymer is present in an amount in the range of about 20 wt% to about 30 wt% based on the total weight of the polyvinyl alcohol resin, the plasticizer is present in an amount in the range of about 15 to about 35 PHR, and the starch is present in an amount in the range of about 0.2 to about 3.0 PHR, and the film may be characterized by a matte-to-gloss coefficient of friction of less than 0.6 and a haze at 100% strain in the range of 0.5 to 20%. In a refinement of the embodiment of the first aspect, the water-soluble film is substantially free of silica and / or SiO2. In a further refinement of the preceding embodiment, the water-soluble film is substantially free of anti-blocking agents.

[0061] In a second aspect, the present disclosure provides a water-soluble film comprising a water-soluble mixture of polyvinyl alcohol resins including a polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 35 cP, about 5 cP to about 15 cP, about 10 cP to about 15 cP, about 5 cP to about 7 cP, about 18 cP to about 27 cP, or about 20 cP to about 5 cP, and a polyvinyl alcohol copolymer having anionic monomer units, wherein the polyvinyl alcohol homopolymer is present in an amount ranging from about 25% to about 75% by weight, e.g., about 30% to about 70% by weight, about 40% to about 60% by weight, or about 45% to about 55% by weight, based on the total weight of the polyvinyl alcohol resin, and the polyvinyl alcohol copolymer is present in an amount ranging from about 75% to about 25% by weight, based on the total weight of the polyvinyl alcohol resin. For example, the starch is present in an amount ranging from about 0.2 to about 6.0 parts by weight based on 100 parts of polyvinyl alcohol resin (PHR), from about 0.2 PHR to about 3.0 PHR, or from about 0.2 PHR to about 1.0 PHR; and the plasticizer is present in an amount ranging from about 15 to about 35 PHR; and the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) in the range of about 3.0 or less, about 1.5 or less, about 1.0 or less, or about 0.60 or less, as determined according to the Coefficient of Friction Test; and a haze at 100% strain in the range of about 0.5% to about 40%, about 0.5 to about 30%, about 0.5 to about 20%, or about 0.5 to about 20%, as determined according to the Haze Test.

[0062] In an embodiment of the second aspect, the water-soluble film of the present disclosure may comprise a polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 7 cP, and a polyvinyl alcohol copolymer comprising methyl acrylate monomer units, wherein the polyvinyl alcohol homopolymer is present in an amount in the range of about 45% to about 55% by weight, based on the total weight of the polyvinyl alcohol resin, the polyvinyl alcohol copolymer is present in an amount in the range of about 55% to about 45% by weight, based on the total weight of the polyvinyl alcohol resin, the starch is present in an amount in the range of about 0.2 to about 1.0 parts by weight, based on 100 parts of the polyvinyl alcohol resin (PHR), and the plasticizer is present in an amount in the range of about 15 to about 35 PHR, and the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) in the range of 0.60 or less, and a haze at 100% strain in the range of about 0.5% to about 40%, as determined according to the Haze Test. In a refinement of the above embodiment, the film may be further characterized by an elongation at break in the range of 300-350%.

[0063] In an embodiment of the second aspect, the water-soluble film of the present disclosure may comprise a polyvinyl alcohol homopolymer having a viscosity in the range of about 20 cP to about 26 cP, and a polyvinyl alcohol copolymer comprising methyl acrylate monomer units, wherein the polyvinyl alcohol homopolymer is present in an amount in the range of about 45% to about 55% by weight, based on the total weight of the polyvinyl alcohol resin, the polyvinyl alcohol copolymer is present in an amount in the range of about 55% to about 45% by weight, based on the total weight of the polyvinyl alcohol resin, the starch is present in an amount in the range of about 0.2 to about 1.0 parts by weight, based on 100 parts of the polyvinyl alcohol resin (PHR), and the plasticizer is present in an amount in the range of about 15 to about 35 PHR, and the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) in the range of 0.60 or less, and a haze at 100% strain in the range of about 0.5% to about 40%, as determined according to the Haze Test.

[0064] In a third aspect, the present disclosure provides a water-soluble film comprising a water-soluble mixture of a polyvinyl alcohol resin comprising a first polyvinyl alcohol copolymer comprising anionic monomer units and a second polyvinyl alcohol copolymer having anionic monomer units, The first polyvinyl alcohol copolymer is present in an amount ranging from about 1% by weight to about 50% by weight, e.g., from about 20% to about 30%, from about 20% to about 40%, from about 20% to about 50%, from about 30% to about 50%, or from about 40% to about 50% by weight, based on the total weight of the polyvinyl alcohol resin; the second polyvinyl alcohol copolymer is present in an amount ranging from about 50% by weight to about 99% by weight, e.g., from about 50% to about 80%, from about 50% to about 70%, from about 50% to about 60% by weight, from about 60% to about 80%, or from about 70% to about 80%, based on the total weight of the polyvinyl alcohol resin; and the starch is present in an amount ranging from about 50% by weight to about 99% by weight, e.g., from about 50% to about 80%, from about 50% to about 70%, from about 50% to about 60% by weight, from about 60% to about 80%, or from about 70% to about 80%, based on the total weight of the polyvinyl alcohol resin. wherein the plasticizer is present in an amount ranging from about 0.2 to about 3.0 parts by weight (PHR), or from about 0.2 PHR to about 1.0 PHR, based on 100 parts alcohol resin; and the plasticizer is present in an amount ranging from about 15 to about 35 PHR, wherein the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) in the range of about 3.0 or less, about 1.5 or less, about 1.0 or less, or about 0.60 or less, as determined according to the Coefficient of Friction Test, and a haze at 100% strain in the range of about 0.5% to about 40%, about 0.5% to about 30%, about 0.5% to about 20%, or about 0.5% to about 20%, as determined according to the Haze Test.

[0065] In an embodiment of the third aspect, the water-soluble film may comprise a first polyvinyl alcohol copolymer comprising maleate monomer units and a second polyvinyl alcohol copolymer comprising methyl acrylate monomer units, the first polyvinyl alcohol copolymer being present in an amount ranging from about 40% to about 50% by weight, based on the total weight of the polyvinyl alcohol resin, the second polyvinyl alcohol copolymer being present in an amount ranging from about 50% to about 60% by weight, based on the total weight of the polyvinyl alcohol resin, the starch being present in an amount ranging from about 0.2 to about 1.0 parts by weight, based on 100 parts of the polyvinyl alcohol resin (PHR), and the plasticizer being present in an amount ranging from about 15 to about 35 PHR, the water-soluble film being characterized by a matte-to-gloss coefficient of friction (COF) in the range of less than or equal to about 0.60, as determined according to the Coefficient of Friction Test, and a haze at 100% strain in the range of about 0.5% to about 30%, as determined according to the Haze Test. In a refinement of the above embodiment, the water-soluble film is further characterized by a tensile strength in the range of 40-50 mPa.

[0066] In an embodiment of the third aspect, the water-soluble film may comprise a first polyvinyl alcohol copolymer comprising maleate monomer units and a second polyvinyl alcohol copolymer comprising methyl acrylate monomer units, the first polyvinyl alcohol copolymer being present in an amount ranging from about 20% to about 30% by weight, based on the total weight of the polyvinyl alcohol resin, the second polyvinyl alcohol copolymer being present in an amount ranging from about 70% to about 80% by weight, based on the total weight of the polyvinyl alcohol resin, the starch being present in an amount ranging from about 0.2 to about 1.0 parts by weight, based on 100 parts of the polyvinyl alcohol resin (PHR), and the plasticizer being present in an amount ranging from about 15 to about 35 PHR, the water-soluble film being characterized by a matte-to-gloss coefficient of friction (COF) in the range of less than or equal to about 0.60, as determined according to the Coefficient of Friction Test, and a haze at 100% strain in the range of about 0.5% to about 20%, as determined according to the Haze Test. In a refinement of the above embodiment, the water-soluble film is further characterized by a tensile strength in the range of 40-50 mPa.

[0067] As shown in the Examples below, it has been unexpectedly and advantageously found that when films prepared according to the methods of the present disclosure comprise a blend of two polyvinyl alcohol homopolymers, even with up to 6 phr of starch, the films exhibit a haze at 100% strain of less than 40%, a matte-to-gloss static coefficient of friction of less than 0.6, and that when the homopolymer constituting the majority of the blend (60-85% by weight of the blend) is used alone, a film having a matte-to-gloss coefficient of friction of greater than 1 is provided, and that the haze of the film can be adjusted to be less than 20% (about 13%) haze at 100% strain, even when it comprises a resin that, when used alone, provides a film with a significantly higher haze value (about 30%).

[0068] Furthermore, as shown in the following examples, it was surprisingly found that when a film prepared according to the method of the present disclosure included a blend of a low-viscosity polyvinyl alcohol homopolymer and a polyvinyl alcohol copolymer containing methyl acrylate monomer units, the film exhibited a matte-to-gloss static friction coefficient of less than 6, and a haze of less than 40% at 100% strain and less than 30% for unstretched films. Instead, such a film containing a polyvinyl alcohol copolymer containing methyl acrylate monomer units was expected to have a significantly higher haze value, considering that a commercially available film containing this polyvinyl alcohol copolymer has a haze value of about 67% when unstretched. Indeed, by comparing the haze value of the example film 2 with that of a commercially available film (film C3), it can be seen that preparing a film according to the method of the present disclosure can contribute to an increase in the transparency of the film compared to the commercial process. Although Film 2 contained less starch than the commercial films (about 0.67 phr versus about 3.4 phr), increasing the amount of starch in Film 2 up to about 6 phr is not expected to significantly increase the haze value (expected to be less than about 40% at 100% strain, similar to Films 14 and 15), which is still substantially lower than the 67% haze in the unstretched state exhibited by the commercial films.

[0069] Moreover, as shown in the examples below, it was surprisingly found that when a film prepared according to the method of the present disclosure included a blend of a first polyvinyl alcohol copolymer containing maleate monomer units and a second polyvinyl alcohol copolymer containing methyl acrylate monomer units, the film exhibited a matte-to-gloss static coefficient of friction of less than 6, and a haze of less than 30% at 100% strain and less than 20% for the unstretched film. As discussed above, such a film containing a polyvinyl alcohol copolymer containing methyl acrylate monomer units was expected to have a significantly higher haze value, considering commercially available films containing this polyvinyl alcohol copolymer have a haze value of about 67% when unstretched.

[0070] The water-soluble film may further have a residual moisture content of at least 4% by weight, preferably in the range of about 4 to about 10% by weight, as measured by Karl Fischer titration.

[0071] How the film is made One contemplated class of embodiments is characterized in that the water-soluble film is formed by solution casting. The process for solution casting of PVOH is well known in the art. For example, in the film-forming process, polyvinyl alcohol resin, plasticizer, and other additives are dissolved in a solvent, typically water, and heated until homogeneous. The solution is maintained at an elevated temperature (but not boiling) until suspended gas is released. The solution is then metered onto a surface and substantially dried (or forced dried) to form a cast film, and the resulting cast film is then removed from the casting surface and wound into a rolled good. The process can be carried out in batches, but is more efficient in a continuous process.

[0072] 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 belt, causing the solvent to be substantially removed from the liquid, thereby forming a self-supporting cast film, and then peeling the resulting cast film from the casting surface and winding it into a roll of goods.

[0073] Optionally, the water-soluble film can be a self-supporting film consisting of one layer or multiple similar layers.

[0074] The method of preparing the film of the present disclosure generally comprises solution casting a mixture comprising a first polyvinyl alcohol homopolymer, a second polyvinyl alcohol homopolymer, a plasticizer, a starch, and optional additives of the present disclosure, in the amounts described herein for each component, onto a surface, the surface being characterized by a gloss unit (GU) value at an angle of 60° of at least about 150. In embodiments, the surface is characterized by a GU value at 60° ranging from about 150 to about 550. In embodiments, the surface may be characterized by a GU value at 60° of at least about 200, at least about 250, at least about 300, at least about 350, at least about 400, or at least about 450. The gloss unit value at 60° may be determined by any method known in the art, for example, using a gloss meter according to ASTM D2457-21. Surfaces having a gloss unit value of at least about 150 may generally be obtained using any suitable method. For example, a cast surface having a gloss unit value of less than about 150 can be polished to achieve higher gloss values, such as about 150, about 200, about 300, about 400, or about 450. Without wishing to be bound by theory, it is believed that as the gloss value of a surface increases beyond about 550 GU, the reduction in haze and increase in clarity at 100% strain is not as significant as compared to the values ​​exhibited for the same film cast on a 550 GU surface.

[0075] In the solution casting of water-soluble films, it is conventional practice to apply a release coating to the casting surface to aid in the removal of the cast film from the casting surface. In the embodiment of the method of the present disclosure in which a release coating is applied to the casting surface and the casting surface is polished to obtain a gloss value of at least 150, the release coating is applied to the surface after polishing the surface. The release coating can generally be applied to the surface before or at the same time as the casting solution is metered onto the casting surface.

[0076] As shown in the following examples, the disclosed method advantageously provides films with low haze values ​​(less than 40%, less than 30%, or less than 20%) at 100% strain for all resin types, even when containing up to about 6 phr starch. This result is surprising considering that commercial films using the same resins have high haze values ​​in the unstretched state (68% for film C1, 67% for film C3) and at 100% strain (95% for film C1). The examples show that haze can be improved by preparing commercial films according to the disclosed method (Table 3, haze of film C1 improved by 25% in the unstretched state and 44% at 100% strain). It is believed that haze can be further improved by casting on a glossier surface than that used in Example 3 or by reducing the amount of starch to less than 6 phr. For example, as shown in Table 5, when films are prepared using the same resin as Film C1, a haze at 100% strain of less than 40% can be achieved for films containing 6 phr or less of starch. Additionally, as shown in Table 5, films containing the same resin as Film C3 (which exhibited a haze of 67% in the unstretched state) can be prepared to exhibit a haze at 100% strain of less than 40% (Films 2, 4, 5, 6, and 7).

[0077] Film properties In embodiments, the water-soluble films of the present disclosure may be characterized by a haze value at 100% strain in the range of about 70% or less, e.g., about 0.5% to about 70%, about 0.5% to about 60%, about 0.5% to about 50%, about 5% to about 45%, about 5% to about 40%, about 5% to about 35%, about 10% to about 30%, about 10% to about 25%, about 10% to about 20%, or about 10% to about 15%, as determined according to the Haze Test disclosed herein. Without intending to be bound by theory, it is believed that the haze value is an indication of how smooth or rough the surface of the water-soluble film is, e.g., as the surface roughness of the film increases, the haze value increases due to scattering of light from surface defects.

[0078] In embodiments, the water-soluble films of the present disclosure may be characterized by a matte-to-gloss (MG) static coefficient of friction of about 5 or less, or from about 0.01 to about 5, from about 0.05 to about 5, from about 0.05 to about 4, from about 0.05 to about 3, from about 0.05 to about 2, from about 0.05 to about 1, from about 0.05 to about 0.90, from about 0.05 to about 0.80, from about 0.05 to about 0.70, from about 0.05 to about 0.65, from about 0.05 to about 0.60, or from about 0.05 to about 0.55, as determined by the Coefficient of Friction Test described herein. The glossy side of the water-soluble film refers to the air side of the water-soluble film that is cast onto the casting surface. The matte side of the water-soluble film refers to the cast side of the water-soluble film that is cast onto the casting surface. The lower the MG static friction coefficient, the less likely the film (or pouch formed therefrom) will adhere to the surface on which it is formed (or converted into, for example, a pouch) and / or to other water-soluble films. As used herein, "glossy-to-glossy static friction coefficient" refers to the static friction coefficient between the glossy side of two water-soluble films with the same formulation. As used herein, "glossy-to-matte static friction coefficient" refers to the static friction coefficient between the glossy side and the matte side of two water-soluble films with the same formulation. As used herein, "matte-to-matte static friction coefficient" refers to the static friction coefficient between the matte side of two water-soluble films with the same formulation. The glossy-to-glossy static friction coefficient is typically higher than the glossy-to-matte static friction coefficient and the matte-to-matte friction coefficient for a given cast water-soluble film. Without intending to be bound by theory, it is believed that the gloss-to-gloss static coefficient of friction of a cast film represents the static coefficient of friction of a blown film having the same film formulation as the cast film, since the blown film is not cast on a casting surface, and therefore all sides of the blown film can be considered as air sides or "glossy" sides. Furthermore, the matte-to-gloss static coefficient of friction represents the ease of unwinding a sheet of polyvinyl alcohol film from a roll with the glossy side in contact with the matte side. In embodiments, the water-soluble films of the present disclosure may be characterized by a gloss-to-gloss coefficient of friction in the range of about 0.05 to about 0.60, about 0.05 to about 0.50, about 0.05 to about 0.40, or about 0.05 to about 0.30, as determined according to the Coefficient of Friction Test.

[0079] It is generally understood in the art that when a polymer solution is deposited on a hard substrate for casting, the polymer solution will adopt some of the surface properties of the substrate as it settles on the substrate.Without intending to be bound by theory, it is believed that the surface properties of the cast film can dramatically affect the processing of the film, especially in rolled goods where layers are in intimate contact.Furthermore, without intending to be bound by theory, it is believed that in general, the smoother the surface of the film, the greater the surface area that is in contact between layers, and therefore the more likely the film can stick to itself on the roll, since there is little protrusion / roughness on the film surface to prevent layers from sticking together.

[0080] Surprisingly and advantageously, the film of the present disclosure having a low haze value of less than about 70%, for example, less than about 60%, less than about 50%, less than about 40%, less than about 30%, or less than about 20%, can also have a low matte-to-gloss coefficient of friction value, for example, less than about 1, less than about 0.9, less than about 0.8, less than about 0.7, or less than about 0.6. Such a combination of advantageous low haze value and advantageous low coefficient of friction value was surprising, due to the understanding in the art that transparency and coefficient of friction are competing properties. However, advantageously, it has been found that when the film formulation of the present disclosure is cast on a smooth surface, not only does the haze value of the film decrease, but the film also exhibits a lower matte-to-gloss coefficient of friction value.

[0081] In embodiments, the water-soluble film may also be characterized by blocking force. Blocking refers to the force required to separate one film layer from another on a roll. Blocking is related to the coefficient of friction, and with a high matte-to-gloss coefficient of friction, the film is likely to exhibit high blocking force. In embodiments, the water-soluble film of the present disclosure may be characterized by a blocking force for the entire roll, as determined by the blocking test herein, ranging from about 0.5N to about 3N, for example, about 3N or less, about 2.9N or less, about 2.8N or less, about 2.7N or less, or about 2.6N or less.

[0082] In embodiments, the water-soluble film may also be characterized by elongation at break and / or tensile strength. Elongation at break and tensile strength generally represent the mechanical properties of the water-soluble film and its ability to withstand processing. Without intending to be bound by theory, it is believed that as the elongation at break value decreases, the ability to wind the film into a roll under tension decreases, and as the elongation at break value increases, the ease of converting the film (e.g., into a pouch) increases. Generally, as the amount of plasticizer in the film increases, the elongation at break increases, but the possibility of blocking increases. In embodiments, the water-soluble film of the present disclosure may be characterized by an elongation at break of at least 300%, e.g., at least 325%, or at least 350%, and up to 700%, e.g., in the range of 300% to 700%, as determined by elongation testing. Without intending to be bound by theory, it is believed that tensile strength represents how much abuse the film can withstand before failure during processing, for example, when peeled from a casting surface. In embodiments, the water-soluble films of the present disclosure may be characterized by a tensile strength, as determined by tensile testing, of at least 40 MPa, such as at least 45 MPa, or at least 50 MPa.

[0083] In some embodiments, the present disclosure provides a water-soluble film comprising a first polyvinyl alcohol homopolymer characterized by a viscosity of about 20 cP to about 25 cP and a degree of hydrolysis of about 85% to about 95% and a second polyvinyl alcohol homopolymer characterized by a viscosity of about 4 cP to about 8 cP and a degree of hydrolysis of about 85% to about 95%, wherein the first polyvinyl alcohol homopolymer constitutes about 65% to about 90% of the total polyvinyl alcohol polymer and the second polyvinyl The alcohol homopolymer constitutes the remainder, and the water-soluble film further comprises starch in an amount ranging from 0 PHR to about 1 PHR, and a plasticizer in an amount ranging from about 18 PHR to about 23 PHR, the plasticizer comprising sorbitol and glycerol, and the water-soluble film is characterized by a matte-to-gloss coefficient of friction ranging from about 0.05 to about 0.55, a haze at 100% strain ranging from about 0.5% to about 20%, an elongation to break of at least 350%, and a blocking force for a total roll of less than 3.

[0084] water soluble articles The films of the present disclosure are useful for creating articles and / or pouches for containing various compositions. The compositions contained in the pouches can be in any form, such as powder, gel, paste, liquid, tablet, or any combination thereof. The films of the present disclosure form at least one side wall of the article and / or pouch, optionally the entire article and / or pouch, and preferably the outer surface of at least one side wall.

[0085] The films described herein can also be used to make articles and / or pouches with two or more compartments, either made from the same film or in combination with films of other polymeric materials. In one type of embodiment, the polymers, copolymers, or derivatives thereof suitable for use as additional films are selected from polyvinyl alcohol (i.e., homopolymers and / or copolymers), polyvinylpyrrolidone, polyalkylene oxides, polyacrylic acids, 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, 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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 present 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.

[0090] 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 itself and sealed at the edges, or alternatively, 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 multiple films with 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.

[0091] In one embodiment, the 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.

[0092] In embodiments, the present disclosure provides a unit dose article comprising at least one compartment and, optionally, a composition contained within the compartment, wherein at least one wall of the compartment comprises a water-soluble film of the present disclosure.

[0093] Item and / or pouch contents The article (e.g., in the form of a pouch or packet) may contain a variety of compositions, e.g., household care compositions, and other compositions for non-household care compositions, such as agricultural compositions and water treatment compositions. A multi-compartment 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.

[0094] 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 pouches may be in liquid, solid, or powder form. 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.

[0095] Non-limiting examples of other useful compositions (e.g., non-household care compositions) include agricultural compositions, aviation compositions, food and nutritional compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office compositions, and recreational and park compositions, pet compositions, water treatment compositions, including cleaning and detergent compositions applicable to any such use, excluding fabric and household care compositions. The compositions used in the pouches may be in the form of liquids, solids, or powders. Liquid compositions may include solids. Solids may include powders or aggregates 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.

[0096] The compositions encapsulated by the films described herein can have any suitable viscosity, depending on factors such as the ingredients being formulated and the purpose of the composition. In one embodiment, the composition has a viscosity of 20 s -1 and a temperature of 20° C.; and a high shear viscosity value of 100 to 3,000 cP, alternatively 300 to 2,000 cP, alternatively 500 to 1,000 cP; and -1 and a temperature of 20°C. Methods for measuring viscosity are known in the art. In accordance with the present disclosure, shear viscosity measurements of compositions other than PVOH polymer solutions are performed using a rotational rheometer, for example, a TA instruments AR550. The instrument includes a 40 mm 2° or 1° cone fixture with a gap of about 50-60 μm for isotropic liquids, or a 40 mm flat steel plate with a gap of 1000 μm for liquids containing particles. Measurements are performed using a flow procedure that includes an adjustment step, a peak hold, and a continuous ramp step. The adjustment step includes setting the measurement temperature at 20°C, ramping for 10 s, and ramping for 10 s. -1The preshear included 10 seconds at a shear rate of 0.05 s at 20°C, and 60 seconds equilibration at the selected temperature. -1 A shear rate of 0.1 to 1200 s was applied for 3 min with sampling every 10 s. Successive ramp steps were performed from 0.1 to 1200 s at 20 °C. -1 The flow is then run for 3 minutes at a shear rate of 100 rpm to obtain a complete flow profile.

[0097] As mentioned above, the composition can be a non-household care composition.For example, the non-household care composition can be selected from agricultural compositions, aviation compositions, food and nutritional compositions, industrial compositions, building and construction compositions, livestock compositions, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office compositions, and recreational and park compositions, pet compositions, water treatment compositions, including cleaning compositions and detergent compositions applicable to any such use, but excluding fabric and household care compositions.

[0098] In one type of embodiment, the composition comprises a pesticide, such as one or more insecticides, fungicides, herbicides, pesticides, acaricides, repellents, attractants, defoliants, plant growth regulators, fertilizers, bactericides, micronutrients, and trace elements. Suitable pesticides and secondary agents are described in U.S. Patent Nos. 6,204,223 and 4,681,228, and EP 0989803 (A1). For example, suitable herbicides include paraquat salts (e.g., paraquat dichloride or paraquat bis(methyl sulfate), diquat salts (e.g., diquat dibromide or diquat alginate), and glyphosate or its salts or esters (e.g., glyphosate isopropylammonium, glyphosate sesquisodium or glyphosate trimesium, also known as sulfosates). Incompatible pairs of crop protection chemicals can be used in separate chambers, for example, as described in U.S. Pat. No. 5,558,228. Incompatible pairs of crop protection chemicals that can be used include, for example, bensulfuron methyl and molinate, 2,4-D and thifensulfuron methyl, 2,4-D and methyl 2-[[[[N-4-methoxy-6-methyl-1,3,5-triazin-2-yl]-N- methylamino]carbonyl]amino]-sulfonyl]benzoate, 2,4-D and metsulfuron methyl, maneb or mancozeb and benomyl, glyphosate and metsulfuron methyl, tralomethrin and any organophosphate such as monocrotophos or dimethoate, bromoxynil and N-[[4,6-dimethoxypyrimidin-2-yl]-amino]carbonyl]-3-(ethylsulfonyl)-2-pyridine-sulfonamide, bromoxynil and methyl 2-[[[[(4-methyl-6-methoxy)-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-benzoate, bromoxynil and methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]-sulfonyl]benzoate.In another related type of embodiment, the composition may include one or more seeds, optionally together with soil, and optionally together with one or more additional components selected from mulch, sand, peat moss, water jelly crystals, and fertilizer, including, for example, the type of embodiments described in U.S. Pat. No. 8,333,033.

[0099] In another type of embodiment, the composition is a water treatment agent. Such agents include aggressive oxidizing chemicals, such as those described in U.S. Patent Application Publication No. 2014 / 0110301 and U.S. Patent No. 8,728,593. For example, sanitizing agents can include hypochlorites, such as sodium hypochlorite, calcium hypochlorite, and lithium hypochlorite, and chlorinated isocyanurates, such as dichloroisocyanuric acid (also called "dichlor" or dichloro-s-triazinetrione, 1,3-dichloro-1,3,5-triazinane-2,4,6-trione) and trichloroisocyanuric acid (also called "trichlor" or 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione). Salts and hydrates of the disinfecting compounds are also contemplated. For example, dichloroisocyanuric acid can be provided as sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, among others. Bromine-containing disinfectants may also be suitable for use in unit dose packaging applications, such as 1,3-dibromo-5,5-dimethylhydantoin (DBDMH), 2,2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyanoacetamide, 1-bromo-3-chloro-5,5-dimethylhydantoin, and 2-bromo-2-nitro-1,3-propanediol, among others. The oxidizing agent may be one described in U.S. Pat. No. 7,476,325, such as potassium hydrogen peroxymonosulfate. The composition may be a pH-adjusting chemical, such as one described in U.S. Patent Application Publication No. 2008 / 0185347, and may include, for example, an acidic component and an alkaline component, such that the composition is effervescent and adjusts the pH of the water when it comes into contact with water. Suitable components include sodium bicarbonate, sodium bisulfate, potassium hydroxide, sulfamic acid, organic carboxylic acids, sulfonic acids, and potassium dihydrogen phosphate. The buffer blend may include, for example, boric acid, sodium carbonate, glycolic acid, and oxone monopersulfate.

[0100] The water treatment agent may be or may include a flocculant, such as those described in U.S. Patent Application Publication No. 2014 / 0124454. The flocculant may include a polymeric flocculant, such as polyacrylamide, polyacrylamide copolymers, such as diallyldimethylammonium chloride (DADMAC), dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEM), 3-methylamidopropyltrimethylammonium chloride (MAPTAC) or acrylamide copolymers of acrylic acid, cationic polyacrylamide, anionic polyacrylamide, neutral polyacrylamide, polyamines, polyvinylamines, polyethyleneimines, polydimethyldiallylammonium chloride, polyoxyethylene, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyphosphoric acid, polystyrene sulfonic acid, or any combination thereof. The flocculant can be selected from chitosan acetate, chitosan lactate, chitosan adipate, chitosan glutamate, chitosan succinate, chitosan malate, chitosan citrate, chitosan fumarate, chitosan hydrochloride, and combinations thereof. The water treatment composition can include one or more phosphate removing materials selected from, for example, zirconium compounds, rare earth lanthanide salts, aluminum compounds, iron compounds, or any combination thereof.

[0101] The composition may be, for example, a limescale removal composition as described in US Patent Application Publication No. 2006 / 0172910, such as citric acid, or maleic acid, or a sulfate thereof, or any mixture thereof.

[0102] Various other types of compositions are contemplated for use in the packets described herein, including particulates, such as feathers, as described, for example, in US RE29059 E; superabsorbent polymers, as described, for example, in US Patent Application Publication Nos. 2004 / 0144682 and 2006 / 0173430; pigments and stains, as described, for example, in US Patent Application Publication Nos. 3,580,390 and 2011 / 0054111; brazing fluxes (e.g., alkali metal fluoroaluminates, alkali metal fluorosilicates, and alkali metal fluorozincates), as described, for example, in US Patent Application Publication No. 8,163,104; food products (e.g., coffee powder or dried soup), as described, for example, in US Patent Application Publication No. 2007 / 0003719; and wound dressings, as described, for example, in US Patent Application Publication No. 4,466,431.

[0103] In the pouches containing the laundry compositions, laundry additive compositions, and / or fabric enhancer compositions, the compositions may contain any of the following non-limiting list of ingredients: fabric care benefit agents; cleaning enzymes; deposition aids; rheology modifiers; builders; bleach; bleaching agents; bleach precursors; bleach boosters; bleach catalysts; perfumes and / or perfume microcapsules (see, e.g., U.S. Pat. No. 5,137,646); perfume loaded zeolites; starch encapsulated accords; polyglycerol esters; whitening agents; pearlescent agents; enzyme stabilization systems; scavenging agents including anionic dye fixing agents, anionic surfactant complexing agents, and mixtures thereof; optical brighteners or fluorescent agents; polymers including, but not limited to, soil release polymers and / or soil suspending polymers; dispersants; defoamers; non-aqueous solvents; fatty acids; suds suppressors, such as silicone suds suppressors (U.S. Publication No. 2003). / 0060390(A1), 65-77); cationic starch (see US 2004 / 0204337(A1) and US 2007 / 0219111(A1)); scum dispersants (see US 2003 / 0126282(A1), 89-90); direct dyes; hueing dyes (see US 2014 / 0162929(A1)); colorants; opacifiers; antioxidants; hydrotropes, color specks such as toluenesulfonates, cumenesulfonates, and naphthalenesulfonates; colored beads, spheres or extrudates; clay softeners; and antimicrobial agents. Any one or more of these ingredients are further described in U.S. Patent Application Publication Nos. 2010 / 305020(A1), 2003 / 0139312(A1), and 2011 / 0023240(A1). Additionally or alternatively, the composition may include a surfactant, a quaternary ammonium compound, and / or a solvent system. Quaternary ammonium compounds may be present in fabric enhancer compositions, such as fabric softeners, and may be represented by the structure NR4 + where R is an alkyl or aryl group.

[0104] Surfactants The detergent composition may comprise from about 1% to 80% by weight of a surfactant. Surfactants are particularly preferred as a component of the first composition. Preferably, the first composition comprises from about 5% to 50% by weight of a surfactant. The second and third compositions may comprise surfactants at levels from 0.1 to 99.9%.

[0105] The detersive surfactant utilized may be of the anionic, nonionic, zwitterionic, amphoteric, or cationic type, or may comprise compatible mixtures of these types. More preferably, the surfactant is selected from the group consisting of anionic, nonionic, cationic surfactants, and mixtures thereof. Preferably, the composition is substantially free of betaine surfactants. Detergent surfactants useful herein are described in U.S. Patent Nos. 3,664,961, 3,919,678, 4,222,905, and 4,239,659. Anionic and nonionic surfactants are preferred.

[0106] Useful anionic surfactants can themselves be of a variety of different types. For example, water-soluble salts of higher fatty acids, i.e. "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by neutralizing free fatty acids. Sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, i.e. sodium or potassium tallow and coconut soaps, are particularly useful.

[0107] Additional non-soap anionic surfactants suitable for use herein include the water-soluble salts, preferably alkali metal and ammonium salts, of organic sulfuric acid reaction products having an alkyl group containing from about 10 to about 20 carbon atoms in their molecular structure, and a sulfonic acid or sulfate ester group. (The term "alkyl" includes the alkyl portion of an acyl group.) Examples of this group of synthetic surfactants include: a) sodium, potassium, and ammonium alkyl sulfates, especially those produced by reducing higher alcohols (C8-C9) such as those produced by reducing glycerides of tallow or coconut oil; 18 ), b) sodium, potassium, and ammonium alkyl polyethoxylate sulfates, especially those in which the alkyl group contains from 10 to 22, preferably from 12 to 18, carbon atoms and the polyethoxylate chain contains from 1 to 15, preferably from 1 to 6, ethoxylate moieties, and c) sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms in a straight or branched chain configuration, such as the types described in U.S. Patents 2,220,099 and 2,477,383. Particularly valuable are those in which the average number of carbon atoms in the alkyl group is from about 11 to 13, and the C 11 ~C 13 Abbreviated as LAS, it is a linear straight-chain alkylbenzene sulfonate.

[0108] Preferred nonionic surfactants are of the formula R1(OC2H4) n OH, where R1 is C 10 ~C 16 Alkyl group or C8-C 12 C is an alkylphenyl group, and n is from 3 to about 80. 12 ~C 15 Condensation products of alcohols with about 5 to about 20 moles of ethylene oxide per mole of alcohol, such as C condensed with about 6.5 moles of ethylene oxide per mole of alcohol. 12 ~C 13 Alcohols are particularly preferred.

[0109] Solvent System The solvent system in the detergent composition may be a solvent system containing only water or a mixture of organic solvent and water. Preferred organic solvents include 1,2-propanediol, ethanol, glycerin, dipropylene glycol, methylpropanediol, and mixtures thereof. Other lower alcohols, low molecular weight polyols, C1-C4 alkanolamines such as monoethanolamine and triethanolamine may also be used. As used herein, a "low molecular weight polyol" is a molecule having three or more hydroxyl groups with a molecular weight ranging from 50 g / mol to 1000 g / mol, 50 g / mol to 800 g / mol, or 50 g / mol to 600 g / mol. The solvent system may not be present in the anhydrous solid detergent embodiments of the present disclosure, for example, but is more typically present at a level ranging from about 0.1% to about 98% by weight, preferably at least about 1% to about 50% by weight, and more typically from about 5% to about 25% by weight. Typically, the detergent composition, especially when in liquid form, contains less than 50% water, preferably about 0.1% to about 20% water, more preferably about 0.5% to about 15%, or about 3% to about 12% water, by weight of the composition. Typically, the detergent composition, especially when in liquid form, contains about 5% to about 20% glycerin, or about 10% to about 15% glycerin, by weight of the composition. Typically, the detergent composition, especially when in liquid form, contains less than 30% propylene glycol, for example, about 0.1% to 25% propylene glycol, 0.5% to 20% propylene glycol, or 5% to 15% propylene glycol, by weight of the composition.

[0110] The detergent compositions herein can generally be prepared by combining and mixing the ingredients. If pearlescent materials are used, they need to be added at a later stage of mixing. If rheology modifiers are used, it is preferred to first form a premix in which the rheology modifiers are dispersed in a portion of the water and, optionally, other ingredients that will ultimately be used to make up the detergent composition. This premix is ​​formed in such a way as to form a structured liquid. Surfactants and essential laundry additive materials can then be added to this structured premix, along with water, while the premix is ​​being stirred, and any detergent composition additives are used.

[0111] The pH of the detergent composition may be from about 2 to about 12, from about 4 to about 12, from about 5.5 to about 9.5, from about 6 to about 8.5, or from about 6.5 to about 8.2. The laundry detergent composition may have a pH of from about 6 to about 10, from about 6.5 to about 8.5, from about 7 to about 7.5, or from about 8 to about 10. The automatic dishwashing composition may have a pH of from about 8 to about 12. The laundry detergent additive composition may have a pH of from about 4 to about 8. The fabric enhancer may have a pH of from about 2 or 4 to about 8, or from about 2 to about 4, or from about 2.5 to about 3.5, or from about 2.7 to about 3.3.

[0112] The pH of a detergent is defined as the pH of a 10% (weight / volume) solution of the detergent in water at 20°C ± 2°C; for solid and powder detergents, it is defined as the pH of a 1% (weight / volume) solution of the detergent in water at 20°C ± 2°C. Any meter capable of measuring pH to ± 0.01 pH units is suitable. An Orion meter (Thermo Scientific, Clintinpark-Keppekouter, Ninovesteenweg 198, 9320 Erembodegem-Aalst, Belgium) or equivalent is an acceptable measuring device. The pH meter should be equipped with a suitable glass electrode based on calomel or silver / silver chloride. An example is the Mettler DB115. The electrode should be stored in the electrolyte solution recommended by the manufacturer.

[0113] A 10% aqueous solution of detergent is prepared according to the following procedure: Weigh out 10±0.05 grams of sample on a balance accurate to ±0.02 grams. Transfer the sample to a 100 mL volumetric flask and dilute to volume with purified water (deionized and / or distilled water are suitable as long as the conductivity of the water is <5 S / cm) and mix thoroughly. Pour approximately 50 mL of the resulting solution into a beaker, adjust the temperature to 20°C±2°C, and measure the pH according to the pH meter manufacturer's standard procedures (it is also important to set up and calibrate the pH assembly according to the manufacturer's instructions).

[0114] For solid and powder detergents, a 1% aqueous solution of the detergent is prepared according to the following procedure: Weigh 10±0.05 grams of sample on a balance accurate to ±0.02 grams. Transfer the sample to a 1000 mL volumetric flask and dilute to volume with purified water (deionized and / or distilled water are suitable as long as the conductivity of the water is <5 S / cm) and mix thoroughly. Pour approximately 50 mL of the resulting solution into a beaker, adjust the temperature to 20°C±2°C, and measure the pH according to the pH meter manufacturer's standard procedures (it is also important to set up and calibrate the pH assembly according to the manufacturer's instructions).

[0115] It is known in the art that when formed into a pouch that encloses a composition, some film components (e.g., plasticizers) may, in some circumstances, migrate from the film to the encapsulated composition, and additionally or alternatively, some components of the encapsulated composition (e.g., plasticizers, solvents) may migrate to the film. Without wishing to be bound by theory, it is believed that this migration of components to / from the film may result in a change in the swelling value of the film.

[0116] Bleach Inorganic and organic bleaching agents are suitable cleaning actives for use herein. Inorganic bleaching agents include perhydrate salts such as perborates, percarbonates, perphosphates, persulfates, and persilicates. Inorganic perhydrate salts are usually alkali metal salts. Inorganic perhydrate salts can be included as crystalline solids without additional protection. Alternatively, the salts can be coated as known in the art.

[0117] Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates for use in the detergent compositions described herein. The percarbonate is most preferably incorporated into the product in coated form and / or encapsulated, which provides in-product stability. Suitable coating materials that provide product stability include water-soluble alkali metal sulfate and carbonate mixed salts. Such coatings, together with coating processes, have been previously described in GB 1,466,799, and U.S. Pat. Nos. 3,975,280, 4,075,116, and 5,340,496, each of which is incorporated herein by reference. The weight ratio of the mixed salt coating material to the percarbonate ranges from 1:99 to 1:9, preferably from 1:49 to 1:19. Preferably, the mixed salt is of sodium sulfate and sodium carbonate with the general formula Na2SO4nNa2CO3, where n is 0.1-3, preferably 0.3-1.0, more preferably 0.2-0.5. Another suitable coating material that provides product stability includes sodium silicate with a SiO2:Na2O ratio of 1.8:1-3.0:1, preferably 1.8:1-2.4:1, and / or sodium metasilicate applied at a level of 2%-10% (usually 3%-5%) SiO2 by weight of inorganic perhydrate salt such as potassium peroxymonopersulfate. Other coatings containing magnesium silicate, silicates and borates, silicates and boric acid, waxes, oils, and fatty soaps may also be used advantageously.

[0118] Organic bleaching agents may include organic peroxyacids including diacyl and tetraacyl peroxides, particularly diperoxydodecanedioic acid, diperoxytetradecanedioic acid, and diperoxyhexadecanedioic acid. Dibenzoyl peroxide is the preferred organic peracid herein. Diacyl peroxides, particularly dibenzoyl peroxide, may preferably be present in the form of particles having a weight average diameter of about 0.1 to about 100 microns, preferably about 0.5 to about 30 microns, more preferably about 1 to about 10 microns. Preferably, at least about 25% to 100%, more preferably at least about 50%, even more preferably at least about 75%, and most preferably at least about 90% of the particles are smaller than 10 microns, preferably smaller than 6 microns.

[0119] Other organic bleaches include peroxyacids, particular examples being the alkylperoxyacids and arylperoxyacids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acid, as well as peroxy-α-naphthoic acid, and magnesium monoperphthalate; (b) aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperazipic acid, and N-nonenylamidopersuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelanic acid, diperoxysebacic acid, diperoxybrassylic acid, diperoxyphthalic acid, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyldi(6-aminopercaproic acid).

[0120] Bleach activators may include organic peracid precursors which enhance bleaching action during washing at temperatures up to 60°C. Bleach activators suitable for use herein include compounds which under perhydrolysis conditions give aliphatic peroxycarboxylic acids, preferably having 1 to 10 carbon atoms, especially 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acids. Suitable materials have O-acyl and / or N-acyl groups of the specified number of carbon atoms, and / or optionally substituted benzoyl groups. Preference is also given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, and 2,5-diacetoxy-2,5-dihydrofuran, and triethylacetyl citrate (TEAC).

[0121] Preferred bleach catalysts for use in the detergent compositions herein include manganese triazacyclononane and related complexes (U.S. Pat. Nos. 4,246,612 and 5,227,084), Co, Cu, Mn, and Fe bispyridylamine and related complexes (U.S. Pat. No. 5,114,611), and pentamine acetate cobalt(III) and related complexes (U.S. Pat. No. 4,810,410).A complete description of bleach catalysts suitable for use herein can be found in U.S. Pat. No. 6,599,871, which is incorporated herein by reference.

[0122] Dishwashing detergent Preferred surfactants for use in automatic dishwashing detergents are low foaming, either by themselves or in combination with other components (e.g., suds suppressors). Preferred for use herein are low cloud point and high cloud point nonionic surfactants and mixtures thereof, including nonionic alkoxylated surfactants (especially C6-C8 18 ethoxylates derived from primary alcohols), ethoxylated-propoxylated alcohols (e.g., POLY-TERGENT® SLF18 from Olin Corporation), epoxy terminated poly(oxyalkylated) alcohols (e.g., POLY-TERGENT® SLF18B from Olin Corporation, see WO-A-94 / 22800), ether terminated poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-polyoxypropylene polymer compounds such as PLURONIC®, REVERSED PLURONIC®, and TETRONIC from BASF-Wyandotte Corp., Wyandotte, Michigan; 12 ~C 20 Amphoteric surfactants such as alkylamine oxides (preferred amine oxides for use herein include lauryl dimethylamine oxide and hexadecyl dimethylamine oxide), alkylamphocarboxylic acid surfactants such as MIRANOL™ C2M, and zwitterionic surfactants such as betaines and sultaines, and mixtures thereof. Surfactants suitable for use herein are disclosed, for example, in U.S. Pat. Nos. 3,929,678 and 4,259,217, European Patent Publication No. 0414549(A1), and PCT Patent Application Publication Nos. 1994 / 007974(A1) and 1994 / 007986(A1). Surfactants may be present in the detergent at a level of about 0.2% to about 30% by weight, more preferably about 0.5% to about 10% by weight, and most preferably about 1% to about 5% by weight, based on the weight of the detergent composition.

[0123] Other Compositions and Additives Builders suitable for use in the detergent compositions described herein include water-soluble builders including citrates, carbonates, silicates, and polyphosphates, such as sodium tripolyphosphate, and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate, and mixed salts of sodium and potassium tripolyphosphate.

[0124] Enzymes suitable for use in the detergent compositions described herein include bacterial and fungal cellulases, including CAREZYME and CELLUZYME (Novo Nordisk A / S); peroxidases; lipases, including AMANO-P (Amano Pharmaceutical Co., Ltd.), M1 LIPASE and LIPOMAX (Gist-Brocades), and LIPOLASE and LIPOLASE ULTRA (Novo); cutinases; proteases, including ESPERASE, ALCALASE, DURAZYM, and SAVINASE (Novo), and MAXATASE, MAXACAL, PROPERASE, and MAXAPEM (Gist-Brocades); and amylases, including PURAFECT OX AM (Genencor), and TERMAMYL, BAN, FUNGAMYL, DURAMYL, and NATALASE (Novo); pectinases; and mixtures thereof. Enzymes herein may be added as prills, granules, or co-granules, typically at levels within the range of about 0.0001% to about 2% by weight of the pure enzyme, based on the weight of the cleaning composition.

[0125] The suds suppressor suitable for use in the detergent composition described herein includes nonionic surfactants with low cloud point. As used herein, "cloud point" is a well-known property of nonionic surfactants that results in the surfactant becoming less soluble with increasing temperature, and the temperature at which the appearance of a second phase can be observed is referred to as "cloud point". As used herein, "low cloud point" nonionic surfactants are defined as nonionic surfactant system components with cloud point less than 30°C, preferably less than about 20°C, even more preferably less than about 10°C, and most preferably less than about 7.5°C. Low cloud point nonionic surfactants can include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Such low cloud point nonionic surfactants can also include, for example, ethoxylated propoxylated alcohols (e.g., BASF POLY-TERGENT SLF18) and epoxy-terminated poly(oxyalkylated) alcohols (e.g., the BASF POLY-TERGENT SLF18B series of nonionics, as described in U.S. Pat. No. 5,576,281).

[0126] Other components suitable for use in the detergent compositions described herein include cleaning polymers with anti-redeposition, soil release, or other cleaning properties.Anti-redeposition polymers for use herein include acrylic acid-containing polymers such as SOKALAN PA30, PA20, PA15, PA10, and SOKALAN CP10 (BASF GmbH), ACUSOL 45N, 480N, 460N (Rohm and Haas), acrylic acid / maleic acid copolymers such as SOKALAN CP5, and acrylic / methacrylic copolymers.Other suitable polymers include amine-based polymers such as alkoxylated polyalkyleneimines (e.g., PEI600 EO20 and / or ethoxysulfated hexamethylenediamine dimethylquat). Soil release polymers for use herein include alkyl and hydroxyalkyl celluloses (U.S. Pat. No. 4,000,093), polyoxyethylene, polyoxypropylene, and copolymers thereof, as well as nonionic and anionic polymers based on terephthalate esters of ethylene glycol, propylene glycol, and mixtures thereof.

[0127] Heavy metal ion sequestrants and crystal growth inhibitors are also suitable for use in the detergents, such as the salt and free acid forms of diethylenetriaminepenta(methylenephosphonate), ethylenediaminetetra(methylenephosphonate), hexamethylenediaminetetra(methylenephosphonate), ethylenediphosphonate, hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate, ethylenediaminotetraacetate, ethylenediamine-N,N'-disuccinate.

[0128] Also suitable for use in the detergent compositions described herein are corrosion inhibitors, such as organic silver coatings (especially paraffins such as WINOG 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (e.g., benzotriazoles and benzimidazoles, see British Patent No. GB-A-1137741), and Mn(II) compounds, especially Mn(II) salts of organic ligands.

[0129] Other components suitable for use in the detergent compositions herein include enzyme stabilizers, such as calcium ions, boric acid, and propylene glycol.

[0130] Other components suitable for use in the detergent compositions herein include humectants, for example, as described in U.S. Patent Application Publication No. 2015 / 0329807.

[0131] Suitable rinse additives are known in the art. Commercially available rinse aids for dishwashing are typically mixtures of low foaming fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (e.g., cumene sulfonate), organic acids (e.g., citric acid), and solvents (e.g., ethanol). The function of such rinse aids is to affect the interfacial tension of water so that it can drain in the form of a thin, coherent film from the rinsed surface, without leaving any drops, streaks, or films after the subsequent drying process. EP 0 197 434 (B1) describes rinse aids that contain mixed ethers as surfactants. Rinse additives such as fabric softeners are also contemplated and are suitable for encapsulation into films according to the present disclosure.

[0132] Elongation and Tensile Tests Films characterized by or tested for tensile strength or elongation at break are analyzed as follows. Procedures include determination of elongation at break based on ASTM D882 ("Standard Test Method for Tensile Properties of Thin Plastic Sheeting") or equivalent. An INSTRON® tensile testing device (Model 5544 Tensile Tester or equivalent) is used to collect film data. A minimum of three specimens, each cut with a reliable cutting tool to ensure dimensional stability and repeatability, are tested in the machine direction (MD) (if applicable) for each measurement. Tests are performed in a standard laboratory atmosphere of 23±2.0°C and 35±5% relative humidity after conditioning in the same environment for 24 hours. One-inch wide (2.54 cm) samples of a single film sheet with a thickness of 3.0±0.10 mils (or 76.2±2.5 μm) are prepared for tensile strength determination and elongation at break determination. A tensile tester equipped with a 500N load cell is prepared and calibrated according to the manufacturer's instructions. The correct grips and faces are installed (INSTRON® grips with model number 2702-032 faces, rubber coated and 25 mm wide, or equivalent). Samples are placed in the tensile tester and analyzed to determine the elongation at break (i.e., Young's modulus is applied) and / or tensile strength (i.e., the stress required to break the film).

[0133] Suitable behavior of films according to the present disclosure is indicated by an elongation at break of at least about 300%. Suitable behavior of films according to the present disclosure is indicated by a tensile strength value (in the machine direction (MD)) of at least about 40 MPa. In various embodiments, films of the present disclosure may have an elongation at break of about 325%, or at least 350%, and / or a tensile strength in the range of at least about 40 MPa to about 60 MPa, e.g., at least 45 MPa, at least 50 MPa, and / or up to about 55 MPa, or up to about 60 MPa.

[0134] Friction Coefficient Test Films according to the present disclosure that are characterized by or tested according to the Coefficient of Friction Test can be analyzed as follows: The Coefficient of Friction method tests the friction of two pieces of material that are rubbed against each other and measures the force required to move one piece of material against the other. Both the force to start the sled (static friction) and the force to keep the sled moving (kinetic friction) are measured by a load cell using ASTM D1894 "Friction Testing of Plastic Film and Sheeting".

[0135] This method uses an Instron® Coefficient of Friction Test Fixture Model 2810-005 or equivalent (representative diagram shown in FIG. 1), and an Instron® Tester Model #5543 or equivalent.

[0136] The test apparatus includes a friction fixture 10 on which rests a friction sled 12 having a film sample 14 secured thereon. The sled 12 is attached to an upper grip 18 via a pull cord 20 that engages a pulley 22 secured to the friction fixture 10. A lower coupling 24 secures the test fixture to an Instron® testing machine (not shown).

[0137] Instron® method from the Blue Hill program: "The system searches for the maximum value of the data from the start value to the end value of a particular channel; determines the first data point above or below by a percentage of the maximum value and assigns this point as the first peak; determines the static friction coefficient using the following equation: Static friction = first peak / sled weight; calculates the average load in the region from the first peak to the end value using the following equation: Average load = energy / change in elongation; determines the kinetic friction coefficient using the following equation: Kinetic friction = average load / sled weight."

[0138] The test specimens to form the test areas should consist of samples having dimensions of 5 in. x 5 in. square (12.7 cm x 12.7 cm square) for the sled and 5 in. x 8 in. square (12.7 cm x 20.3 cm) for the face. Film thickness is not expected to affect the static COF, but the film may have a thickness of 3.0 ± 0.10 mils (or 76.2 ± 2.5 μm). Samples may be cut, for example, using a razor blade and an appropriately sized template. When applicable, samples should be cut with the long dimension parallel to the machine direction of the cast film. Also, when applicable, the 5 in. x 5 in. sample orientation should be noted and oriented during testing so that the direction in which the sled is pulled is parallel to the machine direction of the film sample.

[0139] The test specimens should be conditioned at 75°F ± 5°F and 35% ± 5% relative humidity for at least 8 hours prior to testing, and the tests are performed under the same temperature and relative humidity conditions.

[0140] COF Equipment Installation Procedure 1. Remove the clevis pin from the bottom jaw of the Instron® Coefficient of Friction Test Fixture Model 2810-005 and remove the bottom jaw. 2. Remove the clevis pin from the top jaw and remove the top jaw. 3. Place the friction fixture lower coupling onto the base adapter of an Instron® Tester Model #5543. 4. Attach with clevis pins. 5. Slip the loop on one end of the pull cord onto the upper clevis pin and replace it with the locking clip. 6. Calibration of Test Machine Model #5543 7. Slip the loop on the other end of the pull cord through the hook on the friction sled. 8. Check that the pulleys can rotate freely. 9. Move the sled until there is no slack in the pull cord and it is oriented in the groove around the pulley. 10. Position the moving crosshead (upper hard) of the Instron® Coefficient of Friction Test Fixture Model 2810-005 so that there is enough travel space to pull the friction sled along the full 50 mm of the test without the sled hitting the pulley. 11. Hold the cord taut while the crosshead is moving. 12. Use the JOG control on the Instron #5543 control panel to set the extension limit so that the far end of the friction sled does not extend beyond the backplane of the friction fixture (the plane furthest from the pulley that is perpendicular to the axis of motion). Press the GL button to set the travel limit. This will prevent the friction sled from colliding with the pulley during the test and ensure that the coefficient of friction of the specimen of interest is measured properly. 13.The test fixture is now ready for testing.

[0141] Specimen placement procedure 1. Place the surface sample in the aluminum friction fixture in the appropriate orientation. 2. Pull the surface sample firmly over the edge of the aluminum surface and tape the sample to the bottom side of the rub fixture. 3. It is important to tape along the edge of the friction jig furthest from the coupling to avoid sticking the sled to the surface. 4. Make sure the material is taut but not stretched. 5. Wrap the 5 x 5 inch sample around the friction sled so that the machine direction of the film is parallel to the direction the sled is pulled. 6. Tape the edge of the tip that overlaps the top of the sled, making sure there is no excess material that will stick to the surface sample. 7. Tape the other edge of the sample to the friction sled, making sure the sample is taut on the contact surface to be measured. 8. Ensure that no tape is pinched between the target surface on the sled and the target surface on the rub fixture. 9. The sample on the friction surface and the sample on the friction sled must be taut so that there are no wrinkles or bulges that would cause errors in the COF measurement. 10. Inspect the sled to ensure that no foreign objects are touching the surface being tested. 11. Attach the sled to the pull cord, place the sled very lightly and gently on the friction table to prevent any unnatural sticking between the two specimens, and immediately begin the test. 12. Ensure that when fully extended, the sled fits completely over the specimen placed on the rub fixture and is not touching the tape or extending beyond the edge of the rub fixture.

[0142] Conducting COF tests 1. Test at least three specimens for each required orientation (e.g., air side-to-air side or band side-to-band side). 2. For the air side to band side test combination, the air side orientation of the film shall be the film specimen placed on the aluminum test surface and the band side for testing shall include the material wrapped around the warp. 3. Always wear powder-free, moisture-resistant gloves while handling film specimens, as powder or moisture may impair the accuracy of the test. 4. Cut the sample as described above, for example using a template. 5. Place the friction sled, encased in the first specimen, at the end of the friction fixture farthest from the pulley. 6. Make sure the pull cord is taut. 7. From the test screen, open the Coefficient of Friction test titled “COF.im ptf”. 8. Click the start button on the screen to begin the test. 9. Once the test specimen has been run, click OK to return the friction sled to the starting position, replace the friction sled and film specimen in the fixture, and repeat the test.

[0143] The films may be characterized by a static COF of 4.0 or less, or 2.0 or less, or 1.5 or less, or 1.25 or less, or 1.0 or less, or in small amounts in the 0.5 range, such as 1.0, 0.9, 0.8, 0.7, 0.6, or less. In another aspect, the static COF may be less than 4.0, or less than about 2.5, or less than 2, or less than 1. In embodiments, the films of the present disclosure may be characterized by a matte-to-gloss static coefficient of friction in the range of about 0.05 to about 1.

[0144] Haze Test The films of the present disclosure that are characterized by or tested according to the haze test can be analyzed as follows. The haze of the film can be measured using a BYK Haze Gard i Benchtop Haze Meter or equivalent, using BYK Smart Chart software. The absorption and scattering behavior of the transparent specimen will determine how much light is transmitted and how objects are seen through the transparent product. Haze is the percentage of light that passes through the transparent specimen that deviates from the incident beam by more than 2.5 degrees on average.

[0145] When calibration is required, BYK Calibration Standard Serial Number 1306881 is used. Film samples with a thickness of 3.0 ± 0.10 mils (or 76.2 ± 2.5 μm) are conditioned for 24 hours at approximately 25°C and 35% relative humidity. The film is cut into squares with side lengths ranging from approximately 5 1 / 2 to 6 inches (approximately 14 cm to 15.25 cm). The test area of ​​the film sample is identified and removed of any kind of dirt, fingerprints, and scuffs. 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 haze reading. Film imperfections should be minimized as they can affect how light transmits through the sample.

[0146] Place the film specimen into the haze port. Press the measure button and do not move or shift the sample while the indicator light is flashing. The haze reading is distance dependent and the film should be flush against the haze port opening.

[0147] 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. In some embodiments, the film is conditioned at 100% strain for at least 1 minute and up to 5 minutes before testing. 100% strain refers to uniaxial stretching in the machine direction to twice the film size. Suitable films of the present disclosure preferably have haze values ​​of less than 70%, less than 50%, less than 40%, less than 30%, less than 25%, or less than 20% after conditioning at 100% strain for 1 minute.

[0148] Blocking test Blocking refers to the force required to separate one film layer from another on a roll. In general, when blocking is reduced, the film can be unwound more easily without distorting the film, stretching it, or creating tension in the converting process. Blocking force generally tends to increase as the level of plasticizer in the film increases. The blocking test measures the blocking force between film layers on a roll. The blocking force measurement does not include the frictional force from the outer surface of the roll as it is being unwound.

[0149] Films of the present disclosure that are characterized by or tested according to the Blocking Test may be analyzed as follows: Blocking force is measured in Newtons with a digital force meter or equivalent. Measurements are taken across an entire roll (4-4.5 inches from the outer edge of the core) of film having a thickness of 3.0±0.10 mils (or 76.2±2.5 μm) using a force gauge. The roll is placed on a table so that it is unwound from below, away from the technician. The first measurement is taken after removing the top three layers of film from a selected roll. Approximately 3 inches of film is unwound, and then the film is folded three times on itself to create a 1-inch wide edge. A 1-inch slit is made at the midpoint of the layered edge in the web direction, parallel to the roll axis. The hook of the force gauge is placed in the slit and the force to unwind the roll is measured three times. The force gauge is held level with the table. While holding the force gauge, push the roll at approximately 1 inch per second without pulling on the force gauge. The peak force is recorded. The roll is then cut approximately half way to the core (2 to 2.25 inches from the outer edge of the core) and the measurement is repeated. The roll is then cut to 1 inch from the outer edge of the core and the measurement is repeated. Finally, the roll is cut to 1 / 8 inch from the outer edge of the core and the measurement is repeated. The blocking test is complete when three peak force values ​​are obtained from the full roll, the center of the roll, 1 inch from the core edge, and 1 / 8 inch from the core edge.

[0150] Suitable films generally have a maximum peak force obtained from a full roll of less than 12.00 N, e.g., less than about 10 N, less than about 7.5 N, less than about 5 N, less than about 4 N, or less than about 3 N. In embodiments, the films of the present disclosure have a maximum peak force obtained from a full roll of about 3 N or less, about 2.9 N or less, about 2.8 N or less, about 2.7 N or less, or about 2.6 N or less.

[0151] Dissolution and disintegration test MSTM-205 The films may be characterized or tested for dissolution and disintegration times according to methods known in the art, MonoSol Test Method 205 (MSTM 205), see, e.g., U.S. Patent No. 7,022,656. Equipment and materials: 600mL beaker Magnetic stirrer (Labline model number 1250 or equivalent) Magnetic stirring bar (5cm) Thermometer (0~100℃±1℃) Template, stainless steel (3.8cm x 3.2cm) Timer (0-300 seconds, second precision) Polaroid 35mm slide mount (or equivalent) MonoSol 35mm Slide Mount Holder (or equivalent) Distilled water

[0152] For each film tested, three specimens are cut from the film sample, with each specimen being a 3.8 cm by 3.2 cm specimen. If cut from a film web, the specimens should be cut from equally spaced areas of the web along the cross direction of the web. Each specimen is then analyzed using the following procedure.

[0153] Each specimen is locked into a separate 35 mm slide mount.

[0154] Fill a beaker with 500 mL of distilled water. Measure the temperature of the water with a thermometer and, if necessary, heat or cool the water to maintain a temperature of 20°C (approximately 68°F).

[0155] Record the height of the water column. Place a magnetic stirrer on the base of the holder. Place the beaker on the magnetic stirrer, add a magnetic stir bar to the beaker, turn the stirrer on, and adjust the stirring speed until a vortex develops that is approximately one-fifth the height of the water column. Record the depth of the vortex.

[0156] Secure the 35 mm slide to the alligator clamp of the 35 mm slide holder so that the long end of the slide mount is parallel to the water surface. The depth adjuster on the holder should be mounted so that when dropped, the end of the clip will be 0.6 cm below the water surface. One of the short sides of the slide mount should be next to the side of the beaker and the other directly above the center of the stir bar so that the film surface is perpendicular to the water flow.

[0157] In one motion, drop the clamped slide and clip into the water and start the timer. Disintegration occurs when the film breaks. Once all visible film has been released from the slide mount, lift the slide out of the water while continuing to monitor the solution for undissolved film fragments. Dissolution occurs when all film fragments are no longer visible and the solution becomes clear.

[0158] Results should include the following: complete sample identification, individual and average disintegration and dissolution times, and the water temperature in which the sample was tested.

[0159] The film disintegration time (I) and film dissolution time (I) can be corrected to a standard or reference film thickness using the exponential algorithm shown below in Equation 1 and Equation 2, respectively. I 修正された =I 測定された × (reference thickness / measured thickness) 1.93 [1] S 修正された =S 測定された × (reference thickness / measured thickness) 1.83 [2]

[0160] Water-soluble films according to the present disclosure may be better understood in view of the following examples, which are intended merely to illustrate the water-soluble films and are not meant to limit the scope thereof in any way. EXAMPLES

[0161] In the following examples, various polyvinyl alcohol (PVOH) resins are used. The PVOH resins are as follows: [Table 1]

[0162] Example 1 A water-soluble film of the present disclosure (Film 1) was prepared according to the method of the present disclosure, as set forth in Table 1 below. The ingredients were mixed in water, cast onto a casting surface having a GU value of 450 at 60°, and dried to a moisture content ranging from about 4% to 8%. The resulting water-soluble film had a thickness of 3.0±0.10 mils (or 76.2±2.5 μm) and was tested according to the test methods disclosed herein. Three additional commercially available films were tested according to the test methods disclosed herein and compared to the films of the present invention. The commercially available films are set forth in Table 1 below as Film C1, Film C2, and Film C3. Commercially available Film C2 is considered a "clear" film when compared to other commercially available films, and commercially available Film C3 is considered to have low transparency when compared to other commercially available films. [Table 2]

[0163] In Table 2, films having a matte to gloss static friction coefficient less than 0.6 are identified with a "*", 0.6 to 3 are identified with a "+", and greater than 3 are identified with a "-". In Table 2, films having a full roll blocking force value less than 3N are identified with a "*", 3N to 3.5N are identified with a "+", and greater than 3.5N are identified with a "-". In Table 2, films having an elongation at break greater than 350% are identified with a "*", 300% to 350% are identified with a "+", and less than 300% are identified with a "-". In Table 2, films having a tensile strength greater than 50 MPa are identified with a "*", 40 MPa to 50 MPa are identified with a "+", and less than 40 MPa are identified with a "-". In Table 2, films with dissolution times less than 60 seconds are identified with a "*", 60 to 300 seconds are identified with a "+", and greater than 300 seconds are identified with a "-". In Table 2, films with haze at 0% strain less than 20% are identified with a "*", 20 to 50% are identified with a "+", and greater than 50% are identified with a "-". In Table 2, films with haze at 100% strain less than 20% are identified with a "*", 20 to 40% are identified with a "+", and greater than 40% are identified with a "-". [Table 3]

[0164] Thus, Example 1 shows that the film of the present disclosure (Film 1) advantageously exhibits good matte-to-gloss static coefficient of friction, haze, blocking, elongation at break, and tensile strength while maintaining good dissolution properties. Example 1 further shows that the film according to the present disclosure prepared according to the method of the present disclosure exhibits improved coefficient of friction values ​​and clarity compared to a commercially available "clear" film (Film C2), and exhibits significantly improved clarity compared to a commercially available film prepared from a similar polyvinyl alcohol homopolymer resin without a significant increase in coefficient of friction value.

[0165] Example 2 The transparency of a commercially available "clear" film, Film C2 of Example 1, was compared to Film 1 of Example 1. As shown in Figure 2A, in the unstretched state, the film of the present disclosure, Film 1, exhibits significantly improved transparency over the commercially available "clear" film. As shown in Figure 2B, after each of Film C2 and Film 1 were formed into a pouch containing a pigmented composition, the film of the present disclosure maintained improved transparency over the commercially available film.

[0166] Thus, Example 2 exhibits advantageous clarity over commercially available "clear" films in both the unstretched and stretched states.

[0167] Example 3 To compare the properties of the water-soluble films of the present disclosure with films representative of commercially available films but prepared according to the methods of the present disclosure, water-soluble films having the formulations disclosed in Table 1 of Example 1 were prepared as follows: The ingredients were mixed in water, cast onto a casting surface having a GU value of 200 at 60°, and dried to a moisture content ranging from about 4% to 8%. The resulting water-soluble films had a thickness of 3.0±0.10 mils (or 76.2±2.5 μm) and were tested according to the test methods disclosed herein. The results are shown in Table 3 below.

[0168] In Table 3, films having a matte to gloss static friction coefficient less than 0.6 are identified with an "*", 0.6 to 3 are identified with a "+", and greater than 3 are identified with a "-". In Table 3, films having a haze at 0% strain less than 20% are identified with an "*", 20% to 50% are identified with a "+", and greater than 50% are identified with a "-". In Table 3, films having a haze at 100% strain less than 20% are identified with an "*", 20% to 40% are identified with a "+", and greater than 40% are identified with a "-". [Table 4]

[0169] Thus, Example 3 shows that the film of the present disclosure is superior to the commercially available film, even when both films are cast on a smooth surface. Furthermore, when compared to Example 1, Example 3 shows that the method of the present disclosure can reduce the haze of a film having a formulation representative of the commercially available film.

[0170] Example 4 A series of films were prepared and tested for matte vs. gloss static coefficient of friction, blocking force, elongation at break, tensile strength, dissolution time, and haze. The films were prepared according to the methods of the present disclosure, as set forth in Table 4 below. The ingredients were mixed in water, cast onto a casting surface having a GU value of 450 at 60°, and dried to a moisture content ranging from about 4% to 8%. The resulting water-soluble films had a thickness of 3.0±0.10 mils (or 76.2±2.5 μm) and were tested according to the test methods disclosed herein. [Table 5] [Table 6]

[0171] In Table 5, films having a matte to gloss static friction coefficient less than 0.6 are identified with "*", 0.6 to 3 are identified with "+", and greater than 3 are identified with "-". In Table 5, films having an elongation at break greater than 350% are identified with "*", 300% to 350% are identified with "+", and less than 300% are identified with "-". In Table 5, films having a tensile strength greater than 50 MPa are identified with "*", 40 MPa to 50 MPa are identified with "+", and less than 40 MPa are identified with "-". In Table 5, films having a haze at 0% strain less than 20% are identified with "*", 20% to 50% are identified with "+", and greater than 50% are identified with "-". In Table 5, films with haze at 100% strain less than 20% are identified with a "*", 20%-40% are identified with a "+", and greater than 40% are identified with a "-".

[0172] Thus, Example 4 shows that when films prepared according to the disclosed method were cast on high gloss surfaces, all films showed good haze (less than 40% at 100% strain) when containing up to 6 phr starch. Furthermore, casting on high gloss surfaces does not adversely affect the matte to gloss static coefficient of friction. Without wishing to be bound by theory, it is believed that in films 10-12, conformational changes in the polymer occurred upon casting and drying, which resulted in the higher indicated coefficient of friction values. It is further believed that the higher coefficient of friction values ​​could be mitigated by blending these polymers with polyvinyl alcohol homopolymers having viscosities in the range of 5-7 cP, 20-25 cP, or polyvinyl alcohol copolymers having anionic monomer units including methyl acrylate. Similarly, for films 6 and 8, it is believed that conformational changes in the polyvinyl alcohol polymers having anionic monomer units including maleate modification resulted in higher coefficient of friction, which could be mitigated by blending with a larger proportion of a second polymer, as in films 4 and 5.

[0173] Example 5 also shows that films prepared according to the methods of the present disclosure and including a blend of two polyvinyl alcohol homopolymers can advantageously exhibit a haze at 100% strain of less than 40%, a matte-to-gloss static coefficient of friction of less than 0.6, even when up to 6 phr of starch is included, and when the homopolymer constituting the majority of the blend (60-85 wt % of the blend) is used alone it provides a film having a matte-to-gloss coefficient of friction of greater than 1 (compare Films 1, 14, and 15 with Film 9), and the haze of the film can be adjusted to be less than 20% (about 13%) haze at 100% strain, even when it includes a resin that, when used alone, provides a film with a significantly higher haze value (about 30%, compare Film 1 with Film 13).

[0174] Example 5 further shows that a film prepared according to the method of the present disclosure and comprising a blend of a low-viscosity polyvinyl alcohol homopolymer and a polyvinyl alcohol copolymer comprising methyl acrylate monomer units exhibits a matte-to-gloss static friction coefficient of less than 6, and a haze of less than 40% at 100% strain and less than 30% for unstretched films. This result was unexpected, and instead such a film comprising a polyvinyl alcohol copolymer comprising methyl acrylate monomer units was expected to have a significantly higher haze value, considering that a commercially available film comprising this polyvinyl alcohol copolymer has a haze value of about 67% when unstretched. Indeed, by comparing the haze value of Film 2 with that of a commercially available film (Film C3), it can be seen that preparing a film according to the method of the present disclosure can contribute to an increase in the transparency of the film compared to commercial processes. Although Film 2 contained less starch than the commercial films (about 0.67 phr versus about 3.4 phr), increasing the amount of starch in Film 2 up to about 6 phr is not expected to significantly increase the haze value (expected to be less than about 40% at 100% strain, similar to Films 14 and 15), which is still substantially lower than the 67% haze in the unstretched state exhibited by the commercial films.

[0175] Finally, Example 5 shows that when a film prepared according to the method of the present disclosure included a blend of a first polyvinyl alcohol copolymer containing maleate monomer units and a second polyvinyl alcohol copolymer containing methyl acrylate monomer units, the film exhibited a matte-to-gloss static coefficient of friction of less than 6, and a haze of less than 30% at 100% strain and less than 20% for the unstretched film. This result was also unexpected in view of the expectation that such a film containing a polyvinyl alcohol copolymer containing methyl acrylate monomer units would have a significantly higher haze value in view of commercially available films containing this polyvinyl alcohol copolymer, which has a haze value of about 67% when unstretched.

[0176] 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.

[0177] 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.

[0178] 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. A water-soluble film comprising a water-soluble mixture, The aqueous mixture a polyvinyl alcohol resin comprising a first polyvinyl alcohol homopolymer having a viscosity in the range of about 16 cP to about 35 cP and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 15 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 60 wt % to about 85 wt %, based on the total weight of the polyvinyl alcohol resin, and the second polyvinyl alcohol homopolymer is present in an amount in the range of about 15 wt % to about 40 wt %, based on the total weight of the polyvinyl alcohol resin; starch present in an amount ranging from about 0.2 to about 6.0 parts by weight based on 100 parts of polyvinyl alcohol resin (PHR); a plasticizer present in an amount ranging from about 15 to about 35 PHR; The water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) ranging from about 0.05 to about 3.0, as determined according to the Coefficient of Friction Test, and a haze at 100% strain ranging from about 0.5% to about 40%, as determined according to the Haze Test.

2. 10. The water-soluble film of claim 1, wherein the first polyvinyl alcohol homopolymer is provided in an amount ranging from about 70% to about 80% by weight of the polyvinyl alcohol resin, with the remainder being the second polyvinyl alcohol homopolymer.

3. the first polyvinyl alcohol homopolymer has a viscosity ranging from about 18 cP to about 35 cP; the starch is provided in an amount ranging from about 0.2 PHR to about 5 PHR; the plasticizer is provided in an amount ranging from about 15 to about 30 PHR; The water-soluble film according to claim 1 or 2.

4. the first polyvinyl alcohol homopolymer has a viscosity in the range of about 20 cP to about 25 cP; the second polyvinyl alcohol homopolymer has a viscosity in the range of 5 cP to 7 cP; the starch is provided in an amount ranging from about 0.2 PHR to about 1 PHR; the plasticizer is provided in an amount ranging from about 18 to about 23 PHR; The water-soluble film according to claim 1 or 2.

5. The water-soluble film of claim 3, wherein the plasticizer comprises triethylene glycol, sorbitol, glycerol, diglycerin, ethylene glycol, diethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol of a molecular weight up to 400 Da, hexylene glycol, xylitol, 2-methyl-1,3-propanediol, ethanolamine, or a combination thereof.

6. 3. The water-soluble film according to claim 1, wherein the first polyvinyl alcohol homopolymer and / or the second polyvinyl alcohol homopolymer has a degree of hydrolysis ranging from about 70% to about 99%.

7. the water-soluble film is characterized by a matte-to-gloss static coefficient of friction (COF) ranging from about 0.05 to about 1.0, as determined according to the Coefficient of Friction Test; the water-soluble film is characterized by a gloss-to-gloss static coefficient of friction in the range of about 0.05 to about 0.60, as determined according to the Coefficient of Friction Test; the water-soluble film is characterized by a haze at 100% strain ranging from about 0.5% to about 30%, as determined according to the Haze Test; The water-soluble film according to claim 1 or 2.

8. The water-soluble film characterized by a matte-to-gloss static coefficient of friction (COF) in the range of about 0.05 to about 0.55, as determined according to the Coefficient of Friction Test; the water-soluble film is characterized by a gloss-to-gloss static coefficient of friction in the range of about 0.05 to about 0.30, as determined according to the Coefficient of Friction Test; the water-soluble film is characterized by a haze at 100% strain in the range of about 10% to about 20%, as determined according to the Haze Test; The water-soluble film according to claim 1 or 2.

9. the film is characterized by an elongation at break of at least 300% as determined by elongation testing; the film is characterized by a tensile strength of at least 40 MPa, as determined by tensile testing; the film is characterized by a blocking force for the entire roll of about 3 N or less as determined by a blocking test; The water-soluble film according to claim 1 or 2.

10. The film characterized by an elongation at break of at least 350% as determined by elongation testing; the film is characterized by a tensile strength of at least 50 MPa, as determined by tensile testing; the film is characterized by a blocking force for the whole roll ranging from about 0.5 N to about 3 N as determined by a blocking test; The water-soluble film according to claim 1 or 2.

11. A water-soluble film comprising a water-soluble mixture, the water-soluble mixture comprising: a polyvinyl alcohol resin comprising: (i) a first polyvinyl alcohol homopolymer having a viscosity in the range of about 20 cP to about 25 cP and a degree of hydrolysis of about 85% to about 95%, and (ii) a second polyvinyl alcohol homopolymer having a viscosity in the range of about 4 cP to about 8 cP and a degree of hydrolysis of about 85% to about 95%, wherein the first polyvinyl alcohol homopolymer constitutes about 65% to about 90% of the total polyvinyl alcohol polymer and the second polyvinyl alcohol homopolymer constitutes the remainder; starch present in an amount ranging from about 0.2 to about 1.0 parts by weight based on 100 parts polyvinyl alcohol resin (PHR); a plasticizer present in an amount ranging from about 18 to about 23 PHR, said plasticizer comprising sorbitol and glycerol; Including, The water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) ranging from about 0.05 to about 0.55, as determined according to the Coefficient of Friction Test, a haze at 100% strain ranging from about 0.5% to about 20%, as determined according to the Haze Test, an elongation at break of at least about 350%, as determined by the Elongation Test, and a blocking force for less than 3 full rolls, as determined by the Blocking Test.

12. 12. The water-soluble film of claim 1, 2, or 11, wherein the water-soluble film is substantially free of anti-blocking agents.

13. A water-soluble article comprising a water-soluble film, The water-soluble film is a polyvinyl alcohol resin comprising a first polyvinyl alcohol homopolymer having a viscosity in the range of about 16 cP to about 35 cP and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 7 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 60 wt % to about 85 wt %, based on the total weight of the polyvinyl alcohol resin, and the second polyvinyl alcohol homopolymer is present in an amount in the range of about 15 wt % to about 40 wt %, based on the total weight of the polyvinyl alcohol resin; starch present in an amount ranging from about 0.2 to about 6.0 parts by weight based on 100 parts of polyvinyl alcohol resin (PHR); a plasticizer present in an amount ranging from about 15 to about 35 PHR; The water-soluble article, wherein the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) ranging from about 0.05 to about 3.0, as determined according to the Coefficient of Friction Test, and a haze at 100% strain ranging from about 0.5% to about 40%, as determined according to the Haze Test.

14. 1. A water-soluble unit dose article comprising at least one compartment and, optionally, a composition contained within said compartment, said unit dose article comprising a water-soluble film; The water-soluble film is a polyvinyl alcohol resin comprising a first polyvinyl alcohol homopolymer having a viscosity in the range of about 16 cP to about 35 cP and a second polyvinyl alcohol homopolymer having a viscosity in the range of about 5 cP to about 7 cP, wherein the first polyvinyl alcohol homopolymer is present in an amount in the range of about 60 wt % to about 85 wt %, based on the total weight of the polyvinyl alcohol resin, and the second polyvinyl alcohol homopolymer is present in an amount in the range of about 15 wt % to about 40 wt %, based on the total weight of the polyvinyl alcohol resin; starch present in an amount ranging from about 0.2 to about 6.0 parts by weight based on 100 parts of polyvinyl alcohol resin (PHR); a plasticizer present in an amount ranging from about 15 to about 35 PHR; The water-soluble unit dose article, wherein the water-soluble film is characterized by a matte-to-gloss coefficient of friction (COF) ranging from about 0.05 to about 3.0, as determined according to the Coefficient of Friction Test, and a haze at 100% strain ranging from about 0.5% to about 40%, as determined according to the Haze Test.

15. 12. A method for preparing a water-soluble film according to claim 1, 2, or 11, said method comprising:

1. A method comprising: casting a mixture comprising a first polyvinyl alcohol homopolymer onto a surface, wherein the surface is characterized by a gloss unit (GU) value at a 60° angle of at least about 150.

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