JP2024519681A - Water-dispersible articles comprising a water-dispersible core construction - Patents.com - Google Patents

Abstract

An article for cleaning or hand-washing an object includes a core substrate including a plurality of fibers including a resin. The core substrate has one or more abrasive surfaces and contains an active cleaning formulation. The resin and core substrate become water-dispersible upon contact with low temperature water, such as 40° C. or less, and become water-soluble upon contact with higher temperature water. The present disclosure provides a unit dose article, such as a single unit dose article or a multi-unit dose article, that is easily manufacturable and has a construction that provides an abrasive surface suitable for dry cleaning of debris from cookware and tableware, such as pots, pans, dishes, cooking utensils, eating utensils, glasses and/or cups.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63/185,632, filed May 7, 2021, the entirety of which is expressly incorporated herein by reference.

FIELD The present disclosure relates generally to water-dispersible and/or water-soluble unit dose articles comprising a water-dispersible and/or water-soluble core construct. More particularly, the present disclosure relates to water-dispersible articles comprising a water-dispersible substrate, such as a nonwoven substrate, configured to contain a cleaning formulation, for example for hand washing of objects.

Background Water-soluble packaging materials, such as water-soluble film packaging materials, are commonly used to simplify the dispersion, injection, dissolution and administration of materials to be delivered. Pouches made from conventional water-soluble films are commonly used to package formulations, such as laundry detergent, dish detergent, or personal care formulations. Consumers can add water-soluble film pouches containing dish detergent formulations directly to automatic dishwashers before starting the dishwasher wash cycle. It would be advantageous to provide accurate dosing while eliminating the need for consumers to measure the formulation. However, this single unit dose concept that facilitates the dishwashing process for consumers who choose to wash dishes by hand rather than using an automatic dishwasher has not been extended to hand washing. Instead, consumers who choose to wash by hand must rely on chemical and mechanical means to clean their dishes across a multitude of brands, products and forms, such as bulk dish detergents or powders, and sponges, brushes, cloths or towels that provide a scrubbing action that presents hygiene concerns if not changed frequently.

Thus, there is a need in the art for a unit dose article, such as a single unit dose article or a multi-unit dose article, that has a construction that is easily manufacturable and provides a suitable abrasive surface for dry cleaning of debris from cookware and tableware, e.g., pots, pans, dishes, cooking utensils, eating utensils, glasses and/or cups, while also being dissolvable or soluble when contacted with water at a suitable temperature to deliver a cleaning formulation, e.g., introduced into a sink containing a volume of water to deliver a suitable sanitizing and/or cleaning formulation in which the cookware and tableware can be immersed. After immersion in the water containing the sanitizing and/or cleaning formulation, the cookware and tableware can be easily cleaned and, if necessary, rinsed and dried.

1-4 are schematic cross-sectional views of exemplary articles containing an active cleaning formulation and, optionally, a carrier solvent, according to an exemplary embodiment. 1-4 are schematic cross-sectional views of exemplary articles containing an active cleaning formulation and, optionally, a carrier solvent, according to an exemplary embodiment. 1-4 are schematic cross-sectional views of exemplary articles containing an active cleaning formulation and, optionally, a carrier solvent, according to an exemplary embodiment. 1-4 are schematic cross-sectional views of exemplary articles containing an active cleaning formulation and, optionally, a carrier solvent, according to an exemplary embodiment.

FIG. 5 illustrates an example method of making an article, according to an example embodiment.

DETAILED DESCRIPTION In the exemplary embodiments described herein, an article for cleaning or hand-washing an object is provided. Exemplary unit dose articles, such as single unit dose (SUD) articles or multiple unit dose (MUD) articles, include one or more water-dispersible and/or water-soluble core substrates, such as one or more water-dispersible and/or water-soluble nonwoven, foam or film substrates, with precision dosing to deliver one or more active cleaning formulations, such as carrier solvents containing one or more cleaning agents, for cleaning soiled cookware and tableware, including, but not limited to, pots, pans, dishes, plates, cooking utensils, eating utensils, forks, spoons, knives, glasses and/or cups. The core substrate may be water-dispersible at a temperature of, for example, about 10° C. to about 40° C., and may become water-soluble after multiple uses at such temperatures or higher. In an exemplary embodiment, the article includes a water-dispersible core substrate that includes a water-dispersible resin. The core substrate has one or more abrasive surfaces having a relatively fibrous appearance and/or profile, and one or more smooth surfaces having a relatively smooth appearance and/or profile. The core substrate is configured to contain an active cleaning formulation, e.g., a sanitizing and/or cleaning formulation. A carrier solvent is optionally included.

For example, upon contact of the abrasive surface of the article to a dry or wet surface of a soiled or dirty pan, the consumer simply applies pressure against the soiled or dirty pan surface, causing the abrasive surface to remove baked-on or dried soil from the pan surface. Once the soil is removed from the pan surface, the article can, for example, be contacted with water at a suitable temperature to release the active cleaning formulation for chemical and/or mechanical cleaning action. Alternatively, the consumer may place the article in a sink or container containing an appropriate amount of water such that as the core substrate becomes dispersible or eventually soluble, the active cleaning formulation is released. Once released, the active cleaning formulation disperses, dissolves and/or biodegrades during the hand washing cleaning process without leaving behind undesirable residue.

In an exemplary embodiment, when the core substrate is contacted with water having a temperature greater than 40° C. or greater than 80° C., the water-soluble core substrate becomes soluble and releases the active cleaning formulation. In an exemplary embodiment, the core substrate comprises a water-dispersible or water-soluble polymer, such as, for example, a polyvinyl alcohol (PVOH) polymer, a starch derivative, or a blend thereof with a water-dispersible polymer that otherwise has a high degree of biodegradable activity or is compostable or recyclable.

The article, and more particularly, in an exemplary embodiment, the core substrate is configured to contain one or more active cleaning formulations, such as sanitizing formulations and/or cleaning detergent formulations. By way of example, the active cleaning formulation may include, but is not limited to, a disinfectant and/or dishwashing detergent, a soap or cleaner. Other examples include detergents, soaps or cleaners, fabric softeners, bleaches, laundry enhancers, stain removers, optical brighteners, water softeners, shampoos, conditioners, body washes, face washes, skin lotions, skin treatments, body oils, fragrances, hair treatments, bath salts, essential oils, bath bombs or enzymes, or any suitable combination thereof. In an exemplary embodiment, suitable carrier solvents include solvents having a desired polarity and coating weight to facilitate incorporation of the active cleaning formulation into the polymer matrix of the water-soluble core substrate, including, but not limited to, water, glycerin, polyols such as DPG (dipropylene glycol), and other polar carrier solvents or any combination thereof. In an exemplary embodiment, the carrier solvent containing the active cleaning formulation is disposed on or coated on one or more surfaces of the core substrate, or embedded and/or adhered to the water-soluble core substrate. The core substrate may comprise a single layer, e.g., a single layer of nonwoven core substrate, or may comprise multiple layers, e.g., a sheet of nonwoven core substrate folded into a serpentine arrangement, or cut and overlapped, e.g., to form layers containing the carrier solvent containing the active cleaning formulation disposed between adjacent layers of the water-soluble nonwoven core substrate.

As used herein and unless otherwise indicated, the term "water-dispersible" refers to any nonwoven substrate (or nonwoven web), foam substrate, film, or laminate that, upon immersion in water at a specified temperature, physically dissociates the nonwoven substrate, foam substrate, film, or laminate into smaller constituent pieces. The smaller pieces may or may not be visible to the naked eye, may or may not remain suspended in water, and may or may not ultimately dissolve. In an exemplary embodiment where no dispersion temperature is specified, the nonwoven substrate, foam substrate, film, or laminate disintegrates in 300 seconds or less at about 100°C or less by MSTM-205. For example, the disintegration time may be 200 seconds or less, 100 seconds or less, 60 seconds or less, or 30 seconds or less by MSTM-205 at temperatures of about 80°C, about 70°C, about 60°C, about 50°C, about 40°C, about 20°C, or about 10°C, as appropriate. For example, such dispersion parameters may be characteristic of a nonwoven substrate, foam substrate, film or laminate structure having a thickness of 6 mils (about 152 μm). In an exemplary embodiment, the water-dispersible core substrate has a dispersion time of 300 seconds or less.

As used herein and unless otherwise indicated, the term "water soluble" refers to any nonwoven substrate (or nonwoven web), foam substrate, film or laminate that has a dissolution time of 300 seconds or less at a specified temperature as determined by MSTM-205 as described herein. For example, the dissolution time of the nonwoven substrate, foam substrate, film or laminate may be 200 seconds or less, 100 seconds or less, 60 seconds or less, or 30 seconds or less at a temperature of about 80°C, about 70°C, about 60°C, about 50°C, about 40°C, about 20°C, or about 10°C as required by MSTM-205. In exemplary embodiments where no dissolution temperature is specified, the water soluble nonwoven substrate, foam substrate, film or laminate has a dissolution time of 300 seconds or less at a temperature of about 80°C or less. In an exemplary embodiment, "water soluble nonwoven substrate" or "water soluble nonwoven web" means that at a thickness of 1.5 mils (about 38 μm), the nonwoven substrate dissolves in 300 seconds or less at a temperature of 80° C. or less by MSTM-205. For example, a water soluble nonwoven substrate having a thickness of 1.5 mils (about 38 μm) can have a dissolution time of 300 seconds or less, 200 seconds or less, 100 seconds or less, 60 seconds or less, or 30 seconds or less by MSTM-205 at a temperature of about 70° C., about 60° C., about 50° C., about 40° C., about 30° C., about 20° C., or about 10° C. In an exemplary embodiment, the water soluble core substrate has a dissolution time of 300 seconds or less.

As used herein and unless otherwise indicated, the term "hot water soluble" refers to any water soluble nonwoven substrate, foam substrate, film, or laminate having a dissolution time of 300 seconds or less at a temperature of at least 40°C, e.g., in the range of about 40°C to about 100°C, as determined by MSTM-205. For example, the dissolution time of a hot water soluble nonwoven substrate, foam substrate, film, or laminate may be 200 seconds or less, 100 seconds or less, 60 seconds or less, or 30 seconds at a temperature of greater than about 40°C, e.g., from about 41°C to about 80°C, from about 40°C to about 100°C, from about 40°C to about 60°C, from about 50°C to about 60°C, from about 60°C to about 80°C, or from about 60°C to about 90°C, as appropriate. In exemplary embodiments, a "hot water soluble nonwoven substrate" or "hot water soluble nonwoven web" means that at a thickness of 1.5 mils (about 38 μm), the nonwoven substrate dissolves in 300 seconds or less at a temperature of about 21° C. or greater by MSTM-205. For example, a water soluble nonwoven substrate having a thickness of 1.5 mils (about 38 μm) may have a dissolution time of 300 seconds or less, 200 seconds or less, 100 seconds or less, 60 seconds or less, or 30 seconds or less at a temperature of about 80° C., 70° C., about 60° C., about 50° C., or about 40° C. by MSTM-205. In an exemplary embodiment, a hot water soluble substrate, such as a "hot water soluble nonwoven substrate" or a "hot water soluble nonwoven web", remains stable, e.g., does not dissolve, when contacted with water having a temperature lower than its hot water solubility temperature, but becomes soluble, e.g., dissolves, when contacted with water having a temperature equal to its hot water solubility temperature for an appropriate dissolution time, e.g., at least 300 seconds, between 300 and 600 seconds. For example, in an exemplary embodiment, a hot water soluble nonwoven substrate contacted with water having a temperature of 40° C. for at least 300 seconds, e.g., 300 to 600 seconds, becomes soluble by MSTM-205, but the hot water soluble nonwoven substrate is stable when contacted with water having a temperature less than 40° C. or when contacted with water having a temperature of 40° C. for less than 300 seconds.

As used herein, unless otherwise indicated, the term "nonwoven web" refers to a web or sheet that includes, consists of, or consists essentially of fibers that are arranged (e.g., by a carding process) and bonded to one another. Thus, the term "nonwoven web" can be considered an abbreviation for a web based on nonwoven fibers. Furthermore, as used herein, "nonwoven web" includes any structure that includes a nonwoven web or sheet, including, for example, nonwoven webs or sheets that have films laminated to their surfaces. Methods for preparing nonwoven webs from fibers are well known in the art, for example, as described in Nonwoven Fabrics Handbook, prepared by Ian Butler, edited by Subhash Batra et al., Printing by Design, 1999, which is incorporated herein by reference in its entirety. As used herein, and unless otherwise indicated, the term "film" refers to a continuous film or sheet prepared, for example, by a casting or extrusion process.

As used herein, a "plurality of fibers" can include a single fiber type or can include two or more different fiber types. In exemplary embodiments where the plurality of fibers includes two or more different fiber types, each fiber type can generally be included in any amount, for example, from about 0.5% to about 99.5% by weight of the total weight of the plurality of fibers. In exemplary embodiments where the plurality of fibers consists of a single fiber type, the plurality of fibers is substantially free of the second or more fiber types. The plurality of fibers is substantially free of the second or more fiber types when the plurality of fibers includes less than about 0.5% by weight of the second or more fiber types. In general, the differences between fiber types can be differences in fiber length to diameter ratio (L/D), toughness, shape, stiffness, elasticity, solubility, melting point, glass transition temperature (T _g ), chemical composition, color, or combinations thereof.

As used herein, the terms "resin(s)" and "polymer(s)" should be considered synonymous. In certain embodiments, the terms resin(s) and polymer(s) are used to refer to a polymer optionally combined with one or more additional polymers, and to refer to a single type of polymer, respectively; for example, a resin can include more than one type of polymer.

As used herein, and unless otherwise indicated, the terms "weight percent (wt.%)" and "% by weight (wt. %)" shall refer to the composition of an element specified in "dry" (anhydrous) parts by weight of the entire water-soluble film, including, for example, residual moisture in the water-soluble film, or the composition of an element specified in parts by weight of the entire composition, as appropriate for the context.

As used herein and unless otherwise indicated, the term "PHR" ("phr") shall refer to the composition of the specified element per 100 parts of water-soluble polymeric resin(s) in the water-soluble nonwoven substrate, foam substrate or film, or in the solution used to make the water-soluble nonwoven substrate, foam substrate or film (whether PVOH or other polymeric resin, unless otherwise specified).

As used herein and unless otherwise indicated, the term "comprising" means that various components, ingredients, or steps can be used together in the practice of the present disclosure. Thus, the term "comprising" encompasses the more restrictive terms "consisting essentially of" and "consisting of." The compositions of the present invention can comprise, consist essentially of, or consist of any of the required and optional elements disclosed herein. The present disclosure as illustratively disclosed herein may be practiced in the absence of any element or step not specifically disclosed herein.

When values are expressed as approximations by use of the preceding "about," it will be understood that the particular value forms another embodiment. As used herein, "about X," where X is a numerical value, refers, in exemplary embodiments, to ±10% (e.g., ±5%) of the stated value inclusive.

The articles, water-dispersible and/or water-soluble nonwoven materials, water-dispersible and/or water-soluble foam materials, and water-dispersible and/or water-soluble film materials, and related methods of making and using the articles, water-dispersible and/or water-soluble nonwoven materials, water-dispersible and/or water-soluble foam materials, and water-dispersible and/or water-soluble film materials, are intended to include embodiments that include any combination of one or more of the additional optional elements, features, and steps further described below, unless otherwise noted.

In an exemplary embodiment, the article comprises a water-dispersible and/or water-soluble core substrate comprising a water-dispersible and/or water-soluble resin. In an exemplary embodiment, the core substrate and resin may be water-dispersible at temperatures, for example, from about 10° C. to about 40° C., and may become water-soluble after multiple uses at such temperatures or at higher temperatures, such as 40° C. or higher. The maximum safe temperature of hot water for domestic use is about 48° C. In an exemplary embodiment, the core substrate comprises one of the more water-dispersible nonwoven core substrates. When the core substrate contacts water having a temperature greater than 20° C., or water having a temperature greater than 40° C., or water having a temperature greater than 80° C., the core substrate contains an active cleaning formulation that becomes dispersible or soluble and releases the active cleaning formulation. In an exemplary embodiment, the active cleaning formulation is in the form of at least one of a solid, e.g., a powder, or a plurality of granules or particles, a gel, a liquid, or a slurry form, or any suitable combination thereof. In certain embodiments, the core substrate is saturated with a carrier solvent that includes the active cleaning formulation. In other embodiments, the carrier solvent containing the active cleaning formulation is embedded, disposed, applied, coated and/or adhered to the water-soluble core substrate, e.g., the carrier solvent containing the active cleaning formulation is disposed on the surface of the water-soluble core substrate. In exemplary embodiments, the water-soluble core substrate is at least one of coated with the carrier solvent containing the active cleaning formulation or impregnated with the carrier solvent containing the active cleaning formulation. In exemplary embodiments, the carrier solvent containing the active cleaning formulation is present in the core substrate, e.g., in the fiber-forming composition, the foam-forming composition or the film-forming composition. The carrier solvent is optional.

Referring now to the figures, and initially to Figures 1-4, an article such as a single unit dose article 20 includes a water-dispersible and/or water-soluble nonwoven substrate 22 that includes a plurality of fibers that include a water-dispersible and/or water-soluble resin. In an exemplary embodiment, the nonwoven substrate 22 includes any suitable fiber chemistry, including, but not limited to, PVOH fibers as described herein, or PVOH fibers blended with up to 90% by weight cellulosic type fibers, or PVOH fibers blended with fibers made with other polymers. In some embodiments, the nonwoven substrate is made of water-dispersible fibers.

In an exemplary embodiment, the nonwoven substrate 22 has a basis weight of 15 gsm to 150 gsm (grams per square meter); a fiber length of 10.0 mm to 150 mm; and a suitable fiber diameter of 5 microns to 100 microns. In other exemplary embodiments, the water-soluble nonwoven substrate 22 has any suitable basis weight, fiber length, and/or fiber diameter. For example, in an exemplary embodiment, the fiber diameter is less than 5 microns or greater than 100 microns. The fibers of the nonwoven substrate 22 may be formed using any suitable method, including but not limited to a carded process or any suitable process for making water-soluble nonwoven fibers. Additionally, the fibers of the nonwoven substrate 22 are bonded together using any suitable bonding process or method, including but not limited to heat, thermal, chemical, water and/or solution bonding methods, or any suitable bonding method known in the art for nonwoven fiber bonding. As described below and illustrated in FIGS. 1-4, the nonwoven substrate 22 may include any suitable number of layers or plies, for example, from one layer or ply to fifty layers or plies, or more in some embodiments. The nonwoven substrate 22 may be porous or nonporous and may be cold water soluble, warm water soluble, or hot water soluble. In alternative exemplary embodiments, the nonwoven substrate may be cold water dispersible, warm water dispersible, or hot water dispersible. The water-soluble nonwoven substrate 22 may be formed using any suitable manufacturing process known in the nonwoven manufacturing art, including, but not limited to, carded processes. The construction of the water-soluble nonwoven substrate 22 may include, for example, folded layers or plies, stacked layers or plies, and/or rolled layers or plies.

In an exemplary embodiment, the nonwoven substrate 22 contains an active cleaning formulation 26 and, optionally, a carrier solvent 25. In an exemplary embodiment, the nonwoven substrate 22 has a moisture content of less than 15% by weight, more specifically, less than 10% by weight, and even more specifically, between 2% and 10% by weight, prior to contact with the carrier solvent 25 containing the active cleaning formulation 26. In an exemplary embodiment described herein, upon contact of the carrier solvent 25 with at least one fiber of the plurality of fibers, the at least one fiber exhibits a shrinkage of 0.5% to 65%. In an exemplary embodiment, the active cleaning formulation 26 is a liquid formulation.

In an exemplary embodiment, when the nonwoven substrate 22 is contacted with water having a temperature in the range of 10° C. to 40° C., the nonwoven substrate 22 becomes dispersible and releases the active cleaning formulation 26. When the nonwoven substrate 22 is contacted with water having a temperature greater than 40° C. or greater than 80° C., the water-soluble nonwoven substrate 22 becomes soluble, i.e., dissolves. Further, in an exemplary embodiment, when the nonwoven substrate 22 is contacted with water having a temperature greater than 20° C. or greater than 40° C. for 300 seconds or less, the active cleaning formulation 26 is substantially released from the water-soluble nonwoven substrate 22. In an exemplary embodiment, the nonwoven substrate 22 has a dissolution time of at least 300 seconds at a temperature greater than 40° C., e.g., 60° C. to 100° C., by MSTM-205. In an exemplary embodiment, the core substrate can be evaluated by being completely dissolved in the application and being capable of being completely dissolved in the MSTM 205 test in less than 300 seconds. In an exemplary application test, no residue remains when the water-soluble core substrate is dissolved at 40°C to 100°C in less than 600 seconds using undefined oscillation.

Suitable carrier solvents 25 include, but are not limited to, water, polyols, such as glycerin, DPG, and the like, and other polar solvents having the desired polarity and coating weight to facilitate incorporation of the active cleaning formulation 26 into the polymer matrix of the water-soluble nonwoven substrate 22. The active cleaning formulation 26 may be in the form of a solid, such as a powder or multiple granules or particles, a gel, a liquid, or a slurry formulation, or any suitable combination of, such as a solid, gel, liquid, or slurry formulation. In an exemplary embodiment, the active cleaning formulation 26 is in any suitable phase, including, for example, a solid phase, a liquid phase, a slurry phase (a liquid containing a solid and multiple phases), or any suitable combination of phases. For example, the active cleaning formulation 26 may include fine powder particles or granules, a gel, one or more liquids, or a slurry, or multiple phases. The active cleaning formulation 26 may include, but is not limited to, one or more of the following: disinfectants, sanitizers, detergents, surfactants, emulsifiers, chelating agents, soil suspension agents, stain strippers, enzymes, pH adjusters, builders, soil release polymers, structuring agents, free fragrances, encapsulated fragrances, preservatives, solvents, minerals, oxidizers, foam builders, HLB adjusters, or degreasers, and/or any ingredients suitable for inclusion in a disinfectant and/or dish detergent (or personal care, laundry detergent, and/or household surface cleaner or cleanser). In an exemplary embodiment, the active cleaning formulation 26 may include a disinfectant or sanitizer, or the water soluble nonwoven substrate 22 may include a disinfectant or sanitizer as an adjunct. In an exemplary embodiment, the article 20 includes an active cleaning formulation 26 having a mass of 0.5 grams (g) to 250 grams and a volume of 1.0 milliliters (ml) to 250 ml. In exemplary embodiments in which the active cleaning formulation 26 is in a solid phase, the particles or granules may have a size of, for example, 1 micron to 100 microns, or may be in the form of tablets.

In an exemplary embodiment, the active cleaning formulation 26 is contained in or by the nonwoven substrate 22, for example, by saturating the nonwoven substrate 22 with the carrier solvent 25 comprising the active cleaning formulation 26, by disposing, e.g., applying or coating the carrier solvent 25 comprising the active cleaning formulation 26 on one or more surfaces, e.g., the first surface 28 and/or the second surface 30 of the nonwoven substrate 22 as shown in Figures 1 and 3, by embedding the carrier solvent 25 comprising the active cleaning formulation 26 in the matrix 32 of the nonwoven substrate 22, for example, in one or more layers of the nonwoven substrate 22 as shown in Figures 2 and 4, and/or by disposing, e.g., applying or coating the carrier solvent 25 comprising the active cleaning formulation 26 between different layers, e.g., adjacent layers of the nonwoven substrate 22, for example, by coating one or more surfaces of one or more layers with the carrier solvent 25 comprising the active cleaning formulation 26. The carrier solvent 25 comprising the active cleaning formulation 26 may be adsorbed and/or adhered or bonded, for example, to the surface of the nonwoven substrate 22. In exemplary embodiments, carrier solvent 25 containing one or more active cleaning formulations 26 is suspended in a water-soluble polymer system or resin, such as a PVOH resin described herein, or disposed, e.g., coated, on one or more surfaces of water-soluble nonwoven substrate 22. The various morphologies described herein allow for control over the release and/or delivery of active cleaning formulation 26 and the solubility of article 20. In exemplary embodiments, active cleaning formulation 26 is released at a specific or determined water temperature and/or for a specific or determined amount of time as determined by thermodynamics and capillary pressure. Carrier solvent 25 is optional. In some embodiments, article 20 does not include carrier solvent 25.

In an exemplary embodiment, the one or more first surfaces 28 include an abrasive material 34 that forms a rough area or region of the water-soluble nonwoven substrate 22, e.g., an abrasive portion or region having a fibrous appearance and/or profile. In an exemplary embodiment, the abrasive material 34 includes, but is not limited to, at least one of the following: a plurality of fibers as described herein, an active cleaning formulation in solid form as described herein, silicon dioxide or silica (SiO ₂ ), diatomaceous earth, one or more clays, minerals, jute, or a plurality of natural insoluble fibers, or combinations thereof, to provide the first surface 28 with a desired abrasiveness suitable for scrubbing or scraping dry or wet soiled cookware and tableware without damaging the surface finish of the cookware or tableware. In an exemplary embodiment, the plurality of fibers in the nonwoven substrate 22 and the active cleaning formulation 26 in solid form as the abrasive material 34 provide the first surface 28 with a desired abrasiveness. Other suitable abrasive materials 34 may also be used alone or in combination to provide the first surface 28 with a desired abrasiveness. Generally, in the exemplary embodiment, wear is defined by the change in Ra (gloss) value before and after the metal surface is cleaned, with parameters defined in the X-direction and the rotational direction. In the exemplary embodiment, one or more abrasive materials 34 are contained within the water-soluble nonwoven substrate 22. For example, the abrasive material 34 is embedded, disposed, applied, coated and/or adhered to the first surface 28 and/or embedded in the nonwoven substrate 22, for example, the abrasive material 34 is disposed in the matrix 32 of the nonwoven substrate 22. In the exemplary embodiment, the abrasive material has a surface finish Ra value for carbon steel substrates of about 8 uin (0.2 μm) to about 16 uin (0.4 μm) (XY automatic); 11 uin (0.275 μm) to about 22 uin (0.55 μm) (off-hand short); and about 13 uin (0.325 μm) to about 21 uin (0.525 μm) (off-hand long). In an exemplary embodiment, the abrasive material has a surface finish Ra value for aluminum substrates of about 29 uin (0.725 μm) to about 57 uin (1.425 μm) (XY automatic) and about 33 uin (0.825 μm) to about 60 uin (1.5 μm) (off-hand short).

In an exemplary embodiment, the nonwoven substrate 22 includes one or more relatively smooth second surfaces 30. That is, each second surface 30 has a relatively smooth appearance and/or profile compared to the relatively fibrous appearance and/or profile of the first surface 28. For example, the second surfaces 30 may be coated with water and/or heated to create a continuous smooth surface.

The abrasive material 34 may be applied to the first surface 28 using any suitable application method known to those skilled in the art, including, for example, adhesive or heat application examples. In an exemplary embodiment, a suitable adhesive is applied to the first surface 28 to adhere the abrasive material 34 to the first surface 28, or the first surface 28 is heated and the abrasive material 34 is applied to the first surface 28 using a suitable spray application or by placing the first surface 28 on a suitable abrasive material 34 contained, for example, in a bed or container. In other exemplary embodiments, the nonwoven substrate 22 is impregnated with the abrasive material 34. In an exemplary embodiment, the abrasive material 34 is present in the nonwoven substrate 22, for example, in a fiber forming composition.

In other exemplary embodiments, one or more abrasive materials 34 are embedded, disposed, applied, coated and/or adhered to the second surface 30 and/or embedded in the water-soluble nonwoven substrate 22 to form rough areas or regions of the water-soluble nonwoven substrate 22, e.g., abrasive portions or regions of the second surface 30 having a fibrous appearance and/or profile. In exemplary embodiments, the abrasive materials 34 may be disposed to form an abrasive gradient throughout the thickness of the water-soluble nonwoven substrate 22, with the first surface 28 having a first degree of abrasion and the opposing second surface 30 having a second degree of abrasion that is less than or greater than the first degree of abrasion. In exemplary embodiments, the first surface 28 has a relatively rough appearance and/or rough profile when compared to the appearance and/or profile of the second surface 30. Conversely, the second surface 30 has a relatively smooth appearance and/or smooth profile when compared to the appearance and/or profile of the first surface 28.

In an exemplary embodiment as shown in Figure 1, the article 20 includes one or more layers of nonwoven substrate 22 forming a nonwoven sheet 36 and a carrier solvent 25 comprising an active cleaning formulation 26 in a solid phase disposed on a first surface 28 and/or an opposing second surface 30 of the nonwoven substrate 22. In an exemplary embodiment as shown in Figure 2, the article 20 includes one or more layers of nonwoven substrate 22 forming a nonwoven sheet 36 containing a carrier solvent 25 comprising an active cleaning formulation 26 in a solid phase embedded within a matrix 32 of the nonwoven substrate 22. In an exemplary embodiment as shown in Figure 3, the article 20 includes multiple sheets 36 (e.g., _36n , 36n ₊₁ , 36n ₊₂ , 36n ₊₃ , 36n ₊₄ , 36n ₊₅ , ..., as shown in Figures 3 and 4) of nonwoven substrate 22 joined together to form spheres or spheroids in a solid phase disposed on one or more surfaces of one or more sheets 36, e.g., a first surface 28 and/or an opposing second surface 30 of the sheet 36, and a carrier solvent 25 containing an active cleaning formulation 26. The multiple sheets 36 may be joined together along a centerline 38 of each sheet 36, collectively defining a center point 40 of the article 20 to form a spherical or spheroid shaped article 20, as shown in Figures 3 and 4. In other exemplary embodiments, one or more sheets 36 may be joined together, e.g., along an edge of each sheet 36, collectively defining a center point 40 of the article 20 to form a spherical or spheroid shaped article 20. In an exemplary embodiment, as shown in Figure 3, one or more sheets 36 of nonwoven substrate 22 contain carrier solvent 25 with active cleaning formulation 26 in a solid phase disposed on a first surface 28 and/or an opposing second surface 30 of sheet 36. In an exemplary embodiment, as shown in Figure 4, article 20 includes one or more sheets 36 of nonwoven substrate 22 containing carrier solvent 25 with active cleaning formulation 26 in a solid phase embedded within a matrix 32 of nonwoven substrate 22.

With further reference to FIGS. 1-4, in an exemplary embodiment, the nonwoven substrate 22 includes a plurality of fibers as described herein, although not explicitly shown in FIGS. 1-4. In an exemplary embodiment, one or more fibers of the plurality of fibers are saturated or impregnated with a carrier solvent 25 including an active cleaning formulation 26. The carrier solvent 25 including the active cleaning formulation 26 may be embedded in one or more fibers of the plurality of fibers or between one or more adjacent fibers of the plurality of fibers, or the carrier solvent 25 including the active cleaning formulation may be disposed, e.g., applied or coated, on a surface of one or more fibers of the plurality of fibers.

In an exemplary embodiment, an exemplary water-dispersible and/or water-soluble article 20, such as a water-dispersible and/or water-soluble nonwoven towel, sheet, wipe, loofah, pad, strip, or sponge, is provided that allows a consumer to initially scrub or scrape soiled or dirty cookware and dishware. The article 20, in an exemplary embodiment, is configured to provide one or more abrasive surfaces to facilitate cleaning of wet or dry debris and ingredients from the surfaces of the cookware and dishware, and to deliver an appropriate amount of active cleaning formulation 26 for cleaning a single serving of cookware and dishware that is to be, for example, hand-washed. When the dishware is dry, the consumer may scrub the dishware. Once a desired amount of debris and ingredients has been removed using the article 20, the article 20 can be dissolved in a sink (or in a soaking tub) that delivers a sanitizing and/or cleaning formulation to further remove debris and ingredients from the dishware and sanitize the dishware. As another example, the consumer may add cold water (e.g., water having a temperature of 20° C. or less) to the dish as the consumer scrubs the dish and the article 20 gradually or slowly dissolves during use. Once the dish is clean, the water can be squeezed out of the article 20, which may be reused. After single or multiple uses, the consumer can add warm water (e.g., water having a temperature of at least 40° C., preferably 60° C.-70° C. or higher) to the article 20 to substantially or completely dissolve the article 20 and release the sanitizing agent into the warm water contained in the sink. When the water temperature is close to 40° C., the article 20 begins to dissolve, and dissolves much faster at temperatures of 60° C.-70° C. or higher. As another example, when the dish is washed with warm water (e.g., water having a temperature of at least 40° C.), the article 20 does not dissolve. During the washing process, the carrier solvent 25 containing the active cleaning formulation 26 is substantially continuously released from the article 20. Once the manual dishwashing process is complete, article 20 can be introduced into an automatic dishwashing machine. Article 20 dissolves during the wash cycle to aid in dishwashing. Alternatively, since article 20 exhibits a suitable biodegradation profile, article 20 may be disposed of in the trash or placed in a paper recycling bin.

5, in an exemplary embodiment, a method 100 of making an article 20, such as a single unit dose article, containing an active cleaning formulation and optionally a carrier solvent includes step 102 or steps 102 and 104. In step 102, a core substrate is formed that includes a plurality of fibers that include a water-dispersible and/or water-soluble resin. In an exemplary embodiment, one or more layers of the core substrate or substrate are formed that contain a carrier solvent with an active cleaning formulation. In an exemplary embodiment, the core substrate, e.g., nonwoven substrate 22, is configured to contain a carrier solvent with one or more active cleaning formulations as described herein. In an exemplary embodiment, the carrier solvent 25 with the active cleaning formulation 26 is contained in or by the nonwoven substrate 22, for example, by saturating the nonwoven substrate 22 with the carrier solvent 25 with the active cleaning formulation 26, by disposing, e.g., applying or coating the carrier solvent 25 with the active cleaning formulation 26 on one or more surfaces, e.g., on the first surface 28 and/or the second surface 30 of the nonwoven substrate 22 as shown in Figures 1 and 3, in the matrix 32 of the nonwoven substrate 22, by embedding the carrier solvent 25 with the active cleaning formulation 26 in one or more layers of the nonwoven substrate 22 as shown in Figures 2 and 4, and/or by disposing the carrier solvent 25 with the active cleaning formulation 26 between different layers, e.g., between adjacent layers of the nonwoven substrate 22, e.g., by coating one or more surfaces of one or more layers with the carrier solvent 25 with the active cleaning formulation 26. The active cleaning formulation 26 may, for example, be adsorbed and/or adhered or bonded to the surface of the nonwoven substrate 22. When at least one fiber of the plurality of fibers forming the nonwoven substrate 22 is contacted with an appropriate amount of carrier solvent 25, the at least one fiber exhibits a shrinkage rate of 0.5% to 65%. In an exemplary embodiment, the method 100 includes contacting the carrier solvent with the nonwoven substrate 22, and upon contact with the carrier solvent, the at least one fiber exhibits a shrinkage rate of 0.5% to 65%. In an exemplary embodiment, when the nonwoven substrate 22 is contacted with water having a temperature greater than 20° C., or with water having a temperature greater than 40° C., or with water having a temperature greater than 80° C., the nonwoven substrate 22 becomes dispersible or soluble to release the active cleaning formulation. The carrier solvent 25 is optionally in the article 20. If a carrier solvent 25 is used, it may be dried in the article 20.

In an exemplary embodiment, the method 100 includes step 104. In step 104, an abrasive surface is formed on the water-soluble nonwoven substrate 22. For example, one or more surfaces of the nonwoven substrate 22 are formed having rough or abrasive areas or regions. In an exemplary embodiment, one or more abrasive materials 34 are formed, disposed or adhered to one or more first surfaces 28 of the nonwoven substrate 22 to form rough areas or regions of the nonwoven substrate 22, e.g., abrasive areas or regions having a fibrous appearance and/or profile. Suitable abrasive materials 34 described herein can be used alone or in combination to provide the first surface 28 with the desired abrasiveness. In an exemplary embodiment, one or more abrasive materials 34 are contained within the nonwoven substrate 22. For example, the abrasive material 34 is embedded, disposed, applied, coated and/or adhered to the first surface 28 and/or embedded in the nonwoven substrate 22, e.g., the abrasive material 34 is disposed in the matrix 32 of the nonwoven substrate 22.

In an exemplary embodiment, the method 100 includes forming one or more abrasive materials 34 on the first surface 28 or applying one or more abrasive materials 34 to the first surface 28 using any suitable application method known to those skilled in the art, including, for example, adhesive or heat application examples. In an exemplary embodiment, a suitable adhesive is applied to the first surface 28 to adhere the abrasive materials 34 to the first surface 28, or the first surface 28 is heated and the abrasive materials 34 are applied to the first surface 28 using a suitable spray application or by placing the first surface 28 on a suitable abrasive material 34 contained in, for example, a bed or a container. In other exemplary embodiments, the first surface 28 is at least partially melted and the abrasive materials 34 are applied to the at least partially melted first surface 28, or the nonwoven substrate 22 is impregnated with the abrasive materials 34. In an exemplary embodiment, the abrasive materials 34 are present in the nonwoven substrate 22, for example, in a fiber forming composition or resin.

In an exemplary embodiment, the method 100 includes forming one or more surfaces of the water-soluble nonwoven substrate 22 with relatively smooth areas or regions having a smooth appearance and/or profile. For example, the water-soluble nonwoven substrate 22 may include one or more relatively smooth second surfaces 30. That is, compared to the relatively fibrous appearance and/or profile of the first surface 28, each second surface 30 has a relatively smooth appearance and/or profile. In an exemplary embodiment, the second surface 30 may be coated with water and/or heated to create a continuous smooth surface. In another exemplary embodiment, the method 100 includes forming one or more abrasive areas or regions on the second surface 30. For example, one or more abrasive materials 34 may be embedded, disposed, applied, coated and/or adhered to the second surface 30 and/or embedded in the nonwoven substrate 22 to form rough areas or regions of the nonwoven substrate 22, e.g., abrasive areas or regions on the second surface 30 having a fibrous appearance and/or profile.

In another exemplary embodiment, the method 100 includes forming an abrasive gradient across the thickness of the nonwoven substrate 22. For example, the abrasive material 34 may be disposed such that an abrasive gradient is formed across the thickness of the nonwoven substrate 22, with the first surface 28 having a first degree of abrasiveness and the opposing second surface 30 having a second degree of abrasiveness that is less than or greater than the first degree of abrasiveness. In an exemplary embodiment, the first surface 28 has a relatively rough appearance and/or profile when compared to the appearance and/or profile of the second surface 30. Conversely, the second surface 30 has a relatively smooth appearance and/or profile when compared to the appearance and/or profile of the first surface 28.
Water-soluble film and fiber forming materials

Water-soluble polymers used in the water-soluble fibers, water-soluble nonwoven substrates, water-soluble foam substrates, and water-soluble films include, but are not limited to, polyvinyl alcohol (PVOH) polymers, polyacrylates, water-soluble acrylate copolymers, polyvinylpyrrolidone, polyethyleneimine, pullulan, water-soluble natural polymers including, but not limited to, guar gum, acacia gum, xanthan gum, carrageenan, and starch, water-soluble polymer derivatives including, but not limited to, modified starch, ethoxylated starch, and hydroxypropylated starch, copolymers of the foregoing, and combinations of any of the foregoing. Other water-soluble polymers include polyalkylene oxides, polyacrylamides, polyacrylic acids and salts thereof, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts thereof, polyamino acids, polyamides, gelatin, methylcellulose, carboxymethylcellulose and salts thereof, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and combinations of any of the foregoing. Such water-soluble polymers, whether PVOH or other, are commercially available from a variety of sources.

In general, the fibers, foams and films described herein include polyvinyl alcohol. Polyvinyl alcohol is a synthetic polymer that is generally prepared by the alcoholysis of polyvinyl acetate, usually referred to as "hydrolysis" or "saponification." Fully hydrolyzed PVOH, in which virtually all acetate groups have been converted to alcohol groups, is a strongly hydrogen-bonded, highly crystalline polymer that is soluble only in hot water, e.g., water having a temperature greater than about 140° F. (about 60° C.). If a sufficient number of acetate groups are left after hydrolysis of polyvinyl acetate, i.e., the PVOH polymer is partially hydrolyzed, the polymer is more weakly hydrogen-bonded, less crystalline, and generally soluble in cold water, e.g., water having a temperature less than about 50° F. (about 10° C.). Thus, the partially hydrolyzed polymer is a vinyl alcohol-vinyl acetate copolymer, which is a PVOH copolymer, but is generally referred to as PVOH.

In some embodiments, suitable examples of such polymers include, but are not limited to, polyvinyl alcohol homopolymers, polyvinyl alcohol copolymers, modified polyvinyl alcohol copolymers, and combinations thereof. For example, the polyvinyl alcohol copolymer, in some embodiments, is a copolymer of vinyl acetate and vinyl alcohol. For example, in some embodiments, the modified polyvinyl alcohol copolymer includes an anionically modified copolymer, which may be a copolymer of vinyl acetate and vinyl alcohol further including additional groups such as carboxylate, sulfonate, or combinations thereof. Thus, the partially hydrolyzed polymer is a vinyl alcohol-vinyl acetate copolymer, which is a PVOH copolymer, but is generally referred to as "polyvinyl alcohol (PVOH)" or "PVOH polymer". For simplicity, the term "PVOH polymer" as used herein is understood to encompass homopolymers, copolymers, and modified copolymers that include vinyl alcohol moieties, e.g., 50% or more vinyl alcohol moieties. The term "PVOH fiber" as used herein refers to a fiber that includes a PVOH polymer.

The fibers, foams and/or films described herein may comprise one or more polyvinyl alcohol (PVOH) homopolymers, one or more polyvinyl alcohol copolymers, one or more modified polyvinyl alcohol copolymers, or combinations thereof. As used herein, the term "homopolymer" generally includes polymers having a single type of monomer repeat unit (e.g., a polymer chain consisting of or consisting essentially of a single monomer repeat unit). In the specific case of PVOH, the term "PVOH polymer" further includes copolymers consisting of a distribution of vinyl alcohol monomer units and vinyl acetate monomer units depending on the degree of hydrolysis (e.g., a polymer chain consisting of or consisting essentially of vinyl alcohol and vinyl acetate monomer units). In the limiting case of 100% hydrolysis, a PVOH homopolymer may include a true homopolymer having only vinyl alcohol units. In some embodiments, the fibers, foams and/or films of the present disclosure comprise a polyvinyl alcohol copolymer. In some embodiments, the fibers, foams and/or films of the present disclosure comprise a cold water soluble or hot water soluble polyvinyl alcohol copolymer.

Unless expressly indicated otherwise, the term "degree of hydrolysis" is understood as the percentage (e.g., mole percentage) of hydrolyzed moieties among all hydrolyzable moieties initially possessed by the polymer. For example, for a polymer containing at least one vinyl acetate moiety or vinyl alcohol moiety, partial replacement of ester groups in the vinyl acetate moiety with hydroxyl groups occurs during hydrolysis, and the vinyl acetate moiety becomes a vinyl alcohol moiety. The degree of hydrolysis of a polyvinyl acetate homopolymer is considered to be 0, while the degree of hydrolysis of a polyvinyl alcohol homopolymer is considered to be 100%. The degree of hydrolysis of a copolymer of vinyl acetate and vinyl alcohol is equal to the percentage of vinyl alcohol moieties among the sum of the vinyl acetate and vinyl alcohol moieties, which is between 0 and 100%.

In some embodiments, the polyvinyl alcohol polymer comprises a modified polyvinyl alcohol, e.g., a copolymer. The modified polyvinyl alcohol can comprise a copolymer or a higher polymer (e.g., a terpolymer) that comprises one or more monomers in addition to the vinyl acetate/vinyl alcohol groups. Optionally, the modification is neutral, e.g., provided by ethylene, propylene, N-vinylpyrrolidone, or other uncharged monomer species. Optionally, the modification is a cationic modification, e.g., provided by a positively charged monomer species. Optionally, the modification is an anionic modification. Thus, in some embodiments, the polyvinyl alcohol comprises an anionically modified polyvinyl alcohol.

Anionically modified polyvinyl alcohol can include partially or fully hydrolyzed PVOH copolymers that include anionic monomer units, vinyl alcohol monomer units, and optionally vinyl acetate monomer units (i.e., when not fully hydrolyzed). In some embodiments, modified PVOH copolymers can include two or more types of anionic monomer units. General classes of anionic monomer units that can be used in PVOH copolymers include vinyl sulfonate monomers and their esters, vinyl monocarboxylic acid monomers and their esters and anhydrides, dicarboxylic acid monomers with polymerizable double bonds and their esters and anhydrides, and vinyl polymerized units corresponding to the alkali metal salts of any of the foregoing. Examples of suitable anionic monomer units include vinyl acetate, maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, fumaric acid, monoalkyl fumarates, dialkyl fumarates, itaconic acid, monoalkyl itaconates, dialkyl itaconates, citraconic acid, monoalkyl citraconates, dialkyl citraconates, citraconic anhydride, mesaconic acid, monoalkyl mesaconates, dialkyl mesaconates, glutaconic acid, monoalkyl glutaconates, dialkyl glutamines, and the like. Included are vinyl polymerized units corresponding to vinyl anionic monomers including taconates, alkyl acrylates, alkyl alkacrylates, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid (AMPS), 2-sulfoethyl acrylate, alkali metal salts of the foregoing (e.g., sodium, potassium, or other alkali metal salts), esters of the foregoing (e.g., methyl, ethyl, or other _C1 - _C4 or _C6 alkyl esters), and combinations of the foregoing (e.g., multiple types of anionic monomers or equivalent forms of the same anionic monomer). In some embodiments, the PVOH copolymers can include two or more types of monomer units selected from neutral, anionic, and cationic monomer units.

The level of incorporation of one or more anionic monomer units in the PVOH copolymer is not particularly limited. In certain embodiments, the one or more anionic monomer units are present in the PVOH copolymer in an amount ranging from about 1 mol% or 2 mol% to about 6 mol% or 10 mol% (e.g., at least 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, or 4.0 mol%, and/or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 8.0, or 10 mol%) in various embodiments.

Polyvinyl alcohol can be subject to changes in solubility characteristics. It is known to those skilled in the art that the acetate groups of co-poly(vinyl acetate vinyl alcohol) polymers (PVOH copolymers) can be hydrolyzed by either acid or alkaline hydrolysis. As the degree of hydrolysis increases, polymer compositions made from PVOH copolymers will have high mechanical strength but reduced solubility at low temperatures (e.g., requiring warm water temperatures for complete dissolution). Thus, exposure of a PVOH homopolymer to an alkaline environment (e.g., from laundry bleach additives) can transform the polymer from one that dissolves quickly and completely in a given aqueous environment (e.g., cold water medium) to one that dissolves slowly and/or incompletely in the aqueous environment, possibly resulting in insoluble polymer residues.

The degree of hydrolysis (DH) of the PVOH homopolymers and PVOH copolymers (including modified PVOH copolymers) contained in the water soluble fibers, foams and films of the present disclosure can range from about 75% to about 99.9% (e.g., about 79% to about 92%, about 75% to about 89%, about 80% to about 90%, about 88% to 92%, about 86.5% to about 89%, or about 88%, 90%, or 92%, for cold water soluble compositions; about 90% to about 99.9%, about 90% to about 99%, about 92% to about 99%, about 95% to about 99%, about 98% to about 99%, about 98% to about 99.9%, about 96%, about 98%, about 99%, or more than 99%). As the degree of hydrolysis decreases, fibers, foams, or films made from the polymer will have reduced mechanical strength but faster solubility at temperatures below about 20° C. As the degree of hydrolysis increases, fibers, foams, or films made from the polymer will tend to be mechanically stronger and less thermoformable. The degree of hydrolysis of the PVOH can be selected such that the water solubility of the polymer is temperature dependent, thus affecting the solubility of films, foams, or fibers made from the polymer and additional components. In certain embodiments, the films, foams, and/or fibers are cold water soluble. For co-poly(vinyl acetate vinyl alcohol) polymers without any other monomers (e.g., homopolymers not copolymerized with anionic monomers), cold water soluble fibers, foams, or films that are soluble in water at temperatures below 10° C. can include PVOH with a degree of hydrolysis ranging from about 75% to about 90%, from about 75% to about 89%, or from about 80% to about 90%, or from about 85% to about 90%. In another embodiment, the fiber, foam, or film is hot water soluble. For co-poly(vinyl acetate vinyl alcohol) polymers without any other monomers (e.g., copolymers not copolymerized with anionic monomers), a hot water soluble fiber, foam, or film that is soluble in water at a temperature of at least about 60° C. can include PVOH having a degree of hydrolysis of at least about 98%. In an exemplary embodiment, one or more of the plurality of fibers includes a polyvinyl alcohol polymer having a degree of hydrolysis ranging from about 75% to about 99.9%. In an exemplary embodiment, one or more of the plurality of fibers includes a polyvinyl alcohol polymer having a degree of hydrolysis ranging from about 75% to about 98%. In an exemplary embodiment, one or more of the plurality of fibers includes a polyvinyl alcohol polymer having a degree of hydrolysis ranging from about 75% to about 89%. In an exemplary embodiment, one or more of the plurality of fibers includes a polyvinyl alcohol polymer having a degree of hydrolysis ranging from about 90% to about 99.9%. In an exemplary embodiment, the water-soluble film comprises a polyvinyl alcohol homopolymer or a PVOH copolymer having a degree of hydrolysis ranging from about 75% to about 99.9%. In an exemplary embodiment, the water-soluble film comprises a polyvinyl alcohol copolymer or a modified polyvinyl alcohol copolymer having a degree of hydrolysis ranging from about 75% to about 98%.

）により特徴付けることもできる。例えば、２種またはそれよりも多くのＰＶＯＨポリマーを含むＰＶＯＨポリマーに関する

は、式

により計算され、式中、Ｗ_ｉは、それぞれのＰＶＯＨポリマーのモル百分率であり、Ｈ_ｉは、それぞれの加水分解度である。ポリマーが特定の加水分解度を有する（または持たない）と称されるとき、ポリマーは、指定された位加水分解度を有する単一ポリビニルアルコールポリマー、または指定された平均加水分解度を有するポリビニルアルコールポリマーのブレンドとすることができる。 The degree of hydrolysis of the polymer blends was calculated as the arithmetic weighted average degree of hydrolysis (

For example, for PVOH polymers containing two or more PVOH polymers,

is the formula

where W _i is the mole percentage of the respective PVOH polymer and H _i is the respective degree of hydrolysis. When a polymer is referred to as having (or not having) a particular degree of hydrolysis, the polymer can be a single polyvinyl alcohol polymer having the specified degree of hydrolysis or a blend of polyvinyl alcohol polymers having the specified average degree of hydrolysis.

）に相関し、しばしば粘度が

の代用として使用されることが、当技術分野では周知である。 The viscosity of PVOH polymers (μ) is determined by measuring freshly made solutions using a Brookfield LV type viscometer with a UL adapter as described in British Standard EN ISO 15023-2:2006 Annex E Brookfield test method. It is international convention to refer to the viscosity of a 4% aqueous polyvinyl alcohol solution at 20° C. All viscosities specified herein in centipoise (cP) should be understood to refer to the viscosity of a 4% aqueous polyvinyl alcohol solution at 20° C., unless otherwise specified. Similarly, when a polymer is described as having (or not having) a particular viscosity, unless otherwise specified, the specified viscosity is intended to be the average viscosity of the polymer, inherent with the corresponding molecular weight distribution, i.e., the weighted natural logarithm average viscosity. The viscosity of a PVOH polymer is determined as a function of the weight average molecular weight (

) and viscosity is often

It is well known in the art that .

In exemplary embodiments, the PVOH resin may have a viscosity of about 1.0 to about 50.0 cP, about 1.0 to about 40.0 cP, or about 1.0 to about 30.0 cP, such as about 4 cP, 8 cP, 15 cP, 18 cP, 23 cP, or 26 cP. In exemplary embodiments, the PVOH homopolymer and/or copolymer may have a viscosity of about 1.0 to about 40.0 cP, or about 5 cP to about 23 cP, such as about 1 cP, 1.5 cP, 2 cP, 2.5 cP, 3 cP, 3.5 cP, 4 cP, 4.5 cP, 5 cP, 5.5 cP, 6 cP, 6.5 cP, 7 cP, 7.5 cP, 8 cP, 8.5 cP, 9 cP, 9 cP, 10 cP, 12 cP, 14 cP, 16 cP, 17 cP, 18 cP, 19 cP, 22 cP, 23 cP, 24 cP, 25 cP, 26 cP, 27 cP, 28 cP, 29 cP, 30 cP, 31 cP, 32 cP, 33 cP, 34 cP, 35 cP, 36 cP, 37 cP, 38 cP, 39 cP, 40 cP, 41 cP, 42 cP, 43 cP, 44 cP, 45 cP, 46 cP, 47 cP, 48 cP, 49 cP, 50 cP, 51 cP, 52 cP, 53 cP, 54 cP, 55 cP, 56 cP, 57 c .5 cP, 10 cP, 11 cP, 12 cP, 13 cP, 14 cP, 15 cP, 17.5 cP, 18 cP, 19 cP, 20 cP, 21 cP, 22 cP, 23 cP, 24 cP, 25 cP, 26 cP, 27 cP, 28 cP, 29 cP, 30 cP, 31 cP, 32 cP, 33 cP, 34 cP, 35 cP, or 40 cP. In an exemplary embodiment, the PVOH homopolymer and/or copolymer may have a viscosity of about 21 cP to 26 cP. In an exemplary embodiment, the PVOH homopolymer and/or copolymer may have a viscosity of about 5 cP to about 14 cP. In an exemplary embodiment, the PVOH homopolymer and/or copolymer may have a viscosity of about 5 cP to about 23 cP.
Water-soluble polymers can be blended, whether or not they are polyvinyl alcohol polymers. When the polymer blend comprises a blend of polyvinyl alcohol polymers, the PVOH polymer blend can comprise a first PVOH polymer ("first PVOH polymer"), which can comprise a PVOH copolymer or a modified PVOH copolymer comprising one or more types of anionic monomer units (e.g., a PVOH ter- or higher copolymer), and a second PVOH polymer ("second PVOH polymer"), which can comprise a PVOH copolymer or a modified PVOH copolymer comprising one or more types of anionic monomer units (e.g., a PVOH ter- or higher copolymer). In some embodiments, the PVOH polymer blend comprises only a first PVOH polymer and a second PVOH polymer (e.g., a binary blend of the two polymers). Alternatively, or in addition, the PVOH polymer blend or the fibers, foams, or films made therefrom can be characterized as being free or substantially free of other polymers (e.g., other water-soluble polymers in general, other PVOH-based polymers in particular, or both). As used herein, "substantially free" means that the first PVOH polymer and the second PVOH polymer constitute at least 95%, at least 97%, or at least 99% by weight of the total amount of water-soluble polymer in the water-soluble fiber, foam, or film. In other embodiments, the water-soluble fiber, foam, or film can include one or more additional water-soluble polymers. For example, the PVOH polymer blend can include a third PVOH polymer, a fourth PVOH polymer, a fifth PVOH polymer, etc. (e.g., one or more additional PVOH copolymers or modified PVOH copolymers with or without anionic monomer units). For example, the water-soluble fiber or film can include at least a third (or fourth, fifth, etc.) water-soluble polymer other than a PVOH polymer (e.g., other than a PVOH copolymer or modified PVOH copolymer with or without anionic monomer units). A PVOH homopolymer may also be included in each blend.
Biodegradable

Polyvinyl alcohol polymers are generally biodegradable since they degrade in the presence of water and enzymes under aerobic, anaerobic, soil, and compost conditions. In general, the biodegradation activity of polyvinyl alcohol polymers increases as the degree of hydrolysis of the polyvinyl alcohol polymer increases up to about 80%. Without being bound by theory, it is believed that increasing the degree of hydrolysis beyond 80% does not appreciably affect biodegradability. Furthermore, the stereoregularity of the hydroxyl groups of the polyvinyl alcohol polymer has a significant effect on the biodegradation activity level, the more isotactic the hydroxyl groups in the polymer sequence, the higher the degradation activity. Without being bound by theory, it is believed that in soil and/or compost biodegradation, nonwoven substrates or webs prepared from polyvinyl alcohol fibers will have a higher level of biodegradation activity relative to water-soluble films prepared from similar polyvinyl alcohol polymers due to the increased polymer surface area provided by the nonwoven substrate or web relative to the film. Furthermore, without wishing to be bound by theory, it is believed that the degree of polymerization of a polyvinyl alcohol polymer has little or no effect on the biodegradability of a film, foam or nonwoven substrate or web prepared with the polymer, but the polymerization temperature may affect the biodegradability of the film, foam substrate or nonwoven substrate, since it may affect the crystallinity and aggregation state of the polymer. As the crystallinity decreases, the polymer chain hydroxyl groups become less aligned within the polymer structure, and the polymer chains become more disordered, causing the chains to accumulate as amorphous aggregates, thereby reducing the availability of ordered polymer structures and biodegradation activity is predicted to decrease soil and/or compost biodegradation mechanisms in which the polymer does not dissolve. Without wishing to be bound by theory, it is believed that because the stereoregularity of the hydroxyl groups of a polyvinyl alcohol polymer has a significant effect on the level of biodegradation activity, substitution with a functional group other than the hydroxyl group (e.g., anionic AMPS functional group, carboxylate group, or lactone group) is expected to reduce the level of biodegradation activity relative to a polyvinyl alcohol copolymer having the same degree of hydrolysis, unless the functional group itself is also biodegradable, in which case the biodegradability of the polymer may be increased by the substitution. Furthermore, it is believed that the level of biodegradation activity of a substituted polyvinyl alcohol can be lower than that of the corresponding homopolymer or copolymer, but the substituted polyvinyl alcohol will still be biodegradable.

Methods for determining biodegradation activity are known in the art, for example, as described in Chiellini et al., Progress in Polymer Science, Volume 28, Issue 6, 2003, pp. 963-1014, which is incorporated herein by reference in its entirety. Other methods and standards can be found in ECHA's Annex XV Restriction Report - Microplastics, Version number 1, January 11, 2019, which is incorporated herein by reference in its entirety. Suitable standards include OECD 301B (ready biodegradation), OECD 301B (enhanced biodegradation), OECD 302B (intrinsic biodegradation), OECD 311 (anaerobic), and ASTM D5988 (soil).

In exemplary embodiments, the fibers described herein can be of standard ready biodegradation or enhanced degradation. As used herein, the term "ready biodegradation" refers to a standard that is met if the material (e.g., fiber) reaches 60% biodegradation (mineralization) within 28 days from the start of testing according to OECD 301B testing as described in ECHA's Annex XV. As used herein, the term "enhanced biodegradation" refers to a standard that is met if the material (e.g., fiber) reaches 60% biodegradation within 60 days from the start of testing according to OECD 301B testing as described in ECHA's Annex XV. In exemplary embodiments, the fibers meet the standard for ready biodegradation.
Carrier Solvent

In an exemplary embodiment, the carrier solvent comprises a polar solvent. In an exemplary embodiment, the solvent comprises octanol, heptanol, hexanol, pentanol, butanol, propanol, tetrahydrofuran, dichloromethane, acetone, ethanol, N-methylpyrrolidone, methanol, acetonitrile, ethylene glycol, N,N-dimethylformamide, glycerin, dimethylsulfoxide, formic acid, water, or a combination thereof. In an exemplary embodiment, the carrier solvent comprises n-octanol, n-heptanol, n-hexanol, n-pentanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-propanol, isopropanol, acetone, ethanol, N-methylpyrrolidone, methanol, acetonitrile, N,N-dimethylformamide, dimethylsulfoxide, formic acid, water, or a combination thereof. In exemplary embodiments, the carrier solvent comprises n-propanol, acetone, ethanol, N-methylpyrrolidone, methanol, acetonitrile, N,N-dimethylformamide, dimethylsulfoxide, formic acid, water, or combinations thereof. In exemplary embodiments, the carrier solvent comprises an alcohol that is liquid under the mixed conditions. In exemplary embodiments, the carrier solvent comprises methanol. In exemplary embodiments, the carrier solvent comprises methanol and at least one additional solvent. In embodiments, the carrier solvent comprises methanol and water. In exemplary embodiments, the carrier solvent comprises at least one of butanol, pentanol, hexanol, heptanol, and octanol in combination with water. In exemplary embodiments, the carrier solvent comprises DMSO and water. In exemplary embodiments, the carrier solvent comprises DMSO and water, wherein the DMSO and water are provided in a weight ratio of about 40/60 to 80/20. Without wishing to be bound by theory, it is believed that as the amount of water is increased above 60% or the amount of DMSO is increased above about 80%, the interaction of the respective solvents with the polyvinyl alcohol increases, resulting in increased swelling and gelling of the polymer.

In an exemplary embodiment, the carrier solvent comprises a non-polar solvent. In an exemplary embodiment, the carrier solvent comprises hexane, cyclohexane, methylpentane, pentane, cyclopropane, dioxane, benzene, pyridine, xylene, toluene, diethyl ether, chloroform, or a combination thereof.

In an exemplary embodiment, the carrier solvent comprises a mixture of a first carrier solvent and a second carrier solvent. In an exemplary embodiment, the first carrier solvent comprises a polar solvent and the second carrier solvent comprises a non-polar solvent. In an exemplary embodiment, the first carrier solvent has a first dielectric constant and the second carrier solvent has a second dielectric constant, the dielectric constant of the first carrier solvent being different, e.g., higher, than the dielectric constant of the second carrier solvent. In an exemplary embodiment, the first dielectric constant is 5 or lower, 4 or lower, 3 or lower, or 2 or lower. In an exemplary embodiment, the second dielectric constant is greater than 5, greater than 7.5, greater than 10, greater than 15, greater than 18, greater than 20, greater than 25, or greater than 30. In an exemplary embodiment, the difference between the first dielectric constant and the second dielectric constant is at least 3, at least 5, at least 8, or at least 10. In exemplary embodiments, when the carrier solvent comprises a mixture of a first carrier solvent and a second carrier solvent, the first carrier solvent and the second carrier solvent can be provided in any ratio, provided that the fibers are not soluble in the mixture before, during, and after treatment. In exemplary embodiments, the first carrier solvent and the second carrier solvent can be provided in a weight ratio of about 99/1 to about 1/99, about 95/5 to about 5/95, about 90/10 to 10/90, about 85/15 to about 15/85, about 80/20 to about 20/80, about 75/25 to about 25/75, about 70/30 to about 30/70, about 65/35 to about 35/65, about 60/40 to about 40/60, about 55/45 to about 45/55, or about 50/50.
Active Cleansing Formula

In an exemplary embodiment, the article, particularly the water-dispersible and/or water-soluble core substrate, is configured to contain a carrier solvent containing one or more active cleaning formulations, such as a dishwashing detergent formulation. In an exemplary embodiment, the carrier solvent containing the active cleaning formulation is disposed, e.g., applied or coated, on one or more surfaces of the core substrate, or embedded and/or adhered to the core substrate. The core substrate may include a single layer, e.g., a single layer of nonwoven core substrate, or may include multiple layers, e.g., a sheet of nonwoven core substrate folded into a serpentine arrangement, or formed with a layer containing the carrier solvent containing the active cleaning formulation disposed between adjacent layers of the nonwoven core substrate, e.g., overlapping. By way of example, the active cleaning formulation may include, but is not limited to, an active, a sanitizing agent, and/or a dishwashing detergent, soap, or cleaner. Other examples include laundry detergents, soaps, fabric softeners, bleaches, laundry enhancers, stain removers, optical brighteners, or water softeners, shampoos, conditioners, body washes, face washes, skin lotions, skin treatments, body oils, fragrances, hair treatments, bath salts, essential oils, bath bombs, or enzymes.
Adjuvants

In general, the fibers, nonwoven substrates or webs, foam substrates and/or water-soluble films of the present disclosure, along with the film-forming, foam-forming and/or fiber-forming materials, may contain disinfecting or sanitizing agents, plasticizers, plasticizer compatibilizers, surfactants, lubricants, release agents, fillers, extenders, crosslinking agents, antiblocking agents, antioxidants, anti-adherents, defoamers, nanoparticles, such as layered silicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite, or the like), antifungal agents, antibacterial agents, antifungal agents, antiseptic agents, antifungal ... Adjuvants such as, but not limited to, bittering agents (e.g., denatonium salts, e.g., denatonium benzoate, denatonium saccharide, and denatonium chloride; sucrose octaacetate; quinines; flavonoids, e.g., quercetin and naringenin; and quassinoids, e.g., cassine and brucine), and pungent agents (e.g., capsaicin, piperine, allyl isothiocyanate, and resinferratoxin), and other functional ingredients, may be included in amounts appropriate for their intended purpose. Suitable sanitizing agents include, but are not limited to, one or more of the following sanitizing agents: quaternary ammonium compounds (QACs), halogenated oxidizing agents, hypochlorous acid generating compounds, hypochlorite generating compounds, 1-bromo-3-chloro-5,5-dimethylhydantoin, dichloroisocyanuric acid, alcohols including, but not limited to, methanol, ethanol, isopropyl alcohol and/or other longer chain alcohols, oxygen radical generators, hydrogen peroxide (H ₂ O ₂ ), sulfate generating compounds, methylisothiazolinone (MIT), benzisothiazolinone (BIT), or sodium metabisulfite. As used herein and unless otherwise specified, "adjuvants" include secondary additives, processing agents, and activators. Such specific adjuvants may be selected from those suitable for use with water soluble fibers, water insoluble fibers, nonwoven webs, foams, or water soluble films.

In exemplary embodiments, the fibers, foams, and/or films may be free of adjuvants. As used herein, and unless otherwise specified, "adjuvants free" with respect to fibers means that the fibers contain less than about 0.01%, less than about 0.005%, or less than about 0.001% by weight of adjuvants based on the total weight of the fibers. As used herein, and unless otherwise specified, "adjuvants free" with respect to nonwoven substrates or webs means that the nonwoven substrates or webs contain less than about 0.01%, less than about 0.005%, or less than about 0.001% by weight of adjuvants based on the total weight of the nonwoven substrates or webs. In exemplary embodiments, the water soluble fibers contain a plasticizer. In exemplary embodiments, the water soluble fibers contain a surfactant. In exemplary embodiments, the water insoluble fibers contain a plasticizer. In exemplary embodiments, the water insoluble fibers contain a surfactant. In exemplary embodiments, the nonwoven substrates or webs contain a plasticizer. In exemplary embodiments, the nonwoven substrates or webs contain a surfactant.

A plasticizer is a liquid, solid, or semi-solid that is added to a material (usually a resin or elastomer) to make the material softer, more flexible (by lowering the glass transition temperature of the polymer), or easier to process. Polymers can alternatively be plasticized internally by chemically modifying the polymer or monomer. Additionally or alternatively, polymers can be plasticized externally by the addition of a suitable plasticizer. Water is recognized as a very efficient plasticizer for PVOH polymers and other polymers, including but not limited to water-soluble polymers, however, the volatility of water limits its usefulness as polymer films need to have at least some resistance (robustness) to a variety of ambient conditions, including low and high relative humidity.

Plasticizers can include, but are not limited to, glycerin, diglycerin, sorbitol, xylitol, maltitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols up to 1000 MW, neopentyl glycol, trimethylolpropane, polyether polyols, sorbitol, 2-methyl-1,3-propanediol (MPDiol®), ethanolamine, and mixtures thereof.

Surfactants used in the film are well known in the art and may be suitably used in the fibers, foams, films, and/or compositions of the present disclosure. Optionally, surfactants are included to aid in the dispersion of the fibers during carding. Optionally, surfactants are included as cleaning agents. Suitable surfactants may include nonionic, cationic, anionic, and zwitterionic classes. Suitable surfactants include, but are not limited to, propylene glycol, diethylene glycol, monoethanolamine, polyoxyethylated polyoxypropylene glycol, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylene glycols, and alkanolamides (nonionic), polyoxyethylated amines, quaternary ammonium salts, and quaternized polyoxyethylated amines (cationic), alkali metal salts of higher fatty acids containing about 8 to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylate sulfates, and alkyl benzene sulfonates (anionic), and amine oxides, N-alkyl betaines, and sulfobetaines (zwitterionic). Other suitable surfactants include dioctyl sodium sulfosuccinate, lactylated fatty acid esters of glycerin and propylene glycol, lactylic acid esters of fatty acids, sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerin and propylene glycol, and sodium lauryl sulfate, acetylated esters of fatty acids, myristyl dimethylamine oxide, trimethyltallow alkyl ammonium chloride, quaternary ammonium compounds, alkali metal salts of higher fatty acids containing from about 8 to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylate sulfates, alkyl benzene sulfonates, monoethanolamine, lauryl alcohol ethoxylate, propylene glycol, diethylene glycol, sodium cocoyl isethionate, sodium lauryl sulfate, glucotine, phenamides, cola lipids, cocamides, e.g., cocamide ethanolamine, ethylene oxide based surfactants, saponified avocado and palm oils, salts thereof, and combinations of any of the foregoing. In an exemplary embodiment, the surfactant comprises cocamide. Without wishing to be bound by theory, it is believed that the cocamide can aid in foam formation and enhance the lathering experience of articles containing the personal care composition. In various embodiments, the amount of surfactant in the fiber ranges from about 0.01% to about 10% by weight, from about 0.1% to about 5% by weight, from about 1.0% to about 2.5% by weight, from about 0.01% to about 1.5% by weight, from about 0.1% to about 1% by weight, from about 0.01% to 0.25% by weight, or from about 0.10% to 0.20% by weight.

In exemplary embodiments, the nonwoven substrates or webs, foams and/or films of the present disclosure may further include adjuvants, such as one or more adjuvants from the group of: exfoliants (chemical and mechanical exfoliants), fragrance and/or perfume microcapsules, aversive agents, surfactants, colorants, enzymes, skin conditioners, deoiler agents, and cosmetic agents.

In an exemplary embodiment, the adjunct is provided in or on one or more of the nonwoven web, the foam, the plurality of fibers, and the water-soluble film. In an exemplary embodiment, the active cleaning formulation is provided on or in one or more of the nonwoven web, the plurality of fibers, and the water-soluble film. In an exemplary embodiment, the one or more adjuncts can be provided on a surface of the nonwoven web. In an exemplary embodiment, the one or more adjuncts can be dispersed within the fibers of the nonwoven web. In an exemplary embodiment, the one or more adjuncts can be dispersed on a surface of the nonwoven web. In an exemplary embodiment, the one or more adjuncts can be dispersed in the fibers. In an exemplary embodiment, the one or more adjuncts can be dispersed on the fibers. In an exemplary embodiment, the one or more adjuncts can be provided on a surface of the water-soluble film.

When present, the chemical exfoliants, mechanical exfoliants, fragrance and/or perfume microcapsules, aversive agents, surfactants, colorants, proteins, peptides, enzymes, skin conditioners, deoiler agents, cosmetic agents, or combinations thereof can be provided in an amount of at least about 1% by weight, or in a range of about 1% to about 99% by weight, based on the weight of the polymer mixture (e.g., fiber-forming or film-forming material). In exemplary embodiments, the chemical exfoliants, mechanical exfoliants, fragrance and/or perfume microcapsules, aversive agents, surfactants, colorants, enzymes, skin conditioners, deoiler agents, and/or cosmetic agents can be provided in an amount sufficient to provide additional functionality, such as human skin exfoliation, to the fibers and/or films. The chemical exfoliants, mechanical exfoliants, fragrance and/or perfume microcapsules, aversive agents, surfactants, colorants, enzymes, skin conditioners, degreasing agents, cosmetic agents, or combinations thereof can be in any desired form including solids (e.g., powders, granules, crystals, flakes, or ribbons), liquids, salves, pastes, gases, and the like, and can be encapsulated, such as microcapsules, if desired.

In certain embodiments, the nonwoven substrate or web, foam and/or film may include an enzyme. Suitable enzymes include enzymes classified into one of the six traditional Enzyme Commission (EC) categories: EC 1 oxidoreductases (catalyzing oxidation/reduction reactions), EC 2 transferases (transferring functional groups, such as methyl or phosphate groups), EC 3 hydrolases (catalyzing hydrolysis of various bonds), EC 4 lyases (cleaving various bonds by methods other than hydrolysis and oxidation), EC 5 isomerases (catalyzing isomerization changes within a molecule), and EC 6 ligases (joining two molecules with a covalent bond). Examples of such enzymes include EC 1 dehydrogenases and oxidases, EC 2 transaminases and kinases, EC 3 lipases, cellulases, amylases, mannanases, and peptidases (also known as proteases or proteolytic enzymes), EC 4 decarboxylases, EC 5 isomerases and mutases, and EC 6 synthetases and synthases. Suitable enzymes from each category are described, for example, in U.S. Patent No. 9,394,092, the disclosure of which is incorporated herein by reference in its entirety. In certain embodiments, the enzymes can include bromelain (pineapple extract), papain (papaya), ficin (fig), actinidin (kiwi), hyaluronidase, lipase, peroxidase, superoxide dismutase, tyrosinase, alkaline phosphatase, or combinations thereof. In exemplary embodiments, the enzymes can be encapsulated, for example, in the form of a nanoemulsion, nanocapsule, granules, or combinations thereof.

Enzymes used in laundry and dishwashing applications can include one or more of proteases, amylases, lipases, dehydrogenases, transaminases, kinases, cellulases, mannases, peptidases, decarboxylases, isomerases, mutases, synthetases, synthases, and oxido-reductase enzymes, including oxido-reductase enzymes that catalyze the formation of bleach.

It is contemplated that the enzymes used herein may be obtained from any suitable source or combination of sources, e.g., bacterial, fungal, plant, or animal sources. In one embodiment, a mixture of two or more enzymes will come from at least two different types of sources. For example, a mixture of proteases and lipases may be obtained from bacterial (proteases) and fungal (lipase) sources.

Optionally, the enzymes used herein, including but not limited to any of the enzyme types or members described herein, are those that operate under alkaline pH conditions, for example at a pH in the range of about 8 to about 11. Optionally, the enzymes used herein, including but not limited to any of the enzyme types or members described herein, are those that operate at a temperature in the range of about 5° C. to about 45° C.

In exemplary embodiments, the nonwoven substrate or web, foam, and/or film may include proteins and/or peptides. Suitable proteins and/or peptides may include, but are not limited to, collagen and/or collagen peptides, or amino acids such as aspartic acid, glutamic acid, serine, histidine, glycine, threonine, arginine, alanine, tyrosine, cysteine, valine, methionine, phenylalanine, isoleucine, leucine, lysine, hydroxyproline, or proline.

In an exemplary embodiment, the nonwoven substrate or web, foam and/or film can include a colorant. Suitable colorants can include indicator dyes, such as pH indicators (e.g., thymol blue, bromothymol, thymolphthalein, and thymolphthalein), moisture/water indicators (e.g., hydrochromic inks or leuco dyes), or thermochromic inks, which change color when the temperature increases and/or decreases. Suitable colorants include, but are not limited to, triphenylmethane dyes, azo dyes, anthraquinone dyes, perylene dyes, indigoid dyes, Food, Drug, and Cosmetics (FD&C) colorants, organic pigments, inorganic pigments, or combinations thereof. Examples of colorants include, but are not limited to, FD&C Red #40; Red #3; FD&C Black #3; Black #2; mica-based pearlescent pigments; FD&C Yellow #6; Green #3; Blue #1; Blue #2; titanium dioxide (food grade); brilliant black; and combinations thereof. Other examples of suitable colorants can be found in U.S. Pat. No. 5,002,789, which is incorporated herein by reference in its entirety.

Other embodiments may include one or more fragrances in the nonwoven substrate or web, foam, and/or film of the present disclosure. As used herein, the term "fragrance" refers to any impartable material that is sufficiently volatile to produce a scent. Embodiments that include a fragrance may include fragrances that are pleasant to humans or, alternatively, fragrances that are unpleasant to humans, animals, and/or insects. Suitable fragrances include, but are not limited to, fruit scents, including but not limited to lemon, apple, cherry, grape, pear, pineapple, orange, strawberry, raspberry, musk, and floral scents, including but not limited to lavender-like, rose-like, iris-like, and carnation-like. Optionally, the fragrance is also not a flavoring. Other fragrances include herbal scents, including but not limited to rosemary, thyme, and sage; and woodland scents derived from pine, spruce, and other woodland scents. Fragrances may be derived from various oils, including but not limited to essential oils, or plant materials, including but not limited to peppermint, spearmint, and the like, or any combination thereof. Suitable fragrant oils can be found in U.S. Patent No. 6,458,754, which is incorporated herein by reference in its entirety. Suitable fragrant oils include, but are not limited to, 4-(2,2,6-trimethylcyclohex-1-enyl)-2-en-4-one, acetaldehyde phenylethyl propyl acetal, 2,6,10-trimethyl-9-undecanal, hexanoic acid 2-propenyl ester, 1-octen-3-ol, trans-anethole, isobutyl (z)-2-methyl-2-butenoate, anisaldehyde diethyl acetal, 3-methyl-5-propyl-cyclohezen-1-one, 2,4-dimethyl-3-cyclohexene, 1-methyl-5-propyl-cyclohezen-1-one ... These include sen-1-carbaldehyde, trans-4-decenal, decanal, 2-pentyl cyclopentanone, ethyl anthranilate, eugenol, 3-(3-isopropylphenyl)butanal, methyl 2-octinoate, isoeugenol, cis-3-hexenylmethyl carbonate, linalool, methyl-2-nonynonate, benzoic acid 2-hydroxymethyl ester, nonal, octanal, 2-nonenenitrile, 4-nonanolide, 9-decen-1-ol, and 10-undecen-1-al. Applicable fragrances can also be found in U.S. Pat. Nos. 4,534,981, 5,112,688, 5,145,842, 6,844,302, and Perfumes Cosmetics and Soaps, Second Edition, edited by W. A. Poucher, 1959, all of which are incorporated herein by reference in their entirety. These fragrances include acacia, goldenrod, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily, magnolia, mimosa, daffodil, freshly cut hay, orange blossom, orchid, mignonette, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and the like or any combination thereof.

The fragrance may include a fragrance. The fragrance may include a neat fragrance, an encapsulated fragrance, or a mixture thereof. In an exemplary embodiment, the fragrance includes a pure fragrance. A portion of the fragrance may be encapsulated in a core-shell encapsulation. In another embodiment, the fragrance is no longer encapsulated in a core/shell encapsulation.

As used herein, the term "perfume" encompasses perfume raw materials (PRMs) and perfume accords. As used herein, the term "perfume raw materials" refers to compounds having a molecular weight of at least about 100 g/mol and useful for imparting an odor, fragrance, essence, or smell, either alone or together with other perfume raw materials. As used herein, the terms "perfume ingredient" and "perfume raw materials" are synonymous. As used herein, the term "accord" refers to a mixture of two or more PRMs. In exemplary embodiments, any of the perfume accords, perfume raw materials, or fragrances can be encapsulated in microcapsules, referred to as "perfume microcapsules" as used herein.

Typical PRMs include alcohols, ketones, aldehydes, esters, ethers, nitrites, and alkenes, such as terpenes, among others. Lists of common PRMs can be found in various references, such as "Perfume and Flavor Chemicals", Vols. I and II; Steffen Arctander Allured Pub. Co. (1994), and "Perfumes: Art, Science and Technology", Miller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994). PRMs are characterized by their boiling point (B.P.) measured at atmospheric pressure (760 mmHg) and their octanol/water partition coefficient (P). Based on these characteristics, PRMSs may be classified as Quadrant I, Quadrant II, Quadrant III, or Quadrant IV fragrances.

In exemplary embodiments, the nonwoven web, foam, and/or film may include an exfoliant. In exemplary embodiments, the exfoliant may include a chemical exfoliant or a mechanical exfoliant. Suitable mechanical exfoliants for use herein may include, but are not limited to, apricot shells, sugar, oatmeal, salt, silica, diatomaceous earth, clay, aluminum hydroxide, PVOH microbeads, pumice, or combinations thereof. Suitable chemical exfoliants for use herein may include, but are not limited to, alpha hydroxyl acids, beta hydroxyl acids, enzymes, salicylic acid, glycolic acid, citric acid, malic acid, or combinations thereof.

In certain embodiments, aversive agents, surfactants, colorants, enzymes, skin conditioners, de-oiling agents, cosmetic agents, or combinations thereof are encapsulated and allowed for controlled release. Suitable microcapsules may include or be made from one or more of melamine formaldehyde, polyurethane, urea formaldehyde, chitosan, polymethylmethacrylate, polystyrene, polysulfone, polytetrahydrofuran, gelatin, gum arabic, starch, polyvinylpyrrolidone, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, arabinogalactan, polyvinyl alcohol, polyacrylic acid, ethylcellulose, polyethylene, polymethacrylate, polyamide, poly(ethylene vinyl acetate), cellulose nitrate, silicone, poly(lactideco-glycolide), paraffin, carnauba, spermaceti, beeswax, stearic acid, stearyl alcohol, glyceryl stearate, shellac, cellulose acetate phthalate, zein, and combinations thereof. In one type of embodiment, the microcapsules are characterized by an average particle size (e.g., Dv50) of at least about 0.1 microns, or for example in the range of about 0.1 microns to about 200 microns. In alternative embodiments, the microcapsules may form agglomerates of individual particles, for example the individual particles having an average particle size of at least about 0.1 microns, or in the range of about 0.1 microns to about 200 microns.
Water-dispersible and/or water-soluble fibers

As described, the fibers used in making the core substrate are water dispersible and/or water soluble. The fibers may be dispersible in water at lower temperatures (e.g., 10°C to 40°C) and soluble at higher temperatures (e.g., above 40°C). Such fibers are referred to as water soluble fibers for ease of description. Water soluble fibers include fibers and/or fiber forming materials made of any material that, when provided as the only resin in a film or foam or as the only fiber forming material in a nonwoven, film, foam or nonwoven, dissolves in 300 seconds or less at 80°C or less as determined by MSTM-205. Water soluble fibers can include a single water soluble polymer or a blend of water soluble polymers. Suitable water soluble polymers include, but are not limited to, polyvinyl alcohol homopolymers, polyvinyl alcohol copolymers, modified polyvinyl alcohol copolymers, polyacrylates, water soluble acrylate copolymers, polyvinylpyrrolidone, polyethyleneimine, pullulan, water soluble natural polymers including, but not limited to, guar gum, acacia gum, xanthan gum, carrageenan, and starch, water soluble polymer derivatives including, but not limited to, modified starch, ethoxylated starch, and hydroxypropylated starch, copolymers of the foregoing, and combinations of any of the foregoing. Still other water soluble fibers include polyalkylene oxides, polyacrylamides, polyacrylic acids and salts thereof, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts thereof, polyamino acids, polyamides, gelatin, methylcellulose, carboxymethylcellulose and salts thereof, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and combinations of any of the foregoing. In an exemplary embodiment, the water soluble fiber can include a PVOH copolymer fiber-forming material, a modified PVOH copolymer fiber-forming material, or a combination thereof. In an exemplary embodiment, the water soluble fiber can include a single PVOH homopolymer fiber-forming material or a blend of PVOH copolymer fiber-forming materials. In an exemplary embodiment, the water soluble fiber can include a hot water soluble PVOH homopolymer fiber-forming material. In a further embodiment, the water soluble fiber can include a PVOH copolymer fiber-forming material having a viscosity in the range of 5 cP to 23 cP and a degree of hydrolysis in the range of 86% to 92%.

In an exemplary embodiment, the water-soluble fiber may include the above-mentioned auxiliary agents. In an exemplary embodiment, the water-soluble fiber may be substantially free of the above-mentioned auxiliary agents. In an exemplary embodiment, the water-soluble fiber may include the above-mentioned plasticizers. The total amount of non-aqueous plasticizer provided in the water-soluble fiber may range from about 1% to about 45% by weight, or from about 5% to about 45% by weight, or from about 10% to about 40% by weight, or from about 20% to about 30% by weight, from about 1% to about 4% by weight, or from about 1.5% to about 3.5% by weight, or from about 2.0% to about 3.0% by weight, for example, in the range of about 1%, about 2.5%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, or about 40% by weight. In an exemplary embodiment, the water-soluble fiber includes glycerin, sorbitol, or a combination thereof. In an exemplary embodiment, the water-soluble fiber includes glycerin. In an exemplary embodiment, the water-soluble fiber includes sorbitol. In one particular embodiment, the water-soluble fiber can include glycerin, e.g., about 10% by weight based on the total fiber weight, and sorbitol, e.g., about 5% by weight based on the total fiber weight.

In exemplary embodiments, the water-soluble fiber can include a surfactant as described above. In various embodiments, the amount of surfactant in the water-soluble fiber ranges from about 0.01% to about 2.5%, from about 0.1% to about 2.5%, from about 1.0% to about 2.0%, from about 0.01% to 0.25%, or from about 0.10% to 0.20% by weight.

In an exemplary embodiment, any of the adjuncts disclosed herein can be added to the fibers of the present disclosure. In a refinement of the foregoing embodiment, the adjunct can be added to the fiber-forming material prior to the formation of the fiber such that the adjunct is dispersed in the fiber. Additionally and/or alternatively, the adjunct can be added to the surface of the fiber after the fiber is formed (e.g., dispersed on the fiber).

When included in the water soluble fibers, the colorant can be provided in an amount of 0.01% to 25% by weight of the polymer mixture, for example, 0.02%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, and 24% by weight of the polymer mixture.
Insoluble Fiber

Water insoluble fibers generally include fibers and/or fiber forming materials made of any material which, when provided in a film as the sole film forming material or in a nonwoven web or foam as the sole fiber forming material, does not dissolve in 300 seconds or less at a temperature of 80° C. or less as determined by MSTM-205. Water insoluble fibers can include the sole water insoluble polymeric fiber forming material or a blend of water insoluble polymeric fiber forming materials. Suitable water insoluble fibers and/or water insoluble fiber forming materials include, but are not limited to, cotton, polyester, polyethylene (e.g., high density polyethylene and low density polyethylene), polypropylene, wood pulp, fluff pulp, abaca, viscose, polylactic acid, polyester, nylon 6, insoluble cellulose, insoluble starch, hemp, jute, flax, ramie, sisal, bagasse, banana fiber, lace bark, silk, tendon, catgut, wool, sea silk, mohair, angora, cashmere, collagen, actin, nylon, Dacron, rayon, bamboo fiber, modal, diacetate fiber, triacetate fiber, and combinations thereof. In an exemplary embodiment, the water insoluble fiber forming material and/or fiber comprises one or more of the group: cotton, hemp, jute, flax, ramie, sisal, bagasse, banana, lace bark, silk, tendon, catgut, wool, sea silk, mohair, angora, cashmere, collagen, actin, nylon, dacron, rayon, bamboo, modal, diacetate fiber, triacetate fiber, or combinations thereof.

In an exemplary embodiment, the water-insoluble fiber can include the above-mentioned auxiliary agents. In an exemplary embodiment, the water-insoluble fiber can be substantially free of the above-mentioned auxiliary agents. In an exemplary embodiment, the water-insoluble fiber can include the above-mentioned plasticizers. The total amount of non-water-insoluble plasticizer provided in the water-insoluble fiber can be in the range of about 1% to about 45% by weight, or about 5% to about 45% by weight, or about 10% to about 40% by weight, or about 20% to about 30% by weight, about 1% to about 4% by weight, or about 1.5% to about 3.5% by weight, or about 2.0% to about 3.0% by weight, for example, about 1% by weight, about 2.5% by weight, about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, or about 40% by weight. In an exemplary embodiment, the water-insoluble fiber includes glycerin, sorbitol, or a combination thereof. In an exemplary embodiment, the water insoluble fiber includes glycerin. In an exemplary embodiment, the water insoluble fiber includes sorbitol. In a particular embodiment, the water insoluble fiber can include a plasticizer such as glycerin, for example, about 10% by weight based on the total fiber weight, and sorbitol, for example, about 5% by weight based on the total fiber weight.

In exemplary embodiments, the water insoluble fibers can include a surfactant as described above. In various embodiments, the amount of surfactant in the water soluble fibers ranges from about 0.01% to about 2.5%, about 0.1% to about 2.5%, about 1.0% to about 2.0%, about 0.01% to 0.25%, or about 0.10% to 0.20% by weight.

In an exemplary embodiment, any of the adjuncts disclosed herein can be added to the fibers of the present disclosure. In a refinement of the foregoing embodiment, the adjunct can be added to the fiber-forming material prior to fiber formation such that the adjunct can be added to the surface of the fiber after fiber formation. In a refinement of the foregoing embodiment, the adjunct can be added to the surface of the fiber after fiber formation.

When included in the water insoluble fibers, the colorant can be provided in an amount of 0.01% to 25% by weight of the polymer mixture, for example 0.02%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, and 24% by weight of the polymer mixture.
Nonwoven web or substrate

The nonwoven web or nonwoven substrate of the present disclosure may be water soluble (or water dispersible), water insoluble, or at least partially water insoluble. The articles of the present disclosure may include a nonwoven web, at least a portion of which is soluble in water at a temperature ranging from about 0° C. to about 20° C. according to MSTM-205, or at least a portion of which is not soluble in water at or below 20° C. according to MSTM-205, or the nonwoven web is not soluble in water at or below 20° C. according to MSTM-205, or the nonwoven web is soluble in water at a temperature ranging from about 0° C. to about 20° C. according to MSTM-205. It will be understood that "at least a portion" of a nonwoven web means that if the nonwoven web comprises a plurality of fibers and that fiber type is provided in the nonwoven as the sole fiber type, the fiber type is soluble (or not soluble) at a given temperature, and the nonwoven web made of that fiber type is soluble (or not soluble) at a given temperature according to MSTM-205.

The nonwoven web of the present disclosure comprises a plurality of fibers. Nonwoven web refers to an arrangement of fibers bonded together, the fibers being neither woven nor knitted. The plurality of fibers can be arranged in any orientation. In exemplary embodiments, the plurality of fibers are arranged randomly (i.e., have no orientation). In exemplary embodiments, the plurality of fibers are arranged in one direction. In exemplary embodiments, the plurality of fibers are arranged in two directions. In some embodiments, the plurality of fibers are multidirectional and have different arrangements in different regions of the nonwoven web.

The fibers in any given nonwoven web may comprise any of the fiber-forming materials disclosed herein. The nonwoven web may comprise (1) a monofilament type comprising a monofilament-forming material, (2) a monofilament type comprising a blend of fiber-forming materials, (3) a blend of fiber types, where each fiber type comprises a monofilament-forming material, (4) a blend of fiber types, where each fiber type comprises a blend of fiber-forming materials, or (5) a blend of fiber types, where each fiber type comprises a monofilament-forming material or a blend of fiber-forming materials. In an exemplary embodiment comprising a blend of fiber types, the various fiber types may have differences in one or more of the following groups: length to diameter ratio (L/D), toughness, shape, stiffness, elasticity, solubility, melting point, glass transition temperature (T _g ), chemical nature of the fiber-forming material, and color. In certain embodiments, the fibers may comprise two or more types of water-soluble fibers. In an exemplary embodiment, the fibers may comprise at least one fiber type comprising at least one type of water-soluble fiber-forming material and at least one type of water-insoluble fiber. In an exemplary embodiment, the plurality of fibers can include two or more types, including at least one type of water insoluble fiber forming material.

In exemplary embodiments, the nonwoven web may further include any carrier solvent with any suitable active cleaning formulation and/or any adjunct as disclosed herein with respect to the fibers and/or films. In exemplary embodiments, the carrier solvent, active cleaning formulation and/or adjunct may be added to the fibers themselves, to the nonwoven web during carding of the nonwoven web, to the nonwoven web prior to bonding (e.g., after carding), to the nonwoven web after bonding, or combinations thereof. The carrier solvent, active cleaning formulation and/or adjunct added to the fibers during carding may be distributed throughout the nonwoven web. The carrier solvent, active cleaning formulation and/or adjunct added to the nonwoven web after carding but prior to bonding may be selectively added to one or both sides of the nonwoven web.

The carrier solvent, active cleaning formulation and/or adjuvants can be applied by suitable means to one or more surfaces of the nonwoven web or to the article containing them, e.g., the packet. In an exemplary embodiment, the carrier solvent, active cleaning formulation and/or adjuvants are in the form of a powder. In a refinement of the above embodiment, one or more stationary powder spray guns are used to direct a powder stream from one or more directions toward the web or packet, while the web or packet is transported through the coating zone using a belt conveyor. In an exemplary embodiment, the web or packet is conveyed through a suspension of powder in air. In an exemplary embodiment, the web or packet is tumble mixed with the powder in a trough-like device. In an exemplary embodiment that can be combined with any other embodiment, electrostatic forces are used to enhance the attraction between the powder and the packet or web. This type of process may be based on negatively charging the powder particles and directing these charged particles toward a grounded packet or web. In other alternative embodiments, the powder is applied to the web or packet by a secondary transfer tool, including but not limited to a rotating brush in contact with the powder, or by a powdered glove that can transfer the powder from a container to the web or packet. In yet another embodiment, the powder is applied by dissolving or suspending the powder in a non-aqueous solvent or carrier, which is then atomized and sprayed onto the web or packet. In one embodiment, the solvent or carrier subsequently evaporates, leaving behind the active agent powder. In certain embodiments, the powder is applied to the web or packet in precise doses. These embodiments utilize a closed system dry lubricant application machine, such as Pekutech's Powder Applicator PM 700 D. In this process, the powder is fed into the feed trough of the application machine, batchwise or continuously as needed. The web or packet is transferred from the output belt of a standard rotary drum pouch machine onto the conveyor belt of the powder applicator, which applies a controlled dosage of the powder to the web or packet. The web or packet can then be transported to an appropriate secondary packaging process.

In exemplary embodiments in which the carrier solvent, active cleaning formulation and/or adjuvant are in liquid form or solution, the foregoing can be dispersed within the fibers, dispersed onto the surface of the nonwoven web, or combinations thereof, for example, by spin casting, spraying a solution such as an aerosolized solution, roll coating, flow coating, curtain coating, extrusion, knife coating, and combinations thereof.

Adjuncts, such as chemical exfoliants, mechanical exfoliants, microcapsules of fragrances and/or perfumes, aversive agents, surfactants, colorants, enzymes, skin conditioners, degreasers, cosmetic agents, or combinations thereof, when present in the nonwoven web, are in an amount of at least about 1% by weight, or in a range of about 1% to about 99% by weight, and provide additional functionality to the nonwoven web. The chemical exfoliants, mechanical exfoliants, microcapsules of fragrances and/or perfumes, aversive agents, surfactants, colorants, enzymes, skin conditioners, degreasers, cosmetic agents, or combinations thereof can be in any desired form, including solids (e.g., powders, granules, crystals, flakes, or ribbons), liquids, spreaders, pastes, gases, and the like, and can be encapsulated as needed.

In an exemplary embodiment, the nonwoven web can be colored, pigmented, and/or dyed to provide improved aesthetic effects compared to water-soluble films. Suitable colorants for use in the nonwoven web can include indicator dyes, such as pH indicators (e.g., thymol blue, bromothymol, thymolphthalein, and thymolphthalein), moisture/water indicators (e.g., hydrochromic inks or leuco dyes), or thermochromic inks that change color when the temperature increases and/or decreases. Suitable colorants include, but are not limited to, triphenylmethane dyes, azo dyes, anthraquinone dyes, perylene dyes, indigo dyes, Food, Drug, and Cosmetics (FD&C) colorants, organic pigments, inorganic pigments, or combinations thereof. Examples of colorants include, but are not limited to, FD&C Red #40; Red #3; FD&C Black #3; Black #2; mica-based pearlescent pigments; FD&C Yellow #6; Green #3; Blue #1; Blue #2; titanium dioxide (food grade); brilliant black; and combinations thereof.

In an exemplary embodiment, the nonwoven web can include any of the surfactants disclosed herein. In an exemplary embodiment, the nonwoven web can include one or more of the following group: sodium cocoyl isethionate, glucotein, phenamide, cola lipids, cocamides, e.g., cocamide ethanolamine, ethylene oxide based surfactants, and saponified avocado and palm oils.

The nonwoven webs of the present disclosure can generally have any thickness. Suitable thicknesses can include, but are not limited to, about 5 microns (μm) to about 10,000 μm (1 cm), about 5 μm to about 5,000 μm, about 5 μm to about 1,000 μm, about 5 μm to about 500 μm, about 200 μm to about 500 μm, about 5 μm to about 200 μm, about 20 μm to about 100 μm, or about 40 μm to about 90 μm, or about 50 μm to 80 μm, or about 60 μm to 65 μm, for example, 50 μm, 65 μm, 76 μm, or 88 μm. The nonwoven webs of the present disclosure can be characterized as high loft or low loft. Loft generally refers to the ratio of thickness to mass per unit area (i.e., basis weight). High loft nonwoven webs can be characterized by a high ratio of thickness to mass per unit area. "High loft" as used herein refers to nonwoven webs of the present disclosure having a basis weight as defined herein and a thickness greater than 200 μm. The thickness of the nonwoven web can be determined according to ASTM D5729-97, ASTM D5736, and/or ISO 9073-2:1995, and can include, for example, subjecting the nonwoven web to a load of 2N and measuring the thickness. High loft materials can be used according to methods known in the art, for example, cross-wrapping, where a non-bonded web is folded on itself using a cross wrapper to build loft and basis weight. Without wishing to be bound by theory, in contrast to water-soluble films, where the solubility of the film may depend on the thickness of the film; the solubility of the nonwoven web is not believed to depend on the thickness of the web. In this regard, the parameter that limits the approach of water to the fibers, and thus the dissolution of the fibers, is believed to be the basis weight (i.e., the fiber density in the nonwoven), regardless of the thickness of the nonwoven web, since individual fibers provide a higher surface area than water-soluble films.

In general, the dynamic coefficient of friction and the ratio of the static coefficient of friction to the dynamic coefficient of friction for the nonwoven web of the present disclosure will be lower than the dynamic coefficient of friction and the ratio of the static coefficient of friction to the dynamic coefficient of friction for the water-soluble film due to the increased surface roughness of the nonwoven web relative to the water-soluble film, resulting in reduced surface contact with the nonwoven web. Advantageously, this surface roughness can provide improved consumer feel (i.e., cloth-like hand instead of rubbery hand), improved aesthetics (i.e., less gloss than water-soluble films), and/or ease of processability for thermoformed and/or vertically formed, filled and sealed, and/or multi-chamber packets that require the web to be pulled along the surface of a processing tool/mold. Thus, the water-soluble and/or water-insoluble fibers should be sufficiently rough to provide surface roughness to the resulting nonwoven web without being so rough that it causes drag.

The water solubility of the nonwoven webs of the present disclosure is generally a function of the type of fiber(s) used to prepare the web as well as the basis weight of the web. Without wishing to be bound by theory, it is believed that the solubility profile of the nonwoven web follows the same solubility profile of the fiber(s) used to prepare the nonwoven web, and the solubility profile of the fiber generally follows the same solubility profile of the polymer(s) from which the fiber is prepared. For example, in a nonwoven web comprising PVOH fibers, the degree of hydrolysis of the PVOH polymer can be selected such that the water solubility of the nonwoven web is also affected. In general, at a given temperature, as the degree of hydrolysis of the PVOH polymer increases from partial hydrolysis (88% DH) to full hydrolysis (≧98% DH), the water solubility of the polymer generally decreases. Thus, in an exemplary embodiment, the nonwoven web can be cold water soluble. For co-poly(vinyl acetate vinyl alcohol) polymers that do not contain any other monomers (e.g., not copolymerized with anionic monomers), a cold water soluble web that is soluble in water at temperatures below 10° C. can include fibers of PVOH with a degree of hydrolysis ranging from about 75% to about 90%, or from about 75% to about 89%, or from about 80% to about 90%, or from about 85% to about 90%, or from about 90% to about 99.5%. In other exemplary embodiments, the nonwoven web can be hot water soluble. For example, for co-poly(vinyl acetate vinyl alcohol) polymers that do not contain any other monomers (e.g., not copolymerized with anionic monomers), a hot water soluble web can be soluble in water at temperatures of at least about 60° C. by including fibers of PVOH with a degree of hydrolysis of at least about 98%.

Modification of PVOH generally increases the solubility of the PVOH polymer. Thus, at a given temperature, the solubility of a nonwoven web or film prepared from a PVOH copolymer is expected to be higher than that of a nonwoven web or film prepared from a PVOH homopolymer having the same degree of hydrolysis as the PVOH copolymer. Following these trends, nonwoven webs with specific solubility characteristics can be engineered by blending polymers within the fibers and/or by blending fibers within the nonwoven web. Additionally, as described herein, nonwoven webs may contain multiple fibers, and in some cases, two or more fiber types with different solubilities.

The inclusion of water-insoluble fibers and/or water-insoluble fiber-forming materials in the fibers of the nonwoven web can also be used to design a nonwoven web with a particular solubility and/or extended release characteristics. Without wishing to be bound by theory, it is believed that as the weight percentage of water-insoluble fibers in the nonwoven web increases (relative to the total weight of the nonwoven web), the solubility of the nonwoven web generally decreases and the extended release characteristics of the pouch containing the nonwoven web generally increase. When contacted with water at or above the solubility temperature of the water-soluble fibers, a nonwoven web containing water-soluble and water-insoluble fibers will begin to disperse as the water-soluble fibers dissolve, thereby disrupting the web structure and/or increasing the pore size of the pores in the nonwoven web. In general, the greater the disruption of the web structure or the larger the pore size, the faster water will be able to access the pouch contents and the faster the pouch contents will be released. Similarly, extended release of the contents of a pouch containing a nonwoven web of the present disclosure can be achieved by using a blend of water-soluble fibers having different solubility characteristics and/or different solubility temperatures. As the faster dissolving fibers dissolve, the web is disrupted, and the less soluble fibers have a greater exposed surface area, facilitating dissolution of the less soluble fibers and release of the pouch contents. In exemplary embodiments in which the nonwoven web comprises water soluble and water insoluble fibers, the ratio of soluble to water insoluble fibers is not particularly limited. The water soluble fibers can comprise about 1% to about 99%, about 20% to about 80%, about 40% to about 90%, about 50% to about 90%, or about 60% to about 90% by weight of the total weight of the plurality of fibers, and the water insoluble fibers can comprise about 1% to about 99%, about 20% to about 80%, about 10% to about 60%, about 10% to about 50%, or about 10% to about 40% by weight of the total weight of the fibers. In exemplary embodiments, the plurality of fibers comprises about 10% to about 80% water soluble fiber, with the remainder being water insoluble fiber, based on the total weight of the fibers.

In an exemplary embodiment, the nonwoven web, the plurality of fibers, the foam, the water-soluble film, or combinations thereof disclosed herein can include a biodegradable polymer. In certain embodiments, the plurality of fibers can include water-insoluble fibers forming a material that is biodegradable. In an exemplary embodiment, the plurality of fibers can include a first fiber that is a water-insoluble biodegradable fiber and a second fiber that is soluble in water at a temperature of about 10° C. to about 20° C. according to MSTM-205 or is not soluble in water at a temperature of about 30° C. or less according to MSTM-205. In an exemplary embodiment, the nonwoven web is water-insoluble and biodegradable.

In exemplary embodiments, the nonwoven web is biodegradable. As used herein, when a nonwoven web is said to be biodegradable, at least 50% of the nonwoven web is biodegradable, e.g., at least 60%, at least 70%, at least 80%, at least 90%, or 100% of the nonwoven web is biodegradable.

The nonwoven webs disclosed herein can include a plurality of fibers including a first fiber type and a second fiber type, the first and second fiber types differing in diameter, length, tenacity, shape, stiffness, elasticity, solubility, melting point, glass transition temperature ( _Tg ), chemical composition, color, or combinations thereof. In an exemplary embodiment, the first fiber type can include a PVOH homopolymer fiber forming material, a PVOH copolymer fiber forming material, or a combination thereof. In an exemplary embodiment, the first fiber type can include two or more PVOH homopolymer fiber forming materials, two or more PVOH copolymer fiber forming materials, or a combination thereof. In an exemplary embodiment, the second fiber type can include a PVOH homopolymer fiber forming material, a PVOH copolymer fiber forming material, or a combination thereof. In an exemplary embodiment, the second fiber type can include two or more PVOH homopolymer fiber forming materials, two or more PVOH copolymer fiber forming materials, or a combination thereof. In an exemplary embodiment, the first fiber type and/or the second fiber type are water insoluble fiber forming materials. In an exemplary embodiment, the first fiber type can include a water insoluble polymeric fiber forming material and the second fiber type can include a polyvinyl alcohol fiber forming material that, when provided as the sole fiber forming material of a nonwoven web or as a film, the resulting web or film is soluble in water at temperatures ranging from about 0° C. to about 20° C. by MSTM-205. In an exemplary embodiment, the first fiber type can include a water insoluble polymeric fiber forming material and the second fiber type can include a PVOH homopolymer or copolymer fiber forming material that, when provided as the sole fiber forming material of a nonwoven web or as a film, the resulting web or film is not soluble in water at temperatures at or below 20° C. by MSTM-205. In an exemplary embodiment, the first fiber type includes two or more polyvinyl alcohol homopolymer fiber forming materials, two or more polyvinyl alcohol copolymer fiber forming materials, or a combination of polyvinyl alcohol homopolymer fiber forming materials and polyvinyl alcohol copolymer fiber forming materials. In exemplary embodiments, the second fiber type includes two or more polyvinyl alcohol homopolymer fiber forming materials, two or more polyvinyl alcohol copolymer fiber forming materials, or a combination of polyvinyl alcohol homopolymer fiber forming materials and polyvinyl alcohol copolymer fiber forming materials.

The fibers included in the nonwoven web of the present disclosure can generally have any tenacity. The tenacity of the fiber correlates to the coarseness of the fiber. As the tenacity of the fiber decreases, the coarseness of the fiber increases. The fibers used to prepare the nonwoven web of the present disclosure can have a tenacity of about 1 to about 100 cN/dtex, or about 1 to about 75 cN/dtex, or about 1 to about 50 cN/dtex, or about 1 to about 45 cN/dtex, or about 1 to about 40 cN/dtex, or about 1 to about 35 cN/dtex, or about 1 to about 30 cN/dtex, or about 1 to about 25 cN/dtex, or about 1 to about 20 cN/dtex, or about 1 to about 15 cN/dtex, or about 1 to about 10 cN/dtex, or about 3 to about 8 cN/dtex, or about 4 to about 8 cN/dtex. tex, or from about 6 to about 8 cN/dtex, or from about 4 to about 7 cN/dtex, or from about 10 to about 20, or from about 10 to about 18, or from about 10 to about 16, or about 1 cN/dtex, about 2 cN/dtex, about 3 cN/dtex, about 4 cN/dtex, about 5 cN/dtex, about 6 cN/dtex, about 7 cN/dtex, about 8 cN/dtex, about 9 cN/dtex, about 10 cN/dtex, about 11 cN/dtex, about 12 cN/dtex, about 13 cN/dtex, about 14 cN/dtex, or about 15 cN/dtex. In exemplary embodiments, the plurality of fibers can have a tenacity ranging from about 3 cN/dtex to about 15 cN/dtex, or from about 5 cN/dtex to about 12 cN/dtex, or from about 5 cN/dtex to about 10 cN/dtex.

The toughness of the nonwoven web can be the same or different from the toughness of the fibers used to prepare the web. Without wishing to be bound by theory, it is believed that the toughness of the nonwoven web is related to the strength of the nonwoven web, with higher toughness providing higher strength to the nonwoven web. In general, the toughness of the nonwoven web can be modified by using fibers with different toughness. The toughness of the nonwoven web can also be affected by processing. In general, the nonwoven webs of the present disclosure have relatively high toughness, i.e., the nonwoven web is a self-supporting web that can be used as the sole material to prepare articles and/or pouches. In contrast, nonwoven webs prepared by meltblowing, electrospinning, and/or rotary spinning processes may have low toughness and may not be self-supporting or may not be usable as the sole web to form articles or pouches.

The fibers used to prepare the nonwoven webs of the present disclosure can generally have any fineness. The fineness of the fibers correlates to how many fibers are present in the cross section of a yarn of a given thickness. The fineness of the fibers can be measured by measuring the linear mass density, the ratio of fiber mass per unit length. The main physical unit of linear mass density is 1 tex, which is equal to 1000 m of fiber weighing 1 g. The unit dtex is used to represent 1 g/10,000 m of fiber. The linear mass density can be selected to provide a nonwoven web with suitable stiffness/hand of the nonwoven web, torsional stiffness, light reflection and interaction, absorption of dyes and/or other actives/additives, ease of fiber spinning in the manufacturing process, and uniformity of the finished article. Generally, as the linear mass density of the fibers increases, the nonwovens obtained therefrom demonstrate higher uniformity, improved tensile strength, extensibility, and luster. Further, without being bound by theory, it is believed that finer fibers will result in slower dissolution times compared to larger fibers relative to density. Further, without being bound by theory, when a blend of fiber types is used, the average linear mass density can be determined using a weighted average of the individual fiber types. The fibers can be characterized as very fine (dtex≦1.22), fine (1.22≦dtex≦1.54), medium (1.54≦dtex≦1.93), slightly coarse (1.93≦dtex≦2.32), and coarse (dtex≧2.32). The nonwoven webs of the present disclosure can include fibers that are very fine, fine, medium, slightly coarse, or combinations thereof. In exemplary embodiments, the nonwoven webs have an average linear mass density ranging from about 1 dtex to about 5 dtex, or from about 1 dtex to about 3 dtex, or from about 1.5 dtex to about 2.5 dtex. In an exemplary embodiment, the nonwoven web comprises a blend of fibers, the first fibers having an average linear mass density of 1.7 dtex and the second fibers having an average linear mass density of 2.2 tex.

The fibers used to prepare the nonwoven webs of the present disclosure have diameters ranging from about 10 microns to 300 microns, such as at least 10 microns, at least 25 microns, at least 50 microns, at least 100 microns, or at least 125 microns, and up to about 300 microns, up to about 275 microns, up to about 250 microns, up to about 225 microns, or up to about 200 microns. In exemplary embodiments, the fibers used to prepare the nonwoven webs of the present disclosure can have diameters of more than 100 microns to about 300 microns. In exemplary embodiments, the diameters of the fibers used to prepare the nonwoven webs of the present disclosure have a substantially uniform diameter. In exemplary embodiments, one or more fiber types can have an average diameter ranging from about 10 microns to about 300 microns, or from about 50 microns to 200 microns, or from about 50 microns to about 100 microns.

The fibers used to prepare the nonwoven webs of the present disclosure can generally be of any length. In exemplary embodiments, the length of the fibers can range from about 10 millimeters (mm) to about 100 mm, about 10 mm to about 60 mm, or about 30 mm to about 60 mm, such as at least about 30 mm, at least about 35 mm, at least about 40 mm, at least about 45 mm, or at least about 50 mm, and up to about 100 mm, up to about 95 mm, up to about 90 mm, up to about 80 mm, up to about 70 mm, or up to about 60 mm. In exemplary embodiments, the length of the plurality of fibers can be less than about 30 mm, or in a range of about 0.25 mm to less than about 30 mm, such as at least about 0.25 mm, at least about 0.5 mm, at least about 0.75 mm, at least about 1 mm, at least about 2.5 mm, at least about 5 mm, at least about 7.5 mm, or at least about 10 mm, and up to about 29 mm, up to about 28 mm, up to about 27 mm, up to about 26 mm, up to about 25 mm, up to about 20 mm, or up to about 15 mm. In exemplary embodiments, the fibers have an average length of about 30 mm to about 100 mm, or about 30 mm to about 60 mm. In exemplary embodiments, the nonwoven web comprises a blend of fiber types, with the first fiber type comprising a length of about 38 mm and the second fiber type comprising a length of about 54 mm.

The fibers used to prepare the nonwoven webs of the present disclosure can generally have any length to diameter (L/D) ratio. Advantageously, the toughness of the nonwoven webs of the present disclosure can be controlled using the L/D ratio of the fibers and the respective amounts of fibers having various L/D ratios in the nonwoven composition. Generally, as the L/D of the fibers decreases, the stiffness and resistance to bending increases, providing a rougher hand. The fibers of the present disclosure generally impart a rougher hand to the nonwoven webs containing them when the fibers have a low L/D in the range of about 0.5 to about 15, or about 0.5 to about 25, or about 1 to about 5. Such low L/D fibers can be provided in the nonwoven web in an amount ranging from about 0 to about 50% by weight, for example, from about 0.5% to about 25% by weight, or from about 1% to about 15% by weight, based on the total weight of the fibers in the nonwoven web. If the amount of low L/D fibers in the nonwoven web is unknown, the amount can be estimated by visual inspection of a photomicrograph of the nonwoven web. In an exemplary embodiment in which the first fibers comprise a blend of fiber-forming materials including a first polyvinyl alcohol fiber-forming material, at least a portion of the first fibers can have an L/D ratio of about 0.5 to about 25, or about 0.5 to about 15, or about 1 to about 5.

Pore size can be determined using high magnification and high order surface analytical techniques including, but not limited to, Brunauer-Emmett-Teller theory (BET), small angle X-ray scattering (SAXS), and molecular adsorption.

Nonwoven webs can be characterized by their basis weight. The basis weight of a nonwoven web is the mass per unit area of the nonwoven web. Basis weight can be modified by varying manufacturing conditions, as known in the art. The nonwoven web can have the same basis weight before and after bonding. Alternatively, the bonding method can change the basis weight of the nonwoven web. For example, if bonding occurs through the application of heat and pressure, the thickness of the nonwoven (and therefore the area of the nonwoven) can be reduced, thereby increasing the basis weight. Thus, as used herein and unless otherwise specified, the basis weight of a nonwoven refers to the basis weight of the nonwoven after bonding.

The nonwoven webs of the present disclosure can generally have any basis weight in the range of about 0.1 g/ ^m2 to about 700 g/ ^m2 , about 0.5 g/ ^m2 to about 600 g/ ^m2 , about 1 g/ ^m2 to about 500 g/ ^m2 , about 1 g/ ^m2 to about 400 g/ ^m2 , about 1 g/ ^m2 to about 300 g/ ^m2 , about 1 g/ ^m2 to about 200 g/ ^m2 , about 1 g/ ^m2 to about 100 g/ ^m2 , about 30 g/ ^{m2 to} about 100 g/ ^m2 , about 20 g/m2 to about 100 g/ ^m2 , about 20 g/ ^m2 to about 80 g/ ^m2 , or about 25 g/ ^m2 to about 70 g/ ^m2 .

Furthermore, assuming that fiber composition and web thickness remain constant, as the basis weight of the web increases, the dissolution rate of the web decreases because more material is dissolved. For example, at a given temperature, a water-soluble web prepared from fibers containing PVOH polymer(s) and having a basis weight of, for example, 40 g/ ^m2 is expected to dissolve slower than an otherwise identical water-soluble web having a basis weight of, for example, 30 g/ ^m2 . Thus, basis weight can also be used to modify the solubility characteristics of a nonwoven web. The nonwoven web can generally have any basis weight in the range of about 1 g/ ^m2 to about 700 g/ ^m2 , about 1 g/ ^m2 to about 600 g/ ^m2 , about 1 g/ ^m2 to about 500 g/ ^m2 , about 1 g/ ^m2 to about 400 g/ ^m2 , about 1 g/ ^m2 to about 300 g/ ^m2 , about 1 g/ ^m2 to ^about 200 g/ ^m2 , about 10 g/ ^m2 to about 100 g/ ^m2 , about 30 g/ ^m2 to about 100 g/ ^m2 , about 20 g/ ^m2 to about 100 g/m2, about 20 g/ ^m2 to about 80 g/ ^m2 , about 25 g/ ^m2 to about 70 g/ ^m2 , or about 40 g/ ^m2 to about 60 g/ ^m2 .

The nonwoven webs of the present disclosure can be used as a single layer, layered with other nonwoven webs, or in the form of a laminate with a water-soluble film. In some embodiments, the nonwoven web comprises a single layer of a nonwoven web. In some embodiments, the nonwoven web is a multi-layer nonwoven web comprising two or more layers of a nonwoven web. The two or more layers can be laminated together. In refinements of the foregoing embodiments, the two or more layers can be the same (e.g., prepared from the same fibers and basis weights). In refinements of the foregoing embodiments, the two or more layers can be different (e.g., prepared from different types of fibers, fiber chemistries, and/or have different basis weights).

Generally, a multi-layer nonwoven web can have a basis weight that is the sum of the basis weights of the individual layers, and thus the multi-layer nonwoven web will take longer to dissolve than either of the individual layers provided as a single layer.
Water-soluble foam

In an exemplary embodiment, suitable water-soluble foams include any suitable resin chemistry, such as homopolymer, MA-modified PVOH, MMM-modified PVOH, AMPS-modified PVOH, cellulose and cellulose derivatives, PVP, protein, casein, soy, or any water-dispersible or water-soluble resin. In certain embodiments, the water-soluble foam substrate has a thickness of 3 microns to 3000 microns and can be formed using any suitable manufacturing process known in the foam manufacturing art, including, but not limited to, casting, extrusion, melt processing, coating, chemical blowing, mechanical air entrainment, air injection, and turbulent extrusion processes. The water-soluble foam substrate can be porous or non-porous and can be cold water soluble or hot water soluble. The construction of the water-soluble foam substrate can include, for example, folded layers or plies, laminated layers or plies, or rolled layers or plies.

In an exemplary embodiment, the water-soluble foam substrate may further include any auxiliary agent as a nonwoven web, fiber and/or film as disclosed herein. The auxiliary agent may be applied by suitable means to one or more surfaces of the water-soluble foam substrate or to an article containing them, such as a packet. In an exemplary embodiment, the auxiliary agent is in the form of a powder. In a refinement of the previous embodiment, one or more stationary powder spray guns are used to direct a powder stream from one or more directions toward the water-soluble foam substrate or packet, while the water-soluble foam substrate or packet is transported through a coating zone using a belt conveyor. In an exemplary embodiment, the water-soluble foam substrate or packet is conveyed through a suspension of powder in air. In an exemplary embodiment, the water-soluble foam substrate or packet is tumble mixed with the powder in a trough-like device. In an exemplary embodiment, which may be combined with any other embodiment, electrostatic forces are used to enhance the attraction between the powder and the packet or water-soluble foam substrate. This type of process may be based on negatively charging the powder particles and directing these charged particles toward a grounded packet or water-soluble foam substrate. In other alternative embodiments, the powder is applied to the water-soluble foam substrate or packet by a secondary transfer tool, including but not limited to a rotating brush that is in contact with the powder, or by a powdered glove that can transfer the powder from the container to the water-soluble foam substrate or packet. In yet another embodiment, the powder is applied by dissolving or suspending the powder in a non-aqueous solvent or carrier, which is then atomized and sprayed onto the water-soluble foam substrate or packet. In one embodiment, the solvent or carrier subsequently evaporates, leaving behind the activator powder. In certain embodiments, the powder is applied to the water-soluble foam substrate or packet in precise doses. These embodiments utilize a closed system dry lubricant application machine, such as Pekutech's Powder Applicator PM 700 D. In this process, the powder is fed into the feed trough of the application machine in batches or continuously as needed. The water-soluble foam substrate or packet is transferred from the output belt of a standard rotating drum pouch machine onto the conveyor belt of the powder application machine, which applies a controlled dosage of the powder to the water-soluble foam substrate or packet. The water-soluble foam substrate or packet can then be conveyed to an appropriate secondary packaging process.

In exemplary embodiments where the adjuvant is in liquid form or in solution, the foregoing can be dispersed in the water-soluble foam substrate, dispersed on the surface of the water-soluble foam substrate, or combinations thereof, for example, by spin casting, spraying a solution such as an aerosolized solution, roll coating, flow coating, curtain coating, extrusion, knife coating, and combinations thereof.

Adjuvants, such as chemical exfoliants, mechanical exfoliants, microcapsules of fragrances and/or perfumes, aversive agents, surfactants, colorants, enzymes, skin conditioners, deoiler agents, cosmetic agents, or combinations thereof, when present in the water-soluble foam base, are in an amount of at least about 1% by weight, or in a range of about 1% to about 99% by weight, to provide additional functionality to the water-soluble foam base. The chemical exfoliants, mechanical exfoliants, microcapsules of fragrances and/or perfumes, aversive agents, surfactants, colorants, enzymes, skin conditioners, deoiler agents, cosmetic agents, or combinations thereof can be in any desired form, including solids (e.g., powders, granules, crystals, flakes, or ribbons), liquids, spreaders, pastes, gases, and the like, and can be encapsulated as needed.

In an exemplary embodiment, the water-soluble foam substrate can be colored, pigmented, and/or dyed to provide improved aesthetic effects compared to water-soluble films. Suitable colorants for use with the water-soluble foam substrate can include indicator dyes, such as pH indicators (e.g., thymol blue, bromothymol, thymolphthalein, and thymolphthalein), moisture/water indicators (e.g., hydrochromic inks or leuco dyes), or thermochromic inks that change color when the temperature increases and/or decreases. Suitable colorants include, but are not limited to, triphenylmethane dyes, azo dyes, anthraquinone dyes, perylene dyes, indigo dyes, Food, Drug, and Cosmetics (FD&C) colors, organic pigments, inorganic pigments, or combinations thereof. Examples of colorants include, but are not limited to, FD&C Red #40; Red #3; FD&C Black #3; Black #2; mica-based pearlescent pigments; FD&C Yellow #6; Green #3; Blue #1; Blue #2; titanium dioxide (food grade); brilliant black; and combinations thereof.

In an exemplary embodiment, the water-soluble foam base can include any of the surfactants disclosed herein. In an exemplary embodiment, the water-soluble foam base can include one or more of the following group: sodium cocoyl isethionate, glucotein, phenamide, cola lipids, cocamides, e.g., cocamide ethanolamine, ethylene oxide-based surfactants, and saponified avocado and palm oils.

The water-soluble foam substrate of the present disclosure can have any thickness. Suitable thicknesses can include, but are not limited to, about 5 microns (μm) to about 10,000 μm (1 cm), about 3 μm to about 5,000 μm, about 5 μm to about 1,000 μm, about 5 μm to about 500 μm, about 200 μm to about 500 μm, about 5 μm to about 200 μm, about 20 μm to about 100 μm, or about 40 μm to about 90 μm, or about 50 μm to 80 μm, or about 60 μm to 65 μm, for example, 50 μm, 65 μm, 76 μm, or 88 μm. The water-soluble foam substrate of the present disclosure can be characterized as high loft or low loft. Loft refers to the ratio of thickness to mass per unit area (i.e., basis weight). A high loft water-soluble foam substrate can be characterized by a high ratio of thickness to mass per unit area. "High loft" as used herein refers to water-soluble foam substrates of the present disclosure having a basis weight as defined herein and a thickness greater than 200 μm. The thickness of the water-soluble foam substrate can be determined according to ASTM D5729-97, ASTM D5736, and/or ISO 9073-2:1995, and can include, for example, subjecting the water-soluble foam substrate to a load of 2N and measuring the thickness. High loft materials can be used according to methods known in the art, for example, cross-wrapping, using a cross-wrapper to fold an unbonded web on itself to build loft and basis weight.

In general, the dynamic coefficient of friction and the ratio of the static coefficient of friction to the dynamic coefficient of friction for the water-soluble foam substrate of the present disclosure will be lower than the dynamic coefficient of friction and the ratio of the static coefficient of friction to the dynamic coefficient of friction for the water-soluble film due to the increased surface roughness of the water-soluble foam substrate relative to the water-soluble film, resulting in reduced surface contact to the water-soluble foam substrate. Advantageously, this surface roughness can provide improved consumer feel (i.e., cloth-like hand instead of rubbery hand), improved aesthetics (i.e., less gloss than water-soluble films), and/or ease of processability for thermoformed and/or vertically formed, filled and sealed, and/or multi-chamber packets that require the water-soluble foam substrate to be pulled along the surface of the processing equipment/mold. Thus, the water-soluble and/or water-insoluble fibers should be sufficiently rough to provide surface roughness to the resulting water-soluble foam substrate without being so rough that it causes drag.

The water solubility of the soluble foam substrate of the present disclosure is generally a function of the type of fiber(s) used to prepare the water soluble foam substrate as well as the basis weight of the water soluble foam substrate. Without being bound by theory, it is believed that the solubility profile of the water soluble foam substrate follows the same solubility profile of the fiber(s) used to prepare the water soluble foam substrate, and the solubility profile of the fiber generally follows the same solubility profile of the polymer(s) from which the fiber is prepared. For example, in a water soluble foam substrate comprising PVOH fibers, the degree of hydrolysis of the PVOH polymer can be selected such that the water solubility of the water soluble foam substrate is also affected. At a given temperature, as the degree of hydrolysis of the PVOH polymer increases from partial hydrolysis (88% DH) to full hydrolysis (≧98% DH), the water solubility of the polymer generally decreases. Thus, in an exemplary embodiment, the water soluble foam substrate can be cold water soluble. For co-poly(vinyl acetate vinyl alcohol) polymers that do not contain any other monomers (e.g., not copolymerized with anionic monomers), the cold water soluble web that is soluble in water at temperatures below 10° C. can include fibers of PVOH with a degree of hydrolysis in the range of about 75% to about 90%, or about 75% to about 89%, or about 80% to about 90%, or about 85% to about 90%, or about 90% to about 99.5%. In other exemplary embodiments, the water soluble foam substrate can be hot water soluble. For example, for co-poly(vinyl acetate vinyl alcohol) polymers that do not contain any other monomers (e.g., not copolymerized with anionic monomers), the hot water soluble foam substrate can be soluble in water at a temperature of at least about 60° C. by including fibers of PVOH with a degree of hydrolysis of at least about 98%.

Modification of the PVOH polymer increases the solubility of the PVOH polymer. Thus, at a given temperature, the solubility of a water-soluble foam substrate prepared from a modified PVOH copolymer is expected to be higher than that of a water-soluble foam substrate prepared from a PVOH copolymer having the same degree of hydrolysis as the modified PVOH copolymer. Following these trends, water-soluble foam substrates with specific solubility characteristics can be engineered by blending polymers into the fibers and/or by blending fibers into the water-soluble foam substrate. Additionally, as described herein, the water-soluble foam substrate may include multiple fibers, and in some cases, two or more fiber types with different solubilities.

The inclusion of water-insoluble fibers and/or water-insoluble fiber-forming materials in the fibers of the water-soluble foam substrate can also be used to design a water-soluble foam substrate with a particular solubility and/or extended release characteristics. Without being bound by theory, it is believed that as the weight percentage of water-insoluble fibers included in the water-soluble foam substrate increases (relative to the total weight of the water-soluble foam substrate), the solubility of the water-soluble foam substrate generally decreases and the extended release characteristics of the pouch containing the water-soluble foam substrate generally increase. When contacted with water at or above the solubility temperature of the water-soluble fibers, the water-soluble foam substrate containing water-soluble and water-insoluble fibers will begin to disperse as the water-soluble fibers dissolve, thereby disrupting the foam structure and/or increasing the pore size of the pores in the water-soluble foam substrate. The greater the disruption of the foam structure or the larger the pore size, the faster water can access the pouch contents and the faster the pouch contents will be released. Similarly, extended release of the contents of a pouch containing the water-soluble foam substrate of the present disclosure can be achieved by using a blend of water-soluble fibers with different solubility characteristics and/or different solubility temperatures. As the faster dissolving fibers dissolve, the foam breaks down, leaving less soluble fibers with a larger exposed surface area, facilitating dissolution of the less soluble fibers and release of the pouch contents. In exemplary embodiments in which the foam substrate includes water soluble and water insoluble fibers, the ratio of soluble fiber to water insoluble fiber is not particularly limited. The water soluble fiber can comprise about 1% to about 99%, about 20% to about 80%, about 40% to about 90%, about 50% to about 90%, or about 60% to about 90% by weight of the total weight of the plurality of fibers, and the water insoluble fiber can comprise about 1% to about 99%, about 20% to about 80%, about 10% to about 60%, about 10% to about 50%, or about 10% to about 40% by weight of the total weight of the fibers. In exemplary embodiments, the plurality of fibers includes about 10% to about 80% water soluble fiber by weight of the total weight of the fibers, with the remainder being water insoluble fiber.

In an exemplary embodiment, the nonwoven web, the plurality of fibers, the foam, the water-soluble film, or combinations thereof disclosed herein can include a biodegradable polymer. In certain embodiments, the plurality of fibers can include water-insoluble fibers forming a material that is biodegradable. In an exemplary embodiment, the plurality of fibers can include a first fiber that is a water-insoluble biodegradable fiber and a second fiber that is soluble in water at a temperature of about 10° C. to about 20° C. according to MSTM-205 or is not soluble in water at a temperature of about 30° C. or less according to MSTM-205. In an exemplary embodiment, the nonwoven web is water-insoluble and biodegradable.

In exemplary embodiments, the foam substrate is biodegradable. As used herein, when a foam substrate is said to be biodegradable, at least 50% of the foam substrate is biodegradable, e.g., at least 60%, at least 70%, at least 80%, at least 90%, or 100% of the foam substrate is biodegradable.

The foam substrate disclosed herein can include a plurality of fibers including a first fiber type and a second fiber type, the first and second fiber types differing in diameter, length, toughness, shape, stiffness, elasticity, solubility, melting point, glass transition temperature ( _Tg ), chemical composition, color, or combinations thereof. In an exemplary embodiment, the first fiber type can include a PVOH homopolymer fiber-forming material, a modified PVOH copolymer fiber-forming material, a PVOH copolymer fiber-forming material, or combinations thereof. In an exemplary embodiment, the first fiber type can include two or more PVOH homopolymer fiber-forming materials, two or more PVOH copolymer fiber-forming materials, two or more modified PVOH copolymer fiber-forming materials, or combinations thereof. In an exemplary embodiment, the second fiber type can include a PVOH homopolymer fiber-forming material, a PVOH copolymer fiber-forming material, a more modified PVOH copolymer fiber-forming material, or combinations thereof. In an exemplary embodiment, the second fiber type can include two or more PVOH homopolymer fiber forming materials, two or more PVOH copolymer fiber forming materials, two or more modified PVOH copolymer fiber forming materials, or combinations thereof. In an exemplary embodiment, the first fiber type and/or the second fiber type are water insoluble fiber forming materials. In an exemplary embodiment, the first fiber type can include a water insoluble polymeric fiber forming material and the second fiber type can include a polyvinyl alcohol fiber forming material that, when provided as the sole fiber forming material of a nonwoven web or as a film, the resulting web or film is soluble in water at temperatures ranging from about 0° C. to about 20° C. by MSTM-205. In an exemplary embodiment, the first fiber type can include a water insoluble polymeric fiber forming material and the second fiber type can include a PVOH homopolymer or copolymer fiber forming material that, when provided as the sole fiber forming material of a water soluble foam substrate, the resulting water soluble foam substrate is not soluble in water at temperatures of 20° C. or less by MSTM-205. In an exemplary embodiment, the first fiber type includes two or more PVOH copolymer fiber forming materials, two or more modified PVOH copolymer fiber forming materials, or a combination of a PVOH copolymer fiber forming material and a modified PVOH copolymer fiber forming material. In an exemplary embodiment, the second fiber type includes two or more PVOH copolymer fiber forming materials, two or more modified PVOH copolymer fiber forming materials, or a combination of a PVOH copolymer fiber forming material and a modified PVOH copolymer fiber forming material.

The fibers included in the water-soluble foam substrate of the present disclosure can have any toughness. The toughness of the fiber correlates to the coarseness of the fiber. As the toughness of the fiber decreases, the coarseness of the fiber increases. The fibers used to prepare the nonwoven web of the present disclosure can have a toughness of about 1 to about 100 cN/dtex, or about 1 to about 75 cN/dtex, or about 1 to about 50 cN/dtex, or about 1 to about 45 cN/dtex, or about 1 to about 40 cN/dtex, or about 1 to about 35 cN/dtex, or about 1 to about 30 cN/dtex, or about 1 to about 25 cN/dtex, or about 1 to about 20 cN/dtex, or about 1 to about 15 cN/dtex, or about 1 to about 10 cN/dtex, or about 3 to about 8 cN/dtex, or about 4 to about 8 cN/dtex. tex, or from about 6 to about 8 cN/dtex, or from about 4 to about 7 cN/dtex, or from about 10 to about 20, or from about 10 to about 18, or from about 10 to about 16, or about 1 cN/dtex, about 2 cN/dtex, about 3 cN/dtex, about 4 cN/dtex, about 5 cN/dtex, about 6 cN/dtex, about 7 cN/dtex, about 8 cN/dtex, about 9 cN/dtex, about 10 cN/dtex, about 11 cN/dtex, about 12 cN/dtex, about 13 cN/dtex, about 14 cN/dtex, or about 15 cN/dtex. In exemplary embodiments, the plurality of fibers can have a tenacity ranging from about 3 cN/dtex to about 15 cN/dtex, or from about 5 cN/dtex to about 12 cN/dtex, or from about 5 cN/dtex to about 10 cN/dtex.

The toughness of the water-soluble foam substrate can be the same or different from the toughness of the fibers used to prepare the web. Without being bound by theory, it is believed that the toughness of the water-soluble foam substrate is related to the strength of the nonwoven web, with higher toughness providing higher strength to the nonwoven web. The toughness of the water-soluble foam substrate can be modified by using fibers with different toughness. The toughness of the water-soluble foam substrate can also be affected by processing. The water-soluble foam substrate of the present disclosure has a relatively high toughness, i.e., the water-soluble foam substrate is a free-standing substrate that can be used as the sole material to prepare articles and/or pouches. In contrast, water-soluble foam substrates prepared by meltblowing, electrospinning, and/or rotary spinning processes may have low toughness and may not be free-standing or may not be used as the sole substrate to form articles or pouches.

The water-soluble foam substrate can be characterized by its basis weight. The basis weight of the water-soluble foam substrate is the mass per unit area of the water-soluble foam substrate. The basis weight can be modified by varying manufacturing conditions, as known in the art. The water-soluble foam substrate can have the same basis weight before and after bonding. Alternatively, the bonding method can change the basis weight of the water-soluble foam substrate. For example, when bonding occurs through the application of heat and pressure, the thickness of the water-soluble foam substrate (and therefore the area of the water-soluble foam substrate) can be reduced, thereby increasing the basis weight. Thus, as used herein and unless otherwise specified, the basis weight of the water-soluble foam substrate refers to the basis weight of the water-soluble foam substrate after bonding.

The water-soluble foam substrate of the present disclosure can have any basis weight in the range of about 0.1 g/ ^m2 to about 700 g/ ^m2 , about 0.5 g/ ^{m2 to} about 600 g/ ^m2 , about 1 g/ ^m2 to about 500 g/ ^m2 , about 1 g/ ^m2 to about 400 g/ ^m2 , about 1 g/ ^m2 to about 300 g/ ^m2 , about 1 g/ ^m2 to about 200 g/ ^m2 , about 1 g/ ^m2 to about 100 g/ ^m2 , about 30 g/ ^m2 to about 100 g/ ^m2 , about 20 g/m2 to about 100 g/ ^m2 , about 20 g/ ^m2 to about 80 g/ ^m2 , or about 25 g/ ^m2 to about 70 g/ ^m2 .

Furthermore, assuming that fiber composition and web thickness remain constant, as the basis weight of the water-soluble foam substrate increases, the dissolution rate of the water-soluble foam substrate decreases because more material will dissolve. For example, at a given temperature, a water-soluble foam substrate prepared from fibers containing PVOH polymer(s) and having a basis weight of, for example, 40 g/ ^m2 is expected to dissolve slower than an otherwise identical water-soluble web having a basis weight of, for example, 30 g/ ^m2 . Thus, basis weight can also be used to modify the solubility characteristics of the water-soluble foam substrate. The water-soluble foam substrate can generally have any basis weight in the range of about 1 g/ ^m2 to about 700 g/ ^m2 , about 1 g/ ^m2 to about 600 g/ ^m2 , about 1 g/ ^m2 to about 500 g/ ^m2 , about 1 g/ ^m2 to about 400 g/ ^m2 , about 1 g/ ^m2 to about 300 g/ ^m2 , about 1 g/ ^m2 to ^about 200 g/ ^m2 , about 10 g/ ^m2 to about 100 g/ ^m2 , about 30 g/ ^m2 to about 100 g/ ^m2 , about 20 g/m2 to about 100 g/ ^m2 , about 20 g/ ^m2 to about 80 g/ ^m2 , about 25 g/ ^m2 to about 70 g/ ^m2 , or about 40 g/ ^m2 to about 60 g/ ^m2 .

The water-dispersible or water-soluble foam substrates of the present disclosure can be used as a monolayer, or can be layered with other water-soluble foam substrates, or can be in the form of a laminate with a water-soluble film. In some embodiments, the foam substrate comprises a monolayer. In some embodiments, the foam substrate is a multi-layer foam substrate comprising two or more layers. The two or more layers can be laminated to one another. In refinements of the foregoing embodiments, the two or more layers can be the same (e.g., can be prepared from the same fibers and basis weights). In refinements of the foregoing embodiments, the two or more layers can be different (e.g., can be prepared from different types of fibers, fiber chemistries, and/or have different basis weights).

A multi-layer foam substrate can have a basis weight that is the sum of the basis weights of the individual layers, and thus the multi-layer water-soluble foam substrate will take longer to dissolve than either of the individual layers provided as a single layer.
Water-soluble film

The water-dispersible and/or water-soluble films described herein generally comprise any of the water-dispersible and/or water-soluble polymers disclosed herein. In an exemplary embodiment, the films of the present disclosure comprise a polyvinyl alcohol (PVOH) resin, a modified polyvinyl alcohol resin, or a combination thereof. In an exemplary embodiment, the water-soluble film comprises a PVOH resin selected from the group consisting of a PVOH homopolymer, a PVOH copolymer, a PVOH copolymer having an anionic modification, and a combination of the foregoing. In an exemplary embodiment, the film may comprise a single PVOH polymer or a blend of PVOH polymers. In an exemplary embodiment, the film comprises a PVOH copolymer. In an exemplary embodiment, the film comprises a hot water soluble PVOH copolymer. In an exemplary embodiment, where the nonwoven web comprises a surfactant and/or an exfoliant, the film may comprise a modified PVOH copolymer having an anionic modification. In an exemplary embodiment, the film may comprise a water-soluble polyvinyl alcohol copolymer or modified copolymer that, when provided in the film as the sole film-forming material, is soluble in water at a temperature ranging from about 0° C. to about 20° C. by MSTM-205. In an exemplary embodiment, the film can include a water-soluble polyvinyl alcohol copolymer or modified copolymer that, when provided in the film as the sole film-forming material, is not water-soluble at water temperatures of 20° C. or less by MSTM-205.

The water-soluble film may include other film-forming polymers, including but not limited to polyvinyl alcohol, water-soluble acrylate copolymers, polyethyleneimine, pullulan, water-soluble natural polymers including but not limited to guar gum, acacia gum, xanthan gum, carrageenan, and starch, water-soluble polymer modified starch, copolymers of the foregoing, or combinations of any of the foregoing. Other water-soluble polymers may include polyalkylene oxides, polyacrylamides, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts thereof, polyamino acids, polyamides, gelatin, methylcellulose, carboxymethylcellulose and salts thereof, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, or combinations of any of the foregoing. Such water-soluble polymers are commercially available from a variety of sources. In an exemplary embodiment, the water-soluble film may include a PVOH homopolymer, a PVOH copolymer, a modified PVOH copolymer, or a combination thereof. In an exemplary embodiment, the water-soluble film includes a single PVOH copolymer or a blend of PVOH copolymers. In a further embodiment, the water-soluble film comprises a PVOH copolymer having a viscosity in the range of 5 cP to 23 cP and a degree of hydrolysis in the range of 86% to 92%.

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

In an exemplary embodiment, the water-dispersible and/or water-soluble film may include the above-mentioned adjuvants. In an exemplary embodiment, the film may be substantially free of the above-mentioned adjuvants. In an exemplary embodiment, the water-soluble film may include the above-mentioned plasticizers. The total amount of non-water-soluble plasticizer provided in the water-soluble film may range from about 1% to about 45% by weight, or from about 5% to about 45% by weight, or from about 10% to about 40% by weight, or from about 20% to about 30% by weight, from about 1% to about 4% by weight, or from about 1.5% to about 3.5% by weight, or from about 2.0% to about 3.0% by weight, for example, about 1% by weight, about 2.5% by weight, about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, or about 40% by weight. In an exemplary embodiment, the film includes one or more of propylene glycol, glycerol, diglycerol, sorbitol, xylitol, maltitol, trimethylolpropane (TMP), and polyethylene glycol (100-1000 molecular weight).

In exemplary embodiments, the film can include a surfactant as described above. In various embodiments, the amount of surfactant in the film ranges from about 0.01% to about 2.5% by weight, about 0.1% to about 2.5% by weight, about 1.0% to about 2.0% by weight, about 0.01% to 0.25% by weight, or about 0.10% to 0.20% by weight. In exemplary embodiments, the film includes one or more of polysorbate 80, lecithin from various plant sources, and sodium lauryl sulfate (SLS), and the like.

In an exemplary embodiment, the film adjuvants may include fillers/bulking agents/antiblocking agents/antiblocking agents. Suitable fillers/bulking agents/antiblocking agents include, but are not limited to, crosslinked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, mica, stearic acid and its metal salts, such as magnesium stearate. If desired, additional unmodified or modified starches can be included in the water soluble in addition to one of the specific starch components mentioned above, such as hydroxypropylated starches present in an amount ranging from about 5 phr to about 30 phr, or modified starches having a degree of modification greater than about 2% and present in an amount ranging from about 2.5 phr to about 30 phr, or unmodified starches having an amylose content ranging from about 20% to about 80%, or hydroxypropyl modified starches having an amylose content ranging from about 23% to about 95%, where the polyvinyl alcohol comprises unmodified polyvinyl alcohol or an anionic modified polyvinyl alcohol copolymer, and assuming that the anionic modifier is not an acrylate. Preferred materials are starch, modified starch, and silica. In one embodiment, the amount of filler/bulking agent/antiblocking agent/antisticking agent in the water-soluble film can range, for example, from about 1% to about 6% by weight, or from about 1% to about 4% by weight, or from about 2% to about 4% by weight, or from about 1 phr to about 6 phr, or from about 1 phr to about 4 phr, or from about 2 phr to about 4 phr. In an exemplary embodiment, when starch or modified starch is included in the water-soluble film in addition to one of the specific starch components described above, the additional starch component will be provided in an amount of less than about 50% by weight based on the total weight of all starches included in the film. Without wishing to be bound by theory, it is believed that any benefits provided to the films of the present disclosure from including the starch components described above are not affected by the inclusion of additional starch components that provide less or no benefit to the water-soluble film.

The film may further have a residual moisture content of at least 4% by weight, such as in the range of about 4% to about 10% by weight, as measured by Karl Fischer titration.
Method for preparing fibers

Wet cooling gel spinning

In an exemplary embodiment, the plurality of water soluble fibers can include water soluble fibers prepared according to a wet cryogel spinning process, the wet cryogel spinning process comprising:
(a) dissolving a water-soluble polymer (or polymers) in solution to form a polymer mixture, optionally including adjuvants;
(b) extruding the polymer mixture through a spinneret nozzle into a coagulation bath to form an extruded polymer mixture;
(c) passing the extruded polymer mixture through a solvent exchange bath;
(d) optionally wet drawing the extruded polymer mixture; and (e) finishing the extruded polymer mixture to provide water soluble fibers.

The solvent in which the water-soluble polymer is dissolved may suitably be any solvent in which the water-soluble polymer is soluble. In an exemplary embodiment, the solvent in which the water-soluble polymer is dissolved comprises a polar aprotic solvent. In an exemplary embodiment, the solvent in which the water-soluble polymer is dissolved comprises dimethylsulfoxide (DMSO).

The coagulation bath contains a cooling solvent to gel the extruded polymer mixture. The coagulation bath can generally be at any temperature that facilitates solidification of the extruded polymer mixture. The coagulation bath can be a mixture that includes a solvent in which the polymer is soluble and a solvent in which the polymer is not soluble. The solvent in which the polymer is not soluble is generally the primary solvent, and the solvent in which the polymer is not soluble constitutes greater than 50% by volume of the mixture.

After passing through the coagulation bath, the extruded polymer mixture gel can be passed through one or more solvent exchange baths. The solvent exchange baths are provided to replace the solvent in which the water-soluble polymer is soluble with a solvent in which the water-soluble polymer is not soluble to further coagulate the extruded polymer mixture and to replace the solvent in which the water-soluble polymer is soluble with a solvent that will evaporate more easily, thereby reducing drying time. The solvent exchange baths can include a series of solvent exchange baths having a gradient of solvents in which the water-soluble polymer is soluble as well as solvents in which the water-soluble polymer is not soluble, a series of solvent exchange baths having only solvents in which the water-soluble polymer is not soluble, or a single solvent exchange bath having only solvents in which the water-soluble polymer is not soluble. In an exemplary embodiment, at least one solvent exchange bath can consist essentially of a solvent in which the water-soluble polymer is not soluble.

The finished fibers may also be referred to as staple fibers, short cut fibers, or pulp. In an exemplary embodiment, finishing includes drying the extruded polymer mixture. In an exemplary embodiment, finishing includes cutting or crimping the extruded polymer mixture to form individual fibers. Wet drawing of the extruded polymer mixture can provide a substantially uniform diameter to the extruded polymer mixture from which the fibers are cut. Drawing is quite different from extrusion as is known in the art. Specifically, "extrusion" refers to the act of forcing a resin mixture through a spinneret head to create fibers, whereas drawing refers to mechanically pulling the fibers in the machine direction to promote polymer chain orientation and crystallinity, thereby increasing fiber strength and toughness.

In an exemplary embodiment in which the water soluble fibers are prepared from a wet cryogel spinning process, the water soluble polymer can generally be any water soluble polymer or blend thereof, e.g., two or more different polymers, as generally described herein. In refinements of the foregoing embodiment, the polymer(s) can have any degree of polymerization (DP), e.g., in the range of 10 to 10,000,000, e.g., at least 10, at least 20, at least 50, at least 100, at least 200, at least 300, at least 400, at least 500, at least 750, or at least 1000, and up to 10,000,000, up to 5,000,000, up to 2,500,000, up to 1,000,000, up to 900,000, up to 750,000, up to 500,000, up to 250,000, up to 100,000, up to 90,000, up to 75,000, up to 50,000, up to 25,000, up to 12,000, up to 10,000, up to 5,000, or up to 2,500, for example, 1000 to about 50,000, 1000 to about 25,000, 1000 to about 12,000, 1000 to about 5,000, 1000 to about 2,500, about 50 to about 12,000, about 50 to about 10,000, about 50 to about 5,000, about 50 to about 2,500, about 50 to about 1000, about 50 to about 900, about 100 to about 800, about 150 to about 700, about 200 to about 600, or about 250 to about 500. In an exemplary embodiment, DP is at least 1,000. The above-mentioned adjuvants can be added to the fibers themselves or to the nonwoven web during the carding and/or bonding process.

Thermoplastic fiber spinning

Thermoplastic fiber spinning is well known in the art. Briefly, thermoplastic fiber spinning involves:
(a) preparing a polymer mixture comprising a fiber-forming polymer, optionally including an adjuvant;
(b) extruding the polymer mixture through a spinneret nozzle to form an extruded polymer mixture;
(c) optionally stretching the extruded polymer mixture; and (d) finishing the extruded polymer mixture to obtain fibers.

The full staple fibers of the thermoplastic fiber spinning process can be finished by drying, cutting, and/or crimping so that individual fibers are formed. Stretching the extruded polymer mixture mechanically pulls the fiber in the machine direction, promoting polymer chain orientation and crystallinity, increasing fiber strength and toughness. Preparation of the polymer mixture for thermoplastic fiber spinning can include (a) preparing a solution of fiber-forming materials and a readily volatile solvent and extruding the solution through a spinneret, whereupon the solvent readily evaporates when the solution contacts a stream of hot air, leaving behind a solid fiber, or (b) melting the polymer and allowing the polymer to solidify by extruding the hot polymer through a spinneret followed by a quenching process with cold air. Thermoplastic fiber spinning is distinct from wet chill gel spinning in that at least (a) in thermoplastic fiber spinning, the extruded fiber is solidified by evaporation of a solvent or by quenching the hot solid fiber with cold air rather than using a coagulation bath; and (b) in wet chill gel spinning, any required stretching is performed while the fiber is in a gel state rather than a solid state.

The fiber-forming material for preparing fibers from the thermoplastic fiber spinning process can be any fiber-forming polymer or blend thereof, for example, two or more different polymers, provided that the polymer or blend thereof has a suitable solubility in the easily volatile solvent and/or has a melting point lower than its decomposition temperature and clearly different. Furthermore, when a blend of fiber-forming polymers is used to make the fibers, the fiber-forming materials must have a similar solubility in the easily volatile solvent and/or have a similar thermal profile such that the two or more fiber-forming materials melt at similar temperatures. In contrast, the fiber-forming material for preparing fibers from the wet-cooled gel spinning process is not limited, and the fibers can be prepared from a blend of any two or more polymers that are soluble in the same solvent system, which does not have to be a single solvent or even a volatile solvent.

The fiber-forming polymer(s) for preparing the thermoplastic fiber spun fibers can have a degree of polymerization (DP) ranging from, for example, 10 to 10,000, such as at least 10, at least 20, at least 50, at least 100, at least 200, at least 300, at least 400, at least 500, at least 750, or at least 1000, and up to 10,000, up to 5,000, up to 2,500, up to 1,000, up to 900, up to 750, up to 500, or up to 250. In exemplary embodiments, the DP is less than 1,000.

Melt spinning

Melt spinning is well known in the art and is understood to refer to both spunbond and meltblowing processes. Melt spinning is a continuous process that directly prepares a nonwoven web as fibers form. Thus, the melt spun forming fibers are not completed and cut to any consistent length (e.g., staple fibers are not prepared by these processes). Furthermore, melt spinning does not include a drawing step, and therefore the only control of the diameter of the resulting melt spun fibers is the size of the hole through which the fiber forming materials are extruded, and the polymer chains are not oriented in any particular direction.

In certain embodiments, the melt spinning process comprises:
(a) preparing a polymer mixture comprising a fiber-forming polymer, optionally including an adjuvant;
(b) extruding the polymer mixture into a die assembly to form an extruded polymer mixture;
(c) quenching the extruded polymer mixture;
(d) depositing the quenched extruded polymer mixture onto a belt to form a nonwoven web; and (e) bonding the nonwoven web.

In the spunbond process, the extruded polymer mixture is pumped into a die assembly as a molten polymer and is quenched with cold air as it passes through the die assembly. In the meltblown process, the extruded polymer mixture is pumped into a die assembly with hot air blown into it and is quenched as it leaves the die assembly and comes into contact with air at ambient temperature. In both processes, the fibers are continuously lowered onto a belt or drum, usually facilitated by drawing a vacuum under the belt or drum.

The diameter of the melt spun fibers may range from about 0.1 to about 50 microns, e.g., at least about 0.1 micron, at least about 1 micron, at least about 2 microns, at least about 5 microns, at least about 10 microns, at least about 15 microns, or at least about 20 microns, and up to about 50 microns, up to about 40 microns, up to about 30 microns, up to about 25 microns, up to about 20 microns, up to about 15 microns, up to about 10 microns, from about 0.1 micron to about 50 microns, from about 0.1 micron to about 40 microns, from about 0.1 micron to about 30 microns, From about 0.1 microns to about 25 microns, from about 0.1 microns to about 20 microns, from about 0.1 microns to about 15 microns, from about 0.1 microns to about 10 microns, from about 0.1 microns to about 9 microns, from about 0.1 microns to about 8 microns, from about 0.1 microns to about 7 microns, from about 0.1 microns to about 6 microns, from about 0.1 microns to about 6 microns, from about 5 microns to about 35 microns, from about 5 microns to about 30 microns, from about 7.5 microns to about 25 microns, from about 10 microns to about 25 microns, or from about 15 microns to about 25 microns. Meltblowing processes can provide microfine fibers having an average diameter in the range of about 1-10 microns, however, it is known in the art that meltblowing processes have a very large variation in fiber-to-fiber diameter, for example, a variation of 100-300%. Additionally, spunbond fibers can have a larger average fiber diameter, e.g., about 15 to about 25 microns, but are known in the art to have improved uniformity from fiber to fiber, e.g., about 10% variation.

Fiber-forming materials for thermal extrusion processes (e.g., melt spinning, thermoplastic fiber spinning) are more limited than those for wet-cooled gel spinning processes. For example, the degree of polymerization for thermal extrusion processes is limited to a range of about 200 to about 500. As the degree of polymerization decreases below 200, the viscosity of the fiber-forming material also becomes too low, and individual fibers prepared by pumping the material through the die assembly do not maintain proper separation after exiting the die assembly. Similarly, as the degree of polymerization increases above 500, the viscosity becomes too high to efficiently pump the material through small enough holes in the die assembly to run the process at high speeds, and thus the efficiency of the process and the uniformity of the fibers and/or nonwovens are lost. Furthermore, processes that require heating of the fiber-forming material are unsuitable for polyvinyl alcohol homopolymers, as homopolymers generally do not have the necessary thermal stability.

The wet chill gel spinning process advantageously provides one or more benefits, such as providing fibers comprising a blend of water-soluble polymers, controlling the diameter of the fiber, providing relatively large diameter fibers, controlling the length of the fiber, controlling the tenacity of the fiber, providing high tenacity fibers, providing fibers from polymers having a high degree of polymerization, and/or providing fibers that can be used to provide a self-supporting nonwoven web. Continuous processes such as spunbonding, meltblowing, electrospinning, and rotary spinning generally do not allow blends of water-soluble polymers (e.g., due to the difficulty of matching the melt index of various polymers), forming fibers with large diameters (e.g., greater than 50 microns), controlling the length of the fiber, providing high tenacity fibers, and using polymers with a high degree of polymerization. Furthermore, the wet chill gel spinning process advantageously is not limited to polymers that are only melt processable, and therefore can utilize fibers made from fiber-forming materials with very high molecular weights, high melting points, low melt flow indexes, or combinations thereof, providing fibers with stronger physical properties and various chemical functionalities compared to fibers prepared by thermal extrusion processes. Further still, advantageously, the wet cryogel spinning process is not limited by the viscosity of the polymer. In contrast, processes requiring melting of the fiber-forming material are known in the art to be limited to fiber-forming materials with viscosities of 5 cP or less. Thus, fibers comprising polymers including polyvinyl alcohol homopolymers and copolymers with viscosities greater than 5 cP are only accessible by wet cryogel spinning.
Method for preparing a nonwoven web

The nonwoven web of the present disclosure is a sheet-like structure having two outer surfaces, the nonwoven web comprising a plurality of fibers. The nonwoven web of the present disclosure can be prepared from the fibers using any method known in the art. As known in the art, when the fibers are spunbonded or meltblown, the fibers are continuously laid side by side to form a nonwoven web, after which the fibers are bonded.

The staple fibers are carded or airlaid and bonded to provide a nonwoven web. Carding and airlaid methods are well known in the art.

Methods of bonding nonwoven webs are well known in the art. For example, bonding can include thermal, mechanical, and/or chemical bonding. Thermal bonding can include, but is not limited to, calendaring, embossing, air-through, and ultrasonic. Mechanical bonding can include, but is not limited to, hydroentanglement (spunlace), needle punching, and stitch bonding. Chemical bonding can include, but is not limited to, solvent bonding and resin bonding.

Thermal bonding is achieved by the application of heat and pressure to maintain the pore size, shape, and alignment created by the carding process. Thermal bonding conditions can be readily determined by one skilled in the art. If too little heat and/or pressure is applied, the fibers will not bond sufficiently to form a freestanding web, and if too much heat and/or pressure is applied, the fibers will begin to blend together. The chemical nature of the fibers determines the upper and lower limits of heat and/or pressure for thermal bonding. Without wishing to be bound by theory, it is believed that at temperatures above 235°C, polyvinyl alcohol-based fibers decompose. Embossing methods for thermal bonding of fibers are known. Embossing can be single-sided embossing or double-sided embossing. Embossing of water-soluble fibers includes single-sided embossing using a single embossing roll consisting of an ordered circular array and a steel roll with a flat surface. As embossing increases (e.g., as surface features are imparted to the web), the surface area of the web increases. Without wishing to be bound by theory, as the surface area of the web increases, the solubility of the web increases. Thus, the solubility characteristics of a nonwoven web can be advantageously tailored by varying the surface area through embossing.

Air-through bonding requires high thermoplastic content in the nonwoven web and two different melting point materials. In air-through bonding, the unbonded nonwoven web circulates around a drum while hot air flows from the outside of the drum toward the center of the drum. Air-through bonding can provide nonwovens with low density and higher basis weight (e.g., 20 to greater than about 2000 g/ ^m2 ). Nonwovens bonded by airbond are very soft.

Chemical bonding includes solvent bonding and resin bonding. In particular, chemical bonding may use a binder solution of solvent and resin (e.g., latex, or waste polymers left over from fiber preparation). The nonwoven web can be coated with the binder solution and heat and pressure can be applied to cure the binder and bond the nonwoven. The binder solution can be applied by immersing the nonwoven in a bath of binder solution, spraying the binder solution onto the nonwoven, extruding the binder solution onto the web (foam bonding), and/or applying the binder solution as a print or gravure.

Chemical bonding can result in smaller, less ordered pores versus carded/melt spun pores. Without wishing to be bound by theory, it is believed that if the resin solution used for chemical bonding is sufficiently concentrated and/or sufficient pressure is applied, a non-porous nonwoven web can be formed. The solvent used for chemical bonding induces partial solubilization of existing fibers in the web to weld and bond the fibers together. Thus, the solvent for chemical bonding can be any solvent capable of at least partially solubilizing one or more fiber-forming materials of the fibers of the nonwoven. In an exemplary embodiment, the solvent is selected from the group consisting of water, ethanol, methanol, DMSO, glycerin, and combinations thereof. In an exemplary embodiment, the solvent is selected from the group consisting of water, glycerin, and combinations thereof. In an exemplary embodiment, the binder solution includes a solvent selected from the group consisting of water, ethanol, methanol, DMSO, glycerin, and combinations thereof, and further includes a resin selected from the group consisting of polyvinyl alcohol, latex, and polyvinylpyrrolidone. The binder provided in the solution aids in the welding process to provide a more mechanically robust web. The temperature of the polymer solution is not particularly limited and can be provided at room temperature (about 23°C).

In some embodiments, a second layer of fibers can be used to bond the nonwoven web. In exemplary embodiments, the nonwoven web layers can be bonded using thermal, mechanical, or chemical bonds, either alone or in addition to bonding using additional layers of nonwoven web/fibers.
Method for Laminating Films to Nonwoven Webs or Foam Substrates

Methods for preparing laminates (e.g., water-soluble films and nonwovens) can include, but are not limited to, calendar lamination (heat and pressure) or melt bonding.

Calendar lamination is achieved by applying heat and pressure. The conditions for calendar lamination can be easily determined by one skilled in the art. If the applied heat and/or pressure is too low, the fibers will not bond sufficiently to the water-soluble film forming the laminate, and if the heat and/or pressure is too high, the fibers will begin to melt with each other and with the film. Fiber chemistry and film chemistry determine the upper and lower limits of heat and/or pressure for calendar lamination. Without wishing to be bound by theory, it is believed that at temperatures above 235°C, polyvinyl alcohol-based fibers decompose. In an exemplary embodiment, the heat applied to the overlay nonwoven and water-soluble film is from about 50°C to about 200°C, e.g., from about 100°C to about 200°C, from about 110°C to about 190°C, from about 120°C to about 180°C, or from about 130°C to about 160°C. In an exemplary embodiment, the pressure applied to the overlay nonwoven and water-soluble film is from about 5 psi to about 50 psi, such as from about 10 psi to about 40 psi, from about 15 psi to about 30 psi, or from about 20 psi to about 30 psi. In an exemplary embodiment, the heat applied to the overlay nonwoven and water-soluble film is about 150° C. and the pressure applied is about 25 psi. In an exemplary embodiment, the heat and pressure are applied for about 2-4 seconds. An embossing method for the calender lamination of fibers and/or films is contemplated. The embossing can be single-sided embossing or double-sided embossing. Embossing of water-soluble fibers and/or water-soluble films includes single-sided embossing using a single embossing roll of ordered circular arrays and a steel roll with a flat surface. As the embossing increases (e.g., an increased amount of surface features are imparted to the web and/or film), the surface area of the laminate increases. Without wishing to be bound by theory, it is believed that as the surface area of the article decreases, the solubility of the web and/or film decreases. Thus, the solubility characteristics of the nonwoven web and/or water-soluble film can be advantageously tailored by varying the surface area through embossing. Without wishing to be bound by theory, it is believed that as the degree of lamination of the unit dose article increases, the surface area of the laminate decreases and the bond between the water-soluble film and the nonwoven increases, resulting in decreased solubility and increased liquid release time.

The melt-bonded lamination is achieved by attaching an adhesive directly to the water-soluble film, and then the nonwoven web is placed on top of the water-soluble film with the attached adhesive and subjected to cold lamination for bonding of the nonwoven web and the water-soluble film. As used herein, the term "cold lamination" refers to a lamination process that requires pressure but no additional heat. The adhesive can be any suitable adhesive to one skilled in the art. In an exemplary embodiment, the adhesive is Henkel National adhesive. The attachment of the adhesive directly to the water-soluble film can be applied by any suitable method to one skilled in the art, such as a hot melt spray process. In an exemplary embodiment, the melt-bonded lamination process can include a hot melt spray process at 160°C, followed by cold lamination at a pressure of 94 N/ ^mm2 .

The laminate of the present disclosure may include a water-soluble film and a nonwoven web. In an exemplary embodiment, the laminate may have a lamination degree of about 1% to about 100%, and the lamination degree may range from about 1% to about 90%, or about 25% to about 75%, or about 1% to about 50%, or about 5% to about 25%, or about 25% to about 100%, or about 50% to about 100%. As used herein, "lamination degree" refers to the amount of the total area of the water-soluble film bonded to the nonwoven web. For example, a laminate having a lamination degree of about 25% or less means that about 25% or less of the area of the water-soluble film is bonded to the nonwoven web, e.g., laminated only with a sealant. For example, a laminate having a lamination degree of about 100% means that about 100% of the area of the water-soluble film is bonded to the nonwoven web. In an exemplary embodiment with a lamination degree of about 25% or less, the lamination may be achieved during a heat seal process where lamination occurs with each sealant of the unit dose article. In exemplary embodiments where the laminate has a lamination degree of about 25% or less, this low lamination degree can be advantageous because it provides internal voids where the water-soluble film and nonwoven web are not laminated, providing physical separation of compartments with incompatible chemistries and providing the opportunity for a two-stage delivery system of the composition of the unit dose article. In exemplary embodiments, the lamination degree is in the range of about 5% to about 25%. In exemplary embodiments, the lamination degree is in the range of about 50% to about 100%.
Dissolution and Disintegration Test (Modified MSTM-205)

The nonwoven web, water-soluble film, or laminate structure can be characterized by or tested for dissolution and disintegration times according to MonoSol Test Method 205 (MSTM 205), a method known in the art. See, for example, U.S. Patent No. 7,022,656. The description presented below refers to a nonwoven web, but is equally applicable to a water-soluble film or laminate structure.

Apparatus and method:
600 mL beaker Magnetic stir bar (Labline Model No. 1250 or equivalent)
Magnetic stirring bar (5 cm)
Thermometer (0 to 100°C ±1°C)
Template, stainless steel (3.8cm x 3.2cm)
Timer (0-300 seconds, accurate to the second)
Polaroid 35mm slide mount (or equivalent)
MonoSol 35mm Slide Mount Holder (or equivalent)
Distilled water

For each nonwoven web tested, three test specimens are cut from the nonwoven web sample, being 3.8 cm x 3.2 cm specimens. The specimens should be cut from areas of the web that are evenly spaced along the cross direction of the web. Each test specimen is then analyzed using the following procedure.
Each specimen is mounted on an individual 35 mm slide mount.
Fill a beaker with 500 mL of distilled water. Measure the water temperature with a thermometer and heat or cool the water as necessary to maintain the temperature at which dissolution is determined, e.g., 20° C. (about 68° F.).
Mark the height of the water column. Place a magnetic stir bar at the base of the holder. Place the beaker on the magnetic stir bar, add the magnetic stir bar to the beaker, turn the stir bar and adjust the stirring speed until a vortex is created at approximately one-fifth of the height of the water column. Mark the depth of the vortex.
The 35 mm slide mount is secured in the alligator clamp of the 35 mm slide mount holder with the long side of the slide mount parallel to the water surface. The depth adjustment on the holder should be set so that when lowered, the end of the clamp is 0.6 cm below the surface of the water. One of the short pieces of the slide mount should be adjacent to the side of the beaker and the other is positioned directly above the center of the stir bar so that the surface of the nonwoven web is perpendicular to the water flow.
In one motion, the secured slide and clamp are dropped into the water and a timer is started. Rupture occurs when the sample breaks within the slide, e.g., a hole appears. Disintegration occurs when the nonwoven web tears and no sample material remains in the slide. When all visible nonwoven web is released from the slide mount, the slide is raised out of the water while the solution continues to be monitored for undissolved nonwoven web fragments. Dissolution occurs when all nonwoven web fragments are no longer visible and the solution becomes clear. For nonwoven samples in which fibers are prepared from polyvinyl alcohol polymers with a low degree of hydrolysis (e.g., about 65-88%), rupture and dissolution may occur simultaneously. If the difference between rupture and dissolution is 5 seconds or longer, the dissolution time is recorded independently of the burst time.

Thinning time can also be determined using the MSTM-205. Thinning of a nonwoven web occurs when some of the fibers that make up the nonwoven web dissolve while other fibers remain intact. Thinning of the web occurs prior to web collapse. Thinning is characterized by a decrease in opacity or an increase in transmittance of the nonwoven web. It is a gradual change from opaque to transparent and can be observed visually. During the MSTM-205, the opacity/transmittance of the nonwoven web is monitored after the fixed slide and clamp are lowered into the water. At the point where no change in opacity/transmittance is observed (i.e., the web does not become more opaque or more transparent), the time is recorded as the thinning time.

Results should include: complete sample identification; individual and average disintegration and dissolution times; and the water temperature in which the samples were tested.
I _correction = I _measurement x (reference thickness/measured thickness) ^1.93 [1]
S _correction = S _measurement x (reference thickness / measured thickness) ^1.83 [2]
Method for determining single fiber solubility

The solubility of a single fiber is characterized by its water breakage temperature. The fiber breakage temperature can be determined as follows: A load of 2 mg/dtex is applied to a fiber of fixed length 100 mm. The water temperature starts at 1.5°C and then increases by 1.5°C every 2 minutes until the fiber breaks. The temperature at which the fiber breaks is called the water breakage temperature.

The solubility of a single fiber can also be characterized by the temperature of complete dissolution. The temperature of complete dissolution can be determined as follows: 0.2 g of fiber with a fixed length of 2 mm is added to 100 mL of water. The water temperature starts at 1.5° C. and then increases by 1.5° C. every 2 minutes until the fiber is completely dissolved. The sample is stirred at each temperature. The temperature at which the fiber completely dissolves in less than 30 seconds is designated the complete dissolution temperature.
Diameter Test Method

The diameter of individual fibers or fibers in a nonwoven web is determined by using a scanning electron microscope (SEM) or optical microscope and image analysis software. A magnification of 200 to 10,000 times is selected so that the fibers are appropriately magnified for measurement. When using an SEM, the sample is sputtered with gold or palladium compounds to avoid charging and vibration of the fibers in the electron beam. A manual procedure for determining fiber diameter is used from an image (on a monitor screen) taken with an SEM or optical microscope. Using the mouse and cursor tools, a randomly selected edge of the fiber is located and then both ends of its width (i.e., perpendicular to the fiber direction at that point) are measured to the other edge of the fiber. Scaling and calibration image analysis tools provide scaling to obtain an actual reading in microns. For fibers in a nonwoven web, a number of fibers are randomly selected throughout a sample of the nonwoven web using an SEM or optical microscope. At least two portions of the nonwoven web are cut and tested in this manner. In total, at least 100 such measurements are made and then all data is recorded for statistical analysis. The recorded data is used to calculate the fiber average (mean), fiber standard deviation, and median fiber diameter.
Tensile Strength, Modulus, and Elongation Testing Nonwoven webs, water-soluble films, or laminate structures characterized by or tested for tensile strength by the Tensile Strength (TS) Test, modulus (or tensile stress) by the Modulus (MOD) Test, and elongation by the Elongation Test are analyzed as follows. The description provided below refers to nonwoven webs, but is equally applicable to water-soluble films or laminate structures. The procedure includes determining the tensile strength and determining the modulus at 10% elongation by ASTM D 882 ("Standard Test Method for Tensile Properties of Thin Plastic Sheet Formings") or equivalent. Nonwoven web data is collected using an INSTRON tensile testing device (Model 5544 Tensile Tester or equivalent). A minimum of three specimens, each cut with a reliable cutting tool to ensure dimensional stability and repeatability, are tested in the machine direction (MD) (if applicable) for each measurement. Tests were performed in a standard laboratory atmosphere of 23±2.0° C. and 35±5% relative humidity. For the determination of tensile strength or modulus, a 1" wide (2.54 cm) sample of the nonwoven web is prepared. The sample is then transferred to an INSTRON tensile tester for testing with minimal exposure to a 35% relative humidity environment. The tensile tester is equipped with a 500N load cell and is prepared and calibrated according to the manufacturer's instructions. The correct grips and faces are fitted (INSTRON grips with model number 2702-032 faces, rubber coated, 25 mm wide, or equivalent). The sample is placed in the tensile tester and analyzed to determine the 100% modulus (i.e., the stress required to achieve 100% film elongation), tensile strength (i.e., the stress required to break the film), and % elongation (the length of the sample at break relative to the initial sample length). In general, the higher the % elongation of the sample, the better the processability properties of the nonwoven web (e.g., increased formability into a packet or pouch).
Abrasion Test

Off-hand test:

A 3" diameter disk is attached with a Roloc™ joint. Carbon steel and aluminum test panels are ground with a coated abrasive belt corresponding to any example on a hackstand to apply linear abrasive grain to the test specimen. The average Ra is 75 pins for the carbon steel and 150 pins for the aluminum test panels. The panels and disks are then weighed prior to testing.

Off-hand short test:

Work each panel in the direction of the grit for one minute to remove scratches from the half of the panel containing the nonwoven disk from all of the examples. Work in the direction of the grit for another minute to remove scratches from the second half of the panel. The disk and workpiece are then cleaned and weighed. The Ra of the panels was measured and recorded in five separate areas.

Offhand long test:

Work in the direction of the grit of each panel for one minute to remove scratches from the half of the panel containing the nonwoven disc of all examples. Work in the direction of the grit for another minute to remove scratches from the second half of the panel.

Weigh the panel before and after the 2 minute period to determine the panel's mass loss.

Use a new panel for an additional 2 minutes using the methodology described above.

Continue this process for four panels - a total of 8 minutes off-hand grinding time for each disc. Measure the surface finish of five separate areas per panel on the first and fourth panels. Discard the highest and lowest surface finish numbers and average the middle three Ra numbers. Average the average surface finish from panel 1 and panel 4 to get the final surface finish number.

XY automatic test:

A 3" diameter disk is attached with a Roloc™ joint. The disk is XY tested for 8 cycles. Each cycle is 1 minute long as the disk grinds the flat test panel. During the test, the robot arm moves in the X and Y directions, grinding the surface of the panel. The Ra left behind by the disk after the first cycle and cycle #8 is checked in 5 separate areas. The panel and disk are weighed before cycle 1 and after cycle 8 to determine the mass loss of the substrate and disk.

The forces and RPMs used when grinding carbon steel are either 5 pounds (lbs.) and 9000 RPM, or 10 lbs. and 11,000 RPM. The forces used when grinding aluminum are either 5 lbs. and 9,000 RPM, or 5 lbs. and 11,0000 RPM.
Percent Fiber Shrinkage Test (MSTM)

The percent shrinkage of a fiber when contacted with an appropriate amount of carrier solvent can be determined according to the Percent Fiber Shrinkage Test under MonoSol Standard Operating Procedures.

Equipment and materials:
1. Fiber sample (approximately 3 grams)
2. 500 mL beaker 3. Chilled deionized water (place in refrigerator)
4. Deionized water 5. Paper clip 6. Alligator clamp (solubility stand)
7. Stirring plate 8. Timer

Prepare the samples as follows:
1. Obtain a small bundle of untangled fibers. Hold securely with a paper clip and alligator clamp. The approximate weight of the fiber bundle is 0.013 grams (g) to 0.015 g.
2. Take a paper clip and pull the end of the fiber with the end of the paper clip.
3. For each unique fiber tested, perform N=3 replicates for each test temperature, 23°C and 10°C.

Instrument setup:
1. Fill a 500 ml beaker with 400 ml of water at each temperature. Be sure to check the water temperature with a temperature probe before and during the test.
2. Tape a ruler to the top of the alligator clamp so that the ruler hangs parallel to the clamp.
3. Place the beaker on a stir plate and place the solubility stand next to the stir plate and immerse the ruler in the beaker so that the length can then be read.

Procedure of test:
1. Attach the free end of the fiber clipped with paper in an alligator clamp.
2. Submerge the test sample in the beaker so that it is lined up next to the ruler.
3. Start the timer and record the initial length of the fiber. The test sample fiber length is from the end of the alligator clip to the top of the paper clip.
4. After 2 minutes, record the final length of the fiber.
5. Remove the clamps from the water and remove the specimens from the clamps, being sure to thoroughly dry the outside of the clamps and the inside of the clamps between each test.

Calculate the shrinkage percentage:
Contracted length = initial length - final length [3]
Fiber shrinkage (%) = (shrinkage length/initial length) x 100% [4]
Use of goods

The articles of the present disclosure are suitable for a variety of commercial applications. Commercial applications suitable for articles such as the single unit dose articles of the present disclosure include delivering active cleaning formulations including, but not limited to, laundry detergents, soaps, fabric softeners, bleaches, laundry enhancers, stain removers, optical brighteners, or water softeners. In exemplary embodiments, the active cleaning formulations may include, but are not limited to, actives, detergents, surfactants, emulsifiers, chelating agents, soil suspending agents, stain strippers, enzymes, pH adjusters, builders, soil release polymers, structuring agents, free fragrances, encapsulated fragrances, preservatives, solvents, minerals, and/or any ingredients suitable for personal care, laundry detergents, dish detergents, and/or household surface cleaners or cleansers. Other examples include dish detergents, soaps or cleaners, shampoos, conditioners, body washes, face washes, skin lotions, skin treatments, body oils, fragrances, hair treatments, bath salts, essential oils, bath bombs, or enzymes. The active cleaning formulation may be in the form of a solid, e.g., a powder or a plurality of granules or particles, a gel, a liquid, or a slurry formulation, or any suitable combination, e.g., of a powder, solid, gel, liquid, or slurry formulation.

Additional applications of the unit dose article of the present disclosure can include delivering personal care products such as exfoliating materials, shampoos, conditioners, body washes, face washes, skin lotions, skin treatments, hair treatments, bath salts, essential oils, or combinations thereof. Additional contemplated applications include those that can include a constant flow of water, such as car washing applications and/or dish washing applications. Advantageously, in such applications, the nonwoven web can be used to facilitate lathering and/or hard scrubbing before and/or once at least a portion of the composition is released from the article to remove soils without damaging the surface being cleaned, such as the paint on a car or a non-stick cooking surface.

As described herein, the unit dose article may include one of the following constructions, where a first surface or side of the nonwoven substrate is fibrous in appearance and a second surface or side of the nonwoven substrate is generally smooth or coated with water to create a continuous layer using the application of heat and/or water.
(a) a disposable, cold water dispersible nonwoven cleaning article, such as a towel or pad, having a no or low moisture dishwashing detergent and an abrasive material on one or more surfaces of the nonwoven towel for cleaning dry dishes; the water-soluble nonwoven towel dissolves when contacted with cold water, delivering a disinfectant for soaking the dishes to be cleaned, and once the dishes are cleaned, they can be rinsed and dried, for example, on a rack; or (b) a hot water soluble (>40°C) nonwoven cleaning article, such as a towel or pad, having a dishwashing detergent and an abrasive material for cleaning dishes, the water-soluble nonwoven towel dissolves when contacted with hot water, delivering a disinfectant for soaking the dishes to be cleaned, and once the dishes are cleaned, they can be rinsed and dried, for example, on a rack. The cleaning article may be for disposable or multiple use. The cleaning article may include a single layer or multiple layers of nonwoven sheets.

A nonwoven article such as a towel or pad may be water dispersible at temperatures below 40°C, e.g., in the range of about 10°C to about 40°C, and water soluble at temperatures of 40°C and above, e.g., in the range of about 50°C to about 100°C, or about 60°C to about 70°C. In certain embodiments, a plurality of particles of an active cleaning formulation can be bonded to a core substrate, such as a nonwoven substrate, to form an abrasive surface as described herein. A consumer uses a disposable nonwoven towel to scrub dishes. The towel delivers the cleaning required for an appropriate load of hand-washed dishes, as well as an abrasive to cleanse physical ingredients from the cookware, e.g., pots, pans, plates, utensils, and/or cutlery. In an exemplary embodiment, the cookware is scrubbed when it is dry. Once the appropriate amount of food material has been removed using the towel, the towel can be dissolved in a sink, e.g., or in a soaking tub to deliver a disinfectant or dishwashing soap for further removal of debris and sanitization of the cookware. In other exemplary embodiments, cold water is added to the cookware as it is scrubbed, and the towel gradually or slowly dissolves during use. Once the cookware is washed, warm water is added and the towel completely or substantially completely dissolves to deliver the sanitizing agent. In other exemplary embodiments, the towel does not dissolve during use and the cookware is washed with warm water. The active cleaning formulation is continuously released and the towel does not dissolve during use. In certain embodiments, the cleaning article can be used several times. The cleaning article, such as a towel or pad, can be disposed of in the dishwasher if the core substrate completely or substantially dissolves and aids in dishwashing, or the towel can be placed in the trash or recycled if the disposable towel has an improved biodegradation profile.

In the examples, a nonwoven substrate comprising an active cleaning formulation is described as one example of a core substrate for illustrative purposes. The core substrate and the active cleaning formulation can have any composition and/or form described herein. For example, the core substrate may be a water-dispersible and/or water-soluble nonwoven, foam, film, or any combination thereof. Such a core substrate may comprise one or more PVOH polymers, such as vinyl alcohol-vinyl acetate copolymer. For example, in certain embodiments, the core substrate comprises at least one nonwoven web or sheet comprising a plurality of fibers. The plurality of fibers comprises a first type of fiber comprising a polyvinyl alcohol copolymer having a degree of hydrolysis ranging from about 75% to about 89.9% (e.g., 80%-89.9%), and a second type of fiber comprising a polyvinyl alcohol copolymer having a degree of hydrolysis ranging from about 90% to about 99.9% (e.g., 95%-98%). A suitable ratio of the first type of fiber to the second type of fiber ranges, for example, from about 5:95 to about 25:75 by weight. In certain embodiments, the first type of fibers and the second type of fibers are mixed together in at least one nonwoven web or sheet. In certain embodiments, the at least one nonwoven web or sheet includes a first type of nonwoven fabric made with the first type of fibers and a second type of nonwoven fabric made with the second type of fibers. The two types of fibers may be in different nonwoven webs or sheets. In certain exemplary embodiments, the cleaning article may include PVOH polymeric fibers blended with non-PVOH polymeric fibers such as polyester, polylactic acid, and/or cellulosic fibers.
Fibers used

As shown in Table 1, several types of fibers, namely, fiber 1 ("F1"), fiber 2 ("F2"), fiber 3 ("F3") and fiber 4 ("F4"), comprising copolymers of vinyl acetate and vinyl alcohol with hydrolysis degrees of 88%, 96%, 98% and 99.99%, respectively, were used as starting materials. These fibers have a uniform composition and additional properties as shown in Table 1. In the examples described herein, fibers F1 and F2 each had a fineness of 2.2 dpf - a length of 51 mm. Fiber F3 includes two types of fibers: a first fiber type with a fineness of 1.7 dtex - a length of 38 mm and a second fiber type with a fineness of 2.2 dtex - a length of 51 mm. Fiber F4 had a fineness of 1.7 dtex - a length of 38 mm. The units of fineness dtex and dpf are similar to each other and can be converted using the factor (dtex = dpf / 0.9). For illustrative purposes, polymers containing vinyl alcohol moieties are referred to as "polyvinyl alcohol polymers" and fibers containing such polymers are referred to as "polyvinyl alcohol fibers."

Four types of fibers were used to make the nonwoven core substrate under different bonding conditions, as shown in Table 2. In certain instances, two types of fibers were also mixed to make one type of nonwoven core substrate (referred to as a "blended nonwoven").

Tables 3 and 4 show the properties of Examples 1-17. These properties include solubility data, e.g., burst and disintegration times, tensile strength, softness rating and surface roughness. The nonwoven (NW) samples were applied to test substrates made of aluminum on acrylic polymer. The gloss of the test substrates before and after application was recorded. The Ra values were measured using an SPI Roughness Tester II with a measurement limit of 250 μin. Gloss measurements were performed using a BYK micro-TRI-gloss. All gloss measurements were recorded at 20°.

Based on the composition and property data shown in Tables 2-4, in the exemplary embodiment, at least one nonwoven fabric (as a core substrate) comprises a plurality of fibers made of PVOH copolymer having a degree of hydrolysis in the range of 90-99.99%, more particularly in the range of 90% to 98%. For example, nonwoven substrates made of one or two fibers, such as fiber F3 (D.H. 98%) or a combination of fiber F3 and fiber F2 (D.H. 96%), such as the samples of Examples 1, 5, and 16, provide short disintegration times and good softness in hot water (e.g., at 80°C). Fiber F1 (D.H. 88%) can also be combined with fiber F3 or F2, but the content of fiber F1 in the exemplary embodiment is less than 50% or equal to or less than 25% of the total weight of the fibers. The introduction of F1 (e.g., the samples of Examples 11, 13, and 15) tends to decrease the softness and increase the disintegration time of the nonwoven samples. Most samples were calendered at 180°C. Fiber F1 is more heat sensitive and susceptible to thermal degradation when compared to fibers F2 and F3 which result in stiffer nonwoven samples. As the amount of fiber F4 increases, the disintegration time of the resulting nonwoven samples in hot water tends to increase. As shown in Table 4, the stiffer fibers have higher Ra values, however, there was no observable difference in gloss measurements to assess or differentiate the abrasiveness of experimental samples 1-17.

Experimental samples 18-23 were made from blends of fiber F2 with other fiber chemistries of varying deniers including TREVIRA™ polyester fiber, polylactic acid (PLA) fiber, viscose rayon (cellulose) fiber, polyethylene terephthalate (PET) fiber, VESTERA™ cellulose fiber, and LENZING LYOCELL™ cellulose fiber, as shown in Table 5. Property data for these samples is shown in Table 6. Nonwoven blends with higher denier fibers are expected to be less soft compared to lower denier blends.

As shown in Tables 7 and 8, experimental samples 24-25 were nonwoven samples (70 gsm) made with 100% fiber F3 using different bond styles. These nonwoven samples are water dispersible in warm water and eventually become water soluble. These samples were evaluated with dishwasher detergent both with and without abrasive powder adhered to the surface. The abrasive powder was Cascade Complete and Elmer's Multi-Purpose Spray Adhesive was used to adhere the detergent powder to the surface of the WSNW. Each of experimental samples 24-25 is two samples: the first sample without detergent powder and the second sample with detergent powder. The detergent powder has a dual function as both an active cleaning formulation and an abrasive powder. Compared to the point bond style, the daisy bond style has a higher bond density. The daisy bonded water soluble nonwoven showed higher Ra values than the point bonded material. This increase in Ra corresponded to a rougher subjective feel of the nonwoven. Both nonwovens without abrasive powder were rubbed on aluminum and acrylic surfaces with no change in the gloss of those surfaces. The nonwoven sample with abrasive powder, however, scratched both the acrylic and aluminum surfaces with rubbing, resulting in a significant decrease in gloss.

Exemplary embodiments of the disclosure are described in the following numbered paragraphs. These exemplary embodiments are intended to be illustrative and not limiting in nature.

The following paragraphs further describe aspects of the disclosure:
1. An article for hand washing an object, comprising:
a core substrate having an abrasive surface and containing an active cleaning formulation, the core substrate comprising a plurality of fibers comprising a resin;
An article in which the core substrate becomes water-dispersible and releases the active cleaning formulation from the core substrate upon contact with water having a temperature of 40° C. or less by test method MSTM-205.
2. The article of claim 1, wherein the core substrate has a dispersion time of 300 seconds or less.
3. The article of clause 1 or 2, wherein the core substrate becomes water soluble when contacted with water having a temperature greater than 40° C. by test method MSTM-205.
4. The article of any of clauses 1 to 3, wherein the core substrate has a moisture content of less than 10% by weight.
5. The article of any of clauses 1-4, wherein the abrasive surface has an Ra value of from 8 uin (0.2 μm) to 60 uin (1.5 μm).
6. The article of any of clauses 1-5, wherein the active cleaning formulation is in at least one of a solid, liquid, gel, or slurry form.
7. The article of any of clauses 1-6, wherein the active cleaning formulation comprises one or more of a disinfectant or sanitizing agent, a detergent, a surfactant, an emulsifier, a chelating agent, a soil suspending agent, a stain lifter or stripper, an enzyme, a pH adjuster, a builder, a soil stripper, a structuring agent, a free fragrance, an encapsulated fragrance, a preservative, a solvent, a mineral, a foam builder, an HLB adjuster, or a degreaser, or a combination thereof.
8. The article of any of clauses 1-7, wherein the active cleaning formulation is at least one of disposed on a surface of the core substrate and embedded in the matrix of the core substrate.
9. The article of any of clauses 1-8, wherein the core substrate is at least one of saturated with, coated with, or impregnated with the active cleaning formulation.
10. The article of any of clauses 1-9, wherein the active cleaning formulation is present in a core substrate.
11. The article of any of clauses 1-10, wherein the active cleaning formulation comprises a carrier solvent.
12. The article of any of clauses 1-11, wherein each fiber of the plurality of fibers has a length of 10 mm to 100 mm.
13. The article of any of clauses 1-12, wherein each fiber of the plurality of fibers has a length to diameter ratio (L/D) of 0.5 to 25.
14. The article of any of clauses 1-13, wherein the core substrate comprises a nonwoven substrate in the form of a nonwoven sheet, multiple nonwoven sheets joined together to form a nonwoven block substrate, or multiple nonwoven sheets joined together to form a sphere or spheroid.
15. The article of any of clauses 1-14, wherein the active cleaning formulation comprises one or more of the following sanitizing agents: quaternary ammonium compounds (QACs), halogenated oxidizing agents, hypochlorous acid generating compounds, hypochlorite generating compounds, 1-bromo-3-chloro-5,5-dimethylhydantoin, dichloroisocyanuric acid, alcohols, oxygen radical generators, hydrogen peroxide (H ₂ O ₂ ), sulfate generating compounds, methylisothiazolinone (MIT), benzisothiazolinone (BIT), or sodium metabisulfite.
16. The article of any of the preceding clauses, wherein the core substrate comprises at least one nonwoven sheet comprising a plurality of fibers made of a resin.
17. The article of claim 16, wherein the plurality of fibers are saturated with an active cleaning formulation.
18. The article of clause 16 or 17, wherein the active cleaning formulation is one of disposed on a surface of the plurality of fibers or embedded in the plurality of fibers.
19. The article of any of clauses 16-18, wherein the core substrate comprises a plurality of nonwoven layers, the active cleaning formulation being disposed between adjacent layers of the plurality of layers.
20. The article of any one of clauses 16 to 19, wherein the resin is a polymer that includes vinyl alcohol moieties.
21. The article of clause 20, wherein the polymer comprising vinyl alcohol moieties comprises a polyvinyl alcohol homopolymer, a polyvinyl alcohol copolymer, or a combination thereof.
22. The article of clause 21, wherein the polyvinyl alcohol copolymer is a copolymer or an anionically modified copolymer of vinyl acetate and vinyl alcohol.
23. The article of clause 22, wherein the anionically modified copolymer comprises a carboxylate, a sulfonate, or a combination thereof.
24. The article of any of clauses 16-23, wherein the plurality of fibers comprises a polyvinyl alcohol copolymer having a degree of hydrolysis in the range of about 95% to about 98%.
25. The article of any of clauses 16-23, wherein the plurality of fibers comprises a first type of fiber comprising a polyvinyl alcohol copolymer having a degree of hydrolysis in the range of about 75% to about 89.9%, and a second type of fiber comprising a polyvinyl alcohol copolymer having a degree of hydrolysis in the range of about 90% to about 99.99%.
26. The article of clause 25, wherein the ratio of the first type of fibers to the second type of fibers ranges from about 5:95 to about 25:75 by weight.
27. The article of clause 25 or 26, wherein the first type of fibers comprises a polyvinyl alcohol copolymer having a degree of hydrolysis in the range of about 80% to about 89%, and the second type of fibers comprises a polyvinyl alcohol copolymer having a degree of hydrolysis in the range of about 95% to about 98%.
28. The article of any of clauses 25-27, wherein the core substrate comprises at least one nonwoven sheet comprising a mixture of a first type of fibers and a second type of fibers.
29. The article of any of clauses 20-28, wherein the core substrate comprises fibers made of a polymer other than a polymer that includes vinyl alcohol moieties.
30. The article of any of the preceding clauses, wherein the core substrate comprises multiple layers selected from nonwoven sheets, foam layers, films, or any combination thereof.
31. The article of clause 30, wherein the plurality of layers comprises separate sheets in a stacked construction or a continuous sheet folded into a serpentine construction.
32. The article of any of the preceding clauses, wherein the abrasive surface comprises a plurality of particles comprising the active cleaning formulation bound on a core substrate.
33. The article of any one of clauses 1 to 31, wherein the resin is biodegradable.
34. A method of making an article for hand washing an object, comprising:
A method comprising: forming a nonwoven substrate comprising a plurality of fibers comprising a resin, the fibers containing an active cleaning formulation; and forming an abrasive surface of the nonwoven substrate.
35. The method of claim 34, wherein forming a nonwoven substrate comprising a plurality of fibers comprising a resin containing an active cleaning formulation comprises at least one of saturating the nonwoven substrate with the active cleaning formulation, disposing the active cleaning formulation on a surface of a water-soluble nonwoven substrate, coating a surface of the substrate with the active cleaning formulation, embedding the active cleaning formulation in the nonwoven substrate, or impregnating the nonwoven substrate with the active cleaning formulation.
36. The method of clause 35 or 36, wherein the active cleaning formulation comprises a carrier solvent.
37. The method of clause 36, wherein the nonwoven substrate becomes water-dispersible when contacted with water having a temperature at or below 40° C. and becomes water-soluble when contacted with water having a temperature above 40° C., per test method MSTM-205.
38. The method of any of clauses 34-37, wherein forming the abrasive surface of the nonwoven substrate comprises forming, disposing, embedding, coating, or adhering an abrasive material on a first surface of the nonwoven substrate.
39. The method of any of clauses 34-38, wherein forming the abrasive surface of the nonwoven substrate comprises adhesively bonding an abrasive material to the first surface of the nonwoven substrate.
40. The method of claim 39, wherein the abrasive material comprises a plurality of particles made of an active cleaning formulation.
41. The method of any of clauses 34-40, wherein forming the abrasive surface of the nonwoven substrate comprises heating a first surface of the substrate to adhere the abrasive material to the first surface.
42. The method of any of clauses 34-41, wherein forming the abrasive surface of the nonwoven substrate comprises disposing an abrasive material in a matrix of the nonwoven substrate.
43. The method of any of clauses 34-42, wherein forming the abrasive surface of the nonwoven substrate comprises at least partially dissolving a first surface of the nonwoven substrate and applying an abrasive material to the first surface.
44. The method of any of clauses 34-43, further comprising forming a substantially smooth surface of the nonwoven substrate.
45. The method of claim 44, comprising coating the second surface of the nonwoven substrate with water or heating the second surface to create a continuous, smooth second surface.
46. The method of any of clauses 34-45, wherein forming an abrasive surface on the nonwoven substrate comprises forming an abrasive gradient through a thickness of the nonwoven substrate.

All percentages, parts and ratios referred to herein are of the total dry weight of the fiber composition, film composition, or, as the case may be, the total weight of the packaging material composition of the present disclosure, and all measurements made are at about 25° C., unless otherwise indicated. All percentages, parts and ratios referred to herein with respect to liquid formulations are of the total weight of the liquid formulation. All such weights with respect to listed ingredients are of the active level and thus do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.

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

For any numerical values described herein, e.g., as parameters of the described object or as part of a range related to the described object, alternative examples forming part of this description are expressly contemplated as functionally equivalent ranges surrounding the particular numerical value (e.g., for a dimension disclosed as "40 millimeters (mm)," an alternative embodiment contemplated is "about 40 mm").

References throughout this specification to an "exemplary embodiment" or "embodiment" may mean that a particular structure, structure, or feature described in connection with a particular embodiment may be included in at least one embodiment of the claimed subject matter. Thus, the appearance of the phrase "exemplary embodiment" or "exemplary embodiment" in various places throughout this specification does not necessarily refer to the same embodiment or any one particular embodiment described. Moreover, it should be understood that a particular structure, structure, or feature described may be combined in various ways in one or more embodiments. In general, of course, these and other issues may vary with the particular context of use. Thus, the particular context of the description or use of these terms may provide useful guidance regarding the inferences cited as such.

Although the subject matter has been described in language specific to structural features and/or methodological acts, it should be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described. Rather, the specific features and acts are disclosed as illustrative forms of implementing the claims.

Those skilled in the art will appreciate that a virtually unlimited number of variations are possible to the above description, and that the examples and accompanying figures are only intended to illustrate one or more examples of embodiments.

Those skilled in the art will recognize that various other modifications may be made and equivalents substituted without departing from the claimed subject matter. Additionally, many modifications may be made to adapt a particular situation to the teachings of the claimed subject matter without departing from the central concepts described herein. Therefore, it is not intended that the claimed subject matter be limited to the particular embodiments disclosed, but it is also intended that such claimed subject matter may include all embodiments that fall within the scope of the appended claims and their equivalents.

In the above detailed description, numerous specific details are set forth to provide a thorough understanding of the claimed subject matter. However, it will be understood by one of ordinary skill in the art that the claimed subject matter may be practiced without these specific details. In other instances, methods, apparatus, or systems that are known to those of ordinary skill in the art have not been described in detail so as not to obscure the claimed subject matter.

Claims (46)

1. An article for hand washing an object, comprising:
a core substrate having an abrasive surface and containing an active cleaning formulation, the core substrate comprising a plurality of fibers comprising a resin;
An article wherein said core substrate becomes water-dispersible and releases said active cleaning formulation from said core substrate upon contact with water having a temperature of 40° C. or less by test method MSTM-205. The article of claim 1, wherein the core substrate has a dispersion time of 300 seconds or less. The article of claim 1, wherein the core substrate becomes water soluble when contacted with water having a temperature greater than 40°C by test method MSTM-205. The article of claim 1, wherein the core substrate has a moisture content of less than 10% by weight. The article of claim 1, wherein the abrasive surface has an Ra value of 8 uin (0.2 μm) to 60 uin (1.5 μm). The article of claim 1, wherein the active cleaning formulation is in at least one of a solid, liquid, gel, or slurry form. The article of claim 1, wherein the active cleaning formulation comprises one or more of a disinfectant or sanitizer, a detergent, a surfactant, an emulsifier, a chelating agent, a soil suspension agent, a stain lifter or stripper, an enzyme, a pH adjuster, a builder, a soil stripper, a structuring agent, a free fragrance, an encapsulated fragrance, a preservative, a solvent, a mineral, a foam builder, an HLB adjuster, or a degreaser, or a combination thereof. The article of claim 1, wherein the active cleaning formulation is at least one of disposed on a surface of the core substrate or embedded in a matrix of the core substrate. The article of claim 1, wherein the core substrate is at least one of saturated with, coated with, or impregnated with the active cleaning formulation. The article of claim 1, wherein the active cleaning formulation is present in the core substrate. The article of claim 1, wherein the active cleaning formulation includes a carrier solvent. The article of claim 1, wherein each fiber of the plurality of fibers has a length of 10 mm to 100 mm. The article of claim 1, wherein each fiber of the plurality of fibers has a length to diameter ratio (L/D) of 0.5 to 25. The article of claim 1, wherein the core substrate comprises a nonwoven substrate in the form of a nonwoven sheet, multiple nonwoven sheets joined together to form a nonwoven block substrate, or multiple nonwoven sheets joined together to form a sphere or spheroid. 10. The article of claim 1, wherein the active cleaning formulation comprises one or more of the following sanitizing agents: quaternary ammonium compounds (QACs), halogenated oxidizing agents, hypochlorous acid generating compounds, hypochlorite generating compounds, 1-bromo-3-chloro-5,5-dimethylhydantoin, dichloroisocyanuric acid, alcohols, oxygen radical generators, hydrogen peroxide (H ₂ O ₂ ), sulfate generating compounds, methylisothiazolinone (MIT), benzisothiazolinone (BIT), or sodium metabisulfite. The article of claim 1, wherein the core substrate comprises at least one nonwoven sheet comprising a plurality of fibers made from the resin. The article of claim 16, wherein the plurality of fibers are saturated with the active cleaning formulation. The article of claim 16, wherein the active cleaning formulation is one of disposed on a surface of the plurality of fibers or embedded in the plurality of fibers. The article of claim 16, wherein the core substrate comprises a plurality of nonwoven layers, and the active cleaning formulation is disposed between adjacent layers of the plurality of layers. The article of claim 16, wherein the resin is a polymer containing vinyl alcohol moieties. 21. The article of claim 20, wherein the polymer comprising a vinyl alcohol moiety comprises a polyvinyl alcohol homopolymer, a polyvinyl alcohol copolymer, or a combination thereof. 22. The article of claim 21, wherein the polyvinyl alcohol copolymer is a copolymer of vinyl acetate and vinyl alcohol or an anionically modified copolymer. 23. The article of claim 22, wherein the anionically modified copolymer comprises a carboxylate, a sulfonate, or a combination thereof. The article of claim 16, wherein the plurality of fibers comprises a polyvinyl alcohol copolymer having a degree of hydrolysis ranging from about 95% to about 98%. 17. The article of claim 16, wherein the plurality of fibers comprises a first type of fiber comprising a polyvinyl alcohol copolymer having a degree of hydrolysis ranging from about 75% to about 89.9% and a second type of fiber comprising a polyvinyl alcohol copolymer having a degree of hydrolysis ranging from about 90% to about 99.99%. 26. The article of claim 25, wherein the ratio of the first type of fibers to the second type of fibers ranges from about 5:95 to about 25:75 by weight. 26. The article of claim 25, wherein the first type of fiber comprises a polyvinyl alcohol copolymer having a degree of hydrolysis ranging from about 80% to about 89% and the second type of fiber comprises a polyvinyl alcohol copolymer having a degree of hydrolysis ranging from about 95% to about 98%. 26. The article of claim 25, wherein the core substrate comprises at least one nonwoven sheet comprising a mixture of the first type of fibers and the second type of fibers. 21. The article of claim 20, wherein the core substrate further comprises fibers made of a polymer other than the polymer that includes a vinyl alcohol moiety. The article of claim 1, wherein the core substrate comprises multiple layers selected from nonwoven sheets, foam layers, films, or any combination thereof. 31. The article of claim 30, wherein the multiple layers comprise separate sheets in a stacked construction or a continuous sheet folded into a serpentine construction. The article of claim 1, wherein the abrasive surface comprises a plurality of particles comprising the active cleaning formulation bound onto the core substrate. The article of claim 1, wherein the resin is biodegradable. 1. A method of making an article for hand washing an object, comprising:
A method comprising: forming a nonwoven substrate comprising a plurality of fibers comprising a resin, the fibers containing an active cleaning formulation; and forming an abrasive surface of the nonwoven substrate. 35. The method of claim 34, wherein forming a nonwoven substrate comprising a plurality of fibers comprising a resin containing the active cleaning formulation comprises at least one of saturating the nonwoven substrate with the active cleaning formulation, disposing the active cleaning formulation on a surface of a water-soluble nonwoven substrate, coating a surface of the substrate with the active cleaning formulation, embedding the active cleaning formulation in the nonwoven substrate, or impregnating the nonwoven substrate with the active cleaning formulation. The method of claim 34, wherein the active cleaning formulation includes a carrier solvent. The method of claim 36, wherein the nonwoven substrate becomes water-dispersible when contacted with water having a temperature at or below 40°C and becomes water-soluble when contacted with water having a temperature above 40°C according to test method MSTM-205. 35. The method of claim 34, wherein forming an abrasive surface on the nonwoven substrate comprises forming, disposing, embedding, coating, or adhering an abrasive material on a first surface of the nonwoven substrate. 35. The method of claim 34, wherein forming the abrasive surface of the nonwoven substrate comprises adhesively bonding an abrasive material to a first surface of the nonwoven substrate. The method of claim 39, wherein the abrasive material comprises a plurality of particles made of the active cleaning formulation. 35. The method of claim 34, wherein forming an abrasive surface on the nonwoven substrate comprises heating a first surface of the substrate to adhere an abrasive material to the first surface. 35. The method of claim 34, wherein forming the abrasive surface of the nonwoven substrate comprises disposing an abrasive material in a matrix of the nonwoven substrate. 35. The method of claim 34, wherein forming an abrasive surface on the nonwoven substrate comprises at least partially dissolving a first surface of the nonwoven substrate and applying an abrasive material to the first surface. 35. The method of claim 34, further comprising forming a substantially smooth surface of the nonwoven substrate. The method of claim 44, comprising coating the second surface of the nonwoven substrate with water or heating the second surface to create a continuous, smooth second surface. 35. The method of claim 34, wherein forming an abrasive surface on the nonwoven substrate comprises forming an abrasive gradient through a thickness of the nonwoven substrate.

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