Biobased water-soluble films

Abstract

Disclosed herein is a water-soluble film comprising pullulan, carrageenan, a plasticizer, and a crosslinking agent, wherein the pullulan comprises from about 50 wt.% to about 75 wt.% of the film, and the crosslinking agent, when present, comprises from about 0.001 wt.% to about 5.0 wt.% of the film, based on the total weight of the film.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 615,594 (filed December 28, 2023) and U.S. Provisional Application No. 63 / 673,502 (filed July 19, 2024), each of which is incorporated herein by reference in its entirety. Technical Field

[0003] This disclosure generally relates to water-soluble films and related articles. More specifically, this disclosure relates to water-soluble films comprising a plasticizing mixture of pullulan and carrageenan, and a crosslinking agent. Background Technology

[0004] Water-soluble polymer films are commonly used as packaging materials to simplify the dispensing, pouring, dissolving, and dispensing of materials to be delivered. Consumers can add the pouched composition directly to mixing containers such as buckets, sinks, or washing machines. Advantageously, this provides precise dispensing while eliminating the need for consumers to measure the composition. Additionally, water-soluble polymer film packaging can prevent the consumer from handling potentially strong chemicals, thus protecting them from exposure to irritating chemicals. Pouched compositions also reduce the hassle associated with dispensing similar compositions from containers, such as pouring compositions from bottles. In summary, soluble, pre-measured polymer film pouches offer convenience and safety for consumers in a variety of applications.

[0005] Water-soluble membranes containing pullulan or carrageenan, or blends of pullulan and carrageenan, are known. For example, WO 2004 / 041926A1 describes membranes containing pullulan and carrageenan, wherein the membranes contain little or no cross-linking agents. In this regard, WO 2004 / 041926A1 further describes that minerals (such as calcium) that can cross-link water-soluble polysaccharides to form cross-linked structures should be excluded from the water-soluble membrane to maintain water solubility. Summary of the Invention

[0006] One aspect of this disclosure provides a water-soluble membrane comprising pullulan, carrageenan, a plasticizer, and a crosslinking agent.

[0007] Another aspect of this disclosure provides a water-soluble membrane comprising pullulan, carrageenan, and a divalent or monovalent metal (e.g., as a crosslinking agent), wherein the amount of ι-carrageenan, λ-carrageenan, κ-carrageenan, or combinations thereof accounts for at least about 95% of the carrageenan present in the membrane.

[0008] Another aspect of this disclosure provides a water-soluble article in the form of a small package containing a sealed compartment, the article comprising a water-soluble membrane according to this disclosure sealed to a second water-soluble membrane.

[0009] Another aspect of this disclosure provides a water-soluble membrane comprising pullulan, carrageenan, and a crosslinking agent, wherein the weight ratio of carrageenan to pullulan ranges from about 1:1.8 to about 1:21, or about 1:7.5 to about 1:21, or about 1:36 to about 1:21, or about 1:7 to about 1:12.

[0010] Another aspect of this disclosure provides methods for manufacturing and using water-soluble membranes according to this disclosure, as well as articles made from water-soluble membranes according to this disclosure.

[0011] Another aspect of this disclosure provides a water-soluble membrane comprising pullulan, carrageenan, and a plasticizer, wherein, based on the total weight of the membrane, the carrageenan is present in an amount ranging from about 1 wt.% to about 25 wt.%, or about 1 wt.% to about 15 wt.%, or about 1 wt.% to about 10 wt.%, or about 5 wt.% to about 8 wt.%, and the plasticizer is present in an amount of at least about 20 PHR, or at least about 30 PHR, or at least about 40 PHR. Based on the total weight of the membrane, the total amount of pullulan and carrageenan in the membrane may be at least 50 wt.%, or at least 60 wt.%, or at least 70 wt.%.

[0012] Another aspect of this disclosure provides a water-soluble membrane comprising pullulan, carrageenan, and polyoxyethylene.

[0013] Another aspect of this disclosure provides an edible water-soluble film and edible articles made therefrom.

[0014] For the compositions and methods described herein, optional features are selected from the various aspects, embodiments, claims, and examples provided herein, including but not limited to components and their compositional ranges. For example, features of the embodiments and formulation methods described in Examples 1 to 4 may be combined with any additional features provided in the specification and claims herein.

[0015] Further aspects and advantages will become apparent to those skilled in the art upon review of the following detailed description. While various forms of embodiments are permissible with respect to the films and articles of this disclosure, the following description includes specific examples, wherein this disclosure is to be understood as illustrative and not intended to limit the invention to the specific embodiments described herein.

[0016] Unless otherwise stated, consideration is given to the film, bag, and related methods of use, including embodiments that include any combination of one or more optional elements, features, and steps further described below. Attached Figure Description

[0017] To further facilitate understanding of the present invention, two accompanying drawings are attached.

[0018] Figure 1 It is a bar graph showing the tensile strength of the plasticized film of this disclosure, which contains pullulan and carrageenan and is cross-linked with different concentrations of salts.

[0019] Figure 2 It is a bar graph of the fracture strain of the plasticized film of this disclosure, which contains pullulan and carrageenan and is cross-linked with different concentrations of salts. Detailed Implementation

[0020] Water-soluble polymer films are commonly used as packaging materials to simplify the dispensing, pouring, dissolving, and dispensing of materials to be delivered. Consumers can add the pouched composition directly to mixing containers such as buckets, sinks, or washing machines. Advantageously, this provides precise dispensing while eliminating the need for consumers to measure the composition. Additionally, water-soluble polymer film packaging can prevent the consumer from handling potentially strong chemicals, thus protecting them from exposure to irritating chemicals. Pouched compositions also reduce the hassle associated with dispensing similar compositions from containers, such as pouring compositions from bottles. In summary, soluble, pre-measured polymer film pouches offer convenience and safety for consumers in a variety of applications.

[0021] By using raw materials from renewable sources, the membranes described herein can be designed to have a reduced carbon footprint. Conventional water-soluble membranes typically comprise petrochemical-derived resins, resulting in a low renewable carbon index (RCI). In contrast, bio-based polymers have a much higher renewable carbon index, but their application is limited because these bio-based polymers can be inherently rigid and immiscible or incompatible with other components in conventional water-soluble membranes. The use of bio-based polymers in water-soluble membranes is generally limited because of the need to maintain mechanical properties suitable for conversion into and use as packaging, such as high levels of elongation, deformation recovery, and strength properties.

[0022] As used herein, "bio-based" means a material in which at least a portion is derived from living or formerly living matter, such as raw materials from plants and other renewable agricultural, marine, and forestry materials. Bio-based materials can be naturally occurring or derived from naturally occurring materials. Bio-based polymers include, but are not limited to, polysaccharides (including but not limited to pullulan, carrageenan, alginate, cellulose, starch, dextrin, maltodextrin, xanthan gum, guar gum, and sophora bean gum) and proteins and protein derivatives (e.g., gelatin, collagen, and keratin). Bio-based molecules include, but are not limited to, sugar alcohols (including but not limited to sorbitol, xylitol, erythritol, mannitol, and isomaltitol) and other polyols (including but not limited to glycerol). Based on the total weight of the film-forming resin, the film-forming resin of the water-soluble membrane of this disclosure may contain at least 95 wt.%, at least 96 wt.%, at least 97 wt.%, at least 98 wt.%, at least 99 wt.%, or 100 wt.% bio-based material. Based on the total weight of the membrane, the water-soluble membrane of this disclosure may contain at least 95 wt%, at least 96 wt.%, at least 97 wt.%, at least 98 wt.%, at least 99 wt.%, or 100 wt.% of bio-based material.

[0023] The Renewable Carbon Index (RCI) refers to the fraction (or percentage) of carbon atoms in the average structure of materials derived from sources other than petroleum or natural gas. Typically and desirablely, when the components of a water-soluble membrane are made from natural materials or produced sustainably, the RCI will generally exceed 0.75 or 75%, due to the use of materials found in nature or from sources derived from sustainable sources such as plants, fungi, or algae; products of bacterial fermentation processes; or processing products of plant, fungal, or algae-derived biomass. A major challenge in formulating water-soluble membranes with a desiredly high RCI is selecting several suitable materials that are both economically feasible and deliver performance as good as or better than conventional products. The Renewable Carbon Index of the water-soluble membranes disclosed herein can be at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, or 100%.

[0024] Membranes containing pullulan (a bio-based resin) as the primary or sole film-forming resin can exhibit good flexibility and rapid water solubility. However, the high water solubility of pullulan limits its use in water-soluble membrane applications. For example, when used to package compositions with a water content (e.g., 2-3 wt.% or higher), such packets or bags may fail prematurely due to the partial dissolution of the membrane by the water in the composition, or when placed in water, as they may not retain the liquid contents for a sufficient period. Generally, compositions packaged in water-soluble films can have a water content of up to about 15%; compositions with a water content greater than about 15% may begin to dissolve the water-soluble film.

[0025] It has been found that membranes comprising a blend of pullulan and carrageenan as film-forming resins, and a specific amount of crosslinking agent as described herein, according to this disclosure, can exhibit an advantageous combination of membrane properties. Specifically, incorporating carrageenan into pullulan-based membranes provides membranes with water-soluble and mechanical properties suitable for water-soluble membrane applications, including but not limited to membranes for water-soluble packaging.

[0026] One aspect of this disclosure provides a water-soluble membrane comprising a film-forming resin, a plasticizer, and a crosslinking agent, wherein the film-forming resin comprises a mixture of pullulan and carrageenan, wherein pullulan is present in the membrane in an amount ranging from about 50 wt.% to about 75 wt.% based on the total weight of the membrane; wherein carrageenan is present in the membrane in an amount ranging from about 1 wt.% to about 25 wt.%, about 1 wt.% to about 15 wt.%, about 1 wt.% to about 10 wt.%, or about 5 wt.% to about 8 wt.% based on the total weight of the membrane; and wherein the crosslinking agent is present in an amount ranging from about 0.001 wt.% to about 5.0 wt.%, 0.01 wt.% to about 1.0 wt.%, about 0.02 wt.% to about 0.5 wt.%, about 0.03 wt.% to about 0.3 wt.%, or about 0.05 wt.% to about 0.2 wt.% based on the total weight of the membrane. The crosslinking agent is present in the membrane in wt.% amounts. The crosslinking agent may contain metal ions. Optionally, the crosslinking agent may contain monovalent ions. Optionally, the crosslinking agent may contain divalent ions. Optionally, the crosslinking agent may contain trivalent ions. Optionally, the crosslinking agent contains calcium ions. Optionally, the carrageenan may contain κ-carrageenan. Optionally, the carrageenan may contain ι-carrageenan. Optionally, the carrageenan may contain λ-carrageenan. Optionally, the carrageenan may contain a mixture of κ-carrageenan and ι-carrageenan, or a mixture of κ-carrageenan and λ-carrageenan, or a mixture of ι-carrageenan and λ-carrageenan. Optionally, the carrageenan may contain a mixture of κ-carrageenan, ι-carrageenan, and λ-carrageenan. In one embodiment, the carrageenan is present in the membrane in an amount ranging from about 1 wt.% to about 15 wt.%; the carrageenan comprises at least one selected from ι-carrageenan, λ-carrageenan, and κ-carrageenan; the weight ratio of carrageenan to pullulan ranges from 1:1.8 to about 1:21; the crosslinking agent comprises calcium ions, magnesium ions, potassium ions, or combinations thereof; the plasticizer is selected from polyols, sugar alcohols, and mixtures thereof; and the plasticizer is present in an amount ranging from about 20 PHR to about 50 PHR. In another embodiment, the carrageenan comprises ι-carrageenan, and the ι-carrageenan accounts for at least about 95 wt.% of the carrageenan present in the membrane; the weight ratio of carrageenan to pullulan ranges from about 1:7 to about 1:12; and the crosslinking agent comprises potassium ions.

[0027] Another aspect of this disclosure provides a water-soluble membrane comprising a film-forming resin, a plasticizer, and a crosslinking agent, wherein the film-forming resin comprises pullulan and a mixture of at least one of ι-carrageenan, λ-carrageenan, and κ-carrageenan, wherein the combined amount of ι-carrageenan, λ-carrageenan, and κ-carrageenan accounts for at least about 95 wt.% of the carrageenan present in the membrane, and pullulan is present in the membrane in an amount ranging from about 50 wt.% to about 75 wt.% based on the total weight of the membrane, and wherein the crosslinking agent comprises divalent or monovalent metal ions, and is present in the membrane in an amount ranging from about 0.001 wt.% to about 5.0 wt.%, 0.01 wt.% to about 1.0 wt.%, about 0.02 wt.% to about 0.5 wt.%, about 0.03 wt.% to about 0.3 wt.%, or about 0.05 wt.% to about 0.2 wt.% based on the total weight of the membrane. In an embodiment, based on the total weight of the membrane, the combined amount of ι-carrageenan, λ-carrageenan and κ-carrageenan is present in the membrane in an amount ranging from about 1 wt.% to about 25 wt.%, about 1 wt.% to about 15 wt.%, about 1 wt.% to about 10 wt.%, or about 5 wt.% to about 8 wt.%.

[0028] Another aspect of this disclosure provides a water-soluble membrane comprising a film-forming resin and a polyoxyethylene, wherein the film-forming resin comprises a mixture of pullulan and carrageenan. Optionally, the polyoxyethylene may comprise polyethylene oxide. Optionally, based on the total weight of the membrane, the polyoxyethylene may be present in an amount ranging from about 0.1 wt.% to about 5 wt.%, or about 0.5 wt.% to about 5 wt.%, or about 2 wt.% to about 4 wt.%. Optionally, the weight-average molecular weight of the polyoxyethylene ranges from about 500 Da to about 20,000 Da, or about 1,000 Da to about 10,000 Da, or about 2,000 Da to about 5,000 Da.

[0029] Another aspect of this disclosure provides a water-soluble article in the form of a small package containing a sealed compartment, the article comprising a first water-soluble membrane as a membrane according to this disclosure, and wherein the first water-soluble membrane is sealed to a second water-soluble membrane to form the sealed compartment.

[0030] Another aspect of this disclosure provides a water-soluble membrane comprising a mixture of pullulan and carrageenan, a plasticizer, and a crosslinking agent, wherein, based on the total weight of the membrane, the pullulan and carrageenan mixture comprises at least 50 wt.%, the weight ratio of carrageenan to pullulan ranges from about 1:1.8 to about 1:21, or about 1:7.5 to about 1:21, or about 1:36 to about 1:21, or about 1:5 to about 1:40, or about 1:5 to about 1:30, or about 1:5 to about 1:20, or about 1:6 to about 1:15, or about 1:7 to about 1:12, and based on the total weight of the membrane, the crosslinking agent ranges from about 0.001 wt.% to about 5.0 wt.%, or about 0.01 wt.% to about 1.0 wt.%, or about 0.02 wt.% to about 0.5 wt.%, or about 0.03 wt.% to about 0.3 wt.%. The membrane is present in amounts of wt.%, or about 0.05 wt.% to about 0.2 wt.%.

[0031] As used herein, “comprising” means the different components, ingredients, or steps that may be used in common in practicing this disclosure. Accordingly, the term “comprising” covers the more restrictive terms “generally composed of” and “composed of”. The compositions of the present invention may comprise, consist of, or be composed of any of the necessary and optional elements disclosed herein. For example, a thermoformed package may consist “generally composed of” the film described herein to utilize its thermoforming properties, while also including a non-thermoformed film (e.g., a cap portion). The invention illustratively disclosed herein can be suitably practiced in the absence of any elements or steps not specifically disclosed herein.

[0032] The polymer industry (Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc., 1967, Vol. 6, p. 764) defines a membrane (such as a membrane made according to this disclosure) as “a molded plastic with a relatively thin width and a maximum thickness of 0.010 in”.

[0033] Water-soluble membranes can be self-supporting membranes, i.e., membranes that do not require a substrate to maintain the integrity of the membrane structure, and optionally can be stand-alone membranes, i.e., membranes that do not include such a substrate. A uniform membrane is one with almost no breaks, tears, pores, bubbles, or streaks.

[0034] Unless otherwise stated, all percentages, parts and ratios are based on the total dry weight of the formed film composition, and all measurements were performed at approximately 25°C. Unless otherwise stated, all such weights relating to the listed ingredients are based on activity levels and therefore do not include carriers or byproducts that may be present in commercially available materials.

[0035] All ranges described herein include all possible subsets of ranges and any combination of such subsets. By default, a range includes the stated endpoint value unless otherwise stated. In the case of ranges of values ​​provided, it should be understood that each intermediate value between the upper and lower limits of the range and any other stated value or intermediate value within the stated range is covered within this disclosure. The upper and lower limits of these smaller ranges may be independently included within the smaller range and are also covered within this disclosure, subject to any expressly excluded limits within the stated range. Where a stated range includes one or both limits, it is also contemplated that ranges excluding any one or both of those included limits are part of this disclosure.

[0036] The dimensions and values ​​disclosed herein should not be construed as strictly limited to the exact numerical values ​​listed. Rather, unless otherwise stated, each such dimension is intended to include both the listed value and a functionally equivalent range around the value. For example, a dimension disclosed as “15 mm” is intended to include “about 15 mm”, and “about 15 mm” can include a range from 14.5 mm to 15.4 mm, for example, through numerical rounding.

[0037] As used herein, and unless otherwise specified, the terms “wt.%” and “wt%” are intended to refer to the composition of the identified element in “dry” (non-aqueous) parts by weight of the whole film (where applicable) or in parts by weight of the whole composition encapsulated in a bag (where applicable).

[0038] As used herein, and unless otherwise specified, the terms “PHR” or “phr” are intended to refer to the composition of each hundred parts of the element identified in the water-soluble polymer or resin in the water-soluble membrane.

[0039] The membrane can be manufactured by any suitable method, including solution casting. The membrane can be used to form containers (bags) by any suitable method, including vertical forming, fill and seal (VFFS) or thermoforming. The membrane can be sealed by any suitable method, including, for example, solvent sealing or heat sealing of the membrane layer, such as around the perimeter of a container. For example, the bag can be used to dispense material to be delivered into a large volume of water.

[0040] Unless otherwise stated, the preparation and use of films, articles, bags and related methods are envisioned to include examples, which include any combination of one or more of the elements, features and steps further described below (including the elements, features and steps shown in the examples and figures).

[0041] As used herein, the terms packet and bag should be considered interchangeable. In some embodiments, the terms packet and bag are used to refer, respectively, to a container made of a membrane and a sealed container preferably having a material sealed therein, for example, in the form of a measured dose delivery system. A sealed bag can be made by any suitable method, including processes and features such as heat sealing, solvent welding, and adhesive sealing (e.g., using water-soluble adhesives).

[0042] Water-soluble membrane

[0043] The membranes and related bags described herein comprise plasticized water-soluble membranes. The water-soluble membranes comprise film-forming resins, which include pullulan and carrageenan.

[0044] Water-soluble membranes can have any suitable thickness, and membrane thicknesses of about 76 micrometers (µm) or about 88 µm are typical and particularly considered. For example, membrane thicknesses can range from about 5 µm to about 200 µm, or from about 20 µm to about 100 µm, or from about 40 µm to about 90 µm, or from about 50 µm to about 80 µm, or from about 60 µm to about 65 µm, such as about 65 µm, 76 µm, or 88 µm, or any value in between or a range defined by such values.

[0045] Based on the total weight of the membrane, the membrane may include any suitable amount of resin content; for example, ranging from about 1 wt.% to about 99 wt.% or from about 35 wt% to about 90 wt%, or ranging from about 55% to about 95%, or from about 60% to 90%, or from about 65% to about 85% or at least 50%.

[0046] pullulan

[0047] Pullulan is a polysaccharide containing repeating maltotriose units and is typically produced from starch by a fungus, *Aureobasidium pullulans*. Films containing pullulan as the primary or sole film-forming resin are commonly used in edible applications, including edible films and coatings, because these films typically exhibit high water solubility, flexibility, transparency, and low oxygen permeability. Pullulan is commercially available from a variety of sources.

[0048] The water-soluble membrane disclosed herein may include pullulan as a primary film-forming resin, i.e., pullulan may constitute at least 50% of the film-forming resin content of the membrane. Based on the total weight of the membrane, pullulan may be present in the membrane in an amount of at least about 50% by weight, or ranging from about 50 wt.% to about 75%, or about 55 wt.% to about 70 wt.%, or about 60 wt.% to about 70 wt.%, 60 wt.% to about 65 wt.%, or about 65 wt.% to about 70 wt.%. If the pullulan content is less than 50 wt.%, the water solubility and / or flexibility of the membrane may be insufficient for many water-soluble membrane applications, such as in packaged contents intended for release during a cold wash cycle. If the pullulan content is greater than 75 wt.%, the membrane may have low mechanical strength, or the bag containing the membrane may be prone to failure, such as premature release of the bag contents upon immersion in water.

[0049] Carrageenan

[0050] Carrageenan is a naturally occurring family of polysaccharides composed of sulfated disaccharide repeating units of galactose and 3,6-anhydrogalactose. Carrageenan is typically extracted from red algae. Several types of carrageenan are known, distinguished in part by their sulfate group content. For example, κ-carrageenan, ι-carrageenan, and λ-carrageenan typically contain one, two, and three sulfate groups per disaccharide repeating unit, respectively. Some properties of carrageenan depend on the sulfate group content. For instance, κ-carrageenan usually forms a rigid gel upon crosslinking, ι-carrageenan usually forms a soft gel upon crosslinking, and λ-carrageenan is generally soluble and does not readily form a gel. Carrageenan is commercially available, for example, from CP Kelco.

[0051] Based on the total weight of the membrane, the water-soluble membrane may contain up to about 15 wt.% or 25 wt.% carrageenan, for example, about 1 wt.% to about 25 wt.%, about 1 wt.% to about 15 wt.%, or about 1 wt.% to about 10 wt.%, or about 3 wt.% to about 10 wt.%, or about 5 wt.% to about 10 wt.%, or about 6 wt.%, or about 7 wt.%, or about 8 wt.%, or about 9 wt.%, or a range defined by such values. If the amount of carrageenan exceeds 10 wt.%, 15 wt.%, or 25 wt.%, the mechanical properties of the membrane (such as elongation at break) may be affected. If the amount of carrageenan is less than 1 wt.%, the benefits to membrane properties from the addition of carrageenan may be limited, including but not limited to high mechanical strength under high humidity conditions.

[0052] The weight ratio of carrageenan to pullulan in water-soluble membranes can range from about 1:1.8 to about 1:21, or about 1:7.5 to about 1:21, or about 1:36 to about 1:21, or about 1:5 to about 1:40, or about 1:5 to about 1:30, or about 1:5 to about 1:20, or about 1:6 to about 1:15, or about 1:7 to about 1:12. Membranes with too much carrageenan may have insufficient water solubility, while membranes with too much pullulan may exhibit low mechanical strength, especially under high humidity conditions.

[0053] Other resins

[0054] The water-soluble membrane may further comprise one or more additional bio-based or naturally occurring polymers, including but not limited to guar gum, gum arabic, xanthan gum, locust bean gum, starch, modified starch, cellulose, cellulose ethers, cellulose esters, cellulose amides, methylcellulose, carboxymethyl cellulose and its salts, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, polyamino acids, gelatin, dextrin, maltodextrin, pea protein, casein, copolymers of the foregoing, and combinations thereof. Such polymers are commercially available from various sources. When present in the membrane, one or more additional bio-based or naturally occurring polymers may be present in amounts up to about 50 wt.%, or up to about 40 wt.%, or up to about 30 wt.%, or about 20 wt.%, or up to about 10 wt.%, or up to about 5 wt.%, based on the total weight of the membrane.

[0055] The water-soluble membrane may further comprise one or more synthetic (i.e., non-naturally occurring) polymers, including but not limited to polyvinyl alcohol (PVOH) homopolymers, PVOH copolymers, polyacrylates, polymethacrylates, polyacrylic acid and its salts, polymethacrylates and their salts, water-soluble acrylate copolymers, polyvinylpyrrolidone, and polyethyleneimine. Other synthetic water-soluble polymers may include polyoxyethylene (e.g., polyethylene oxide, also known as polyethylene glycol (PEG)), polyacrylamide, polyvinyl acetate, polycarboxylic acids and their salts, polyamides, copolymers of any of the foregoing, and combinations of any of the foregoing. Such synthetic polymers are commercially available from various sources. When present in the membrane, one or more synthetic polymers may be present in amounts of up to about 20 wt.%, up to about 10 wt.%, or up to about 5 wt.%, based on the total weight of the membrane.

[0056] Water-soluble membranes may include bio-based polyvinyl alcohol. Bio-based polyvinyl alcohol includes polyvinyl alcohol containing at least a portion of the carbon atoms of the polyvinyl alcohol derived from biogenic material. Specifically, bio-based polyvinyl alcohol may include polyvinyl alcohol produced by hydrolyzing or saponifying a blend of bio-based polyvinyl acetate or polyvinyl acetate comprising bio-based polyvinyl acetate. Furthermore, bio-based polyvinyl acetate may include polyvinyl acetate produced by polymerizing a blend of bio-based vinyl acetate or vinyl acetate comprising bio-based vinyl acetate. Generally, bio-based vinyl acetate includes vinyl acetate containing at least a portion of the carbon atoms of the vinyl acetate derived from biogenic material. For example, vinyl acetate can be obtained by a gas-phase reaction of ethylene, acetic acid, and oxygen; bio-based vinyl acetate may refer to vinyl acetate containing at least a portion of ethylene and / or acetic acid derived from biogenic material. For example, bio-based vinyl acetate includes vinyl acetate obtained by reacting ethylene, acetic acid, and oxygen, wherein at least a portion of the ethylene and / or at least a portion of the acetic acid is bio-based. Therefore, bio-based polyvinyl alcohol includes polyvinyl alcohol, which contains a portion of the carbon in polyvinyl alcohol derived from bio-based ethylene and / or bio-based acetic acid.

[0057] Plants that can serve as sources of bio-based ethylene and / or bio-based acetic acid include, but are not limited to, potatoes, sweet potatoes, sugar beets, rice, wheat, palm oil, algae, corn, sugarcane, sorghum, and cassava. Similarly, bio-based acetic acid can also be produced via the bioethanol route.

[0058] Bio-based polyvinyl alcohol is characterized by its carbon-14 ( 14 C) Content. Generally speaking, relative to petroleum-derived resources... 14 The abundance of carbon, and the resources derived from biomass. 14 The abundance of C (i.e., 14 The percentage of carbon in the total carbon content is higher. Specifically, it is higher compared to petroleum-derived ethylene and acetic acid. 14 The abundance of C, bio-based ethylene and acetic acid 14 The abundance of C is typically higher, and consequently, relative to fully petroleum-derived polyvinyl alcohol. 14 The abundance of C, bio-based polyvinyl alcohol 14 C abundance is usually higher. Therefore, in polymers (such as polyvinyl alcohol resins) 14 The abundance of carbon (C) can serve as an indicator of the bio-based content of polymers. (Materials) 14 The C content can be measured by known methods (e.g., by mass spectrometry).

[0059] The membranes disclosed herein may include bio-based polyvinyl alcohol, as described in U.S. Patent Application Publication No. 2023 / 0257491A1, U.S. Patent Application Publication No. 2023 / 0070770A1, and International Patent Application Publication WO 2022 / 034906A1, the entire contents of which are hereby incorporated by reference. The polyvinyl alcohol resin comprising the membranes of this disclosure may comprise petroleum-derived polyvinyl alcohol only, or bio-based polyvinyl alcohol only, or a blend of petroleum-derived polyvinyl alcohol and bio-based polyvinyl alcohol. For membranes comprising blends of petroleum-derived (i.e., non-bio-based) polyvinyl alcohol and bio-based polyvinyl alcohol, the ratio (by weight) of bio-based polyvinyl alcohol to non-bio-based polyvinyl alcohol is not particularly limited, and may, for example, range from about 99:1 to about 1:99, or about 95:5 to about 5:99, or about 80:20 to about 20:80, or about 70:30 to about 30:70, or about 60:40 to about 40:60.

[0060] plasticizer

[0061] Plasticizers are liquids, solids, or semi-solids added to materials (typically resins or elastomers) to make them softer, more flexible (by lowering the glass transition temperature of the polymer), or easier to process. Alternatively, polymers can be internally plasticized by chemically modifying the polymer or monomers. Additionally or alternatively, polymers can be externally plasticized by adding suitable plasticizers. Water is considered a very effective plasticizer for many polymers, including but not limited to water-soluble polymers; however, the volatility of water limits its practicality because polymer films typically need to have at least some resistance (toughness) to a variety of environmental conditions, including both low and high relative humidity.

[0062] The water-soluble film disclosed herein further comprises one or more plasticizers. Plasticizers may include, but are not limited to, sugar alcohols, polyols, and combinations thereof. For example, plasticizers may comprise glycerol, diglycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polypropylene glycol, polyethylene glycol with a molecular weight of up to 400 Da, hexanediol, neopentyl glycol, trimethylolpropane, polyether polyols, polyether glycols, polyether triols, xylitol, 2-methyl-1,3-propanediol (MPD; MPDiol®), ethanolamine, glycerol propylene oxide polymers (e.g., Voranol, available from The Dow Chemical Company). TM (or mixtures thereof). Renewable or bio-based plasticizers were considered. Sorbitol, glycerol, and combinations thereof were specifically considered as plasticizers.

[0063] Based on the total film weight, the total amount of non-aqueous plasticizer can range from about 10 wt.% to about 45 wt.%, or about 15 wt.% to about 35 wt.%, or about 20 wt.% to about 30 wt.%, or about 20 wt.% to about 45 wt.%, for example, about 25 wt.%. The amount of plasticizer can also be characterized by PHR, and the total amount of non-aqueous plasticizer can be at least 20 PHR, or at least about 30 PHR, or at least about 40 PHR, or at most about 50 PHR, or at most about 40 PHR, or range from about 10 PHR to about 75 PHR, or about 15 PHR to about 60 PHR, or about 20 PHR to about 50 PHR, or about 25 PHR to about 45 PHR, or about 20 PHR to about 40 PHR, or about 30 PHR to about 40 PHR. In one specific embodiment, the specific amount of plasticizer may be selected based on factors described herein, including the desired membrane flexibility and conversion characteristics of the water-soluble membrane. At low plasticizer levels, the membrane may become brittle, difficult to process, or prone to breakage. At high plasticizer levels, the membrane may be too soft, too weak, or difficult to process for the desired application.

[0064] Crosslinking agent

[0065] In a general sense, a polymer crosslinking agent is an additive that can form covalent or non-covalent bonds (i.e., crosslinking) between polymer chains. By adding a crosslinking agent to incorporate crosslinking into one or more polymers comprising a polymer-based membrane, the effective polymer molecular weight can be increased, and membrane properties, including but not limited to mechanical properties and solubility, can be affected. Some carrageenans are known to form crosslinked gels when a sufficient amount of one or more cations are added as crosslinking agents, including but not limited to ammonium, sodium, potassium, or calcium ions. The properties of crosslinked gels formed by adding cationic crosslinking agents to carrageenan depend on the type of carrageenan and the choice of crosslinking agent. For example, κ-carrageenan forms a stronger gel with potassium ions than with calcium ions, and κ-carrageenan gels tend to be more brittle; ι-carrageenan forms a stronger gel with calcium ions than with potassium ions, and ι-carrageenan gels tend to be soft and elastic; and λ-carrageenan typically does not form crosslinked gels.

[0066] The water-soluble membrane of this disclosure may further comprise a crosslinking agent. The crosslinking agent may comprise one or more metal cations. The crosslinking agent may comprise one or more monovalent or divalent cations. Cations that promote the gelation of one or more carrageenan ions, including but not limited to ammonium ions, sodium ions, potassium ions, magnesium ions, and calcium ions, are considered crosslinking agents. Specifically, monovalent metal ions are considered crosslinking agents; divalent metal ions are considered crosslinking agents; calcium ions are particularly considered. The crosslinking agent can be provided to the water-soluble membrane, for example, by including a salt containing the crosslinking agent in the preparation of the water-soluble membrane, such as by adding the salt to the resin solution in which the water-soluble membrane is cast. The metal ions may be provided in the form of a salt containing counter anions, said counter anions comprising acetate ions, chloride ions, ascorbate ions, phosphate ions, or combinations thereof. Calcium chloride is particularly considered as a source of crosslinking agents. Potassium acetate is particularly considered as a source of crosslinking agents. Combinations of κ-carrageenan with potassium or calcium crosslinking agents, such as calcium crosslinking agents or potassium salt crosslinking agents, are considered. Combinations of ι-carrageenan with potassium or calcium crosslinking agents, such as calcium crosslinking agents or potassium salt crosslinking agents, are considered. Combinations of λ carrageenan with potassium or calcium crosslinking agents, such as calcium crosslinking agents or potassium salt crosslinking agents, were considered. Combinations of mixtures of more than one type of carrageenan with potassium or calcium crosslinking agents, such as calcium crosslinking agents or potassium salt crosslinking agents, were also considered. Based on the total weight of the membrane, the crosslinking agent may be present in the membrane in the range of about 0.001 wt.% to about 5.0 wt.%, or 0.01 wt.% to about 1.0 wt.%, or about 0.02 wt.% to about 0.5 wt.%, or about 0.03 wt.% to about 0.3 wt.%, or about 0.05 wt.% to about 0.2 wt.%.

[0067] Polyoxyethylene

[0068] Water-soluble membranes may optionally include polyoxyethylene. The molecular weight of polyoxyethylene ranges from about 500 Da to 20,000 Da, for example, about 1,000 Da to about 19,000 Da, about 1,000 Da to about 18,000 Da, about 1,000 Da to about 17,000 Da, about 1,000 Da to about 16,000 Da, about 1,000 Da to about 15,000 Da, about 1,000 Da to about 14,000 Da, about 1,000 Da to about 13,000 Da, about 1,000 Da to about 12,000 Da, about 1,000 Da to about 11,000 Da, about 1,000 Da to about 10,000 Da, about 1,000 Da to about 9,000 Da, about 1,000 Da to about 8,000 Da, about 1,000 Da to about 7,000 Da, about 1,000 Da to about 6,000 Da, and about 1,000 Da to about 5,000 Da. Da, about 1000 Da to about 4000 Da, about 1000 Da to about 3000 Da, about 1000 Da to about 1500 Da, or about 2000 Da to about 5000 Da. Compared to the same membrane excluding any medium molecular weight polyoxyethylene, the polyoxyethylene can be included in the membrane in any amount suitable for reducing the maximum adhesive force of the membrane. Medium molecular weight polyoxyethylene can be included in the membrane in amounts ranging from about 0.25 PHR to about 25 PHR, for example, about 0.5 PHR to about 22 PHR, about 0.7 PHR to about 20 PHR, about 1 PHR to about 15 PHR, about 1 PHR to about 14 PHR, about 1 PHR to about 13 PHR, about 1 PHR to about 12 PHR, about 2 PHR to about 10 PHR, about 2 PHR to about 6 PHR, or about 4 PHR. The polyoxyethylene can be polyethylene oxide, also referred to herein as polyethylene glycol (PEG). Renewable or bio-based polyoxyethylene is considered. Based on the total weight of the membrane, polyoxyethylene may be included in the membrane in an amount ranging from about 0.5 wt.% to about 5 wt.% or from about 2 wt.% to about 4 wt.%.

[0069] Additives

[0070] Water-soluble membranes may optionally contain other additives and processing agents, including but not limited to surfactants, lubricants, release agents, fillers, extenders, antiblocking agents, detackifiers, defoamers (defoaming agents), nanoparticles such as layered silicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfate, or others), bittering agents (e.g., denatamine salts, such as denatamine benzoate, denatamine sugar, and denatamine chloride; sucrose octaacetate; quinine; flavonoids, such as quercetin and naringenin; and quassinolide, such as quassinolide and strychnine), aversive agents and irritants (e.g., capsaicin, piperine, allyl isothiocyanate, and resin fluroxypyr), and other functional ingredients in amounts suitable for their intended purpose. For example, the membrane may include fillers, surfactants, antiblocking agents, or any or all of the foregoing.

[0071] Surfactants for use in water-soluble membranes are well known in the art. Optionally, surfactants are included to aid in the dispersion of the resin solution during casting. Surfactants suitable for the membranes disclosed herein include, but are not limited to, propylene glycol, diethylene glycol, monoethanolamine, polyoxyethylene polyoxypropylene glycol, alcohol ethoxylates, alkylphenol ethoxylates, tert-acetylenols and alkanolamides (nonionic), polyoxyethylene amines, quaternary ammonium salts and quaternized polyoxyethylene amines (cationic), alkali metal salts of higher fatty acids containing about 8 to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylated sulfates and alkylbenzene sulfonates (anionic), as well as amine oxides, N-alkyl betaine and sulfobetaine (amphoteric), dialkyl sulfosuccinates, lactic acidified fatty acid esters of glycerol and propylene glycol, and lipids. Lactates of fatty acids, sodium alkyl sulfate, polysorbates (e.g., Tween® surfactants), polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, sorbitol esters (e.g., Span™ surfactants), sorbitol monostearate, sorbitol tristearate, sorbitol monolaurate, alkyl polyethylene glycol ethers, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, sodium lauryl sulfate, acetylated esters of fatty acids, myristyl dimethylamine oxide, trimethyl tallow alkyl chloride, quaternary ammonium compounds, their salts, and combinations thereof.

[0072] The amount of surfactant in a water-soluble membrane can range from about 0.1 wt.% to about 8.0 wt.%, or about 1.0 wt.% to about 7.0 wt.%, or about 3.0 wt.% to about 7.0 wt.%, or about 5.0 wt.% to about 7.0 wt.%, or about 0.1 wt.% to 2.5 wt.%. Too little surfactant may sometimes result in pores in the membrane, while too much surfactant may result in an excess of surfactant on the membrane surface, causing the membrane to feel greasy or oily.

[0073] Defoaming agents can help foam bubbles coalesce. Suitable defoaming agents for use in membranes according to this disclosure include, but are not limited to, hydrophobic silica, such as fine-grained silica or fumed silica, including Foam Blast® defoaming agents available from Emerald Performance Materials, comprising FoamBlast® 327, Foam Blast® UVD, Foam Blast® 163, Foam Blast® 269, Foam Blast® 338, Foam Blast® 290, Foam Blast® 332, Foam Blast® 349, Foam Blast® 550, and FoamBlast® 339, which are proprietary non-mineral oil defoaming agents. Other suitable silicone-based defoaming agents include Foam-a-Tac® defoaming agents available from Enterprise Specialty Products. Other suitable defoaming agents may include non-silicone-based defoaming agents, including but not limited to defoaming HL23, defoaming HL27, defoaming HL36, defoaming HL40, defoaming HL52 and defoaming HL550, available from Harcros Chemicals. Optionally, the defoaming agent may be used in amounts ranging from 0.5 PHR or less, or from 0.5 PHR to 0.01 PHR, for example, 0.3 PHR, 0.2 PHR, 0.1 PHR, 0.05 PHR, 0.04 PHR, 0.03 PHR, 0.02 PHR or 0.01 PHR.

[0074] Suitable fillers, extenders, and detackifiers may include, but are not limited to, starch, modified starch, croscarmellose, croscarmellose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, mica, and stearic acid and their metal salts, such as magnesium stearate. Fillers particularly considered include starch and modified starch (e.g., high amylose starch, amorphous silica, hydroxyethylated starch), silica, talc, or combinations thereof.

[0075] The filler comprising the water-soluble membrane of this disclosure may include one or more anti-blocking agents. Silica is particularly considered as an anti-blocking agent. Clay and clay minerals (such as kaolinite) are particularly considered as anti-blocking agents. The anti-blocking agent may be present in an amount sufficient to reduce the adhesive strength between the two membrane surfaces. The anti-blocking agent may be present in amounts of at least 0.1 PHR, or at least 0.5 PHR, or at least 1 PHR, or ranging from about 0.1 PHR to about 8.0 PHR, or about 0.1 PHR to about 6.0 PHR, or about 0.1 PHR to about 5.0 PHR, or about 0.1 PHR to about 3.0 PHR, or about 0.4 PHR to 1.0 PHR, or about 0.5 PHR to about 0.9 PHR, or about 0.5 PHR to about 2 PHR, or about 0.5 PHR to about 1.5 PHR, or about 0.1 PHR to about 1.2 PHR, or about 0.1 PHR to about 0.7 PHR, such as about 0.5 PHR, 0.6 PHR, 0.7 PHR, 0.8 PHR, or 0.9 PHR.

[0076] The median size of the anti-blocking agent ranges from about 3 micrometers to about 35 micrometers, or about 3 micrometers to about 25 micrometers, or about 25 micrometers to about 35 micrometers, or about 3 micrometers to about 11 micrometers, or about 4 micrometers to about 8 micrometers, or about 5 micrometers to about 6 micrometers, for example, 5 micrometers, 6 micrometers, 7 micrometers, or 8 micrometers. Suitable silica is untreated synthetic amorphous silica designed for use in aqueous systems.

[0077] Polyethylene glycol is also considered an anti-blocking agent. In particular, polyethylene glycols with an average molecular weight greater than about 1,000 Da, or greater than about 1,500 Da, or greater than about 2,000 Da, and at most about 20,000 Da, or 10,000 Da, or 6,000 Da, or 5,000 Da, or 4,000 Da, or 3,000 Da are considered.

[0078] The anaphylactic agent may be incorporated into the membrane or applied to the membrane as a coating. The anaphylactic agent may be added in an amount that induces an anaphylactic reaction (such as bitterness), diluted from its commercial form, or otherwise mixed with a solvent to facilitate mixing with other water-soluble membrane components or application as a coating to water-soluble membranes. Such solvents may be selected from water, low molecular weight alcohols (such as methanol or ethanol), or plasticizers disclosed herein.

[0079] A membrane is considered comprising pullulan, carrageenan, a crosslinking agent (e.g., potassium or calcium based), a plasticizer (e.g., comprising sugar alcohols and / or polyols), and optionally one or more additives selected from surfactants, defoamers, and antiblocking agents. A membrane is particularly considered comprising pullulan, carrageenan, a potassium or calcium crosslinking agent, a plasticizer comprising sugar alcohols and polyols, a surfactant, a defoamer, and an antiblocking agent. Based on the total weight of the membrane, pullulan may be present in such membranes in an amount ranging from about 50 wt.% to about 75%, or about 55 wt.% to about 70 wt.%, or about 60 wt.% to about 70 wt.%, 60 wt.% to about 65 wt.%, or about 65 wt.% to about 70 wt.%. Based on the total weight of the membrane, carrageenan may be present in such membranes in amounts ranging from about 1 wt.% to about 25 wt.%, or about 1 wt.% to about 15 wt.%, or about 1 wt.% to about 10 wt.%, or about 3 wt.% to about 10 wt.%, or about 5 wt.% to about 10 wt.%. Based on the total weight of the membrane, crosslinking agent in such membranes may be present in amounts ranging from about 0.001 wt.% to about 5.0 wt.%, or about 0.01 wt.% to about 1.0 wt.%, or about 0.02 wt.% to about 0.5 wt.%, or about 0.03 wt.% to about 0.3 wt.%, or about 0.05 wt.% to about 0.2 wt.%. Membranes comprising ι-carrageenan or κ-carrageenan or blends of ι-carrageenan and κ-carrageenan are considered for use in such membranes; specifically, carrageenan consisting only of ι-carrageenan is considered. This type of membrane considers membranes containing plasticizers comprising sugar alcohols and polyols. For example, combinations of pullulan, carrageenan, crosslinking agents, sugar alcohols, and polyols are considered for use in such membranes. Based on the total weight of the membrane, the total amount of non-aqueous plasticizer in such membranes can range from about 10 wt.% to about 45 wt.%, or about 15 wt.% to about 35 wt.%, or about 20 wt.% to about 30 wt.%, or about 20 wt.% to about 45 wt.%.

[0080] Such membranes, based on the total weight of the membrane, include one or more surfactants in a total amount ranging from about 0.1 wt.% to about 8.0 wt.%, or about 1.0 wt.% to about 7.0 wt.%, or about 3.0 wt.% to about 7.0 wt.%, or about 5.0 wt.% to about 7.0 wt.%, or about 0.1 wt.% to 2.5 wt.%. Membranes of this type, including one or more defoamers in a total amount ranging from about 0.5 PHR or less, or from 0.5 PHR to 0.01 PHR, for example, 0.3 PHR, 0.2 PHR, 0.1 PHR, 0.05 PHR, 0.04 PHR, 0.03 PHR, 0.02 PHR, or 0.01 PHR, are also considered. Such films are considered to include one or more antiblocking agents in a total amount ranging from at least 0.1 PHR, or at least 0.5 PHR, or at least 1 PHR, or ranging from about 0.1 PHR to 5.0 PHR, or from about 0.1 PHR to about 3.0 PHR, or from about 0.4 PHR to 1.0 PHR, or from about 0.5 PHR to about 0.9 PHR, or from about 0.5 PHR to about 2 PHR, or from about 0.5 PHR to about 1.5 PHR, or from about 0.1 PHR to 1.2 PHR, or from about 0.1 PHR to 2.7 PHR, such as about 0.5 PHR, 0.6 PHR, 0.7 PHR, 0.8 PHR, or 0.9 PHR.

[0081] Membrane properties

[0082] As described herein, the water-soluble membranes of this disclosure can be characterized by disintegration time, as determined according to the MonoSol test method MSTM-205. For example, when the membrane is provided with a thickness of about 88 micrometers, the disintegration time can range from about 10 seconds to 150 seconds, or from about 20 seconds to about 100 seconds, or from about 30 seconds to 50 seconds.

[0083] As described herein, the water-soluble membranes of this disclosure can be further characterized by dissolution time, as determined according to the MonoSol test method MSTM-205. For example, when the membrane is provided with a thickness of about 88 micrometers, the dissolution time can range from about 15 seconds to about 500 seconds, or about 10 seconds to about 500 seconds, or about 10 seconds to about 300 seconds, or about 30 seconds to about 200 seconds, or about 10 seconds to about 150 seconds, or about 60 seconds to about 100 seconds.

[0084] The water-soluble membrane of this disclosure can be further characterized by tensile strength, as determined by the tensile strength test described herein. For example, after conditioning at 28°C / 50% relative humidity (RH) for at least 18 hours, the tensile strength of the membrane can be in the range of about 10 N / mm². 2(MPa) to approximately 50 N / mm 2 or approximately 15 N / mm 2 Approximately 40 N / mm 2 or approximately 20 N / mm 2 Approximately 30 N / mm 2 or approximately 20 N / mm 2 Up to 25 N / mm 2 Alternatively, after conditioning at 28°C / 65% RH for at least 18 hours, the tensile strength of the membrane can range from approximately 5 N / mm. 2 Approximately 20 N / mm 2 or approximately 5 N / mm 2 Up to 15 N / mm 2 or approximately 10 N / mm 2 Approximately 15 N / mm 2 Generally, a higher tensile strength value is desirable because it corresponds to a stronger bag that is less likely to break.

[0085] The water-soluble membrane of this disclosure can be further characterized by Young's modulus, as determined by the tensile strength test described herein. For example, after conditioning at 28°C / 50% RH for at least 18 hours, the Young's modulus of the membrane can be in the range of about 20 N / mm. 2 Approximately 300 N / mm 2 or approximately 30 N / mm 2 Approximately 200 N / mm 2 or approximately 50 N / mm 2 Approximately 100 N / mm 2 Alternatively, after conditioning at 28°C / 65% RH for at least 18 hours, the Young's modulus of the membrane can range from approximately 10 N / mm. 2 Approximately 100 N / mm 2 or approximately 20 N / mm 2 Approximately 50 N / mm 2 Young's modulus is typically a measure of the stiffness of a membrane, and a higher Young's modulus indicates greater stiffness.

[0086] The water-soluble membrane of this disclosure can be further characterized by elongation at break (i.e., strain at break), as determined by the elongation at break test described herein. For example, after conditioning at 28°C / 50% RH for at least 18 hours, the strain at break of the membrane can range from about 50% to about 400%, or from about 80% to about 300%, or from about 100% to about 200%. Alternatively, after conditioning at 28°C / 65% RH for at least 18 hours, the strain at break of the membrane can range from about 50% to about 500%, or from about 80% to about 300%, or from about 100% to about 250%, or from about 125% to about 200%.

[0087] The water-soluble membrane of this disclosure can be further characterized by its sealing strength, as determined by the sealing strength test described herein. For example, the sealing strength of the membrane can be about 5 Newtons (N) or greater, or about 10 N or greater, or about 12 N or greater, or about 15 N or greater, or range from about 5 N to about 30 N, or about 10 N to about 25 N, or about 12 N to about 20 N, or about 15 N to about 20 N.

[0088] The water-soluble membranes of this disclosure can be further characterized by adhesive force, as determined by the adhesive test described herein. For example, the adhesive force of the membrane can be less than about 30 N, or less than about 20 N, or less than about 12 N, or less than about 10 N, or less than about 5 N, or less than about 3 N, or less than about 1 N. The adhesive behavior of the water-soluble membranes according to this disclosure can be characterized by adhesive force values ​​of less than about 12 N, or less than about 10 N, or less than about 5 N, or less than about 3 N, or less than about 1 N.

[0089] fiber

[0090] The compositions described herein for use in the membranes of this disclosure can also be used as compositions for fibers.

[0091] Fibers having the same composition as the membranes of this disclosure are also considered. As described herein, such fibers may comprise film-forming materials including pullulan and carrageenan, as well as crosslinking agents. Fibers may include any secondary components disclosed herein for use in the membranes of this disclosure. For example, fibers may contain amounts suitable for their intended purpose of plasticizers, surfactants, lubricants, release agents, fillers, extenders, antiblocking agents, antioxidants, detackifiers, defoamers, nanoparticles such as layered silicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite, or others), aversive agents such as bittering agents, irritants, or combinations of any of the foregoing.

[0092] Methods for preparing fibers are known in the art. For example, U.S. Patent Application Publication No. 2022 / 0228305A1 describes wet cooling gel spinning, thermoplastic fiber spinning, and melt spinning methods for preparing fibers containing water-soluble polymers or blends of water-soluble polymers. Such methods are generally suitable for preparing fibers according to this disclosure.

[0093] The fibers disclosed herein can be used as components of nonwoven webs comprising multiple fibers. A nonwoven web generally refers to an arrangement of fibers bonded together, wherein the fibers are neither woven nor braided. Generally, multiple fibers can be arranged in any orientation. Multiple fibers can be arranged randomly (i.e., without orientation). Multiple fibers can be arranged in a unidirectional orientation. Multiple fibers can be arranged in a bidirectional orientation. Multiple fibers can be multidirectional, with different arrangements in different regions of the nonwoven web.

[0094] This disclosure provides a unit-dose article comprising at least one compartment and optionally a composition contained within said compartment, wherein at least one wall of said compartment comprises a nonwoven web of this disclosure. The composition contained within said compartment may be any composition disclosed herein.

[0095] Water-soluble products

[0096] The water-soluble membranes disclosed herein can be used to manufacture sealed articles in the form of bags, the bags defining an internal bag volume to contain compositions intended for release into an aqueous environment. "Sealed article" optionally encompasses a sealed compartment with vents, for example, in embodiments where the compartment encapsulates waste gas solids, but more commonly a completely sealed compartment will be used.

[0097] The bag may contain a single compartment or multiple compartments. Water-soluble bags may be formed from two layers of water-soluble polymer film sealed at the interface, or from a single film that folds itself and seals. The film forms at least one sidewall of the bag, optionally forming the entire bag, and preferably forming the outer surface of said at least one sidewall. In another type of embodiment, the film forms the inner wall of the pouch, for example, as a partition wall between compartments.

[0098] This disclosure further provides a water-soluble article in the form of a small package containing a sealed compartment. The article comprises a first water-soluble film and a second water-soluble film, wherein the first water-soluble film is a water-soluble film according to this disclosure, and the first water-soluble film is sealed to the second water-soluble film to form the sealed compartment. The second water-soluble film may have the same composition as the first water-soluble film. The second water-soluble film may have a different composition than the first water-soluble film. The article may contain a composition contained within the sealed compartment. The composition may contain any composition disclosed herein. The composition may contain a home care composition. The composition may contain a non-home care composition.

[0099] Water-soluble films, nonwovens, and articles may include printed areas. The printed areas can be achieved using standard techniques such as flexographic printing or inkjet printing.

[0100] Sealing products

[0101] Water-soluble unit-dose articles can be heat-sealed or solution-sealed using any suitable method and apparatus, such as those known in the art for sealing other water-soluble films, or can be readily modified simply through routine experimentation. For example, water-soluble unit-dose articles can be heat-sealed on three sides. For example, the water-soluble film can be folded onto itself and sealed with a heat pulse sealing machine at the edge opposite the fold and along one of the remaining open edges to provide a bag of the desired size. An injection system such as a pump or syringe can be used to fill the bag with a liquid composition (e.g., a home care composition). In other embodiments, the water-soluble film can be stretched over a cavity of a specified size, and heat and vacuum can be applied to thermoform the film into the shape of the cavity. The cavity can then be filled with the desired composition (e.g., a home care composition). The filled bag can then be sealed with a second film. The second film can be pulled over the top of the cavity, and the side of the second film facing the filled bag can be wetted for solution sealing. The second film can have the same composition as the film forming the cavity (i.e., the first film), or the second film can have a different composition than the first film. Pressure can be applied, and the filled bag can be bonded to a second membrane around the forming cavity to form an encapsulated composition in a water-soluble unit dose article. For example, solution sealing can be achieved using a Mespack-Cloud sampler, etc.

[0102] For example, the membrane disclosed herein can be heat-sealed according to the following method:

[0103] 1. Seal the membrane at 28℃ / 50% RH for 24 hours.

[0104] 2. Using a TS-12 heat sealer (or equivalent), select the sealing temperature and sealing time, and bring the heat sealer to the target temperature.

[0105] 3. Cut tensile strips from the membrane. Place two strips on top of each other.

[0106] 4. Place the strip on the rubber platform and insert the strip into the TS-12 heat sealer.

[0107] 5. Press down the pedal under the machine to begin sealing the film and maintain the seal for the specified time.

[0108] 6. Remove the sealing strip from the machine and repeat as needed, for example, repeat at least three replica samples.

[0109] 7. Allow the seal to cool for at least 10 minutes. Pay attention to the sealing area of ​​the membrane. If the membrane has started to bubble, the temperature may be too high or the sealing time may have been too long.

[0110] The composition encapsulated in the bag is not particularly limited, and may include, for example, any of the various compositions described herein. In embodiments comprising multiple compartments, each compartment may contain the same and / or different compositions. Furthermore, the compositions may take any suitable form, including but not limited to liquids, solids, gels, pastes, abrasives, compressed solids (tablets), and combinations thereof (such as solids suspended in a liquid). In embodiments, the bag comprises a first compartment, a second compartment, and a third compartment, each of which contains a different first composition, a second composition, and a third composition, respectively.

[0111] Products and / or bag contents

[0112] In any embodiment, the water-soluble bag may contain (encapsulate) a composition. The composition may be selected from liquids, solids, or combinations thereof. As used herein, “liquid” includes free-flowing liquids, as well as pastes, gels, foams, and mousses. Non-limiting examples of liquids include light and heavy-duty liquid detergent compositions, fabric strengtheners, detergent gels commonly used for laundry, bleach, and laundry additives. Non-limiting examples of liquids include agricultural compositions, automotive compositions, aerospace compositions, food and nutritional compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, trade compositions, military and paramilitary compositions, office compositions, recreational and park compositions, pet compositions, water treatment compositions, including cleaning and detergent compositions suitable for any such use. Gases (e.g., suspended bubbles) or solids (e.g., particles) may be included within the liquid. As used herein, “solid” includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include granules, microcapsules, beads, strips, and pearlescent spheres. Solid compositions may provide technical benefits, including but not limited to full wash benefits, pretreatment benefits, and / or aesthetic effects.

[0113] In embodiments, the water-soluble unit-dose product may comprise a household care composition. The household care composition may be selected from light liquid detergent compositions, heavy-duty liquid detergent compositions, hard surface cleaning compositions, laundry detergent gels, bleach compositions, laundry additives, fabric strengthening compositions, shampoos, shower gels, other personal care compositions, and combinations thereof, optionally liquid laundry detergent compositions.

[0114] In another aspect of this disclosure, the household care composition may be selected from the group comprising laundry and automatic dishwashing compositions, including liquid laundry detergent compositions.

[0115] In another aspect of this disclosure, the household care composition may be selected from non-laundry and non-automatic dishwashing compositions, such as light liquid detergent compositions, heavy liquid detergent compositions, hard surface cleaning compositions, bleaching compositions, shampoos, shower gels, other personal care compositions, and other compositions as non-laundry and non-automatic dishwashing compositions or mixtures of any of the foregoing.

[0116] The term 'liquid laundry detergent composition' refers to any laundry detergent composition comprising a liquid capable of wetting and treating fabrics, and includes, but is not limited to, liquids, gels, pastes, dispersions, etc. Liquid compositions may include solids or gases in appropriately subdivided forms, but liquid compositions exclude forms that are not fluid in bulk, such as tablets or granules.

[0117] The liquid detergent composition can be used for hand washing of fabrics or for automatic machine washing of fabrics.

[0118] To accommodate technological and scientific advancements, European Commission Regulation 1297 / 2014 of 5 December 2014 amended European Parliament and European Commission Regulation 1272 / 2008 (EC) on the classification, labelling and packaging of substances and mixtures, requiring additional regulations for single-use liquid consumer laundry detergents contained in soluble packaging. These regulations include the requirement that the soluble packaging retain its liquid contents for at least 30 seconds when placed in water at 20°C. Therefore, liquid laundry detergent pouches according to the disclosure herein are optionally designed to retain their liquid contents for at least 30 seconds when placed in water at 20°C, and thereafter dissolve rapidly and completely.

[0119] In other respects, the household care composition may be an automatic dishwashing detergent composition comprising an ingredient selected from: surfactants, builders, sulfonated / carboxylated polymers, silicone foam inhibitors, silicates, metal and / or glass care agents, enzymes, bleach, bleach activators, bleach catalysts, alkaline sources, fragrances, dyes, solvents, fillers, and mixtures thereof.

[0120] In other embodiments, the water-soluble unit-dose article may comprise a home care composition. Non-home care compositions may be selected from agricultural compositions, aerospace compositions, food and nutrient compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, trade compositions, military and paramilitary compositions, office compositions, recreational and park compositions, pet compositions, pool and / or water treatment compositions, and combinations thereof. In an embodiment, the non-home care composition is a pool and / or water treatment composition.

[0121] The composition contained in the water-soluble bag, whether a home care composition or a non-home care composition, may contain water. For example, based on the total weight of the composition, the composition may contain water in amounts of about 1 wt.% to about 15 wt.%, or about 3 wt.% to about 15 wt.%, or about 5 wt.% to about 15 wt.%, or about 10 wt.% to about 15 wt.%.

[0122] In embodiments, the water-soluble unit-dose article may be provided in any size suitable for fitting through the neck of a snap-on spray bottle (e.g., a spray bottle with a screw cap neck diameter of about 28 mm). The length of the water-soluble unit-dose article may optionally be about 250 mm or less, or range from about 5 mm to about 250 mm, about 10 mm to about 250 mm, about 25 mm to about 250 mm, about 50 mm to about 225 mm, about 100 mm to about 225 mm, about 150 mm to about 225 mm, about 175 mm to about 225 mm, or about 200 mm. The width of the water-soluble unit-dose article may optionally be about 50 mm or less, or range from about 2 mm to about 50 mm, about 5 mm to about 45 mm, about 10 mm to about 40 mm, about 15 mm to about 35 mm, or about 20 mm to about 30 mm. The length of the water-soluble unit-dose product may be from about 175 mm to about 225 mm or about 200 mm, and its width may be from about 20 mm to about 30 mm or about 25 mm. In embodiments in which the water-soluble unit-dose product is provided to fit through the neck of a snap-on spray bottle, the water-soluble unit-dose product optionally contains a home care composition with a pH less than or equal to 2.

[0123] Fabric and home care products are optionally used or consumed in the form they are sold and are intended for use on fabrics, hard surfaces, and any other surfaces in the fabric and home care field, including: air care agents, including air fresheners and fragrance delivery systems; car care products; dishwashing liquids; fabric conditioners (including softeners and / or fresheners); laundry detergents; laundry and rinsing additives and / or conditioning agents; hard surface cleaners and / or treatments, including floor and toilet cleaners; and other cleaners for fabric or household use.

[0124] Cleaning and / or treatment compositions include, but are not limited to, products for treating fabrics, hard surfaces, and any other surfaces in the fabric and home care fields, including: air care agents comprising air fresheners and fragrance delivery systems; car care products; dishwashing detergents; fabric conditioners (including softeners and / or fresheners); laundry detergents; laundry and rinsing additives and / or conditioning agents; hard surface cleaners and / or treatment agents, including floor and toilet cleaners; granular or powdered general-purpose or “heavy-duty” detergents, particularly cleaning detergents; liquid, gel, or paste-type general-purpose detergents, particularly so-called heavy-duty liquid types; liquid fine fabric detergents; hand dishwashing or light-duty dishwashing detergents, particularly high-foaming types; machine dishwashing detergents, including various tablet, granule, liquid, and rinsing aid types for fabric and home use; car or carpet shampoos; bathroom cleaners, including toilet cleaners; and cleaning aids such as bleach additives and “stain sticks” or pre-treatment types; substrate-loaded products, such as sheets with added desiccants.

[0125] Unless otherwise stated, fabric and / or hard surface cleaning and / or treatment compositions include granular or powdered general-purpose or “heavy-duty” detergents, particularly cleaning detergents; liquid, gel, or paste-type general-purpose detergents, particularly so-called heavy-duty liquid types; liquid fine fabric detergents; hand dishwashing liquids or light dishwashing liquids, particularly high-foaming types; machine dishwashing liquids, including various tablet, granule, liquid, and rinsing aid types for household and institutional use; liquid cleaners and disinfectants; car or carpet shampoos; bathroom cleaners, including toilet cleaners; fabric conditioning products containing softeners and / or fresheners, which may be in liquid, solid, and / or desiccant sheet form; and cleaning aids such as bleach additives and “stain sticks” or pretreatment types; substrate-loaded products, such as sheets with added desiccants. All applicable such products may be in standard, concentrated, or even highly concentrated forms, even if such products may be non-aqueous in some respects.

[0126] This document further provides a water-soluble unit-dose article comprising a pouch including an outer wall having an outer surface and an inner surface defining an inner pouch volume, the outer wall comprising a water-soluble film according to the disclosure herein and a composition optionally contained within the inner pouch volume.

[0127] This document further provides a method for dispensing a bulk water composition, the method comprising the steps of: contacting a water-soluble unit dose product as described herein with bulk water, thereby dissolving at least a portion of the water-soluble film, and releasing the composition into the bulk water.

[0128] Generally, bulk water can be any bulk water that requires or benefits from the home care or non-home care composition provided therein. For example, bulk water can be a pool or spa. Generally, the temperature of bulk water can be any temperature sufficient to dissolve or disintegrate at least a portion of the water-soluble film. In embodiments, the temperature of the bulk water can be at least about 10°C, for example, ranging from about 10°C to about 100°C, from about 10°C to about 70°C, from about 10°C to about 60°C, from about 20°C to about 50°C, or from about 20°C to about 40°C. Generally, bulk water can be characterized by any pH value. For example, the pH range of bulk water can be from about 4 to about 10, from about 5 to about 9, or from about 6 to about 7.

[0129] The edible water-soluble film disclosed herein can be used to package food and / or beverage components, including but not limited to convenience foods, seasonings, preservatives, and food manufacturing ingredients. The edible water-soluble film can be in the form of a bag or pouch defining an internal bag volume. Food and / or beverage components can be encapsulated within the internal bag volume of a bag or pouch prepared from one or more of the water-soluble films disclosed herein.

[0130] This document discloses packaged foods, including ready-to-eat foods, and methods for preparing such products for human and / or animal consumption. Generally, packaged foods according to this disclosure include cooking containers having a sealed internal volume and containing at least two sealable food items. One of the food items may be a dehydrated food (such as instant noodles or instant rice), which can be regenerated relatively quickly (e.g., within minutes or seconds) by adding a fluid (such as hot or boiling water, or even cold or room temperature water). Other food items may be flavorings (such as seasonings) that alter the flavor of the dehydrated food, and / or cooking agents (such as oil or butter) that alter the cooking properties of the dehydrated food. To keep the food items separate from each other during storage and distribution, the flavorings and / or cooking agents may be encapsulated in packets until use. Another example may be a beverage portion, where the container / cup has packets or compartments containing various ingredients (such as coffee, milk particles, flavorings, spices, etc.). The ingredient packets may be made of different water-soluble films with different barrier properties. The packet dissolves in hot or cold liquid (water, cream, or milk) dispensed through this cup or container, releasing its contents and extracting the ingredients for use in a beverage prepared for consumption or combined with other ingredients. The packet can be made of a water-soluble material, causing it to dissolve and release its contents when water is added to the cooking container. This reduces the burden on consumers who would otherwise have to cut or tear the packet, thus improving convenience and reducing the likelihood of packet contents spilling out of the packaged product. In addition to being water-soluble, the packet material can be edible and even tasteless (at least to humans), so the packet has little or no impact on the taste of the cooked food product. Furthermore, the packet can be positioned between the dehydrated food and the bottom of the container, making it invisible. Placing the packet out of sight reduces the likelihood of consumers unnecessarily trying to tear or cut it.

[0131] Food and / or beverage components may include, but are not limited to, beverage mixtures (such as energy drink powders, rehydration drink powders, sports drink powders / concentrates, protein powders, hot cocoa, tea concentrates, tea leaves, mocha coffee, fruit juice concentrates and coffee, chicory), flavor and texture enhancers (such as energizing concentrates (e.g., fruit tea)), flavor improvers, color improvers, texture improvers, freeze-dried fruit and protein shakes, food supplements (such as fiber supplements and natural food supplements), dairy products (e.g., cream), processed food products, meat products (e.g., sausages), and convenience foods (such as...). Instant noodle seasoning packets), soup concentrates, baked goods and confectionery, condiments and preservatives (such as pickles, salted vegetables, salad dressings, ketchup), various spices (such as taco powder, dried chili peppers, chili sauce, bean paste), milk powder, broth (in liquid or solid form, as well as in concentrate form) and food manufacturing ingredients (such as basic ingredients (such as yeast, salt, spices, food coloring, texture modifiers, flour, sugar, milk powder)), egg products (e.g., liquid eggs, egg whites or yolks) and other ingredients (e.g., cream, gelatin, fruit fillings, broth (in liquid or solid form), ketchup, dried chili peppers, chili sauce or bean paste).

[0132] The water-soluble films and nonwovens of this disclosure can be used to form laundry sheets. Laundry sheets may include one or more layers of the water-soluble films or nonwovens of this disclosure. Laundry sheets may also include one or more layers of the water-soluble films or nonwovens of this disclosure, as well as one or more layers of known water-soluble or water-dispersible films or nonwovens. Laundry sheets may further include laundry additives, such as detergents, bleaching agents, bleaching components, etc., disclosed herein.

[0133] The water-soluble films and nonwovens disclosed herein can be used to form various cosmetic face masks, including sheet masks, for example, those shaped to conform to the human face. Face masks can contain various active ingredients for moisturizing, wrinkle reduction, etc. Face masks deliver active substances to target organs and may degrade and dissolve over time of use. Water can be applied to the face mask before application to the face. Face masks may include one or more personal care compositions.

[0134] Methods for preparing membranes

[0135] Methods for producing water-soluble films by solution casting are well known in the art. Typically, polymers and secondary additives are dissolved in a solvent (usually water), and the solution is metered onto a casting surface and allowed to dry substantially or be forced to dry with heated air to form a cast film. The resulting cast film is removed from the casting surface and optionally wound onto a roller. The method can be performed in batches and is more efficient when carried out as a continuous process.

[0136] In forming continuous film webs, conventional practice involves metering a solution of resin and secondary components onto a moving casting surface (e.g., a continuously moving metal cylinder or belt), then allowing or enabling the solvent to be substantially removed from the liquid, thereby forming a self-supporting cast film, and then peeling the resulting cast film off the casting surface. The solution may optionally be metered or coated onto a carrier film, release liner, or removable backing, whereby, after solvent removal, the resulting cast film or coating may be separated from the carrier film, release liner, or removable backing (e.g., immediately after drying or at a later point in time (e.g., before use)) or remain attached to the carrier film, release liner, or removable backing. The film or coating prepared on the carrier film, release liner, or removable backing may be self-supporting or non-self-supporting. Such carrier films, release liners, and removable backings can be prepared from a variety of materials known in the art, such as polyethylene, polyethylene oxide, polyethylene terephthalate, polyolefins, oriented polypropylene, polytetrafluoroethylene, polyvinyl chloride, and cross-linked polyvinyl alcohol.

[0137] Generally, the casting surface can be any suitable substrate known to those skilled in the art for producing polymer films. In embodiments, the substrate can be a casting roller or cylinder, a casting tape, or a combination thereof. As used herein, the substrate is used to produce a polymer film from one or more polymer resins or polymer resin solutions. The substrate includes a substrate surface, and the substrate surface may be coated with a release coating. The polymer resin solution can be cast onto the substrate while the substrate is being moved (e.g., rotated). In embodiments, the substrate is a casting cylinder. In embodiments, the substrate is a casting tape. The substrate may comprise stainless steel and optionally may have a stainless steel surface. The substrate may comprise stainless steel, which may optionally be plated, for example, chromium plated, nickel plated, zinc plated, or a combination thereof.

[0138] The films disclosed herein can be produced using a solvent-based belt casting system. The system may include tanks for mixing and / or storing a water-soluble resin solution, the water-soluble resin solution having optional secondary additives, for use with a belt casting machine having at least a first rotating drum and a second rotating drum, the casting surfaces of the at least first rotating drum and the second rotating drum being tensioned to travel as the drum rotates. As the solution composition travels as a sheet on the casting surface, the solvent is removed from the solution composition using a drying chamber at least a portion of the casting surface line of the encapsulation mold.

[0139] Additionally, a release coating can be applied to the cast surface to provide one or more advantages to the film and / or method. For example, a release coating can significantly reduce or eliminate air bubbles in the resulting film, or it can improve the ease with which the resulting film is released from the cast surface. A roll coater release coating machine connected to a batch of release coatings and a portion of the tape can transfer the fluid release coating to the cast surface before applying the resin solution to the tape. Suitable solvent tape casting systems and related materials are further described in U.S. Patent Application Publications No. 2006 / 0081176 A1 and No. 2007 / 0085234 A1, the disclosures of which are incorporated herein by reference in their entirety.

[0140] Generally, a release coating may comprise one or more surfactants and an optional carrier, such as water. The release coating may comprise one or more surfactants, such as those selected from fluorinated surfactants, non-fluorinated anionic surfactants, or non-fluorinated zwitterionic surfactants, their salts, or any combination thereof. In embodiments, the anionic or zwitterionic surfactant may be non-fluorinated and contain C6-C. 30 Phosphate ester, C6-C 30 Phosphodiester, C6-C 30 Carboxylic esters, C6-C 30 Dicarboxylic acid esters, C6-C 30 Sulfate, C6-C 30 Disulfate esters or salts thereof. In embodiments, the release coating comprises a nonfluorinated amphoteric surfactant or a salt thereof. In embodiments, the release coating comprises a nonfluorinated anionic surfactant or a salt thereof. In embodiments, the nonfluorinated anionic surfactant comprises C6-C... 30 Phosphate ester or C8-C 16 Phosphate ester, C6-C 60 Phosphodiester, C 16 -C 32 Phosphodiester, C6-C 30 Carboxylic esters, C6-C 30 Dicarboxylic acid esters, C6-C 30 Sulfate, C6-C 30 Disulfate esters or their salts. In the examples, the nonfluorinated anionic surfactants comprise C6-C. 30 Phosphate ester or C6-C 18 Phosphate ester, C6-C 60 Phosphodiester, C 18 -C 32Phosphate diesters or their salts. In the examples, the anionic surfactant may be selected from one or more of the following: C6-based fluorinated aliphatic ammonium phosphate; tridecyl ethoxyphosphate POE-12; tridecyl ethoxyphosphate POE-3; lauryl ether-11 carboxylic acid; crypto-anionic surfactant lauryl ether-6 carboxylic acid; or sodium lauryl ether sulfate POE-4.

[0141] As used herein, the term "non-fluorinated" refers to a surfactant having less than 0.01 wt% fluorine based on the total molecular weight of the compound, or less than 0.001 wt% fluorine based on the total molecular weight of the compound, or less than 0.0001 wt% fluorine based on the total molecular weight of the compound.

[0142] In embodiments, the release coating may include a fluorinated surfactant, such as a perfluoroalkyl compound. In embodiments, the fluorinated surfactant may include a solution of ZONYL FSP surfactant (EI du Pont deNemours and Company). The range of surfactant in the release coating is considered to be from about 0.05% by weight to about 5.0% by weight. The amount of surfactant required to provide sufficient wetting may vary depending on the film coated on the strip. Other products may require higher concentrations to improve release properties. Higher surfactant concentrations result in more efficient spreading and wetting of hard surfaces before the surfactant solution reaches a critical micelle concentration (CMC). This concentration represents a threshold beyond which additional surfactants will not produce any further efficiency in spreading and wetting. However, increasing the concentration beyond the CMC may improve wetting via the polymer solution and improve the release properties of some film formulations.

[0143] The release coating can be applied to a substrate surface and optionally subsequently dried before a polymeric resin or polymeric resin solution is cast onto the surface-coated substrate. In embodiments, the pH of the release coating when applied to the substrate surface can be from about 1 to about 5 before drying. In embodiments, the surfactant comprises a non-fluorinated anionic surfactant, a non-fluorinated zwitterionic surfactant, salts thereof, and combinations thereof, and the pH of the release coating when applied to the substrate surface can be from about 1 to about 8, or from about 1 to about 5, before drying. For example, the pH of the release coating when applied to the substrate surface can be about 1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, about 5, about 6, about 7, or about 8. In an embodiment, the pH of the release coating when it is applied to the substrate surface may be about 1 to about 7, or about 1 to about 6, or about 1 to about 4, or about 1 to about 3, or about 2 to about 7, or about 2 to about 6, or about 2 to about 5, or about 2 to about 4, or about 2 to about 3, or about 3 to about 7, or about 3 to about 5, or about 1.5 to about 3.5, or about 4 to about 7.

[0144] Generally, the surfactant concentration of the release coating can range from about 0.001 wt% to about 100 wt% based on the total weight of the release coating. In embodiments, the surfactant concentration of the release coating can range from about 0.001 wt% to about 20 wt% before drying the release coating on the substrate surface. For example, the surfactant concentration of the release coating can range from about 0.001 wt% to about 10 wt%, or about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 4 wt%, or about 0.01 wt% to about 3 wt%, or about 0.01 wt% to about 2 wt%, or about 0.05 wt% to about 2 wt%, or about 0.1 wt% to about 2 wt%, or about 0.5 wt% to about 2 wt%. In embodiments, the surfactant concentration of the release coating can range from about 0.01 wt% to about 4.00 wt% based on the total weight of the release coating before drying the release coating on the substrate surface. In an embodiment, before drying the release coating on the substrate surface, the surfactant concentration of the release coating can range from about 0.05 wt% to about 2.00 wt% based on the total weight of the release coating. In an embodiment, after drying the release coating on the substrate surface, the surfactant concentration of the release coating can range from about 2.5 wt% to about 100 wt% based on the total weight of the release coating. For example, after drying the release coating on the substrate surface, the surfactant concentration of the release coating can range from about 3 wt% to about 100 wt%, or about 4 wt% to about 90 wt%, or about 4 wt% to about 80 wt%, or about 4 wt% to about 70 wt%, or about 4 wt% to about 50 wt%, or about 4 wt% to about 30 wt%, or about 4 wt% to about 20 wt%, or about 4.7 wt% to about 100 wt%, or about 5 wt% to about 90 wt%. In an embodiment, after the release coating on the substrate surface has dried, the surfactant concentration of the release coating can range from about 4.7 wt% to about 100 wt%, based on the total weight of the release coating. For example, the release coating can include an amount of ZONYL surfactant ranging from about 0.05 wt% to about 5.0 wt%, based on the total weight of the release coating.

[0145] Generally, the hydrophilic-lipophilic balance of the release coating as described herein can range from about 1 to about 30. In embodiments, the hydrophilic-lipophilic balance of the release coating can range from about 1 to about 20, or about 1 to about 18, or about 1 to about 17, or about 1 to about 16, or about 1 to about 15, or about 2 to about 17, or about 3 to about 17, or about 4 to about 15, or about 5 to about 12, or about 8 to about 12. In embodiments, the hydrophilic-lipophilic balance of the release coating can range from about 1 to about 20. In embodiments, the hydrophilic-lipophilic balance of the release coating can range from about 3 to about 17.

[0146] Generally, the thickness of the release coating on the substrate surface is from about 0.1 nm to about 100 nm. In embodiments, the thickness of the release coating on the substrate surface is from about 0.1 nm to about 80 nm, or from about 0.1 nm to about 60 nm, or from about 0.1 nm to about 40 nm, or from about 0.1 nm to about 40 nm, or from about 0.1 nm to about 20 nm, or from about 0.1 nm to about 10 nm, or from about 1 nm to about 5 nm. In embodiments, the thickness of the release coating on the substrate surface is from about 0.1 nm to about 40 nm. In embodiments, the thickness of the release coating on the substrate surface is from about 0.1 nm to about 10 nm.

[0147] The amount of water in the metering solution of the resin and / or secondary components used for film casting can be selected such that the solution has the highest solids level below the viscosity inflection point when heated to the casting temperature. Methods for determining the amount of solids at the viscosity inflection point are known in the art. Generally, the metering solution may contain 60% to 85% water, or 60% to 75% water, to provide a suitable solution for casting. The viscosity of each casting solution at 175℉ (about 80°C) may be, for example, at least about 5,000 cPs, or at least about 6,000 cPs, or at least about 7,000 cPs, or at least about 8,000 cPs, or at least about 9,000 cPs. The viscosity of each casting solution at 175℉ (approximately 80°C) may be, for example, no more than about 15,000 cPs, or no more than 14,000 cPs, or no more than about 13,000 cPs, or no more than about 12,000 cPs, or no more than about 11,000 cPs.

[0148] The solution can be cast at any suitable temperature, such that the temperature range of the membrane during drying is optionally from about 50°C to about 105°C. Without intending to be bound by theory, it is believed that as the temperature of the cast solution and the membrane decreases significantly below about 50°C, the amount of time required for membrane drying undesirably increases, and the length of the drying chamber required for complete drying of the cast solution undesirably increases. Furthermore, without intending to be bound by theory, it is believed that as the temperature of the solution and the membrane increases significantly above about 105°C, the solvent may rapidly boil out of the membrane, leading to defects on the membrane surface such as pores or bubbles in the finished membrane and / or promoting undesirable reactions between adjacent backbones, resulting in reduced membrane solubility.

[0149] In continuous or semi-continuous casting processes, the moving casting surface can have any desired linear velocity, ranging from about 5 m / min to about 50 m / min. Linear velocity can sometimes affect the properties of the resulting film, such as physical properties, thickness, residual moisture content, and film quality. Generally, assuming a constant solution delivery rate, the thickness of the resulting film increases as the linear velocity decreases, and decreases as the linear velocity increases. Generally, as the linear velocity increases, the residence time of the film in a fixed-size dryer decreases, thus requiring an increase in drying temperature, which may lead to drying defects or viscous properties at sufficiently high temperatures. Conversely, as the linear velocity decreases, the residence time of the film in the dryer increases.

[0150] Method for preparing bags

[0151] Methods for forming containers from membranes are known in the art. Membranes can be used to form containers (bags) by any suitable method, including vertical forming, fill and seal (VFFS) or thermoforming. Membranes can be sealed by any suitable method, including, for example, solvent sealing or heat sealing of the membrane layer, such as around the perimeter of the container. For example, the bag can be used to dispense material to be delivered into a large volume of water.

[0152] Bags and pouches can be made using any suitable equipment and methods. For example, individual compartment bags can be manufactured using vertical filling, horizontal filling, or rotary drum filling techniques common in the art. Such processes can be continuous or intermittent. The membrane can be damped and / or heated to increase its ductility. The method may also involve using a vacuum to draw the membrane into a suitable mold. Once the membrane is on the horizontal portion of the surface, the vacuum drawing the membrane into the mold can be applied for about 0.2 seconds to about 5 seconds, or about 0.3 seconds to about 3 seconds, or about 0.5 seconds to about 1.5 seconds. For example, this vacuum can provide a negative pressure ranging from 10 mbar to 1000 mbar or from 100 mbar to 600 mbar.

[0153] Depending on the desired bag size, the molds used to prepare the small bags can have any shape, length, width, and depth. The size and shape of the molds can also differ if desired. For example, the final bag volume can be from about 5 mL to about 300 mL, or from about 10 mL to 150 mL, or from about 20 mL to about 100 mL, and the mold size can be adjusted accordingly.

[0154] thermoforming

[0155] A thermoformable film is a film that can be shaped by applying heat and force. Thermoforming a film is a process of heating the film, shaping it (e.g., in a mold), and then cooling the film so that it retains its shape, such as the shape of the mold. Heat can be applied using any suitable method. For example, the film can be directly heated by passing it under a heating element or through hot air before or once it is supplied to a surface. Alternatively, the film can be indirectly heated, for example, by heating the surface or applying a hot article to the film. In this embodiment, infrared light is used to heat the film. The film can be heated to temperatures ranging from about 50°C to about 150°C, about 50°C to about 120°C, about 60°C to about 130°C, about 70°C to about 120°C, or about 60°C to about 90°C. The film can be heated to temperatures ranging from about 30°C to about 100°C, or about 40°C to about 100°C, or about 50°C to about 100°C, or about 60°C to about 100°C, or about 30°C to about 90°C, or about 40°C to about 90°C, or about 50°C to about 90°C. The film can also be heated to temperatures ranging from about 30°C to about 80°C, or about 40°C to about 80°C, or about 50°C to about 80°C, or about 60°C to about 80°C, or about 30°C to about 70°C, or about 30°C to about 60°C, or about 30°C to about 50°C. Thermoforming can be performed by any one or more of the following methods: manually covering a heat-softened film onto a mold, or pressure-induced forming of a softened film into a mold (e.g., vacuum forming), or automatically feeding a fresh extruded sheet with an accurately known temperature at high speed to a forming and trimming station, or automatic placement, insertion, and / or pneumatic stretching and pressurizing of the film.

[0156] Alternatively, the membrane can be wetted by any suitable method, such as directly by spraying a wetting agent (including water, a solution of the membrane composition, a plasticizer for the membrane composition, or any combination thereof) onto the membrane before or once it is supplied to the surface, or indirectly by wetting the surface or by applying a wet article to the membrane.

[0157] Once the film is heated and / or wetted, it can preferably be stretched into a suitable mold using a vacuum. The filling of the molding film can be accomplished using any suitable method. In embodiments, the most preferred method will depend on the product form and the desired filling speed. In embodiments, the molding film is filled using an in-line filling technique. The filled open pouches are then sealed using a second film by any suitable method, thereby forming a bag. This can be done simultaneously in a horizontal position and with continuous, constant movement. Sealing can be accomplished by continuously supplying a second film, preferably a water-soluble film, above and over the open pouches, and then preferably sealing the first and second films together, typically in the area between the molds and thus between the pouches.

[0158] Generally, thermoformed films are characterized by their draw ratio, which is the ratio of the die surface area to the film area before stretching. The thermoformed film according to this disclosure, or an article comprising the thermoformed film according to this disclosure, is characterized by a draw ratio of at least 2.0, or at least 2.5, or at least 2.6, or at least 3.0, or at least 3.5.

[0159] After conditioning at 25°C / 50% RH for 18 to 24 hours, a suitable behavior of the water-soluble membrane according to this disclosure is indicated by a tensile strength of at least about 10 N / mm². 2 Or at least 15 N / mm 2 or in the range of approximately 5 N / mm 2 Approximately 30 N / mm 2 or approximately 10 N / mm 2 Approximately 25 N / mm 2 or approximately 15 N / mm 2 Approximately 20 N / mm 2 As determined by the tensile strength test described herein. After conditioning at 25°C / 65% RH for 18 to 24 hours, a suitable behavior of the water-soluble membrane according to this disclosure is indicated by a tensile strength value of at least about 5 N / mm. 2 or at least about 10 N / mm 2 or at least 15 N / mm 2 or in the range of approximately 5 N / mm 2 Approximately 30 N / mm 2 or approximately 10 N / mm 2 Approximately 25 N / mm 2 or approximately 15 N / mm 2 Approximately 20 N / mm 2 The tensile strength value is as determined by the tensile strength test described herein. Generally, a higher tensile strength value is desirable because when the membrane is the limiting or weakest element of the seal, the tensile strength value corresponds to a stronger bag seal.

[0160] After conditioning at 25°C / 50% RH for 18 to 24 hours, a suitable behavior of the water-soluble membrane according to this disclosure is indicated by a Young's modulus value of at least about 20 N / mm. 2 25 N / mm 2 27 N / mm 2 30 N / mm 2 35 N / mm 2 40 N / mm 2 Or 45 N / mm 2 and / or up to about 300 N / mm 2 200 N / mm 2 150 N / mm 2 130 N / mm 2 120 N / mm 2 110 N / mm 2 100 N / mm 2 90 N / mm 2 80 N / mm 2 70 N / mm 2 60 N / mm 2 50 N / mm 2 40 N / mm 2 Or 30 N / mm 2 or approximately 20 N / mm 2 Approximately 300 N / mm 2 or approximately 20 N / mm 2 Approximately 200 N / mm 2 or approximately 40 N / mm 2 Approximately 100 N / mm 2 After conditioning at 25°C / 65% RH for 18 to 24 hours, a suitable behavior of the water-soluble membrane according to this disclosure is indicated by a Young's modulus value of at least about 5 N / mm. 2 10 N / mm 2 15 N / mm 2 Or 20 N / mm 2 and / or up to about 100 N / mm 2 90 N / mm 2 80 N / mm 2 70 N / mm 2 60 N / mm 2 Or 50 N / mm 2 .

[0161] Generally, the tensile strength and Young's modulus of a membrane can be adjusted by one or more of the following: (1) changing the absolute and / or relative amounts of pullulan and carrageenan in the membrane; (2) including one or more additional film-forming resins as described herein; (3) changing the amount of plasticizer in the membrane; (4) changing the type of plasticizer in the membrane; (5) changing the water content of the membrane; and (6) changing the thickness of the membrane. Without intending to be bound by theory, changes that may increase the tensile strength and / or Young's modulus of a membrane containing carrageenan and pullulan as film-forming resins include one or more of the following: (a) increasing the ratio of carrageenan to pullulan in the membrane; (b) increasing the total film-forming resin content of the membrane; (c) decreasing the amount of plasticizer in the membrane; (d) decreasing the water content of the membrane; and (e) increasing the thickness of the membrane.

[0162] Test methods

[0163] Dissolution and disintegration test (MSTM-205)

[0164] According to MonoSol test method 205 (MSTM-205), a membrane can be characterized by or tested for dissolution time and disintegration time, as known in the art. See, for example, U.S. Patent No. 7,022,656.

[0165] Equipment and materials:

[0166] 600 mL beaker

[0167] Magnetic stirrer (Labline model 1250 or equivalent)

[0168] Magnetic stirring rod (5 cm)

[0169] Thermometer (0℃ to 100℃ ± 1℃)

[0170] Stainless steel formwork (3.8 cm x 3.2 cm)

[0171] Timer (0-300 seconds, accurate to the nearest second)

[0172] Polaroid 35 mm slider mount (or equivalent)

[0173] MonoSol 35 mm slider mount retainer (or equivalent)

[0174] distilled water

[0175] For each membrane to be tested, three test samples are cut from the membrane sample (i.e., a 3.8 cm x 3.2 cm sample). If cutting from the membrane web, the samples should be cut from areas of the web that are evenly spaced along the transverse direction of the web. Each test sample is then analyzed using the following procedure.

[0176] Each sample is locked in a separate 35 mm slider mount.

[0177] Fill the beaker with 500 mL of distilled water. Measure the water temperature with a thermometer and, if necessary, heat or cool the water to maintain the temperature at 20°C (approximately 68°F).

[0178] Mark the height of the water column. Place the magnetic stirrer on the base of the holder. Place the beaker on the magnetic stirrer and add the magnetic stirring rod to the beaker. Turn on the stirrer and adjust the stirring speed until a vortex is formed at approximately one-fifth of the water column height. Mark the depth of the vortex.

[0179] Secure the 35 mm slider mount to the alligator clips of the 35 mm slider mount holder, ensuring the long end of the slider mount is parallel to the water surface. The holder's depth adjuster should be set so that, upon lowering, the end of the clip will be 0.6 cm below the water surface. One of the short sides of the slider mount should be flush against the side of the beaker, while the other short side should be positioned directly above the center of the stir bar, ensuring the membrane surface is perpendicular to the water flow.

[0180] In one operation, the fixed slider is lowered and clamped into the water, and a timer is started. Disintegration occurs when the membrane ruptures. As all visible membrane fragments are released from the slider mount, the slider is raised from the water while monitoring for undissolved membrane fragments in the solution continues. Dissolution occurs when all membrane fragments are no longer visible and the solution becomes clear.

[0181] After 300 seconds, if any membrane residue remains in the frame, the percentage of the remaining membrane surface area is estimated by visual inspection.

[0182] The results should include the following: complete sample identification; individual and average disintegration and dissolution times; and the water temperature at which the sample was tested.

[0183] The membrane disintegration time (I) and membrane dissolution time (S) can be corrected to the standard or reference membrane thickness using the exponential algorithms shown in Equations 1 and 2 below, respectively.

[0184] I 校正的 = I 测得的 x (Reference thickness / Measured thickness) 1.93 [1]

[0185] S校正的 = S 测得的 x (Reference thickness / Measured thickness) 1.83 [2]

[0186] Tensile strength test

[0187] Water-soluble membranes characterized by tensile strength (TS) testing, or tested for tensile strength, were analyzed as follows. The procedure involved determining the tensile strength according to ASTM D 882 (“Standard Test Method for Tensile Properties of Thin Plastic Sheets”) or its equivalent. An INSTRON tensile testing apparatus (Model 5544 tensile tester or equivalent) was used to collect membrane data. For each measurement, at least three test specimens were tested in machine orientation (MD), where applicable, and each specimen was cut with a reliable cutting tool to ensure dimensional stability and reproducibility. Testing was conducted in a standard laboratory atmosphere at 23 ± 2.0 °C and 35 ± 5% RH. For tensile strength, samples of a single membrane sheet, 1” wide and 88 µm thick, were prepared. The samples were then transferred to an INSTRON tensile testing machine for testing, with exposure minimized in an environment of 35% relative humidity. The tensile testing machine, equipped with a 500 N force sensor, was prepared according to the manufacturer's instructions and calibrated. The correct grip and facet (INSTRON grip, model 2702-032 facet, rubber-coated and 25 mm wide, or equivalent) were installed. The samples were mounted in the tensile testing machine and analyzed to determine the tensile strength (i.e., the stress required to cause the membrane to break).

[0188] Young's modulus is determined based on the slope of a linear fit of stress-strain data. For the membranes described herein, unless otherwise stated, Young's modulus is determined based on the slope of a linear fit of stress-strain data in the range of 0.1–3% strain. As described herein, for some membranes, Young's modulus is determined based on the slope of a linear fit of stress-strain data in the range of 1–20% strain.

[0189] As reported below, tensile strength and Young's modulus were measured on membranes conditioned for 18 to 24 hours at 23°C / 35% RH, 28°C / 50% RH, or 28°C / 65% RH. These high humidity measurements were intended to simulate high humidity conditions that products containing membranes according to this disclosure might encounter, such as during warehouse storage in humid areas.

[0190] Elongation at break test

[0191] The procedure involves determining the elongation at break (i.e., the strain at break) based on ASTM D 882 (“Standard Test Method for Tensile Properties of Thin Plastic Sheets”) or its equivalent. INSTRON is used.® Tensile testing equipment (Type 5544 tensile tester or equivalent) was used to collect membrane data. For each measurement, at least three test samples were tested in machine orientation (MD), where applicable, and each sample was cut with a reliable cutting tool to ensure dimensional stability and reproducibility. As reported below, membrane samples were conditioned for at least 18 hours at 23°C / 35% RH, 28°C / 50% RH, or 28°C / 65% RH prior to measurement. Testing was conducted in a standard laboratory atmosphere at 23 ± 2.0°C and 35 ± 5% RH. For elongation at break determination, single membrane sheet samples 1” wide (2.54 cm) with a thickness of 1.4 ± 0.15 mils (approximately 35.6 ± 3.8 µm) were prepared. The samples were then transferred to INSTRON. ® The test was conducted on a tensile testing machine, while minimizing exposure in an environment with 35% relative humidity. The tensile testing machine was prepared according to the manufacturer's instructions, equipped with a 500 N force sensor, and calibrated. The correct grip and face were installed. ® The grip has a surface designated 2702-032, which is coated with rubber and has a width of 25 mm (or equivalent). The sample is mounted in a tensile testing machine and analyzed to determine the elongation at break (i.e., Young's modulus, where applicable).

[0192] Sealing strength test

[0193] The seal strength test measures the seal strength between two sealed membrane surfaces. A sealed membrane surface can be the surface of two different membranes sealed to each other, the surface of two membranes having the same composition, or the surface of a single membrane sealed to itself.

[0194] Membrane data are collected using an INSTRON tensile testing apparatus (Model 5544 tensile tester or equivalent). Membranes can be sealed to each other by any suitable method, including heat-sealing or water-sealing methods known in the art. For example, an ESIPROOF prototyping apparatus with an anilox roller 140 / 10 or equivalent can be used to water-seal two membrane sheets. Alternatively, two membrane sheets can be heat-sealed. Therefore, the seal strength between the two sealed membrane surfaces can be characterized as either water-sealing strength or heat-sealing strength. For each measurement, at least three test samples are tested in the machine orientation (MD), where applicable, each sample being cut with a reliable cutting tool to ensure dimensional stability and reproducibility. Prior to testing, the membranes are conditioned at 28°C / 35% RH for 18 to 24 hours and tested in a standard laboratory atmosphere at 23 ± 2.0°C and 35 ± 5% RH.

[0195] The sample used to measure the watertightness can be prepared as follows. Test samples are prepared by cutting four 100 mm × 300 mm membrane sheets, each 300 mm in size, in the machine direction (MD). For two sheets, tape the four corners of one sheet to a surface. Cover the tapered sheet with the other sheet, ensuring the suitable surfaces are in contact. Place the remaining sheet on top of the tapered sheet, ensuring the two surfaces to be sealed are in contact. Tape one 100 mm end of each top sheet to secure it to the bottom sheet. Use a 140 / 10 anilox roller to pass the loose end of each top sheet through the ESIPROOF sample roller. Apply 0.5 mL of water to the doctor blade. Pull the roller at a constant speed (75 mm / s) to coat the upper membrane and attach it to the lower sheet. Allow the membrane to weld for 10–15 minutes. Use a strip punch or sample cutter to cut a 25.4 mm wide sample in the transverse direction (TD).

[0196] Transfer the water-sealed or heat-sealed sample to the INSTRON testing machine for testing while minimizing environmental exposure. For the seal strength test, the rubber grips are spaced 0.50'' (1.27 cm) apart, and all four grips are flat and square. Cut three (or more) 1'' wide (2.54 cm) samples in the machine direction (MD). Place the unsealed flaps of the sample in the grips of the testing machine, ensuring the sample is aligned and parallel to the grips, and that the sample is not pulled too tightly in the clamps of the testing machine. Balance the load and start the test according to the equipment manufacturer's instructions. At the end of the test, the tension (in N) required to tear or separate the layers is recorded as the seal strength.

[0197] The manner in which the seal sample tears or separates at the end of the seal strength test provides information about the seal quality. The seal quality can be reported as "pass" or "fail". Generally, if a seal sample breaks during the seal strength test due to delamination (peeling) of the membrane at the seal, the seal is considered a weakness (fail), while if a seal sample breaks during the seal strength test due to tearing or breakage of one or both membranes, the seal is not considered a weakness (pass).

[0198] Adhesion test

[0199] Adhesion refers to the force required to separate one film layer from another on a roll. Generally, as adhesion decreases, the film can be unrolled more easily without applying strain or stretching to the film, or generating tension during conversion. Adhesion force typically tends to increase with increasing plasticizer levels in the film. Adhesion tests measure the adhesive force between film layers on a roll. Adhesion force measurements do not include any frictional forces from the outer surface of the roll as it is unrolled.

[0200] The membrane of this disclosure, characterized by adhesion testing or tested according to adhesion testing, can be analyzed as follows.

[0201] 1. Using BYK Draw squares or a squeegee of appropriate size, cast a sheet of film approximately 4.5 inches x 3 feet (approximately 11.4 cm x 91.4 cm).

[0202] 2. Using a constant adjustable torque rewinder or equivalent, load a 3-inch diameter x 10-foot length (approximately 7.5 cm diameter x 3.05 m length) core onto the rewinder.

[0203] 3. Use tape to secure the film to the roll core.

[0204] 4. Using approximately 50% torque in the setup, wind the membrane into the core to ensure that the membrane itself is layered and the wrinkles are smoothed out.

[0205] 5. Use a thin absorbent paper towel (such as Kimwipe® or equivalent) to secure approximately 0.5 inches (about 1.3 cm) between the top layer of the film and the rest of the core to ensure that the top layer section does not stick to the rest of the core.

[0206] 6. Condition the roll at 50% RH for 24 hours.

[0207] 7. Cut the film off the roll to obtain several flat sheets and remove the paper towels.

[0208] 8. Using a sample cutter, cut three strips approximately 6'' (about 15 cm) long.

[0209] 9. Load the device in the MonoSol peel test method using a tensile testing apparatus (e.g., an INSTRON 5544 tensile tester or equivalent) equipped with a 50 N force sensor at a half-inch gap. Load the two loose ends into the T-type.

[0210] 10. Run a peel test and record the failure mode (fracture, tear, or peel). The peel test records the tension (in N) during the mutual displacement of the membranes.

[0211] 11. Optionally, repeat the test on two additional replicate samples.

[0212] Data Interpretation

[0213] 1. Record the peak / maximum force required to separate the two membranes.

[0214] 2. The greater the force required for the delamination of the membrane, the more severe the adhesion. Membranes with high adhesion forces typically tear or break during testing (i.e., the failure mode is denoted as "tear" or "break").

[0215] 3. The less force required for a delamination membrane, the less adhesion. Membranes with low adhesion typically peel off during testing (i.e., the failure mode is denoted as "peeling").

[0216] Adhesion failure modes can be determined based on how the membranes separate from each other during adhesion testing. For example, if the membranes separate from each other by peeling or delamination, allowing the membranes to maintain their respective integrity, the adhesion failure mode can be designated as "peeling," or if the separation of the membranes results in the tearing or rupture of one or both membranes, it can be designated as "rupture."

[0217] Example

[0218] The following examples are provided for illustration and are not intended to limit the scope of the invention. Generally, a resin solution is prepared by mixing water and the components listed in the examples, and a film is prepared by casting the resin solution and drying the cast film, and then removing the dried film from the cast substrate to obtain a stand-alone film. The amount of each component is shown as a percentage by weight of the total non-aqueous components of the film. Comparative examples (i.e., examples not according to the invention) are indicated by the prefix 'C'.

[0219] Comparison Example 1

[0220] Example films C1a-C1f were prepared by solution casting according to the formulations listed in Table 1 to obtain a dry film thickness of 88 µm. PEG 400 represents polyethylene glycol with an average molecular weight of 400 Da.

[0221] Table 1

[0222]

[0223] The single-resin membranes of Comparative Example 1 typically exhibit high mechanical strength or high elongation combined with rapid dissolution, but not both. Membrane C1a, containing ι-carrageenan as the sole film-forming resin, exhibits high tensile strength and Young's modulus, but low flexibility and slow dissolution. Compared to the membrane of Example C1a, membranes C1b-C1f, containing pullulan as the sole film-forming resin, exhibit significantly lower tensile strength and Young's modulus, but greater flexibility and faster dissolution.

[0224] Example 1

[0225] Example membranes 1a-1f were prepared by solution casting according to the formulations listed in Table 2 to obtain a dry membrane thickness of 88 µm. The amount of each component is shown as the weight percentage of the total non-aqueous components of the membrane.

[0226] Table 2

[0227]

[0228] The membrane of Example 1, containing a blend of pullulan and carrageenan as well as a crosslinking agent, exhibited good mechanical strength, good elongation properties, and good dissolution time. Notably, compared to the membrane of Comparative Example 1, which contained pullulan as the sole film-forming resin, the membrane of Example 1 exhibited a prolonged dissolution time. Without intending to be bound by theory, it is believed that the prolonged dissolution time indicates that the addition of carrageenan and the crosslinking agent improved the water resistance of the pullulan-based membrane while simultaneously achieving good mechanical properties.

[0229] Example 2

[0230] Based on the formulations listed in Table 3, example films 2a-2g were prepared by solution casting to obtain a dry film thickness of 88 µm. Example 2a does not contain calcium chloride, and example 2c contains 5 times more calcium chloride than the other calcium chloride-containing films.

[0231] Compared to the membrane containing 0.1 wt.% calcium chloride, Example 2a, which does not contain calcium chloride, exhibits lower tensile strength and Young's modulus. Without being bound by theory, it is believed that incorporating some crosslinks into the membrane can improve mechanical strength by creating a more rigid membrane structure.

[0232] The mechanical properties of Example 2c, containing 0.5 wt.% calcium chloride, are significantly different from those of the example membrane containing 0.1 wt.% calcium chloride. Specifically, compared to other example membranes, including Example 2b, which has the same additives as Example 2c except for a different level of calcium chloride, Example 2c exhibits lower strength, higher tensile strain, and a longer dissolution time. Without intending to be bound by theory, it is believed that the higher level of crosslinking agent increases the crosslinking of carrageenan within the membrane, partially disrupting the membrane structure and affecting its mechanical strength, while also prolonging the dissolution time due to additional crosslinked (and therefore less water-soluble) polymers within the membrane.

[0233] Table 3

[0234]

[0235] Example 3

[0236] Based on the formulations listed in Table 4, example films 3a-3f were prepared by solution casting to obtain a dry film thickness of 88 µm. The film in Example 3 containing a plasticizer blend contained less than 12 wt.% sorbitol. The composition in Example 3g, containing 8.0 wt.% calcium chloride, could not be cast into a film.

[0237] Table 4

[0238]

[0239] Among a range of plasticizer combinations and additives, Examples 3a-3f exhibited a combination of mechanical strength, good elongation, and rapid dissolution time.

[0240] Example 4

[0241] Example films 4a-4c were prepared by solution casting according to the formulations listed in Table 5 to obtain a dry film thickness of 88 µm. These films contain pullulan, κ-carrageenan, or λ-carrageenan, and optionally one or more other film-forming resins.

[0242] Table 5

[0243]

[0244] After conditioning at 28°C / 50% RH, all membranes in Example 4 exhibited suitable mechanical properties, and their solubility characteristics varied. Specifically, the membrane containing κ-carrageenan (4b) showed slower solubility compared to the membrane containing a blend of ι-carrageenan and κ-carrageenan (4a), while the membrane containing λ-carrageenan (4c) showed faster solubility compared to the membrane containing κ-carrageenan or a blend of ι-carrageenan and κ-carrageenan.

[0245] Without being bound by theory, it is believed that changing the type of carrageenan in pullulan-containing membranes can provide membranes with suitable mechanical properties and different dissolution times.

[0246] Example 5

[0247] Example films 5a-5d were prepared by solution casting according to the formulations listed in Table 6 to obtain a dry film thickness of 88 µm. These films contained pullulan, 1-carrageenan, and varying amounts of calcium chloride crosslinking agent.

[0248] Table 6

[0249]

[0250] After conditioning at 28°C / 50% RH or 28°C / 65% RH, the membrane in Example 5 exhibited suitable mechanical properties. Compared to the membrane containing less calcium chloride, the membrane containing 1.0 wt.% calcium chloride (5d) dissolved more slowly and was more flexible (i.e., exhibited higher fracture strain).

[0251] Example 6

[0252] Using the method described herein, sealed bags filled with a liquid laundry detergent composition containing 13 wt.% water were prepared from the membrane of Example 2b. After storage for one month under ambient temperature and humidity conditions, no leakage of the bag contents or visible degradation of the membrane was observed.

[0253] Example 7

[0254] Example membranes 7a-7f were prepared by solution casting according to the formulations listed in Table 7 to obtain a dry film thickness of 88 µm. These membranes contained pullulan, 1-carrageenan, and varying amounts of calcium chloride crosslinking agent. The membranes were conditioned at 50% RH or 65% RH, and their mechanical and solubility properties were evaluated.

[0255] The addition of calcium chloride, even at concentrations as low as 0.02 wt.%, generally increases the Young's modulus of membranes without calcium chloride compared to those without. For calcium chloride loadings above 1.0 wt.%, the mechanical strength of the membrane typically decreases, while elasticity (as indicated by fracture strain) typically increases. Membranes containing 0.3 wt.% or 1.0 wt.% calcium chloride exhibit significantly longer dissolution times than membranes containing less or no calcium chloride; however, membranes containing 2.0 wt.% calcium chloride show very short disintegration and dissolution times.

[0256] Without being bound by theory, it is believed that increasing the calcium chloride content in carrageenan-containing membranes can crosslink a portion of the carrageenan, and that such crosslinking can improve the mechanical strength of the membrane.

[0257] Table 7

[0258]

[0259] Example 8

[0260] Example films C8a, 8b-8g, and C8h were prepared by solution casting according to the formulations listed in Table 8 to obtain a dry film thickness of 88 µm. These films contained different ratios of pullulan and ι-carrageenan, as well as additives. The mechanical and solubility properties of the films were evaluated, and the films were subjected to heat sealing and thermoforming according to the methods described herein. The films were thermoformed by heating at 255℉ (approximately 125°C) and stretching into a mold under reduced pressure (0.1 bar) at a stretch ratio of 2.6 for 30 seconds, except for films 8f, 8g, and 8h, which were attempted to be thermoformed by heating at 280℉ (approximately 138°C). “Pass” indicates that the film can be thermoformed to the target stretch ratio of 2.6 without breaking; “Fail” indicates that the film cannot be thermoformed to the target stretch ratio of 2.6, i.e., the film did not contact the bottom surface of the mold to which it was stretched. As indicated in Table 8, each membrane was subjected to heat sealing at one or more temperatures, and the seal pass / fail of the sealed samples was evaluated according to the seal strength test described above. The Young's modulus of the membrane in Example 8 was determined by fitting stress-strain data over a strain range of 1-20%.

[0261] Compared to membranes containing pullulan as the sole film-forming resin, membranes containing as low as 2.0 wt.% carrageenan exhibited improved Young's modulus and tensile strength. Mechanical strength generally increased with increasing carrageenan content, while the strain at break generally decreased. Membranes containing a mixture of pullulan and carrageenan exhibited faster decomposition and dissolution compared to Example C8h (a membrane containing carrageenan as the sole film-forming resin).

[0262] After evaluation based on the seal strength test, the membrane containing up to 5.0 wt.% carrageenan exhibited good sealing, as indicated by the results (i.e., failure by tearing one or two membranes rather than failure by peeling the membrane at the sealing interface). The membrane containing more than 5.0 wt.% carrageenan failed by peeling the membrane at the sealing interface; the membrane containing ι-carrageenan as the sole film-forming resin (Example C8h) failed to form a seal and could not be evaluated based on the seal strength test.

[0263] The membranes typically exhibit high adhesion strength, and the failure mode for most membranes is the breakage or tearing of one or both membranes. Membranes containing 25.0 wt.% carrageenan showed improved adhesion (i.e., lower adhesion strength, and failure by peeling rather than breakage or tearing) compared to membranes containing less than 25.0 wt.% carrageenan. Example C8h, containing carrageenan as the sole film-forming resin, did not exhibit measurable adhesion strength.

[0264] Table 8

[0265]

[0266] Example 9

[0267] Based on the formulations listed in Table 9, example films 9a-9g were prepared by solution casting to obtain a dry film thickness of 88 µm. These films contained varying amounts of pullulan and 1-carrageenan, optionally calcium chloride, and various additives. PEG 4000 represents polyethylene glycol with an average molecular weight of 4000 Da. The Young's modulus of the films in Example 9 was determined by fitting stress-strain data over a strain range of 1-20%.

[0268] Table 9

[0269]

[0270] Membranes containing 20.0 wt.% carrageenan typically exhibit high rigidity but low flexibility, as demonstrated by their high Young's modulus and low fracture strain. These membranes become particularly stiff after conditioning at 35% RH.

[0271] A membrane containing 8.0 wt.% carrageenan, sealed at 255℉, passed the seal strength test. A membrane containing 20.0 wt.% carrageenan, sealed at 255℉, failed the seal strength test, although two membranes containing 20.0 wt.% carrageenan passed the seal strength test after being sealed at 300℉ (approximately 150°C). The presence or absence of calcium chloride does not appear to affect the membrane's sealing performance.

[0272] For all tested combinations of pullulan / carrageenan levels and adjuvant selections, membranes containing PEG 4000 exhibited very low adhesion, meaning that minimal force was required to separate two membranes in contact with each other.

[0273] Example 10

[0274] Films are prepared by casting and drying according to the following formulations.

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290] The mechanical properties of the membrane were tested. The results are shown in the table below.

[0291]

[0292]

[0293] The membrane's anti-adhesion ability was tested. The results are shown in the table below.

[0294]

[0295] The heat-sealing capability of the membrane was tested. The results are shown in the table below.

[0296]

[0297] The disintegration and dissolution times of the membranes were tested using the MSTM-205 method. The results are shown in the table below.

[0298]

[0299] Example 11

[0300] Example films 11a-11n were prepared by solution casting according to the formulations listed in Table 10 to obtain a dry film thickness of 88 µm. In addition to these components, formulations 11a, 11b, and 11c also contain 1 wt.% surfactant. The amount of each component is shown as a percentage of the total non-aqueous components by weight.

[0301] Several crosslinking agents according to this disclosure were tested at the concentrations indicated in Table 10 to demonstrate the effects of monovalent and divalent crosslinking agents with different anions.

[0302] The mechanical and solubility properties of membranes 11a-11m are shown in Table 11. Membrane 11n containing 3 wt.% of the composition is unusable during formulation phase separation. Without being bound by theory, it is believed that phase separation can be reduced or avoided by including or increasing the amount of emulsifier included in the membrane.

[0303] like Figure 1 As shown, example membranes 11a-11c and 11j-11L containing potassium salt crosslinking agents exhibit concentration-dependent tensile strengths that are generally higher than those containing other crosslinking cations. Without intending to be bound by theory, it is believed that incorporating monovalent potassium crosslinking ions into the membrane can improve mechanical strength without compromising membrane solubility, for example, by preventing the formation of gel particles. Furthermore, the reinforcing effect can be tuned by selecting different concentrations of the crosslinking agent.

[0304] Table 10

[0305]

[0306] Figure 2 Membranes containing magnesium and calcium crosslinking agents can exhibit greater fracture strain than those containing potassium-based crosslinking agents, indicating higher flexibility. Without intending to be bound by theory, it is believed that divalent cations can interact strongly with ι-carrageenan and form crosslinks even at low concentrations, thereby promoting the formation of flexible membranes. The flexibility of the membrane can be further tuned by selecting different anion and / or crosslinking agent concentrations. Furthermore, without intending to be bound by theory, it is believed that with increasing concentrations of divalent cations in the membrane formulation (e.g., based on an increase in the total weight of the membrane to above 5 wt.%), the interaction between divalent cations and ι-carrageenan leads to the formation of gel particles, which ultimately results in defects in the resulting membrane.

[0307] Table 11

[0308]

[0309] The foregoing description is provided for clarity of understanding only, and should not be construed as an unnecessary limitation, as modifications within the scope of this invention will be readily apparent to those skilled in the art.

[0310] All patents, publications, and references cited in this document are hereby incorporated herein by reference in their entirety. In the event of any conflict between this disclosure and the incorporated patents, publications, and references, this disclosure shall prevail.

Claims

1. A water-soluble membrane comprising a film-forming resin, a plasticizer, and a crosslinking agent, The film-forming resin comprises a mixture of pullulan and carrageenan, wherein pullulan is present in the membrane in an amount ranging from about 50 wt.% to about 75 wt.% based on the total weight of the membrane, and carrageenan is present in the membrane in an amount ranging from about 1 wt.% to about 25 wt.% based on the total weight of the membrane. The crosslinking agent is present in the membrane in an amount ranging from about 0.001 wt.% to about 5.0 wt.% based on the total weight of the membrane.

2. The water-soluble membrane according to claim 1, wherein the crosslinking agent comprises metal ions.

3. The water-soluble membrane according to claim 2, wherein the metal ions comprise monovalent metal ions, divalent metal ions, or a combination thereof.

4. The water-soluble membrane of claim 2, wherein the metal ions are provided in the form of a salt containing a counter anion, and the counter anion comprises acetate ions, chloride ions, ascorbate ions, phosphate ions, or combinations thereof.

5. The water-soluble membrane according to claim 1, wherein the crosslinking agent comprises calcium ions, magnesium ions, potassium ions, or a combination thereof.

6. The water-soluble membrane according to claim 1, wherein the crosslinking agent comprises calcium ions.

7. The water-soluble membrane of claim 6, wherein the membrane comprises calcium chloride, calcium acetate, or a combination thereof to provide the calcium ions.

8. The water-soluble membrane according to claim 1, wherein the crosslinking agent comprises potassium ions.

9. The water-soluble membrane of claim 8, wherein the membrane comprises potassium chloride, potassium acetate, or a combination thereof to provide the potassium ions.

10. The water-soluble membrane according to claim 1, wherein the crosslinking agent comprises magnesium ions.

11. The water-soluble membrane of claim 10, wherein the membrane comprises magnesium chloride, magnesium acetate, or a combination thereof to provide the magnesium ions.

12. The water-soluble membrane according to claim 1, wherein the carrageenan comprises at least one of ι-carrageenan, λ-carrageenan, and κ-carrageenan.

13. The water-soluble membrane according to claim 1, wherein carrageenan is present in the membrane in an amount not exceeding 8 wt.% based on the total weight of the membrane.

14. The water-soluble membrane according to claim 1, wherein the plasticizer is selected from polyols, sugar alcohols, glycerol, diglycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol with a molecular weight of up to 400 Da, hexanediol, neopentyl glycol, trimethylolpropane, polyether polyols, polyether diols, polyether triols, xylitol, 2-methyl-1,3-propanediol, ethanolamine, glycerol propylene oxide polymers, and mixtures thereof.

15. The water-soluble film according to claim 14, wherein the plasticizer is selected from polyols, sugar alcohols and mixtures thereof.

16. The water-soluble membrane of claim 1, wherein the plasticizer is present in an amount ranging from about 20 PHR to about 50 PHR.

17. The water-soluble membrane according to claim 1, wherein the membrane comprises one or more additives selected from the group consisting of fillers, surfactants, anti-blocking agents, antioxidants, defoamers, bleaching agents, irritants, and agitators.

18. The water-soluble membrane of claim 1, wherein the membrane, when provided with a thickness of 88 µm, has a disintegration time ranging from about 10 seconds to about 150 seconds, as measured by MSTM-205.

19. The water-soluble membrane of claim 1, wherein the dissolution time, when provided with a thickness of 88 µm, ranges from about 10 seconds to about 500 seconds, as measured by MSTM-205.

20. The water-soluble membrane according to claim 1, wherein after conditioning at 28°C / 50% RH for at least 18 hours, the fracture strain of the membrane ranges from about 50% to about 400%, as determined by an elongation at break test.

21. The water-soluble membrane according to claim 1, wherein after conditioning at 28°C / 65% RH for at least 18 hours, the fracture strain of the membrane ranges from about 50% to about 500%, as determined by an elongation at break test.

22. The water-soluble membrane according to claim 1, wherein after conditioning at 28°C / 50% RH for at least 18 hours, the tensile strength of the membrane is in the range of about 10 N / mm. 2 (MPa) to approximately 50 N / mm 2 For example, as measured by tensile strength test.

23. The water-soluble membrane according to claim 1, wherein after conditioning at 28°C / 65 RH for at least 18 hours, the tensile strength of the membrane is in the range of about 5 N / mm. 2 Approximately 20 N / mm 2 For example, as measured by tensile strength test.

24. The water-soluble membrane of claim 1, wherein the membrane has a sealing strength of about 5 N or greater when it is sealed to itself by sealing a first portion of the surface of the membrane to a second portion of the surface of the membrane, as determined by a sealing strength test.

25. The water-soluble membrane according to claim 1, wherein the film-forming resin further comprises one or more bio-based resins selected from: guar gum, gum arabic, xanthan gum, locust bean gum, starch, modified starch, cellulose, cellulose ether, cellulose ester, cellulose amide, methylcellulose, carboxymethyl cellulose and its salts, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, polyamino acids, gelatin, dextrin, maltodextrin, copolymers of the foregoing, and combinations thereof.

26. The water-soluble membrane of claim 1, wherein the membrane comprises at least 95 wt.% bio-based material.

27. The water-soluble membrane of claim 26, wherein the membrane comprises at least 99 wt.% bio-based material.

28. The water-soluble membrane according to claim 1, wherein: The carrageenan is present in the membrane in an amount ranging from about 1 wt.% to about 15 wt.%. The carrageenan comprises at least one of ι-carrageenan, λ-carrageenan, and κ-carrageenan; The weight ratio of carrageenan to pullulan ranges from 1:1.8 to approximately 1:21; The crosslinking agent comprises calcium ions, magnesium ions, potassium ions, or a combination thereof; The plasticizer is selected from polyols, sugar alcohols, and mixtures thereof; and The plasticizer is present in an amount ranging from about 20 PHR to about 50 PHR.

29. The water-soluble membrane according to claim 28, wherein: The carrageenan comprises ι-carrageenan, and the ι-carrageenan accounts for at least about 95 wt.% of the carrageenan present in the membrane. The weight ratio of carrageenan to pullulan ranges from about 1:7 to about 1:12; and The crosslinking agent contains potassium ions.

30. A water-soluble membrane comprising a film-forming resin, a plasticizer, and a crosslinking agent. The film-forming resin comprises pullulan and at least one of 1-carrageenan, λ-carrageenan, and κ-carrageenan, such that the combined amount of 1-carrageenan, λ-carrageenan, and κ-carrageenan accounts for at least about 95 wt.% of the carrageenan present in the membrane. Pullulan is present in the membrane in an amount ranging from about 50 wt.% to about 75 wt.% based on the total weight of the membrane. The crosslinking agent comprises divalent or monovalent metal ions, and is present in the membrane in an amount ranging from about 0.001 wt.% to about 5.0 wt.% based on the total weight of the membrane.

31. The water-soluble membrane according to claim 30, wherein the combined amount of ι-carrageenan, λ-carrageenan and κ-carrageenan is present in the membrane in an amount ranging from about 1 wt.% to about 15 wt.% based on the total weight of the membrane.

32. The water-soluble membrane according to claim 30, wherein the crosslinking agent comprises calcium ions, magnesium ions, potassium ions, or a combination thereof.

33. The water-soluble membrane according to claim 30, wherein the plasticizer is selected from polyols, sugar alcohols, glycerol, diglycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol with a molecular weight of up to 400 Da, hexanediol, neopentyl glycol, trimethylolpropane, polyether polyols, polyether diols, polyether triols, xylitol, 2-methyl-1,3-propanediol, ethanolamine, glycerol propylene oxide polymers, and mixtures thereof.

34. The water-soluble film according to claim 33, wherein the plasticizer is selected from polyols, sugar alcohols and mixtures thereof.

35. The water-soluble film of claim 34, wherein the plasticizer comprises sorbitol and glycerol.

36. The water-soluble membrane of claim 30, wherein the plasticizer is present in an amount ranging from about 20 PHR to about 50 PHR.

37. The water-soluble membrane of claim 30, wherein the membrane comprises one or more additives selected from the group consisting of fillers, surfactants, antiblocking agents, antioxidants, defoamers, bleaching agents, irritants, and agitators.

38. The water-soluble membrane of claim 30, wherein the membrane, when provided with a thickness of 88 µm, has a disintegration time ranging from about 10 seconds to about 150 seconds, as measured by MSTM-205.

39. The water-soluble membrane of claim 30, wherein the dissolution time, when provided with a thickness of 88 µm, ranges from about 10 seconds to about 500 seconds, as measured by MSTM-205.

40. The water-soluble membrane according to claim 30, wherein after conditioning at 28°C / 50% RH for at least 18 hours, the fracture strain of the membrane ranges from about 80% to about 300%, as determined by an elongation at break test.

41. The water-soluble membrane according to claim 30, wherein the film-forming resin further comprises one or more bio-based resins selected from: guar gum, gum arabic, xanthan gum, locust bean gum, starch, modified starch, cellulose, cellulose ether, cellulose ester, cellulose amide, methylcellulose, carboxymethyl cellulose and its salts, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, polyamino acids, gelatin, dextrin, maltodextrin, copolymers of the foregoing, and combinations thereof.

42. A water-soluble film comprising a film-forming resin and a plasticizer, The film-forming resin comprises a mixture of pullulan and carrageenan, and the total amount of pullulan and carrageenan in the membrane is at least 50 wt.% based on the total weight of the membrane. The plasticizer is present in an amount of at least about 20 PHR.

43. The water-soluble membrane according to claim 42, wherein carrageenan is present in an amount ranging from about 1 wt.% to about 25 wt.% based on the total weight of the membrane.

44. The water-soluble membrane of claim 42, wherein the carrageenan comprises at least one of ι-carrageenan, λ-carrageenan and κ-carrageenan, such that the combined amount of ι-carrageenan, λ-carrageenan and κ-carrageenan accounts for at least 95% of the carrageenan in the membrane.

45. The water-soluble membrane according to claim 42, wherein the plasticizer is selected from polyols, sugar alcohols, glycerol, diglycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol with a molecular weight of up to 400 Da, hexanediol, neopentyl glycol, trimethylolpropane, polyether polyols, polyether diols, polyether triols, xylitol, 2-methyl-1,3-propanediol, ethanolamine, glycerol propylene oxide polymers, and mixtures thereof.

46. ​​The water-soluble film according to claim 45, wherein the plasticizer is selected from polyols, sugar alcohols and mixtures thereof.

47. The water-soluble membrane of claim 42, wherein the membrane, when provided with a thickness of 88 µm, has a disintegration time ranging from about 10 seconds to about 150 seconds, as measured by MSTM-205.

48. The water-soluble membrane of claim 42, wherein the dissolution time, when provided with a thickness of 88 µm, ranges from about 10 seconds to about 500 seconds, as measured by MSTM-205.

49. The water-soluble membrane according to claim 42, wherein after conditioning at 28°C / 65% RH for at least 18 hours, the fracture strain of the membrane ranges from about 80% to about 300%, as determined by an elongation at break test.

50. The water-soluble membrane according to claim 1, further comprising polyoxyethylene.

51. The water-soluble membrane of claim 50, wherein the polyoxyethylene comprises polyethylene oxide.

52. The water-soluble membrane according to claim 51, wherein the polyoxyethylene is present in an amount ranging from about 0.5 wt.% to about 5 wt.% based on the total weight of the membrane.

53. The water-soluble membrane according to claim 51, wherein the weight-average molecular weight of the polyoxyethylene ranges from about 500 Da to about 20,000 Da.

54. The water-soluble membrane according to claim 51, wherein the membrane is characterized in that the adhesive force is not greater than 5 N, as measured by an adhesion test.

55. A water-soluble article, in the form of a small package containing a sealed compartment, said article comprising a first water-soluble film and a second water-soluble film. The first water-soluble membrane is a water-soluble membrane according to any one of claims 1 to 54; and The first water-soluble membrane is sealed to the second water-soluble membrane to form the sealed compartment.

56. The water-soluble article of claim 55, wherein the article comprises a composition contained in the sealed compartment.

57. The water-soluble article of claim 56, wherein the composition comprises a home care composition.

58. The water-soluble article of claim 57, wherein the household care composition is selected from light liquid detergent compositions, heavy liquid detergent compositions, hard surface cleaning compositions, laundry detergent gels, bleach compositions, laundry additives, fabric strengthening compositions, shampoos, shower gels, other personal care compositions, and combinations thereof.

59. The water-soluble article of claim 57, wherein the home care composition comprises water in an amount ranging from about 1 wt.% to about 15 wt.% based on the weight of the home care composition.

60. The water-soluble article of claim 59, wherein the home care composition comprises water in an amount ranging from about 10 wt.% to about 15 wt.% based on the weight of the home care composition.

61. The water-soluble article of claim 56, wherein the composition comprises a non-home care composition.

62. The water-soluble article according to claim 55, wherein the first water-soluble film is a thermoformed film.

63. The water-soluble article according to claim 55, wherein the second water-soluble film has the same composition as the first water-soluble film.

64. The water-soluble article of claim 55, wherein the first water-soluble film has a sealing strength of about 5 N or greater when it is sealed to itself by sealing a first portion of the surface of the first water-soluble film to a second portion of the surface of the first water-soluble film, as determined by a sealing strength test.

65. The water-soluble product according to claim 55, wherein the first water-soluble film and the second water-soluble film are edible.

66. The water-soluble article of claim 65, wherein the composition comprises ready-to-eat food and / or beverage components.

67. The water-soluble membrane according to claim 66, wherein the first water-soluble membrane comprises a film-forming resin, a plasticizer, and a crosslinking agent. Based on the total weight of the membrane, the film-forming resin comprises at least 50 wt.% of a mixture of pullulan and carrageenan. The weight ratio of carrageenan to pullulan ranges from 1:1.8 to approximately 1:21, and The crosslinking agent is present in the membrane in an amount ranging from about 0.001 wt.% to about 5.0 wt.%, the crosslinking agent contains potassium ions, and the membrane contains potassium acetate to provide the potassium ions.

68. A water-soluble membrane comprising a film-forming resin, a plasticizer, and a crosslinking agent, Based on the total weight of the membrane, the film-forming resin comprises at least 50 wt.% of a mixture of pullulan and carrageenan. The weight ratio of carrageenan to pullulan ranges from about 1:1.8 to about 1:21, and The crosslinking agent is present in the membrane in an amount ranging from about 0.001 wt.% to about 5.0 wt.% based on the total weight of the membrane.

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