RU2810334C2 - Water soluble polyvinyl alcohol film, related methods and related products - Google Patents

Abstract

FIELD: polymer materials.

SUBSTANCE: group of inventions is related to a water-soluble film used for manufacturing of packaging, and to a product for storing a liquid composition containing said film in form of a bag. The proposed film has a crystallinity of at least 15% and contains a mixture of polyvinyl alcohol (PVA) resins, including a first PVA copolymer, in which the first anionic monomer unit selected from maleic anhydride and an alkali metal salt of maleic anhydride is present in an amount of 1-3 mol.%; a second PVA copolymer, in which the second anionic monomer unit selected from maleic anhydride and the alkali metal salt of maleic anhydride is present in an amount of 3-8 mol.%, these quantities differ from each other, and the amount of the first PVA copolymer in the specified mixture is 10-70 wt.%, wherein the first and second PVA copolymers contain side groups, the first PVA copolymer has a first level of side groups (a1) derived from the first anionic monomer unit, and the second PVA copolymer has a second level of side groups (a2) obtained from the second anionic monomer unit, and the difference between a1 and a2 is 4-10 mol.%.

EFFECT: group of inventions ensures the preservation of the rigidity, elasticity and acceptable transparency of the film without compromising its final solubility during use.

24 cl, 2 dwg, 23 tbl, 127 ex

Description

TECHNICAL FIELD

[0001] This description generally relates to water-soluble films and associated packages. More specifically, this description relates to water-soluble polyvinyl alcohol films that contain a mixture of polyvinyl alcohol (PVA) resins and which can be used for contact with liquids, solids, or combinations thereof with one or more advantages, such as maintaining film stiffness and maintaining pouch elasticity when enclosing liquid compositions such as low molecular weight polyols without compromising film solubility.

BACKGROUND OF THE ART

[0002] Water-soluble polymer films are typically used as packaging materials to facilitate dispersion, pouring, dissolving and dispensing of the delivered material. For example, bags made from water-soluble film are typically used to package home care compositions such as laundry detergents and dishwashing detergents. The consumer may directly add the pouched composition to a mixing container such as a bucket, sink or washing machine. Advantageously, this provides accurate dosing while eliminating the need for the consumer to measure the composition. A packaged composition can also reduce the mess that may be associated with dispensing a similar composition from a container, such as pouring liquid laundry detergent from a bottle. Overall, pre-measured dissolvable polymer film pouches provide consumer convenience in a variety of applications.

[0003] Some water-soluble polymer films used to make pouches currently on the market react with pouch components (eg, detergents), which affects pouch properties, such as the ability to maintain film rigidity. For example, bags may exhibit film softening over time upon contact with contents therein, such as liquid solvents typically used in liquid detergent compositions and low molecular weight polyols. Such softening may, for example, reduce the elasticity of the package and give the package a loose and saggy appearance and feel. In another type of problem, the clarity of the film may be affected by the clouding effect of package components migrating through the film. In another type of problem, the solubility of the film may decrease over time upon contact with its contents, resulting in an unwanted residue remaining after washing. In another type of problem, the mechanical properties of the film may change over time when in contact with its contents, resulting in undesirable increases in film stiffness or increased film fragility.

[0004] In addition, COMMISSION REGULATION (EU) No. 1297/2014 of 5 December 2014 amended, in order to adapt it to technical and scientific progress, Regulation (EC) No. 1272/2008 of the European Parliament and the Council on Classification , labeling and packaging of substances and mixtures, requiring additional provisions for liquid consumer laundry detergents in single-use dosages contained in dissolvable packaging. Among these provisions were requirements that the dissolvable package retain its liquid content for at least 30 seconds when the dissolvable package is placed in water at 20°C. Naturally, the film should then break down and preferably dissolve completely to release the contents of the bag.

[0005] Thus, there is a need in the art for a water-soluble film that is water-soluble and can be formed into packages for storing liquid compositions that can be thermoformed or vertically filled, that maintain the rigidity of the film and remain resilient and/or retain acceptable transparency properties without compromising the final solubility of the water-soluble film.

BRIEF DESCRIPTION OF THE INVENTION

[0006] In one aspect of this disclosure, a water-soluble film is provided comprising a polyvinyl alcohol (PVA) resin mixture comprising a first PVA copolymer containing a first anionic monomer unit comprising maleic anhydride or an alkali metal salt of maleic anhydride, wherein said first anionic monomer unit is present in the first PVA copolymer in an amount of from about 1 to about 3 mol. %, and the second PVA copolymer contains a second anionic monomer unit, wherein said second anionic monomer unit is present in the second PVA copolymer in an amount of about 3 mol. % up to 10 mol. %; the amount of the first anionic monomer unit present in the first PVA copolymer is different from the amount of the second anionic monomer unit present in the second PVA copolymer, and optionally, the first PVA copolymer is contained in the mixture in an amount from about 10 wt.% to about 70 wt. % based on the total weight of the PVA resin mixture.

[0007] Another aspect of this specification relates to an article comprising a water-soluble film as described herein in the form of a pouch defining the interior volume of the pouch and optionally containing a liquid composition within the interior volume of the pouch.

[0008] Additional aspects and advantages will become apparent to those of ordinary skill in the art upon examination of the following detailed description. Although the film, bag, and methods for making them are capable of being embodied in various forms, the description below includes specific embodiments of the invention with the understanding that this description is illustrative and is not intended to limit the invention to the specific embodiments described herein. .

BRIEF DESCRIPTION OF GRAPHIC MATERIALS

[0009] FIG. 1 illustrates a wire frame cage (shown with the top open to better illustrate the water-soluble packets contained therein) for use in the liquid release test described herein.

[0010] In FIG. 2 illustrates a liquid release test apparatus comprising a beaker mounted on a stand, a stand holding a rod for lowering a cell into the beaker, the rod being secured by a clamp with a set screw (not shown).

DETAILED DESCRIPTION OF THE INVENTION

[0011] In one aspect of this disclosure, a water-soluble film is provided comprising a polyvinyl alcohol (PVA) resin mixture comprising a first PVA copolymer comprising a first anionic monomer unit comprising maleic anhydride or an alkali metal salt of maleic anhydride, wherein said first anionic monomer unit is present in the first PVA copolymer in an amount of from about 1 to about 3 mol. %, and the second PVA copolymer contains a second anionic monomer unit, wherein said second anionic monomer unit is present in the second PVA copolymer in an amount of about 3 mol. % up to 10 mol. %; wherein the first PVA copolymer is contained in said mixture in an amount of from about 10 wt.% to about 70 wt.% based on the total weight of the mixture of PVA resins and the amount of the first anionic monomer unit present in the first PVA copolymer is different from the amount of the second anionic monomer unit , present in the second PVA copolymer.

[0012] In embodiments of the invention, the first PVA copolymer is present in an amount ranging from about 10 wt.% to about 40 wt.% of the total weight of the mixture of PVA resins. In embodiments of the invention, the second PVA copolymer is present in an amount ranging from about 30 wt% to about 90 wt%, or from about 60 wt% to about 80 wt%, based on the total weight of the PVA resin mixture.

[0013] In embodiments of the invention, the first and second PVA copolymers contain side groups provided by an anionic monomer unit. A pendant group as used herein includes pendant groups from any monomer copolymerized with a vinyl ester and does not include residual ester groups or hydrolyzed ester groups from a vinyl ester. For example, acetate groups resulting from the polymerization of vinyl acetate and hydroxyl groups formed from hydrolysis of residual acetate groups are not considered pendant groups. In embodiments of the invention, the first PVA copolymer has a first level of side groups (a ₁ ), and the second PVA copolymer has a second level of side groups (a ₂ ), wherein the difference between a ₁ and a ₂ is from about 2 mol. % to about 15 mol. %. The first side group and the second side group may together be present in a combined amount ranging from about 8 mol. % up to 25 mol. %. In embodiments of the invention, the first PVA copolymer is a maleic anhydride copolymer having a first level of anionic monomer content (b ₁ ), the second PVA copolymer is a maleic anhydride copolymer having a second level of anionic monomer content (b ₂ ), wherein the difference between b ₁ and b ₂ is from about 2 to 3 mol. %. In embodiments of the invention, the first PVA copolymer has a 4% solution viscosity at 20° C. ranging from about 4 cP to about 30 cP. In embodiments of the invention, the second PVA copolymer has a 4% solution viscosity at 20° C. ranging from about 12 cP to about 30 cP.

[0014] In embodiments of the invention, said water-soluble film has a residue value of about 20 wt.% or less as measured in a dissolution chamber test (“CR residue”). In embodiments of the invention, said water-soluble film has a swelling coefficient value that is no more than 60% of the swelling coefficient value of a comparative film that is identical but differs in a second PVA copolymer that is an individual resin, and the amount of this second PVA copolymer in the comparative film is equal to the total the amount of resins in the water-soluble film of this invention.

[0015] In embodiments of the invention, said PVA resin mixture consists essentially of a first PVA copolymer and a second PVA copolymer. In embodiments of the invention, said water-soluble film further comprises at least a third water-soluble polymer that is different from the PVA polymer. In embodiments of the invention, the first PVA copolymer and the second PVA copolymer independently have a degree of hydrolysis ranging from about 75% to about 99%.

[0016] In embodiments of the invention, said first PVA copolymer comprises a first anionic monomer unit selected from one or more of a maleic anhydride monomer and an alkali metal salt of maleic anhydride, the first PVA copolymer being present in an amount ranging from about 10 wt.% to about 70 wt.% wt.% of the total weight of the mixture of PVA resins, the second PVA copolymer contains a second anionic monomer unit selected from the group consisting of maleic anhydride and an alkali metal salt of maleic anhydride, the second PVA copolymer is present in an amount ranging from about 30 wt.% to about 90 wt.% of the total mass of the mixture of PVA resins, in which the difference between a ₁ and a ₂ is from about 3 mol. % to about 6 mol. %, a ₁ is in the range from about 3 mol. % to about 5 mol. %, a ₂ is in the range from about 7 mol. % to about 9 mol. %, and the first side group and the second side group are together present in a combined amount ranging from about 2 mol. % up to 15 mol. %.

[0017] In embodiments of the invention, the first PVA copolymer contains a maleic anhydride monomer unit and is present in an amount ranging from about 10 wt.% to about 60 wt.% of the total weight of the mixture of PVA resins, and the water-soluble film further contains a plasticizer in an amount of less than 30 m.h.

[0018] In embodiments of the invention, the first PVA copolymer contains a maleic anhydride monomer unit and is present in an amount ranging from about 10 wt.% to about 60 wt.% of the total weight of the mixture of PVA resins, and the water-soluble film further contains a first plasticizer having a molar mass greater than or equal to 92 g/mol, and a second plasticizer having a molar mass greater than or equal to 150 g/mol. Optionally, said water-soluble film may further comprise a third plasticizer.

[0019] In embodiments of the invention, the first PVA copolymer contains a maleic anhydride monomer unit and is present in an amount ranging from about 10 wt.% to about 70 wt.% of the total weight of the mixture of PVA resins, and the water-soluble film additionally contains at least 2 m .h. a filler selected from a bulking agent, an anti-adhesive agent or combinations thereof.

[0020] In another aspect of the present invention, there is provided an article comprising a water-soluble film as described herein in the form of a pouch defining the internal volume of the pouch. In embodiments of the invention, the specified product further includes a composition contained in the internal volume of the package. Optionally, the composition contained in the interior of the package is a liquid composition. Optionally, said liquid composition is a liquid detergent. Optionally, said liquid detergent contains a low molecular weight polyol. Optionally, the composition contained in the interior of the package is solid.

[0021] In embodiments of the invention, the composition contained in the interior of the pouch is a liquid, and the article has a delayed release time of at least 30 seconds as measured by a liquid release test. In embodiments of the invention, the composition contained in the interior of the pouch is a liquid, and the product has a compressive strength of greater than 300 N as measured in a compression test. In embodiments of the invention, the composition contained in the interior of the pouch is a liquid, and the product has a compressive strength of less than 2000 N as measured in a compression test.

[0022] As used herein, the term “comprising” or “comprising” means various components, ingredients or steps that may be used together in the practice of this description. Accordingly, the term “comprising” covers the more restrictive terms “consisting essentially of” and “consisting of.” These compositions may include, consist essentially of, or consist of any of the required and optional elements described herein. For example, a thermoformed pouch may be “consisting substantially of” a film described herein to utilize its thermoforming characteristics, also including a non-thermoformed film (eg, a lid portion) and additional markings on the film, such as by inkjet printing. The invention illustrated herein may be suitably practiced in the absence of any element or step not specifically described herein.

[0023] All percentages, parts and ratios mentioned herein are based on the total dry weight of the film composition or the total dry weight of the pouch contents herein, as applicable, and all measurements made are at approximately 25°C, unless otherwise indicated. All weights related to ingredients listed are based on active level and therefore do not include carriers or by-products that may be contained in commercially available materials unless otherwise noted.

[0024] All ranges specified herein include all possible subsets of ranges and any combinations of such subsets of ranges. By default, ranges include the specified endpoints unless otherwise specified. Where a range of values is proposed, it is intended that every intervening value between the upper and lower limits of that range and any other stated or intermediate value within that specified range is covered herein. The upper and lower limits of these smaller ranges may be independently included in the smaller ranges and are also included herein, subject to any specifically excluded limit within that range. If a specified range includes one or both limits, ranges excluding one or both included limits are also considered part of this description.

[0025] It is specifically intended that for any numerical value described herein, for example, as a parameter of the subject matter described or part of a range associated with the described subject matter, the alternative that forms part of this description is a functionally equivalent range surrounding the particular a numerical value (for example, for a size specified as "40 mm", the contemplated alternative embodiment of the invention is "about 40 mm").

[0026] As used herein, the terms “bag(s)” and “bag(s)” should be considered interchangeable. In certain embodiments of the invention, the terms pouch(s) and pouch(s) are respectively used to refer to a film-based container and a fully sealed container, preferably containing material sealed therein, for example, in the form of a metered dose delivery system. The sealed pouches may be manufactured by any suitable method, including methods and features such as heat sealing, solvent sealing, and bonding (eg, using a water-soluble adhesive).

[0027] As used herein, and unless otherwise indicated, the terms "wt.%" are intended to indicate the composition of the identified element of the "dry" (non-water) portions by weight of the entire film, including residual moisture in the film (if applicable) or parts by weight of the entire composition enclosed in the package (if applicable).

[0028] As used herein, and unless otherwise indicated, the term "m.h." is intended to indicate the composition of the identified element in parts per hundred parts of the water-soluble polymer resin (whether PVA or other polymer resins, unless otherwise specified) in the water-soluble film or in the solution used to make that film.

[0029] The film may be manufactured by any suitable method, including solution casting. The film can be used to form the container (pouch) by any suitable method, including vertical form, fill and seal (VFFS) or thermoforming. The film can be sealed by any suitable method, including, for example, solvent sealing or heat sealing of film layers, for example, around the periphery of the container. Said bags can be used, for example, for dosing materials that must be delivered into a bulk aqueous medium.

[0030] Film, pouches, and related methods of preparation and use are contemplated to include embodiments of the invention including any combination of one or more additional optional elements, features, and steps further described below (including those shown in the examples and drawings) , unless otherwise specified.

[0031] In any embodiment of the invention, said water-soluble pouch may contain a composition. Said composition may be selected from a liquid, a solid, or a combination thereof. As used herein, the term "liquid" includes free-flowing liquids, as well as pastes, gels, foams and mousses. Non-limiting examples of liquids include liquid detergent compositions for mild and harsh conditions, fabric enhancers, detergent gels typically used for laundry, bleaches and laundry additives. Non-limiting examples of liquids include agricultural compositions, automotive compositions, aviation compositions, food and nutritional compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office compositions, and recreational and park compositions. compositions for pets, compositions for water purification, including cleaning and detergent compositions useful for any such application. Said liquid may contain gases, such as suspended bubbles, or solids, such as particles. As used herein, the term “solid” includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include: granules, microcapsules, beads, noodles and pearl beads. Solid compositions may provide technical benefits including, but not limited to, wash benefits, pre-treatment benefits and/or aesthetic effects.

[0032] In any of the laundry oriented embodiments, said composition may be selected from the group of, for example, liquid detergent compositions for mild conditions and liquid detergent compositions for severe conditions, powdered detergent compositions, fabric enhancers, detergent gels, generally , used for washing, and bleaches (for example, organic or inorganic bleaches) and laundry additives.

[0033] Water Soluble Film

[0034] The film and associated bags described herein contain a water-soluble film. In one aspect, said water-soluble film comprises a mixture of polyvinyl alcohol (PVA) resins containing a first PVA copolymer containing a first anionic monomer unit selected from the group consisting of alkyl acrylates, alkyl alkacrylates, hydrolyzed alkali metal salts of the foregoing and combinations of the foregoing and a second PVA copolymer containing a second anionic monomer unit. The film may be of any suitable thickness, and a film thickness of about 76 microns (µm) is typical and particularly contemplated. Other contemplated values and ranges include values in the range of about 5 to about 200 microns, or in the range of about 20 to about 100 microns, or from about 40 to about 90 microns, or from about 50 to 80 microns, or from about 60 to 65 µm, for example 65 µm, 76 µm or 88 µm.

[0035] PVA RESIN

[0036] Polyvinyl alcohol is a synthetic resin typically produced by alcoholysis, commonly referred to as hydrolysis or saponification, of polyvinyl acetate. Fully hydrolyzed PVA, in which virtually all acetate groups have been converted to alcohol groups, is a highly crystalline, highly hydrogen-bonded polymer that dissolves only in hot water - above 140°F (about 60°C). If sufficient acetate groups remain after hydrolysis of polyvinyl acetate, that is, the PVA polymer is partially hydrolyzed, then the polymer is less hydrogen bonded, less crystalline, and generally soluble in cold water - less than about 50 °F (about 10 °C). Essentially, said partially hydrolyzed polymer is a copolymer of vinyl alcohol and vinyl acetate, which is a copolymer of PVA, but is generally referred to as PVA.

[0037] Specifically, the PVA resin will include a partially or fully hydrolyzed PVA copolymer that contains an anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate monomer unit.

[0038] Water-soluble PVA-based polymer films may be subject to changes in solubility characteristics. The acetate group in the co-poly(vinyl acetate-vinyl alcohol) copolymer is known to those skilled in the art to be hydrolyzable by acid or alkaline hydrolysis. As the degree of hydrolysis increases, the polymer composition produced from the PVA homopolymer resin will have increased mechanical strength, but reduced solubility at lower temperatures (eg, requiring hot water temperature to completely dissolve). Accordingly, exposing a PVA resin homopolymer to an alkaline environment (for example, through the use of a laundry bleach additive) can convert the resin from a resin that dissolves quickly and completely in a given aqueous environment (for example, a cold water environment) to a resin that dissolves slowly and/or incompletely in a given aqueous medium, which may result in the formation of undissolved polymer residue at the end of the wash cycle. This is a natural disadvantage when using films based solely on vinyl acetate/vinyl alcohol copolymer, as typified by commercial PVA homopolymer resins.

[0039] PVA copolymer resins with pendant carboxyl groups, such as, for example, vinyl alcohol/hydrolyzed sodium methyl acrylate resins, can form lactone rings between adjacent pendant carboxyl and alcohol groups, thereby reducing the solubility of the PVA copolymer resin in water. In the presence of a strong base, such as laundry bleach, lactone rings can open over several weeks under relatively warm (ambient) conditions and high humidity (e.g., through lactone ring-opening reactions to form the corresponding pendant carboxyl and alcohol group) with increased solubility in water. Thus, in contrast to the effect observed with PVA homopolymer films, it is believed that such a PVA copolymer film may become more soluble due to chemical interactions between the film and the alkaline composition within the pouch during storage. Consequently, as they age, these packages may become increasingly prone to premature dissolution during a hot wash cycle (nominally 40°C) and may in turn reduce the effectiveness of some laundry actives due to the presence of bleaching agent and the effect of the resulting pH.

[0040] When creating a suitable film for a given application (eg, a pouched laundry product), many factors must be considered. These factors include: (1) film strength, where higher strength desirably translates into greater pouch sealing when the film is the weak link in the seal; (2) a change in the modulus of elasticity of the film after exposure to liquid, where a positive change in modulus desirably provides a lower likelihood of softening, loosening and sagging when forming a package encapsulating the liquid composition, and/or deformation and adhesion to other films when loaded on top of each other during production, or in final consumer packaging; (3) the value of the film swelling coefficient after exposure to the liquid solution, with a lower value of the swelling coefficient desirably providing greater film rigidity, less change in film area (length x width) after exposure to the liquid solution and higher elasticity of the package and a lower likelihood of softening, loosening and sagging when putting together a package encapsulating a liquid composition; (4) dissolution residue, where a lower residue value desirably reduces the likelihood of residual film remaining after aggressive wash conditions (eg, low water quantities (eg, overloading a washing machine) and cold wash water conditions); (5) the degree and type of anionic modification in which certain polymer modifications desirably reduce the risk of clouding of pouch components, such as plasticizers, and/or film softening when the film is part of a pouch encapsulating the composition; and (6) film crystallinity, where a lower crystallinity value desirably reduces the likelihood of residual film remaining after aggressive washing conditions, and a higher crystallinity value desirably reduces the likelihood of softening, loosening or sagging when forming a package encapsulating the liquid composition. Often, water-soluble polymer resins, whether PVA or others, may have good performance with respect to some of these factors, but they may have poor performance with respect to others of these factors. Accordingly, it is desirable to provide a water-soluble film in which many, if not all, of these factors have favorable properties in said film.

[0041] In view of these factors, this disclosure includes a water-soluble film comprising a polyvinyl alcohol (PVA) resin mixture and, optionally, one or more additional components including plasticizers, fillers, surfactants and other additives, as described in more detail below. The PVA resin mixture includes a first PVA resin that is a PVA copolymer (“first PVA copolymer”) containing one or more types of anionic monomer units (e.g., a three-component (or higher-component) PVA copolymer) and a second PVA resin that is a copolymer PVA (“second PVA copolymer”) containing one or more types of anionic monomer units (eg, a three-component (or higher-component) PVA copolymer). In some aspects, said PVA resin mixture comprises only a first PVA copolymer and a second PVA copolymer (eg, a binary mixture of the two polymers). Alternatively or additionally, the PVA resin blend, the water-soluble film, or both may be characterized as containing little or no other polymers (eg, generally other water-soluble polymers, particularly other PVA-based polymers, or both). As used herein, the term “substantially free” means that the first and second PVA copolymers constitute at least 95 wt%, at least 97 wt%, or at least 99 wt% of the total water-soluble polymers in water-soluble film. In other aspects, said water-soluble film may contain one or more additional water-soluble polymers. For example, the PVA resin mixture may contain a third PVA polymer, a fourth PVA polymer, a fifth PVA polymer, etc. (eg, one or more additional PVA homopolymers or PVA copolymers with or without anionic monomer units). For example, said water-soluble film may comprise at least a third (or fourth, fifth, etc.) water-soluble polymer that is not a PVA polymer (eg, other than PVA homopolymers or PVA copolymers, with or without anionic monomer units).

[0042] Said PVA copolymer (e.g., the first PVA copolymer, the second PVA copolymer, and any other PVA copolymers in the resin mixture) may be a three-component PVA copolymer containing vinyl alcohol monomer units, vinyl acetate monomer units (i.e., when not completely hydrolyzed), and the individual type of anionic monomer unit (eg, wherein said individual type of monomer unit may include equivalent acid forms, salt forms, and optionally ester forms of the anionic monomer unit). In some aspects, said PVA copolymer may contain two or more types of anionic monomer units. General classes of anionic monomer units that can be used for a PVA copolymer include vinyl polymerization units corresponding to monocarboxylic acid vinyl monomers, their esters and anhydrides, dicarboxylic acid monomers having a polymerizable double bond, their esters and anhydrides, and alkali metal salts of any of the above. Examples of suitable anionic monomer units include vinyl polymerization units corresponding to vinyl anionic monomers including vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, fumaric anhydride, itaconic acid, monoalkyl taconate, dialkylite aconate, itaconic anhydride, citraconic acid , monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconic anhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, alkyl acrylates, alkyl alkacrylates, alkali metal salts of the above, hydrolyzed salts alkali metals of the above, esters of the above and combinations of the above.

[0043] In one type of embodiment, said PVA is a copolymer modified with carboxyl groups. In another aspect, said PVA can be modified with a dicarboxyl type monomer. In one class of these embodiments, the α-carbons of both carbonyls are linked to an unsaturated bond (eg, maleic acid, fumaric acid). In another class of these embodiments, the α-carbons of both carbonyls are bonded to an unsaturated bond, and said unsaturated bond is further substituted, for example, by a methyl group (eg, citraconic acid, mesaconic acid). In another class of these embodiments, the β-carbon of one carbonyl and the α-carbon of the other carbonyl are linked to an unsaturated bond (eg, itaconic acid, cis-glutaconic acid, trans-glutaconic acid). Monomers that contain alkylcarboxyl groups are expected. Particularly contemplated is a maleate type comonomer (eg, a dialkyl maleate or a monoalkyl maleate including monomethyl maleate).

[0044] In embodiments of the invention, the first PVA copolymer contains a first anionic monomer selected from the group consisting of maleic anhydride, alkali metal salts of maleic anhydride, and combinations of the above. In embodiments of the invention, the second PVA copolymer contains a second anionic monomer selected from the group consisting of maleic anhydride, alkali metal salts thereof, and combinations thereof.

[0045] The level of one or more anionic monomer units in the PVA copolymers (ie, the degree of anionic modification of the PVA copolymer) is not particularly limited. In embodiments of the invention, one or more anionic monomer units are present in the PVA copolymer in an amount ranging from about 1 mol. % or 2 mol. % to about 6 mol. % or 10 mol. % (for example, 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 of the invention).

[0046] PVA copolymers can also be characterized by the level of pendant carboxyl groups present in the copolymer. PVA copolymer resins with pendant carboxyl groups can form lactone rings between adjacent pendant carboxyl and alcohol groups. Lactone rings can be opened in the presence of a caustic alkaline agent, as is known in the art. A polymer containing a lactone can be treated with an alkali so that all or only some of the lactone rings are opened. For example, PVA-methyl acrylate copolymers form lactone rings and can be processed so that, for example, 70% of the lactone rings are opened. Accordingly, the level of side groups represents the maximum number of side groups that can be present in the copolymer based on the level of side groups in the copolymer, regardless of whether these side groups are free or in the form of lactone rings, for example, with adjacent alcohol groups. The level of side groups present in the copolymer may or may not correspond to the level of anionic monomer units. For example, if methyl acrylate is contained in PVA at a level of 5 mol. %, the resulting copolymer will contain about 5 mol. % side groups, even if only 70% of the lactone rings are open (i.e. 3.5 mol.%). In addition, if the anionic monomer is a dicarboxylate, such as a salt, an acid of maleic anhydride or an ester thereof, the copolymer contains two side groups per anionic monomer unit contained in the copolymer.

[0047] The level of side groups in PVA copolymers is not particularly limited. In embodiments of the invention, side groups are present in the PVA copolymer in an amount ranging from about 0.5 mol. %, 1 mol. %, 2 mol. %, 2.5 mol. % or 3 mol. % to about 6 mol. % or 10 mol. % (for example, at least 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 5.0 mol % and (or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0 or 10 mol % in various embodiments of the invention). A mixture of PVA resins may have an arithmetic average number of side groups ( ) ranging from about 2 mol. % to about 10 mol. %. That is, the first side group and the second side group together are present in a combined amount ranging from about 2 mol. % to about 10 mol. %, from about 2 mol. % to about 15 mol. %, from about 3 mol. % to about 9 mol. %, from about 4 mol. % to about 15 mol. % or from about 5 mol. % to about 15 mol. %. Weighted arithmetic average of side groups calculated by the formula Where is the percentage by weight of the corresponding PVA copolymer and represents the corresponding pier. % of side groups in the specified PVA copolymer.

[0048] Said water-soluble film may contain at least about 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt. % or 90 wt%, and/or up to about 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt% or 99 wt% of the PVA resin mixture. In embodiments of the invention, the first PVA copolymer is present in the water-soluble film in an amount of from about 10 wt.% to about 70 wt.% (or from about 10 wt.% to about 60 wt.%, from about 15 wt.% to about 55 wt. .%, from about 20 wt.% to about 50 wt.%, from about 10 wt.% to about 50 wt.%, or from about 10 wt.% to about 40 wt.%) of the total amount of PVA polymers and PVA copolymers in said film (that is, relative to the weight of the PVA resin mixture). For example, the first PVA copolymer may be present in an amount of at least 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt. % or 50 wt.% and/or up to about 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 70 wt.% or 80 wt.% of the total polymers PVA and PVA copolymers in the specified film. In embodiments of the invention, the above concentrations of the first PVA copolymer may alternatively or additionally refer to the total content of water-soluble polymer in the film, PVA or other.

[0049] In embodiments of the invention, the second PVA copolymer is present in the water-soluble film in an amount of from about 30 wt.% to about 90 wt.% (or from about 40 wt.% to about 90 wt.%, from about 65 wt.% to about 85 wt.%, from about 20 wt.% to about 80 wt.%, from about 50 wt.% to about 90 wt.%, or from about 60 wt.% to about 90 wt.%) of the total amount of PVA polymers and PVA copolymers in said film (that is, relative to the weight of the PVA resin mixture). In another aspect, the above second PVA copolymer concentrations may alternatively or additionally refer to the total water-soluble polymer content of the film, PVA or other. In embodiments of the invention, said first PVA copolymer may be present in an amount of at least 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt.% or 50 wt.% and/or up to about 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 70 wt.% or 80 wt.% of the total amount of PVA polymers and PVA copolymers in the film, and the second PVA copolymer may be present in an amount of at least 30 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt% or 65 wt.% and/or up to about 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.% or 90 wt.% of the total amount of PVA polymers and PVA copolymers in film.

[0050] In a water-soluble film aspect, said first PVA copolymer has a first level of anionic monomer units (i.e., a first level of anionic modification), and the second PVA copolymer has a second level of anionic monomer units (i.e., a second level of anionic modification). modifications). It should be understood that the first level of anionic monomer units differs from the second level of anionic monomer units in various embodiments of the invention. For reference, a first PVA copolymer is designated as having a first level of side groups (a ₁ ) and a first level of anionic monomer units (b ₁ ), and a second PVA copolymer is designated as having a second level of side groups (a ₂ ) and a second level (b ₂ ) anionic monomer units.

[0051] To clarify this aspect, the first and second PVA copolymers are selected such that the difference between a ₁ and a ₂ is in the range of about 0.5 mol. % to about 18 mol. % (or from about 1 mol. % to about 18 mol. %, from about 2 mol. % to about 16 mol. %, from about 3 mol. % to 14 mol. %, from about 4 mol. % to about 10 mol %, from about 4 mol % to about 8 mol %, from about 3 mol % to 6 mol %, or from about 4 mol % to about 5 mol %), and more generally may be at least 0.5, 1, 2 or 4 mol. % and/or up to about 1, 2, 3, 4, 5, 10, 12, 14, 16 or 18 mol. %. Individually, the level of side groups (a ₁ ) for the first PVA copolymer can range from about 2 mol. % to about 6 mol. % (or from about 3 mol. % to about 6 mol. %, from about 3 mol. % to about 5 mol. %, from about 3 mol. % to about 4 mol. %, from about 4 mol. % to about 6 mol.% or about 2 mol.%, about 2.5 mol.%, about 3 mol.%, about 3.5 mol.%, about 4 mol.%, about 4.5 mol.%, about 5 mol. .%, about 5.5 mol.% or about 6 mol.%). Alternatively or additionally, the level of side groups (a ₂ ) for the second PVA copolymer can be in the range of about 6 mol. % to about 20 mol. % (or about 6 mole % to about 16 mole %, about 6 mole % to about 10 mole %, or about 7 mole % to about 9 mole %, or about 6 mole %, about 6.5 mol.%, about 7 mol.%, about 7.5 mol.%, about 8 mol.%, about 8.5 mol.%, about 9 mol.%, about 9.5 mol.%, about 10 mol %, about 10.5 mol %, about 11 mol %, about 11.5 mol % or about 12 mol %).

[0052] In embodiments of the invention, the first and second PVA copolymers are selected such that the difference between b ₁ and b ₂ is in the range of about 0.2 mol. % to about 9 mol. % (or from about 0.3 mole % to about 8 mole %, from about 0.4 mole % to about 7 mole %, from about 0.5 mole % to about 6 mole %, from about 1 mol % to about 5 mol %, from about 1.5 mol % to about 4 mol %, or from about 2 mol % to about 3 mol %, for example at least 0.2, 0. 3, 0.4, 0.6, 0.8, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, 2.75 or 3.0 mol % and/or up to about 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0 or 9.0 mol % Individually, the first level of (b ₁ ) anionic monomer units may range from about 1 mol % to about 3 mol % (or from about 1.5 mol % to about 3 mol %, from about 1 .5 mol % to about 2.5 mol % or from about 1.5 mol % to about 2 mol %, for example about 1.75 mol %) in the first PVA copolymer. Alternatively or additionally, the second level of (b ₂ ) anionic monomer units may range from about 3 mol % to about 10 mol % (or from about 3 mol % to about 8 mol %, from about 3 mol % to about 5 they say %, from about 3.5 mol. % to about 4.5 mol. %, for example about 4 mol. %) in the second PVA copolymer.

[0053] The degree of hydrolysis (DH) of the PVA homopolymers and PVA copolymers contained in the water-soluble films herein may range from about 75% to about 99% (e.g., from about 79% to about 92%, from about 88% to 92%, from about 86.5% to about 89% or about 88%, 90%, 91% or 92%, for example, for cold water soluble compositions; from about 90% to about 99%, from about 92 % to about 99%, from about 95% to about 99%, about 98%, about 99% or greater than 99%). As the degree of hydrolysis decreases, a film made from the resin will have reduced mechanical strength but more rapid solubility at temperatures less than about 20 °C. As the degree of hydrolysis increases, a film made from the said polymer will tend to become mechanically stronger, and thermoformability will be reduced. The degree of hydrolysis of PVA can be selected so that the solubility of the polymer in water depends on temperature, and thus also affects the solubility of the film made from said polymer and additional ingredients. In one embodiment, the film is cold water soluble. For a co-poly(vinyl acetate and vinyl alcohol) polymer that does not include any other monomers (e.g., not copolymerized with an anionic monomer), the cold water soluble film, soluble in water below 10°C, may contain PVA with degree of hydrolysis ranging from about 75% to about 90%, or in the range from about 80% to about 90%, or in the range from about 85% to about 90%. In another embodiment, the film is hot water soluble. For a co-poly(vinyl acetate and vinyl alcohol) polymer that does not include any other monomers (e.g., not copolymerized with an anionic monomer), a hot water soluble film, soluble in water at a temperature of at least about 60°C, may contain PVA with a degree of hydrolysis of at least about 98%.

[0054] The degree of hydrolysis of a resin mixture can also be characterized by the weighted arithmetic average degree of hydrolysis ( $$\overline{H^o}$$ ). For example, $$\overline{H^o}$$ for PVA resin containing two or more PVA polymers, calculated by the formula $$\overline{H^o}={\displaystyle \sum \left(Wi\cdot H_i\right)}$$ where _Wi represents the percentage by weight of the corresponding PVA polymer, and H _i represents the corresponding degrees of hydrolysis.

[0055] PVA polymer viscosity (μ) is determined by measuring the freshly prepared solution using a Brookfield LV viscometer with a UL adapter, as described in the British standard EN ISO 15023-2:2006 Annex E Brookfield method. In international practice, it is customary to indicate the viscosity of 4% aqueous solutions of polyvinyl alcohol at 20 °C. All viscosity values stated herein in centipoise (cP) should be understood to refer to the viscosity of a 4% aqueous polyvinyl alcohol solution at 20°C unless otherwise stated. Likewise, when a resin is described as having (or not having) a particular viscosity, unless otherwise stated, the stated viscosity is meant to represent the average viscosity for a resin that inherently has a corresponding molecular weight distribution.

[0056] For reference, the first PVA copolymer is designated as having the viscosity of the first 4% solution at 20 °C (μ ₁ ), and the second PVA copolymer is designated as having the viscosity of the second 4% solution at 20 °C (μ ₂ ). In various embodiments of the invention, the first viscosity μ ₁ may range from about 4 cP to about 30 cP (for example, at least about 4, 8, 10, 12 or 16 cP and/or up to about 12, 16, 20, 24 or 30 cP, e.g., about 4 cP to about 24 cP, about 10 cP to about 16 cP, about 10 cP to about 20 cP, about 20 cP to about 26 cP, or about 20 cP to about 30 cP cP). Alternatively or additionally, the second viscosity μ ₂ may range from about 4 cP to about 30 cP (for example, at least about 4, 8, 10, 12 or 16 cP and/or up to about 12, 16, 20 , 24 or 30 cP, for example, from about 12 cP to about 30 cP, from about 10 cP to about 16 cP, from about 10 cP to about 20 cP, or from about 20 cP to about 30 cP). When the PVA resin mixture contains three or more PVA resins selected from PVA polymer and PVA copolymer resins, the above viscosity values can be applied to each PVA polymer or PVA copolymer individually. It is well known in the art that the viscosity of PVA resins correlates with the weight average molecular weight $$\left(\overline{M}w\right)$$ PVA resins, and viscosity is often used as an indicator $$\overline{M}w$$ . Thus, the weight average molecular weight of the water-soluble polymers comprising the first PVA copolymer and the second PVA copolymer may range, for example, from about 30,000 to about 175,000, from about 30,000 to about 100,000, or from about 55,000 to about 80,000. With respect to the average viscosity mixtures of PVA resins, use the weighted average natural logarithmic viscosity $$\left(\overline{\mu }\right)$$ . $$\overline{\mu }$$ for a PVA resin that contains two or more PVA polymers, is calculated using the formula $$\overline{\mu }=e^{{\displaystyle \sum W_i\cdot \ln {\mu }_i}}$$ where _μι represents the viscosity of the corresponding PVA polymers.

[0057] In another aspect of the water-soluble film, the first PVA copolymer and the second PVA copolymer are selected for the PVA resin mixture such that the resulting water-soluble film maintains film rigidity and maintains the resiliency of the pouch (e.g., is less likely to loosen and sag) upon contact with the liquid contents of the pouch and preferably maintaining or improving dissolution, residue and mechanical properties. In some embodiments, said water-soluble film has the property that (a) the water-soluble film has a residue value of about 20 wt.% or less, about 25 wt.% or less, about 30 wt.% or less, about 35 wt.% or less, about 40 wt.% or less, about 45 wt.% or less, or about 48 wt.% or less (for example, in the range of about 1 wt.% to about 20 wt.%, from about 3 wt.% to about 20% by weight, from about 5% by weight to about 25% by weight, from about 12% by weight to about 48% by weight, from about 25% by weight to about 48% by weight, from about 10% by weight .% to about 45 wt.%, from about 20 wt.% to about 45 wt.%, or from about 25 wt.% to about 40 wt.%) as measured in the dissolution chamber test (described below). In some embodiments, said water-soluble film has the property that (b) the water-soluble film has a crystallinity value of at least 15% (e.g., in the range of about 15% to about 50%, from about 15% to about 40%, from about 15% to about 35%, about 15% to about 30%, about 15% to about 25%, or about 15% to about 20%) as measured in a crystallinity test (described below). In some embodiments, said water-soluble film has the property that (c) the water-soluble film is resistant to clouding, as determined by visual inspection of the film opacity of the pouch material relative to the film's manufacturing opacity. In some embodiments, said water-soluble film has the property that (d) the water-soluble film has a swelling coefficient value that is no more than 60% of the swelling coefficient value of an identically prepared film that contains only the second PVA copolymer, as measured in the test on film swelling (described below). It should be appreciated that not each of properties (a) - (d) must be satisfied to provide a water soluble film having retained film stiffness and retained pouch resiliency (e.g., less likely to flake and sag) upon contact with the liquid contents of the pouch, and , preferably maintaining or improving dissolution, residue and mechanical properties. For example, a water-soluble film having a crystallinity value of less than 15% that exhibits maintained film stiffness and retained pouch resiliency can be developed, for example, by varying the type and/or amount of plasticizer contained in the film. In various embodiments of the invention, said water-soluble film has properties (a) and (b), (a) and (c), (a) and (d), (b) and (c), (b) and (d), (c) and (d), (a) and (b) and (c), (a) and (b) and (d), (a) and (c) and (d), (b) and (c ) and (d), or (a) and (b) and (c) and (d). In general, water-soluble films that exhibit the above properties exhibit these properties before exposure to a liquid composition (eg, liquid laundry detergent) and retain the above properties after exposure to the liquid composition. Water-soluble films herein “retain” a property after exposure to a liquid composition if the property has a value after exposure to the liquid composition that is within the ranges described herein for said property. Water-soluble films herein do not necessarily have to retain exactly the same property value after exposure to the liquid composition that the film exhibited before exposure to the liquid composition. For example, in one type of embodiments of the invention, the specified property after exposure may be within 20% or 10% of the original value and still be within the range described herein for the specified property.

[0058] PVA resin blends according to this disclosure unexpectedly produce water-soluble films having a combination of desired physical and chemical properties, even when the PVA copolymers contained in the resin blend are individually deficient in one or more physical or chemical properties. For example, each PVA copolymer in the mixture has at least one undesirable feature for a particular property, but a water-soluble film comprising the mixture provides the desired feature for a particular property of each PVA copolymer. For example, a PVA resin mixture may contain first and second PVA copolymers such that that the corresponding water-soluble film of the first PVA copolymer has property (a), and the corresponding water-soluble film of the second PVA copolymer does not have property (a). Alternatively or additionally, the PVA resin mixture may comprise first and second PVA copolymers such that the corresponding water-soluble film of the first PVA copolymer does not have property (b) and the corresponding water-soluble film of the second PVA copolymer has property (b). Alternatively or additionally, the PVA resin mixture may comprise first and second PVA copolymers such that the corresponding water-soluble film of the first PVA copolymer does not have property (c) and the corresponding water-soluble film of the second PVA copolymer has property (c). Alternatively or additionally, the PVA resin mixture may comprise first and second PVA copolymers such that the corresponding water-soluble film of the first PVA copolymer does not have property (d) and the corresponding water-soluble film of the second PVA copolymer has property (d). A corresponding PVA copolymer means a water-soluble film containing only the first PVA copolymer or the second PVA copolymer as the water-soluble polymer resin, but otherwise containing the same type and amounts of plasticizers and other additives, having the same thickness, etc.

[0059] OTHER WATER SOLUBLE POLYMERS

[0060] Other water-soluble polymers for use in addition to the first and second PVA copolymers may include, but are not limited to, vinyl alcohol-vinyl acetate copolymer, sometimes referred to as PVA homopolymer, polyacrylates, water-soluble acrylate copolymers, polyvinylpyrrolidone, polyethylenimine, pullulan, water-soluble natural polymers , including, but not limited to, guar gum, acacia gum, xanthan gum, carrageenan and starch, derivatives of water-soluble polymers, including, but not limited to, modified starches, ethoxylated starch and hydroxypropylated starch, copolymers of the foregoing and combinations of any of the above. Still other water-soluble polymers may include polyalkylene oxides, polyacrylamides, polyacrylic acids and their salts, celluloses, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and their salts, polyamino acids, polyamides, gelatins, methylcelluloses, carboxymethylcelluloses and salts thereof, dextrins, ethylcelluloses, hydroxyethylcelluloses, hydroxypropylmethylcelluloses, maltodextrins, polymethacrylates and combinations of any of the above. Such water-soluble polymers, whether PVA or others, are commercially available from a variety of sources.

[0061] In embodiments of the invention, said PVA resin mixture consists essentially of a first PVA copolymer and a second PVA copolymer. In embodiments of the invention, said water-soluble film contains at least a third water-soluble polymer that is different from the PVA polymer.

[0062] Said water-soluble film may contain other auxiliary agents and processing agents such as, but not limited to, plasticizers, plasticizer compatibilizers, surfactants, lubricants, release agents, fillers, diluents, cross-linking agents, agents anti-caking agents, antioxidants, anti-tack agents, defoamers, nanoparticles such as layered silicate type nanoclays (e.g. sodium montmorillonite), bleaching agents (e.g. sodium metabisulfite, sodium bisulfite or others), aversive agents such as bitters substances (eg, denatonium salts such as denatonium benzoate, denatonium saccharide and denatonium chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and naringen; and quassinoids such as quassin and brucine) and pungent substances (eg capsaicin, piperine, allyl isothiocyanate and resinferatoxin) and other functional ingredients in quantities suitable for the intended purposes. Embodiments of the invention containing plasticizers are preferred. The amount of such agents may be up to about 50 wt%, 20 wt%, 15 wt%, 10 wt%, 5 wt%, 4 wt% and/or at least 0.01 wt%, 0.1 wt.%, 1 wt.% or 5 wt.% separately or together.

[0063] PLASTICIZERS

[0064] A plasticizer is a liquid, solid, or semi-solid that is added to a material (usually a resin or elastomer), making the material softer, more flexible (by lowering the glass transition temperature of the polymer), and easier to process. Alternatively, said polymer may be internally plasticized by chemically modifying said polymer or monomer. Additionally or alternatively, said polymer may be externally plasticized by adding a suitable plasticizing agent. Water is recognized as a very effective plasticizer for PVA and other polymers; including, but not limited to, water-soluble polymers, however, the volatility of water limits its use since polymer films must have at least some resistance to a variety of environmental conditions, including low and high relative humidity.

[0065] Said plasticizer may include, but is not limited to, glycerin, diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol up to 400 MW, neopentyl glycol, trimethylolpropane, polyether polyols, sorbitol, 2-methyl-1, 3-propanediol (MPDiol®), ethanolamines and mixtures thereof. A preferred plasticizer is glycerin, sorbitol, triethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, or a combination thereof. The total amount of non-aqueous plasticizer may range from about 10 wt.% to about 40 wt.%, from about 15 wt.% to about 35 wt.%, or from about 20 wt.% to about 30 wt.%, for example, about 25 wt.% of the total mass of the film. Combinations of glycerin, dipropylene glycol and sorbitol can be used. Optionally, glycerin can be used in an amount of from about 5 wt% to about 30 wt%, or from 5 wt% to about 20 wt%, such as about 13 wt%. Optionally, dipropylene glycol can be used in an amount of from about 1 wt% to about 20 wt%, or from about 3 wt% to about 10 wt%, such as 6 wt%. Optionally, sorbitol can be used in an amount of from about 1% by weight to about 20% by weight, or from about 2% by weight to about 10% by weight, such as about 5% by weight. Specific amounts of plasticizers may be selected in a particular embodiment based on the desired flexibility of the film and the processability of the water-soluble film. At low levels of plasticizer, films may become brittle, difficult to process, or prone to breaking. At higher levels of plasticizer, films may be too soft, weak, or difficult to process for the desired application.

[0066] In some embodiments, the plasticizer may include glycerin, sorbitol, and trimethylolpropane. Optionally, the plasticizer may be contained in an amount greater than or equal to 30 ppm. or more than 40 phr, for example in the range of about 30 phr. to about 75 m.h., from about 30 m.h. to about 70 m.h., from about 30 m.h. to about 60 m.h., from about 30 m.h. up to about 50 m.h. or from about 30 m.h. up to about 45 m.h.

[0067] In some embodiments, the plasticizer may include glycerin, sorbitol, and 2-methyl-1,3-propanediol. Optionally, the plasticizer may be contained in an amount of less than 30 ppm. or less than 25 phr, for example, in the range of about 5 phr. to about 30 m.h., from about 10 m.h. to about 30 m.h., from about 15 m.h. to about 30 m.h., from about 5 m.h. to about 29 m.h., from about 5 m.h. to about 25 m.h., from about 10 m.h. up to about 25 m.h. or from about 15 m.h. up to about 25 m.h.

[0068] In some embodiments, the plasticizer may include a first plasticizer having a molecular weight of 92 g/mol or more and a second plasticizer having a molecular weight of 150 g/mol or more. For example, the first plasticizer may have a molecular weight ranging from about 92 g/mol to about 149 g/mol, from about 92 g/mol to about 140 g/mol, from about 92 g/mol to about 130 g/mol. from about 92 g/mol to about 120 g/mol, from about 92 g/mol to about 110 g/mol, or from about 92 g/mol to about 100 g/mol, and the second plasticizer may have a molecular weight ranging from about 150 g/mol to 200 g/mol, for example, from about 150 g/mol to about 190 g/mol, from about 160 g/mol to about 190 g/mol, from about 170 g/mol to about 190 g/mol or from about 180 g/mol to about 190 g/mol.

[0069] It is understood that individual plasticizers may have Hansen solubility parameters that are outside a defined Hansen region, but that when plasticizers are mixed, the resulting combination or ratio may then fall within a given Hansen region. Accordingly, when more than one plasticizer is used for a polymer resin, the combination will be selected to exhibit the Hansen Solubility Parameters (HSP) described herein.

[0070] The solubility characteristics of a material can be characterized by three distinct forces: dispersion forces ( _δD ), polar forces ( _δP ), and hydrogen bonding forces ( _δH ). The individual forces can be combined into a total cohesive energy value (δ _T ), as shown in Equation 1: (δ _T ) ² =(δ _D ) ² +(δ _P ) ² +(δ _H ) ² . (1) In addition to representative solubility parameters for a single component, a Hansen region can be defined in Hansen space as a sphere with the individual solubility parameters ( _δD ), ( _δP ) and ( _δH ) as the center and radius RAD defining the volume spheres.

[0071] In another aspect, the definition of the Hansen region may further include "core" values. The fundamental values determine how much the center of the sphere (defined by _δD , _δP , _δH , and RAD) can in some sense move in the _δD , _δP , and _δH directions (+or -) to expand the Hansen region. Thus, the larger the fundamental values, the less closely the Hansen region approaches a truly spherical region.

[0072] Calculations to estimate various HSP values can be performed using a commercially available software package such as HSPIP (available on the Hansen Solubility Parameters website, currently in its 4th edition). Good plasticizers and bad plasticizers can be tested experimentally, and the HSP coordinates _δD , _δP , and _δH for the material can be determined experimentally. Alternatively, the individual HSP coordinates _δD , _δP and _δH can be calculated using the Y-MB methodology (included in the HSPIP software). Regardless of the method chosen to estimate HSP parameters, it is prudent to use a consistent method for all plasticizers and polymer components of interest. For example, HSP parameters for common plasticizers are shown in the table below.

Name Abbr δD δP δH Propylene glycol PG 16.8 10.4 21.3 2-methylpropanediol 2M-1.3PD 17.1 9.4 20.7 Diethylene glycol DEG 16.6 12 19 Trimethylolpropane TMP 17.1 9.9 21.1 Diglycerin DG 17.4 11.9 26.6 Dipropylene glycol DPG 16.5 10.6 17.7 Triethylene glycol TEG 16 12.5 18.6 Glycerol GLY 17.4 11.3 27.2 Polyethylene glycol 200 PEG200 16.4 9.4 15.3

[0073] SURFACTANTS

[0074] Surfactants for use in water-soluble films are well known in the art. Optionally, surfactants are added to help disperse the resin solution during casting. Suitable surfactants for water-soluble films herein include, but are not limited to, dialkyl sulfosuccinates, glycerol propylene glycol esters of lactic fatty acids, lactic acid esters of fatty acids, sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80 , polyethylene glycol alkyl esters, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, sodium lauryl sulfate, acetylated fatty acid esters, myristyl dimethylamine oxide, trimethyl (fatty alkyl) ammonium chloride, quaternary ammonium compounds, alkali metal salts of higher fatty acids containing from about 8 up to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylate sulfates, alkyl benzene sulfonates, monoethanolamine, lauryl alcohol ethoxylate, propylene glycol, diethylene glycol, their salts and combinations of any of the above.

[0075] Suitable surfactants may include the nonionic, cationic, anionic, and zwitterionic classes. Suitable surfactants include, but are not limited to, propylene glycols, diethylene glycols, monoethanolamine, polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylene glycols and alkanolamides (non-ionic), polyoxyethylenated amines, quaternary ammonium salts and quaternized polyoxyethylenated amines (cationic), alkali metal salts of higher fatty acids containing from 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 sodium dioctyl sulfosuccinate, glycerol propylene glycol esters of lactic fatty acids, lactic acid esters of fatty acids, sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, acetylated fatty acid esters and combinations thereof. In various embodiments, the amount of surfactant in the water-soluble film ranges from about 0.1 wt% to 2.5 wt%, optionally from about 1.0 wt% to 2.0 wt%. In embodiments of the invention, the amount of surfactant in the water-soluble film is expressed in parts per 100 parts of total water-soluble polymer (TSP) in the water-soluble film and is present in the range of about 0.5 TPM. to about 4 m.h., from about 0.75 m.h. to about 3.0 m.h., from about 1.0 m.h. to about 2.5 m.h., from about 1.0 m.h. up to about 2.0 m.h. or about 1.5 m.h.

[0076] Surfactants can be characterized in terms of hydrophilic-lipophilic balance (HLB). Griffin's method was described in 1954 (Griffin WC: "Calculation of HLB Values of Non-Ionic Surfactants," Journal of the Society of Cosmetic Chemists 5 (1954): 259) and is used in the art to determine HLB values for non-ionic surfactants. surfactants as follows: HLB=20*Mh/M, where Mh represents the molecular weight of the hydrophilic part of the molecule, and M represents the molecular weight of the entire molecule, which gives an HLB value on a scale from 0 to 20. An HLB value of 0 corresponds completely lipophilic/hydrophobic molecule, and a value of 20 corresponds to a completely hydrophilic/lipophobic molecule.

[0077] Surfactant mixtures have been found to be preferred for water-soluble films containing anionic monomers selected from the group consisting of maleic acid, maleic anhydride, monoalkyl maleates, dialkyl maleates, and combinations thereof. Thus, in one aspect of the present disclosure, the second PVA copolymer contains an anionic monomer selected from the group consisting of maleic acid, maleic anhydride, monoalkyl maleates, dialkyl maleates, and combinations thereof, wherein the total level of anionic side groups from the first PVA copolymer and the second PVA copolymer is at least at least about 3 mol. %, at least about 3.5 mol. %, at least about 4.0 mol. %, at least about 6 mol. % or at least about 8 mol. %, and the water-soluble film further contains a nonionic surfactant, an amine oxide surfactant, an anionic surfactant, a cationic surfactant, or combinations thereof. In refinements to the above aspect, the nonionic surfactant is selected from the group consisting of polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylene glycols, alkanolamides, and combinations thereof. In the specifications, said amine oxide surfactant is selected from the group consisting of dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyldodecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide, dimethyloctadecylamine oxide, and combinations of the above. It should be understood that commercially available amine oxide surfactants may be mixtures of the above, since the amine source may contain a distribution of amines of varying chain lengths. Accordingly, by way of example, in some embodiments, “dimethyldodecylamine oxide” may include a distribution of amine oxides in which the middle amine oxide and/or the major amine oxide fraction includes a dodecyl chain. In specifications, said anionic surfactant may include sodium dioctyl sulfosuccinate. In specifications, said cationic surfactant may be selected from the group consisting of polyoxyethylenated amines, quaternary ammonium salts, quaternized polyoxyethylenated amines, and combinations thereof. In embodiments of the invention, the total amount of combined surfactants in the water-soluble film ranges from about 0.5 ppm. to about 4 m.h., from about 0.75 m.h. to about 3.0 m.h., from about 1.0 m.h. to about 2.5 m.h., from about 1.0 m.h. up to about 2.0 m.h. or about 1.5 m.h.

[0078] In refinements to the above aspect, each of the surfactants present in the water-soluble film may be present in an amount ranging from about 1 wt.% to about 98 wt.% of the total amount of surfactants, or about 10 wt. % to about 80 wt.%, from about 15 wt.% to about 70 wt.%, from about 16 wt.% to about 68 wt.%, from about 17 wt.% to about 42 wt.%, or from about 30 wt.% to about 40 wt.%.

[0079] Suitable lubricants/release agents may include, but are not limited to, fatty acids and their salts, fatty alcohols, fatty acid esters, fatty amines, fatty amine acetates, and fatty amides. Preferred lubricants/release agents are fatty acids, fatty acid salts and fatty amine acetates. In one type of embodiment, the amount of lubricant/release agent in said water-soluble film ranges from about 0.02 wt.% to about 1.5 wt.%, optionally from about 0.1 wt.% to about 1 wt. %.

[0080] Fillers may be contained in water-soluble films and may include bulking agents, diluents, antiblocking agents, tack reducing agents, and combinations thereof. Suitable fillers/bulking agents/diluents/anti-blocking agents/anti-tack agents include, but are not limited to, starches, modified starches, cross-linked polyvinylpyrrolidone, cross-linked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, mica, stearic acid and its metal salts, for example magnesium stearate. Preferred materials are starches, modified starches and silica. In one type of embodiment, the amount of filler/diluent/anti-blocking agent/tack-reducing agent in the water-soluble film may range, for example, from about 1 wt.% to about 6 wt.%, from about 1 wt.% to about 4 wt.%, from about 2 wt.% to about 4 wt.%, or from about 1 phr. to about 6 m.h., from about 1 m.h. up to about 4 m.h. or from about 2 m.h. up to about 4 m.h.

[0081] In some embodiments, said water-soluble film may contain 2 or more parts by weight. (for example, from 2 parts to 6 parts or from 2 parts to 4 parts) filler. In some embodiments of the invention, said film contains 2 or more parts by weight. (eg, 2 parts by weight to 6 parts by weight or 2 parts by weight to 4 parts by weight) of filler, and said filler includes a bulking agent, an anti-blocking agent, or a combination thereof. Without being limited by theory, it is believed that the content of 2 or more parts. (eg, 2 parts to 6 parts or 2 parts to 4 parts) of filler may be useful to prevent bleed or migration of plasticizer from the film when the plasticizer is contained in an amount greater than or equal to 30 m.h., for example, in the range from 30 m.h. up to 50 m.h.

[0082] The antiadhesive agent (eg, SiO ₂ and/or stearic acid) may be present in the film in an amount of at least 0.1 phr, at least 0.5 phr, or at least 1 phr. , or in the range from about 0.1 to 5.0 phr, from about 0.1 to about 3.0 phr, from about 0.4 to 1.0 phr, from about 0 .5 to about 0.9 m.h., from about 0.5 to about 2 m.h., from about 0.5 to about 1.5 m.h., from 0.1 to 1.2 m.h. h. or from 0.1 to 2.7 parts, for example, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts. or 0.9 m.h.

[0083] Suitable average particle size for the anti-adhesive agent includes an average size in the range of about 3 microns to about 11 microns, from about 4 microns to about 11 microns, from about 4 microns to about 8 microns, or from about 5 microns to about 6 microns eg 5, 6, 7, 8 or 9 microns. Suitable SiO ₂ is a raw synthetic amorphous silica intended for use in aqueous systems.

[0084] The water-soluble film may further have a residual moisture content of at least 4 wt.%, for example, in the range of about 4 to about 10 wt.% as measured by Karl Fischer titration.

[0085] To be considered a water-soluble film as used herein, a film approximately 1.5 mils (about 0.038 mm) thick dissolves in water in 300 seconds or less at 20 °C (68 °F) according to the MonoSol MSTM test method -205.

Film Production Method

[0086] One contemplated class of embodiments of the invention is characterized in that said water-soluble film is formed by dipping into a solution. Methods for forming PVA by solution dipping are well known in the art. For example, in a film forming process, polyvinyl alcohol polymers and secondary additives are dissolved in a solvent, typically water, metered onto a surface, allowed to dry substantially (or forced dry) to form a cast film, and then the resulting cast film is removed from the casting surface. This method can be performed periodically, but it is more efficient to perform it continuously.

[0087] When forming continuous films of polyvinyl alcohol, a common practice is to dispense a solution onto a moving casting surface, such as a continuously moving metal drum or belt, remove substantially the solvent from the liquid whereby a self-supporting cast film is formed, and then remove the resulting cast film from casting surface.

[0088] Optionally, said water-soluble film may be a free-standing film consisting of a single layer or a plurality of such layers.

[0089] PACKAGES

[0090] The film described herein is suitable for the manufacture of bags containing a composition therein. The packet composition can be in any form such as powders, gels, pastes, liquids, tablets or any combination thereof. This film is also suitable for any other application in which improved liquid resistance and low cold water residue are desired. Said film forms at least one side wall of the pouch, optionally the entire pouch, and preferably the outer surface of at least one side wall.

[0091] The film described herein can also be used to make a pouch with two or more compartments made from the same film or in combination with films of other polymeric materials. Additional films can be produced, for example, by casting, blow molding, extrusion or blown extrusion of the same or a different polymeric material, as is known in the art. In one type of embodiments of the invention, said polymers, copolymers or derivatives thereof suitable for use as an additional film are selected from polyvinyl alcohols, polyvinylpyrrolidone, polyalkylene oxides, polyacrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and their salts, polyamino acids or peptides, polyamides, polyacrylamide, maleic/acrylic acid copolymers, polysaccharides including starch and gelatin, natural gums such as xanthan and carrageenans. For example, these polymers can be selected from polyacrylate and water -soluble copolymers of acrylates, methyl cellulose, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, maltodecstrin, polymetakrilates and their combinations, or selected from polyvinyl alcohols, polyvillers of polyvillers, popriomas nille alcohols and hydroxypropylmethyl cellulose (GPMC), and their combinations. One contemplated class of embodiments is characterized by a level of polymer in the pouch material, such as the PVA copolymer described above, as described above, of from at least 60 wt.% and up to 99 wt.%.

[0092] The bags of this description may contain at least one sealed compartment. Thus, said packages may contain one or more compartments. The water-soluble pouch may be formed from two layers of water-soluble polymer film sealed at the interface, or from a single film that is folded and sealed. One or both films include the PVA film described above. The films define the internal volume of a container package that contains any desired composition for release into an aqueous environment. The composition is not particularly limited, for example, including any of a variety of compositions described below. In embodiments of the invention containing multiple compartments, each compartment may contain identical and/or different compositions. In turn, these compositions can take any suitable form, including, but not limited to, liquid, solid, and combinations thereof (eg, solid suspended in liquid). In embodiments of the invention, said bags comprise first, second and third compartments, each of which respectively contains a different first, second and third composition.

[0093] These compartments of multi-compartment bags may have the same or different sizes and/or volumes. These compartments of multi-compartment bags may be separate or connected in any suitable manner. In embodiments of the invention, the second and/or third and/or subsequent compartments are superimposed on the first compartment. In one embodiment of the invention, said third compartment may be superimposed on a second compartment, which in turn is superimposed on the first compartment in a sandwich configuration. Alternatively, said second and third compartments may be superimposed on the first compartment. However, it is also equally contemplated that the first, second and optionally third and subsequent compartments may be attached to each other side by side. Said compartments may be packed in tape, each compartment being separately separated by a perforation line. Therefore, each compartment can be individually torn from the remainder of the tape by the end user, for example, to pre- or post-treat the fabric with a composition from that compartment. In embodiments of the invention, the first compartment may be surrounded by at least a second compartment, for example, in a tire and rim configuration or a bag-in-bag configuration.

[0094] In embodiments of the invention, multi-compartment pouches contain three compartments, consisting of a large first compartment and two smaller compartments. Said second and third smaller compartments are superimposed on the first larger compartment. The size and geometry of these compartments are chosen in such a way that this arrangement is achievable. The geometry of these compartments may be the same or different. In embodiments of the invention, said second and optionally third compartment has a different geometry and shape compared to the first compartment. In these embodiments, the second and optionally third compartment are arranged in a structure on the first compartment. Said design may be decorative, educational or illustrative, for example to illustrate a concept or instruction and/or to indicate the origin of a product. In embodiments of the invention, the first compartment is the largest compartment having two large surfaces sealed around the perimeter, and the second compartment is smaller in size, covering less than about 75% or less than about 50% of the surface area of one side of the first compartment. In embodiments of the invention that have a third compartment, the above structure may be the same, but the second and third compartments cover less than about 60%, less than about 50%, or less than about 45% of the surface area of one side of the first compartment.

[0095] Packages as described herein may contain one or more different films. For example, in single compartment embodiments, the pouch may consist of one wall that folds over itself and seals at the edges, or alternatively, two walls that seal at the edges. In multi-compartment embodiments, the pouch may be composed of one or more films, such that any given pouch compartment may contain walls made from a single film or multiple films having different compositions. In one embodiment of the invention, the multi-compartment pouch comprises at least three walls: an outer top wall; outer bottom wall; and a partition. Said outer top wall and outer bottom wall are generally located on opposite sides and form the outer part of the package. This partition is located inside the package and is attached to, as a rule, opposite external walls along the seal line. Said partition divides the interior of the multi-compartment pouch into at least a first compartment and a second compartment.

[0096] The bags can be made using any suitable equipment and in any way. For example, single compartment pouches can be made by vertical mold filling, horizontal mold filling, or rotary drum filling methods well known in the art. Such methods can be either continuous or intermittent. Said film can be moistened and/or heated to increase its plasticity. The method may also include applying a vacuum to draw the film into a suitable mold. Vacuum drawing of said film into the mold can be accomplished for about 0.2 to about 5 seconds, about 0.3 to about 3 seconds, or about 0.5 to about 1.5 seconds from the time the film is placed on horizontal part of the surface. This vacuum may be such as to provide a reduced pressure in the range of 10 mbar to 1000 mbar or, for example, in the range of 100 mbar to 600 mbar.

[0097] The molds in which the bags can be made can be of any shape, length, width, and depth depending on the required dimensions of the bags. If desired, said casting molds may also vary in size and shape. For example, the volume of the finished bags may be from about 5 ml to about 300 ml, from about 10 ml to 150 ml, or from about 20 ml to about 100 ml, and the sizes of the molds are adjusted accordingly.

[0098] In one embodiment of the invention, said bag comprises a first and a second sealed compartment. The second compartment is typically combined with the first sealed compartment such that the second sealed compartment and the first sealed compartment share a common internal pouch divider.

[0099] In one embodiment of the invention, said pouch containing first and second compartments further comprises a third sealed compartment. The third sealed compartment is typically combined with the first sealed compartment such that the third sealed compartment and the first sealed compartment share a common internal partition of the package.

[00100] In embodiments of the invention, said first composition and second composition are selected from one of the following combinations: liquid, liquid; liquid, powder; powder, powder; and powder, liquid.

[00101] In some embodiments, said first, second and third compositions are selected from one of the following combinations: solid, liquid, liquid and liquid, liquid, liquid.

[00102] In one embodiment of the invention, said individual compartment or plurality of sealed compartments contains a composition. Each of the plurality of compartments may contain the same or different compositions. Said composition is selected from a liquid, a solid, or a combination thereof.

[00103] In one embodiment, the composition may be selected from the group of, for example, liquid detergent compositions for mild conditions and liquid detergent compositions for severe conditions, powder detergent compositions, hand-washing detergents and/or dishwashers; hard surface cleaning compositions, fabric enhancers, detergent gels typically used for laundry, and bleaches and laundry additives, shampoos and body washes, agricultural compositions, automotive compositions, aviation compositions, food and nutritional compositions, industrial compositions, compositions for livestock, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office compositions and compositions for recreational areas and parks, compositions for pets, compositions for water purification, including cleaning and detergent compositions suitable for any such application .

Vertical Form, Filling and Sealing

[00104] One traditional automated process involves the vertical form, fill and seal (VFFS) process. VFFS involves a device, such as a builder, that winds a single piece of film around a vertically oriented feed tube. The machine heat seals or otherwise secures the opposite edges of the film together to create a side seal and form a hollow tube of film. Said machine then heat seals or otherwise creates a bottom seal, thereby forming an open top portion of the container where the top seal will later be formed. Said machine introduces a specified amount of fluid product into the container through the open top end. Once the container contains the desired amount of product, said machine advances the film to another heat sealing device, for example to create a top seal. Finally, said machine advances the film to a cutter, which cuts the film just above the top seam to produce a filled package.

[00105] During operation, the assembly machine advances the film from the roll to form the package. Accordingly, said film should be able to move easily through the installation and not stick to the installation assembly or be so fragile that it breaks during processing.

Molding, sealing and thermoforming

[00106] Thermoformable film is a film that can be shaped by applying heat and force. In general, the films of this disclosure are thermoformable.

[00107] As is known in the art, film thermoforming is the process of heating the film, shaping it (eg, in a mold), and then cooling the film so that the film retains its shape, such as the shape of a mold. Heat can be applied by any suitable means. For example, the film can be heated directly by passing it under a heating element or through hot air, before being applied to the surface or once on the surface. Alternatively, it can be heated indirectly, for example by heating the surface or placing a hot object on the film. In embodiments of the invention, said film is heated using infrared light. The film may be heated to a temperature ranging from about 50 to about 150°C, from about 50 to about 120°C, from about 60 to about 130°C, from about 70 to about 120°C, or from about 60 to about 90 °C. Thermoforming can be performed by any one or more of the following methods: manually laying a thermally softened film onto a mold, molding a softened film onto a mold under pressure (e.g., vacuum forming), automatically sending a freshly extruded sheet at a precisely known temperature into a mold at high speed and trimming station, or automatic placement, insertion and/or pneumatic stretching and pressure forming of the film.

[00108] Alternatively, the film may be wetted by any suitable means, for example, directly by spraying a wetting agent (including water, a film composition solution, a film composition plasticizer, or any combination thereof) onto the film before it is applied to the surface, or indirectly , by wetting the surface or by placing a wet object on the film.

[00109] Once the film is heated and/or wetted, it can be drawn into a suitable mold, preferably using a vacuum. Filling of the cast film can be accomplished by any suitable means. In embodiments of the invention, the most preferred method will depend on the form of the product and the required filling speed. In embodiments of the invention, said cast film is filled with current filling technologies. The filled open pouches are then sealed to form pouches using a second film in any suitable manner. This can be done in a horizontal position and with continuous, constant movement. Said sealing can be accomplished by continuously feeding a second film, preferably a water-soluble film, over and onto the open bags, and then preferably sealing the first and second films together, typically in the area between the molds and thus between the bags.

[00110] Any suitable method for sealing the pouch and/or its individual compartments can be used. Non-limiting examples of such methods include heat sealing, solvent sealing, solvent sealing or wet sealing, and combinations thereof. Typically, only the area that is to form a seal is treated with heat or solvent. Heat or solvent can be applied in any manner, typically to the closure material and typically only to the areas that are to form a seal. If wet or solvent sealing or welding is used, combined application of heat may be preferable. Preferred wet or solvent sealing/welding methods involve selectively applying a solvent to the area between molds or to the sealing material, such as by spraying or printing on these areas and then applying pressure to these areas to form a seal. For example, compaction rollers and belts can be used as described above (optionally also providing heat).

[00111] The formed bags can then be cut with a cutting device. Cutting can be done in any suitable manner. It may be preferable that the cutting is also carried out continuously, preferably at a constant speed and preferably in a horizontal position. Said cutting device may be, for example, a sharp object, a hot object or a laser, wherein in the latter cases said hot object or laser “burns” through the film/sealing area.

[00112] The various compartments of multi-compartment pouches may be constructed together in a side-by-side style, wherein the resulting jointly joined pouches may or may not be separated by cutting. Alternatively, said compartments can be manufactured separately.

[00113] In embodiments of the invention, bags can be manufactured in accordance with a method including the following steps: a) forming a first compartment (as described above); b) forming a recess within or throughout the closed compartment formed in step (a) to create a second molded compartment superimposed over the first compartment; c) filling and sealing the second compartments with a third film; d) sealing the first, second and third films; and e) cutting the films to form a multi-compartment pouch. Said recess formed in step (b) can be achieved by applying a vacuum to the compartment produced in step (a).

[00114] In embodiments of the invention, the second and/or third compartment(s) may be manufactured in a separate step and then combined with the first compartment, as described in US Patent Application Publication No. 2014/345064 A1 or US Patent Application Publication No. 2009/312220 A1.

[00115] In embodiments of the invention, the bags may be manufactured in accordance with a method comprising the following steps: a) forming a first compartment, optionally using heat and/or vacuum, using a first film on a first molding machine; b) filling the first compartment with the first composition; c) on a second forming machine, deforming the second film, optionally using heat and vacuum, to produce a second and optionally third molded compartment; d) filling the second and, optionally, third compartments; e) sealing the second and optionally third compartments using a third film; f) placing sealed second and optionally third compartments on the first compartment; g) sealing the first, second and optionally third compartments; and h) cutting the films to produce a multi-compartment pouch.

[00116] The first and second molding machines may be selected based on their suitability for performing the above process. In embodiments of the invention, said first molding machine is preferably a horizontal molding machine, and said second molding machine is preferably a rotating drum molding machine, preferably located above the first molding machine.

[00117] It should be understood that with the use of appropriate dispensing stations, it is possible to produce multi-compartment pouches containing a number of different or distinctive compositions and/or different or distinctive liquid, gel or paste compositions.

[00118] In embodiments of the invention, the film and/or pouch is sprayed or sprinkled with a suitable material, such as an active agent, lubricant, aversive agent, or mixtures thereof. In embodiments of the invention, said film and/or package is printed, for example, using ink and/or an active agent.

Package Contents

[00119] These products (eg, in the form of bags) may contain various compositions, for example, home care compositions. A multi-compartment pouch may contain the same or different compositions in each individual compartment. This composition is close to a water-soluble film. The composition may be located less than about 10 cm, less than about 5 cm, or less than about 1 cm from the film. Typically, said composition is adjacent to or in contact with said film. Said film may be in the form of a package or compartment containing the composition.

[00120] This feature of this disclosure can be used to keep compositions containing incompatible ingredients (eg, bleach and enzymes) physically separated from each other. It is believed that such separation may extend the service life and/or reduce the physical instability of such ingredients. Additionally or alternatively, such separation may provide aesthetic benefits, as described in US Pat. No. 8,835,372.

[00121] A fabric or home care composition includes fabric, hard surface, air, car, dishwashing, fabric conditioning and softening agents, detergents, additive and/or agent wash and rinse care products, cleaning and/or hard surface treatment products and other types of cleaning products for consumer or institutional use. Compositions not related to home care are intended for other purposes.

[00122] Non-limiting examples of suitable compositions (e.g., home care compositions) include liquid detergent compositions for mild and harsh environments, hard surface cleaning compositions, detergent gels typically used for laundry, bleaches and laundry additives, enhancer compositions fabrics (such as fabric softeners), shampoos, body washes and other personal care products. Compositions for use in these packages may be in the form of a liquid, solid or powder. Liquid compositions may contain solid matter. The solids may include powder or agglomerates such as microcapsules, beads, noodles, one or more pearlescent beads, or mixtures thereof. Such a solid element may provide technical benefit in washing or as a pre-treatment, delayed or sequential release component; additionally or alternatively, it can provide an aesthetic effect.

[00123] Non-limiting examples of other suitable compositions (e.g., non-home care compositions) include agricultural compositions, automotive compositions, aviation compositions, food and nutritional compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office and recreational and park compositions, compositions for pets, water purification compositions, including cleaning and detergent compositions useful for any such application, excluding fabric and home care compositions. Compositions for use in these packages may be in the form of a liquid, solid or powder. Liquid compositions may contain solid matter. The solids may include powder or agglomerates such as microcapsules, beads, noodles, one or more pearlescent beads, or mixtures thereof. Such a solid element may provide technical benefit in washing or as a pre-treatment, delayed or sequential release component; additionally or alternatively, it can provide an aesthetic effect.

[00124] The compositions encapsulated in the films described herein can have any suitable viscosity depending on factors such as the ingredients of the composition and the purpose of the composition. In one embodiment, the composition has a high shear viscosity at a shear rate of 20 s ^-1 and a temperature of 20 °C, from 100 to 3000 cP, in an alternative embodiment from 300 to 2000 cP, in an alternative embodiment from 500 to 1000 cP and low shear viscosity at a shear rate of 1 s ^-1 and a temperature of 20°C from 500 to 100 000 cP, alternatively from 1000 to 10 000 cP, alternatively from 1300 to 5000 cP. Methods for measuring viscosity are known in the art. In accordance with this description, measurements of shear viscosity of compositions other than PVA polymer solutions are carried out using a rotational rheometer, for example, TA instruments AR550. This instrument consists of a 40 mm 2(or 1(1) cone with a gap of about 50-60 µm for isotropic liquids or a 40 mm flat steel plate with a gap of 1000 µm for liquids containing particles. The measurement is carried out using a flow technique that includes conditioning stage, peak hold and continuous ramp stage. Specified conditioning stage includes setting the measurement temperature to 20 °C, pre-shift for 10 seconds at a shear rate of 10 s ^-1 and equilibration for 60 seconds at the selected temperature. Specified peak hold includes application of speed 0.05 s ^-1 shear at 20°C for 3 minutes, sampling every 10 seconds.This continuous ramp step is performed at shear rates from 0.1 to 1200 s ^-1 for 3 minutes at 20°C to obtain full flow profile.

[00125] As described above, the composition may be a non-home care composition. For example, said non-home care composition may be selected from agricultural compositions, automotive compositions, aviation compositions, food and nutritional compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office compositions and compositions for recreational areas and parks, compositions for pets, compositions for water purification, including cleaning and detergent compositions suitable for any such application, excluding compositions for fabric care and home care.

[00126] In one type of embodiment, the composition may contain an agrochemical, for example, one or more insecticides, fungicides, herbicides, pesticides, miticides, repellents, attractants, defoliants, plant growth regulators, fertilizers, bactericides, micronutrients and trace elements. Suitable agrochemicals and secondary agents are described in US Pat. Nos. 6,204,223 and 4,681,228 and EP 0989803 A1. For example, suitable herbicides include salts of paraquat (for example, paraquat dichloride or paraquat bis(methyl sulfate), diquat salts (for example, diquat dibromide or diquat alginate) and glyphosate or a salt or ester thereof (for example, isopropylammonium glyphosate, sesquinate glyphosate or glyphosate trimesium , also known as sulfosate.) Incompatible pairs of plant protection chemicals can be used in separate chambers, for example, as described in US Pat. No. 5,558,228. Incompatible pairs of plant protection chemicals that can be used include, for example, bensulfuron-methyl and molinate; 2,4-D and thifensulfuron-methyl; 2,4-D and methyl 2-[[[[N-4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino] carbonyl]amino]sulfonyl]benzoate; 2,4-D and metsulfuron-methyl; maneb or mancozeb and benomyl; glyphosate and metsulfuron-methyl; tralomethrine and any organophosphate such as monocrotophos or dimethoate; bromoxynyl and N-[[4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-3-(ethylsulfonyl)-2-pyridine sulfonamide; bromoxynyl and methyl 2-[[[[(4-methyl-6-methoxy)-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate; bromoxynyl and methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]sulfonyl]benzoate. In another related embodiment of the invention, said composition may contain one or more seeds, optionally together with soil, and additionally, optionally, together with one or more additional components selected from mulch, sand, peat moss, water jelly crystals and fertilizers, for example including types of embodiments of the invention , described in US patent No. 8333033.

[00127] In another type of embodiment, the composition is a water treatment agent. Such agents include harsh oxidizing chemicals, for example, as described in US Patent Application Publication No. 2014/0110301 and US Patent No. 8,728,593. For example, disinfectants may include hypochlorite salts such as sodium hypochlorite, calcium hypochlorite and lithium hypochlorite; chlorinated isocyanurates such as dichloroisocyanuric acid (also called "dichlor" or dichloro-s-triazinetrione, 1,3-dichloro-1,3,5-triazinan-2,4,6-trione) and trichloroisocyanuric acid (also called " trichlor" or 1,3-trichloro-1,3,5-triazinan-2,4,6-trione). Salts and hydrates of said disinfectant compounds are also provided. For example, dichloroisocyanuric acid may be present as sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, among others. Brominated disinfectants may also be suitable for use in unit dose packaging, such as 1,3-dibromo-5,5-dimethylhydantoin (DBDMH), 2,2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyanoacetic acid amide, 1- bromo-3-chloro-5,5-dimethylhydantoin; and 2-bromo-2-nitro-1,3-propanediol, among others. Said oxidizing agent may be an agent described in US Patent No. 7,476,325, for example potassium hydroperoxymonosulfate. Said composition may be a pH adjusting chemical, for example as described in US Patent Application Publication No. 2008/0185347, and may contain, for example , an acidic component and an alkaline component such that said composition becomes effervescent upon contact with water and regulates the pH of the water. Suitable ingredients include sodium hydrogen carbonate, sodium hydrogen sulfate, potassium hydroxide, sulfamic acid, organic carboxylic acids, sulfonic acids and potassium dihydrogen phosphate. The buffer mixture may include, for example, boric acid, sodium carbonate, glycolic acid and oxon monopersulfate.

[00128] The water treatment agent may be or may contain a flocculant, for example, as described in US Patent Application Publication No. 2014/0124454. Said flocculant may include a polymeric flocculant such as polyacrylamide, a polyacrylamide copolymer such as acrylamide copolymers of diallyldimethylammonium chloride (DADMAC), dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEM), 3-methylamidepropyltrimethylammonium chloride (MAPTAC) or acrylic acid; cationic polyacrylamide; anionic polyacrylamide; neutral polyacrylamide; polyamine; polyvinylamine; polyethylenimine; polydimethyldiallylammonium chloride; polyoxyethylene; polyvinyl alcohol; polyvinylpyrrolidone; polyacrylic acid; polyphosphoric acid; polystyrene sulfonic acid; or any combination thereof. Said flocculant may be selected from chitosan acetate, chitosan lactate, chitosan adipate, chitosan glutamate, chitosan succinate, chitosan malate, chitosan citrate, chitosan fumarate, chitosan hydrochloride and combinations thereof. Said water treatment composition may contain a phosphate removing agent, for example one or more selected from a zirconium compound, a rare earth lanthanide salt, an aluminum compound, an iron compound or any combination thereof.

[00129] The composition may be a descaling composition such as citric or maleic acid or a sulfate salt thereof, or any mixture thereof, for example as described in US Patent Application No. 2006/0172910.

[00130] Various other types of compositions are contemplated for the pouch applications described herein, including particles, for example, down feathers, for example, as described in US RE29059 E; superabsorbent polymers, for example, as described in US Patent Application Publications No. 2004/0144682 and 2006/0173430; pigments and dyes, for example, as described in US Pat. No. 3,580,390 and US Patent Application Publication No. 2011/0054111; solder flux (eg, alkali metal fluoroaluminates, alkali metal fluorosilicates and alkali metal fluorozincates), for example, as described in US Pat. No. 8,163,104; food products (eg, coffee powder or dried soup) as described in US Patent Application Publication No. 2007/0003719; and wound dressings, for example, as described in US Pat. No. 4,466,431.

[00131] In packages containing laundry compositions, laundry additives and/or fabric enhancers, said compositions may contain one or more of the following non-limiting list of ingredients: fabric care enhancer; detergent enzyme; settling agent; rheology modifier; modifier; bleach; whitening agent; bleach precursor; whitening enhancer; bleaching catalyst; fragrances and/or microcapsules of fragrances (see, for example, US patent No. 5137646); zeolite loaded with fragrance; a combination of fragrances encapsulated in starch; polyglycerol esters; whitening agent; pearlescent agent; enzyme stabilization systems; absorbers, including fixatives for anionic dyes, complexing agents for anionic surfactants and mixtures thereof; optical brighteners or fluorescence enhancers; a polymer including, but not limited to, a dirt-repellent polymer and/or a dirt-suspending polymer; dispersants; defoamers; non-aqueous solvent; fatty acid; suds suppressants, for example, silicone suds suppressants (see: US Patent Application Publication No. 2003/0060390 A1, par. 65-77); cationic starches (see: US 2004/0204337 A1 and US 2007/0219111 A1); scale dispersants (see: US 2003/0126282 A1, par. 89-90); basic dyes; tint dyes (see: US 2014/0162929 A1); dyes; opacifying agent; antioxidant; hydrotropes such as toluenesulfonates, cumenesulfonates and naphthalene sulfonates; colored splashes; colored granules, spheres or extrudates; clay-based emollients; antibacterial agents. Any one or more of these ingredients is further described in US Patent Application Publication No. US 2010/305020 A1, US Patent Application Publication No. 2003/0139312 A1, and US Patent Application Publication No. 2011/0023240 A1. Additionally or alternatively, these compositions may contain surfactants, quaternary ammonium compounds, and/or solvent systems. Quaternary ammonium compounds may be present in fabric enhancer compositions such as fabric softeners and contain quaternary ammonium cations, which are positively charged polyatomic ions of the NR structure₄ ⁺where R represents an alkyl group or an aryl group.

Surfactants

[00132] Detergent compositions may contain from about 1% to 80% by weight of surfactant. A surfactant is particularly preferred as a component of the first composition. Preferably, the first composition contains from about 5% to 50% by weight of surfactant. The second and third compositions may contain surfactant in an amount of from 0.1 to 99.9%.

[00133] The detergent surfactants used may be of anionic, nonionic, zwitterionic, ampholytic, or cationic type, or may contain compatible mixtures of these types. More preferably, said surfactants are selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof. Preferably, said compositions contain substantially no betaine surfactants. The detergent surfactants used herein are described in US Pat. No. 3,664,961; 3919678; 4222905; and 4239659. Anionic and nonionic surfactants are preferred.

[00134] Suitable anionic surfactants may be of several different types themselves. For example, water-soluble salts of higher fatty acids, ie "soaps", are useful anionic surfactants in the compositions of this invention. These include alkali metal soaps such as sodium, potassium, ammonium and alkyl ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soaps can be produced by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly suitable are the sodium and potassium salts of mixtures of fatty acids obtained from coconut oil and animal fat, that is, sodium or potassium animal and coconut soap.

[00135] Additional non-soap anionic surfactants suitable for use herein include water-soluble salts, preferably alkali metal salts and ammonium salts of organic sulfur-containing products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms, and a sulfonic acid or sulfuric acid ester group. (The term "alkyl" includes the alkyl moiety of acyl groups.) Examples of this group of synthetic surfactants include: a) sodium, potassium and ammonium alkyl sulfates, especially those prepared by sulfation of higher alcohols (C ₈ -C ₁₈ ), such as those obtained by reduction glycerides of animal or coconut oil; b) sodium, potassium and ammonium alkyl polyethoxylate sulfates, especially those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and where the polyethoxylate chain contains from 1 to 15, preferably from 1 to 6 ethoxylate residues; and c) sodium and potassium alkylbenzenesulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms in a straight or branched chain configuration, for example, of the type described in US Pat. Nos. 2,220,099 and 2,477,383. Particularly valuable are straight chain linear alkylbenzenesulfonates, wherein the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated C ₁₁ -C ₁₃ LAS.

[00136] Preferred nonionic surfactants are those having the formula R ₁ (OC ₂ H ₄ ) _n OH, where R ₁ is a C ₁₀ -C ₁₆ alkyl group or a C ₈ -C ₁₂ alkylphenyl group, and n is from 3 to about 80. Particularly preferred are condensation products of C ₁₂ -C ₁₅ alcohols with about 5 to about 20 moles of ethylene oxide per mole of alcohol, for example, a C ₁₂ -C ₁₃ alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol .

[00137] Solvent System

[00138] The solvent system in detergent compositions may be a solvent system containing only water or mixtures of organic solvents with water. Preferred organic solvents include 1,2-propanediol, ethanol, glycerin, dipropylene glycol, methylpropanediol, and mixtures thereof. Other lower alcohols, low molecular weight polyols, C ₁ -C ₄ alkanolamines such as monoethanolamine and triethanolamine can also be used. As used herein, the term "low molecular weight polyol" means a molecule with more than two hydroxyl groups having a molecular weight in the range of 50 g/mol to 1000 g/mol, 50 g/mol to 800 g/mol, or 50 g/mol to 600 g/mol. Solvent systems may not be present, for example, in the anhydrous solid detergent embodiments herein, but are typically present at levels ranging from about 0.1% to about 98%, preferably at least about 1% up to about 50%, more often from about 5% to about 25% by weight. Typically, these detergent compositions, especially when in liquid form, contain less than 50% water, preferably from about 0.1% to about 20% water, or more preferably from about 0.5% to about 15% or from about 3% to about 12% water by weight of the composition. Typically, these detergent compositions, especially when in liquid form, contain from about 5% to about 20% or from about 10% to about 15% glycerol by weight of the composition. Typically, these detergent compositions, especially when in liquid form, contain less than 30% propylene glycol, for example, from about 0.1% to 25% propylene glycol, from 0.5% to 20% propylene glycol, or from 5% to 15% propylene glycol by weight of the composition.

[00139] The detergent composition herein can generally be prepared by mixing the ingredients together. If pearlescent material is used, it should be added at a later stage of mixing. If a rheology modifier is used, it is preferable to first form a pre-mix in which the rheology modifier is dispersed in a portion of the water and, optionally, other ingredients ultimately used for inclusion in the detergent compositions. This pre-mixture is formed in such a way that it forms a structured liquid. The surfactant(s) and basic laundry aids, as well as water and any additional detergent composition additives to be used, can then be added to this structured premix while the premix is being stirred.

[00140] The pH of said cleaning composition may be from about 2 to about 12, from about 4 to about 12, from about 5.5 to about 9.5, from about 6 to about 8.5, or from about 6.5 to about 8.2. Laundry detergent compositions may have a pH of from about 6 to about 10, from about 6.5 to about 8.5, from about 7 to about 7.5, or from about 8 to about 10. Automatic dishwashing compositions may have a pH from about 8 to about 12. Laundry detergent additive compositions may have a pH from about 4 to about 8. Fabric enhancers may have a pH from about 2 or 4 to about 8, from about 2 to about 4, from about 2.5 to about 3.5 or from about 2.7 to about 3.3.

[00141] Detergent pH is defined as the pH of a 10% (w/v) aqueous detergent solution at 20°C (2°C; for solids and powder detergent, it is defined as pH 1% (w/v). ) aqueous detergent solution at 20 °C (2 °C. Any meter capable of measuring pH with an accuracy of (0.01 pH units) is suitable. Orion meters (Thermo Scientific, Clintinpark -Keppekouter, Ninovesteenweg 198, 9320 Erembodegem -Aalst, Belgium ) or equivalent are acceptable instruments. The pH meter should be equipped with a suitable glass calomel or silver chloride reference electrode. An example includes the Mettler DB 115. The electrode should be stored in the electrolyte solution recommended by the manufacturer.

[00142] A 10% aqueous detergent solution is prepared according to the following procedure. A sample weighing 10 (0.05 grams) is weighed using a balance capable of measuring to within (0.02 grams). The sample is transferred to a 100 ml volumetric flask, diluted to volume with purified water (deionized and/or distilled water is suitable if conductivity water <5 µS/cm) and mix thoroughly. About 50 ml of the resulting solution is poured into a beaker, the temperature is adjusted to 20 °C (2 °C and the pH is measured according to the pH meter manufacturer's standard procedure (it is also essential to follow the manufacturer's instructions on setting up and calibrating a pH meter).

[00143] For solid and powder detergents, a 1% aqueous detergent solution is prepared according to the following procedure. A sample weighing 10 (0.05 grams) is weighed using a balance capable of measuring to within (0.02 grams). The sample is transferred to a 1000 ml volumetric flask, diluted to volume with purified water (deionized and/or distilled water is suitable if conductivity water <5 µS/cm) and mix thoroughly. About 50 ml of the resulting solution is poured into a beaker, the temperature is adjusted to 20 °C (2 °C and the pH is measured according to the pH meter manufacturer's standard procedure (it is also essential to follow the manufacturer's instructions on setting up and calibrating a pH meter).

[00144] It is known in the art that when forming a pouch containing a composition therein, some components of the film (e.g., plasticizers) may in some cases migrate from the film into the enclosed composition and, additionally or alternatively, some components of the enclosed composition (eg plasticizer, solvent) can migrate into the film. Without being limited by theory, it is believed that this migration of components into/out of the film may result in changes in the amount of swelling of the film.

[00145] Bleaches

[00146] Inorganic and organic bleaches are suitable cleaning actives for use herein. Inorganic bleaches include perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts. Inorganic perhydrate salts are generally alkali metal salts. The inorganic perhydrate salt may be present as a crystalline solid without further protection. Alternatively, said salt may be coated, as is known in the art.

[00147] Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates for use in the detergent composition described herein. Said percarbonate is most preferably introduced into products in a coated and/or encapsulated form to provide stability within the product. A suitable coating material that provides stability within the product includes a mixed salt of a water-soluble sulfate and an alkali metal carbonate. Such coatings, together with coating methods, have previously been described in GB 1,466,799 and US Pat. No. 3,975,280; 4075116; and 5340496, each of which is incorporated herein by reference in its entirety. The weight ratio of the mixed salt of the coating material to the percarbonate is in the range from 1:99 to 1:9 and preferably from 1:49 to 1:19. Preferably, said mixed salt is sodium sulfate and sodium carbonate, which has the general formula Na ₂ SO ₄ ⋅n⋅Na ₂ CO ₃ where n is from 0.1 to 3, preferably from 0.3 to 1.0 and , more preferably from 0.2 to 0.5. Other suitable coating material to provide stability within the product includes sodium silicate with a SiO ₂ :Na ₂ O ratio of 1.8:1 to 3.0:1, preferably 1.8:1 to 2.4:1, and /or sodium metasilicate, preferably applied at a level of 2% to 10% (typically 3% to 5%) SiO ₂ by weight of an inorganic perhydrate salt such as potassium peroxymonopersulfate. Other coatings containing magnesium silicate, silicate and borate salts, silicate and boric acids, waxes, oils and fatty soaps can also be successfully used.

[00148] Organic bleaches may contain organic peroxyacids, including diacyl and tetraacyl peroxides, especially diperoxydecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Dibenzoyl peroxide is the preferred organic peroxyacid herein. The diacyl peroxide, especially dibenzoyl peroxide, may preferably be present in the form of particles having a weight average diameter of from about 0.1 to about 100 microns, preferably from about 0.5 to about 30 microns, more preferably from about 1 to about 10 microns. Preferably at least about 25% to 100%, more preferably at least about 50%, even more preferably at least about 75%, most preferably at least about 90% of the particles are of size less than 10 µm, preferably less than 6 µm.

[00149] Other organic brighteners include peroxy acids, specific examples of which are alkyl peroxy acids and aryl peroxy acids. Preferred representatives are: (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) aliphatic or substituted aliphatic peroxyacids such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamideperoxycaproic acid and N-nonenylamide persuccinates; and (c) aliphatic and arylaliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassilic acid, diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-N-dioic acid, N, N-terephthaloyldi(6-aminopercaproic acid).

[00150] Bleaching activators may contain organic peracid precursors that enhance the bleaching effect during cleaning at temperatures of 60°C and below. Bleaching activators suitable for use herein include compounds which, under perhydrolysis conditions, yield aliphatic peroxycarboxylic acids containing preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and/or optionally substituted perbenzoic acid. Suitable substances bear O-acyl and/or N-acyl groups of the indicated number of carbon atoms and/or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular acylated phthalic anhydride polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, as well as triethylacetyl citrate (TEAC).

[00151] Bleaching catalysts preferred for use in the detergent composition described herein include manganese triazacyclononane and related complexes (US Pat. Nos. 4,246,612 and 5,227,084); Co, Cu, Mn and Fe-bipyridylamine and related complexes (US Patent No. 5114611); and cobalt(III) pentamin acetate and related complexes (US Pat. No. 4,810,410). A complete description of bleach catalysts suitable for use herein can be found in US Pat. No. 6,599,871, incorporated herein by reference.

[00152] Dishwashing detergents

[00153] A preferred surfactant for use in automatic dishwashing detergents is a low-sudsing surfactant alone or in combination with other components (eg, suds suppressants). Preferred for use herein are low and high cloud point nonionic surfactants and mixtures thereof, including nonionic alkoxylated surfactants (especially ethoxylates derived from primary C ₆ -C ₁₈ alcohols), ethoxylated-propoxylated alcohols ( e.g. Poly-Tergent(SLF18 from Olin Corporation), epoxy-terminated poly(oxyalkylated)alcohols (e.g. Poly-Tergent(SLF18B from Olin Corporation - see WO-A-94/22800), surfactants based ether-terminated poly(oxyalkylated)alcohol and block polyoxyethylene-polyoxypropylene polymer compounds such as PLURONIC®, REVERSED PLURONIC (and TETRONIC (from BASF-Wyandotte Corp., Wyandotte, Michigan; amphoteric surfactants such as C ₁₂ -C ₂₀ alkyl amine oxides (preferred amine oxides for use herein include lauryl dimethyl amine oxide and hexadecyl dimethyl amine oxide) and alkyl amphocarboxyl surfactants such as Miranol(C2M; and zwitterionic surfactants such as betaines and sultaines; and mixtures thereof. Surfactants suitable for use herein are described, for example, in US Patent Nos. 3,929,687 and 4,259,217, European Patent Application Publication EP 0414549 A1, and PCT Patent Application Publications WO 1994/007974 A1 and WO 1994/007986 A1. Surfactants may be present in the detergent at a level of from about 0.2% to about 30% by weight, more preferably from about 0.5% to about 10% by weight, most preferably from about 1% to about 5% by weight % by weight of the cleaning composition.

[00154] Other Compositions and Additives

[00155] Modifiers suitable for use in the detergent composition described herein include water-soluble modifiers including citrates, carbonates, silicates and polyphosphates, for example, sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate and sodium and potassium tripolyphosphate mixed salts.

[00156] Enzymes suitable for use in the detergent composition described herein include bacterial and fungal cellulases including CAREZYME and CELLUZYME (Novo Nordisk A/S); peroxidases; lipases including AMANO-P (Amano Pharmaceutical Co.), M1 LIPASE and LIPOMAX (Gist-Brocades) and LIPOLASE and LIPOLASE ULTRA (Novo); cutinases; proteases including ESPERASE, ALCALASE, DURAZYM and SAVINASE (Novo) and MAXATASE, MAXACAL, PROPERASE and MAXAPEM (Gist-Brocades); (and (amylases, including PURAFECT OX AM (Genencor) and TERMAMYL, BAN, FUNGAMYL, DURAMYL and NATALASE (Novo); pectinases; and mixtures thereof. Enzymes can be added to this composition in the form of granules, granules or cogranulates at levels such as typically ranging from about 0.0001% to about 2% pure enzyme by weight of the cleaning composition.

[00157] Soap suppressants suitable for use in the detergent composition described herein include nonionic surfactants having a low cloud point. "Cloud point", as used herein, is a well-known property of non-ionic surfactants, which results from the surfactant becoming less soluble with increasing temperature, the temperature at which the second phase appears is called the "temperature cloudiness." As used herein, a "low cloud point" nonionic surfactant is defined as an ingredient of a nonionic surfactant system having a cloud point of less than 30°C, preferably less than about 20°C, and even more preferably, less than about 10°C, and most preferably less than about 7.5°C. Low cloud point nonionic surfactants may include nonionic alkoxylated surfactants, especially primary alcohol-derived ethoxylates and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block copolymers. In addition, such low cloud point nonionic surfactants may include, for example, ethoxylated-propoxylated alcohol (e.g. BASF POLY-TERGENT SLF18) and epoxy-terminated poly(oxyalkylated) alcohols (e.g. BASF POLY-TERGENT series of nonionic surfactants TERGENT SLF18B, as described, for example, in US-A-5576281).

[00158] Other suitable components for use in the cleaning composition described herein include cleaning polymers having anti-deposition, dirt release or other cleaning properties. Anti-deposition polymers for use herein include acrylic acid containing polymers such as SOKALAN PA30, PA20, PA15, PA10 and SOKALAN CP10 (BASF GmbH), ACUSOL 45N, 480N, 460N (Rohm and Haas), acrylic acid copolymers /maleic acid, such as SOKALAN CP5 and acrylic/methacrylic copolymers. Other suitable polymers include amine-based polymers such as alkoxylated polyalkylene imines (eg PEI600 EO20 and/or ethoxysulfated hexamethylenediamine dimethyl quaternary compounds). Stain-resistant polymers for use herein include alkyl and hydroxyalkylcelluloses (US-A-4000093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, as well as nonionic and anionic polymers based on ethylene glycol terephthalate ethers, propylene glycol and mixtures thereof.

[00159] Heavy metal sequestrants and crystal growth inhibitors are also suitable for use in these detergents, for example diethylenetriamine penta(methylenephosphonate), ethylenediamine tetra(methylenephosphonate), hexamethylenediamine tetra(methylenephosphonate), ethylene diphosphonate, hydroxyethylene-1,1-diphosphonate, nitrilotriacetate, ethylenediamine tetraacetate, ethylenediamine-N, N'-disuccinate in their salt and free acid forms.

[00160] Also suitable for use in the cleaning composition described herein is a corrosion inhibitor, for example, organic silver plating agents (especially waxes such as WINOG 70, available from Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds ( for example benzotriazole and benzimidazole - see GB-A-1137741) and Mn(II) compounds, especially Mn(II) salts of organic ligands.

[00161] Other suitable components for use in the detergent composition described herein include enzyme stabilizers, for example, calcium ion, boric acid and propylene glycol.

[00162] Other suitable components for use in the detergent composition described herein include humectants, for example, as described in US Patent Application Publication No. 2015/0329807.

[00163] Suitable rinse aids are known in the art. Commercial dishwashing rinses are typically mixtures of polyethylene/polypropylene glycol ethers of low-foaming fatty alcohols, solubilizers (eg, cumene sulfonate), organic acids (eg, citric acid), and solvents (eg, ethanol). The function of such rinses is to influence the surface tension of water so that it can flow off the rinsed surfaces in the form of a thin adhesive film, so that no water drops, streaks or films remain after the subsequent drying process. European Patent 0197434 B1 describes rinses that contain mixed ethers as surfactants. Also provided are rinse additives, such as fabric softeners and the like, which are suitable for encapsulation in a film as described herein.

[00164] Suitable liquid laundry detergents (LLDs) for testing the compatibility of the water-soluble films described herein with liquid laundry detergents are described in the tables below:

ZhMS One Wt.% Monoethanolamine 8-9% Dodecylbenzenesulfonic acid 22-26% Oleic acid 18-21% Lauryl Alcohol Ethoxylate 22-26% Propylene glycol 8-11% Diethylene glycol 8-11% Water 4-7%

ZhMS Two Wt.% Monoethanolamine 8-9% Dodecylbenzenesulfonic acid 22-26% Oleic acid 18-21% Lauryl Alcohol Ethoxylate 22-26% Propylene glycol 5-7% Diethylene glycol 5-7% Glycerol 5-7% Water 4-8%

[00165] Methods of application

[00166] The films and articles described herein, as well as the compositions contained therein, can be used to treat a substrate, such as fabric or a hard surface, for example, by contacting the substrate with the film, article and/or composition contained in them. Said contacting may be carried out manually or in an automatic machine, for example an automatic washing machine (top or front loading) or an automatic dishwasher. The contacting step may be carried out in the presence of water, which may have a temperature of up to about 80 °C, up to about 60 °C, up to about 40 °C, up to about 30 °C, up to about 20 °C, up to up to about 15°C, up to about 10°C or up to about 5°C. As noted above, the films and articles thereof of this invention are particularly suitable for dissolution in cold water and therefore provide benefits in cold water washes (e.g., from about 1°C to about 30°C or from about 5°C to about 20°C C). The contacting step may be followed by a multiple rinse cycle or just one rinse cycle; Since said film has good dissolution properties, less water is required to dissolve the film and/or release the contents contained therein.

Residue Dilution Chamber Test

[00167] A water-soluble film characterized or tested for the presence of undissolved residue in accordance with the dissolution chamber (DC) test is analyzed as follows using the following materials: 1. Beaker (4000 ml); 2. Stainless Steel Washers (3.5" (88.9mm) OD, 1.875" (47.6mm) ID, 0.125" (3.18mm) Thickness); 3. SBR gaskets (3.375 in. (85.7 mm) OD, 1.91 in. (48.5 mm) ID, 0.125 in. (3.18 mm) thickness); 4. Stainless steel screens (3.0 inch (76.2 mm) OD, 200x200 mesh, 0.0021 inch (0.053 mm) wire OD, 304SS stainless steel mesh); 5. Thermometer (0°C to 100°C, accuracy+/-1°C); 6. Die-cutting die (diameter 1.5 inches (38.1 mm)); 7. Timer (accurate to the second); 8. Reverse osmosis (RO) water; 9. Clamps (size No. 5 or similar); 10. Aluminum trays (2.0 inch (50.8 mm) outer diameter); and 11. Sonicator.

[00168] For each film to be tested, three test specimens are cut from the selected test film having a thickness of 76 μm using a punching die. When cutting from a continuous film web, these samples must be cut from sections of the web that are evenly spaced along the transverse direction of the web (i.e., perpendicular to the machine direction). Each test sample is then analyzed using the following procedure: 1. Weigh the film sample and monitor the sample throughout the test. Record the initial mass of the film (F _o ). 2. Weigh a set of two sonicated, clean, dry sieves for each sample and monitor them throughout the test. Record the initial masses of the sieves (together S _o for the total mass of the two sieves). 3. Assemble the sample dissolution chamber by placing the film sample evenly between the center of the two sieves, followed by applying two rubber gaskets (one gasket on each side between the sieve and the washer), and then applying the two washers. 4. Secure the dissolution chamber assembly with four clamps evenly spaced around the washers, with the handles bent away from the sieve.5. Fill a beaker with 1500 ml of RO water at laboratory room temperature (72+/- 3°F, 22+/- 2°C) and record the room temperature. 6. Set the timer for the prescribed dive time of 5 minutes.7. Place the dissolution chamber assembly in the glass and immediately start the timer by placing the dissolution chamber assembly at an angle of approximately 45 degrees to the surface of the water. This entry angle helps remove air bubbles from the chamber. The dissolution chamber assembly rests on the bottom of the beaker such that the film of the test sample is horizontal about 10 mm from the bottom. The four folded-back clamps of the dissolution chamber assembly allow a gap of approximately 10 mm to be maintained between the film and the bottom of the beaker, but any other equivalent means of support may be used. 8. After the prescribed immersion time of 5 minutes, slowly remove the dissolution chamber assembly from the beaker at an angle of approximately 45 degrees. 9. Hold the dissolution chamber assembly horizontally over the aluminum pan to catch drips from the screens, and carefully remove the fastening clips, washers and gaskets. Do not disassemble jammed sieves. 10. Place the clamped sieves (i.e. sieve/residual undissolved film/sieve) on an aluminum tray and in the oven at 100°C for 30 minutes to dry. 11. Weigh the dried set of clamped sieves containing all the residual undissolved film in it. Measure and add to this mass of dried screens any drops of dried film captured and removed from the tray (e.g. by scraping) when the dissolution chamber assembly was first removed from the beaker and during drying. Record the final mass of the clamped sieves (collectively S _f , including the dried film droplets). 12. Calculate the % of residue (“CR residue”) remaining for the film sample: % CR residue = 100*((S _f - S _o )/F _o ). 13. Clean the jammed screens by soaking them in a glass of RO water for about 20 minutes. Then separate them and do a final rinse in the sonicator (on and filled with RO water) for at least 5 minutes or until the remains will not disappear in sith.

[00169] Suitable behavior of water-soluble films according to this description is characterized by values of the residual CR of about 35 wt.% or less, about 40 wt.% or less, about 45 wt.% or less, or about 48 wt.% or less as measured in the CR trial. In general, lower CR residue values are desirable to reduce the likelihood of residual film remaining on a laundered item after harsh wash conditions (eg, low water conditions (eg, overloading a washing machine) and cold wash water conditions). In various embodiments of the invention, said water-soluble film has a residual CR value of at least 1, 2, 5, 10, 12, 15, 25, 30 or 35 wt.% and/or up to about 15, 20, 30, 35 , 40, 45 or 48 wt.%; (e.g., from about 3 wt.% to about 48 wt.%, from about 5 wt.% to about 48 wt.%, from about 12 wt.% to about 48 wt.%, from about 25 wt.% to about 48 wt.%, from about 10 wt.% to about 45 wt.%, from about 20 wt.% to about 45 wt.%, from about 25 wt.% to about 40 wt.%, from about 30 wt.% up to 40% by weight, from about 3% by weight to about 40% by weight, or from about 3% by weight to about 35% by weight).

Dissolution and Decay Test (MSTM 205)

[00170] The film can be characterized or tested for dissolution time and disintegration time in accordance with the MonoSol 205 (MSTM 205) test method known in the art. See, for example, US Pat. No. 7,022,656.

Device and Materials

Glass 600 ml

Magnetic stirrer (Labline, model #1250 or similar)

Magnetic stir stick (5 cm)

Thermometer (0 to 100 °C (1 °C)

Template, stainless steel (3.8 cm x 3.2 cm)

Timer (0-300 seconds, accurate to the second)

35mm Polaroid slide (or similar)

35mm MonoSol slide holder (or equivalent)

Distilled water

[00171] For each film tested, three test specimens are cut from the film sample, which is a sample measuring 3.8 cm x 3.2 cm. When cutting from a film web, these samples must be cut from sections of the web that are evenly spaced along the transverse direction canvases. Each test sample is then analyzed using the following procedure.

[00172] Fix each sample on a separate 35 mm glass slide.

[00173] Fill a beaker with 500 ml distilled water. Measure the temperature of the water with a thermometer and, if necessary, heat or cool the water to maintain the temperature at 20 °C (about 68 °F).

[00174] Note the height of the water column. Place the magnetic stirrer on the base of the holder. Place the beaker on a magnetic stirrer, add a magnetic stir bar to the beaker, turn on the stirrer and adjust the stirring speed until a swirl is formed that is about one-fifth the height of the water column. Mark the depth of the swirl.

[00175] Secure the 35 mm slide into the alligator clip of the 35 mm slide holder so that the long end of the slide is parallel to the surface of the water. The holder depth adjuster 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 sides of the slide should be close to the side of the beaker, and the other should be positioned directly over the center of the stir stick so that the surface of the film is perpendicular to the flow of water.

[00176] In one motion, lower the fixed slide and clamp into the water and start the timer. Disintegration occurs when the film ruptures. When all visible film has been released from the slide, lift the slide out of the water while continuing to monitor the solution for undissolved film fragments. Dissolution occurs when all film fragments are no longer visible and the solution becomes clear.

[00177] The results should include the following: complete identification of the sample; individual and average decay and dissolution times; and the temperature of the water at which the samples were tested.

[00178] Film disintegration time (I) and film dissolution time (I) can be adjusted to a standard or reference film thickness using the exponential algorithms shown below in Equation 1 and Equation 2, respectively.

I _adjusted =I _measured x (reference thickness/measured thickness) ^1.93 [1]

S _correct =S _measured x (reference thickness/measured thickness) ^1.83 [2]

Tensile Strength Test and Elastic Modulus Test

[00179] A water-soluble film characterized or subject to testing for tensile strength in accordance with the tensile strength (TS) test and for modulus of elasticity (or tensile stress) in accordance with the modulus of elasticity (MOE) test is analyzed as follows. This procedure includes determination of tensile strength and determination of elastic modulus at 10% elongation in accordance with ASTM D 882 (Standard Test Method for Tensile Properties of Thin Plastic Sheets) or equivalent. An INSTRON Tensile Tester (Model 5544 Tensile Tester or equivalent) is used to collect film data. For each machine direction (MD) measurement (if applicable), a minimum of three test specimens are tested, each cut with reliable cutting tools to ensure dimensional stability and repeatability. Tests are carried out in a standard laboratory atmosphere at a temperature of 23 (2.0°C) and a relative humidity of 35 (5%). To determine the tensile strength or modulus of elasticity, samples of one sheet of film 1 inch (2.54 cm) wide and 76 microns thick are prepared. The sample is then transferred to the INSTRON Tensile Tester for testing, minimizing exposure to a 35% relative humidity environment.The tensile tester is prepared according to the manufacturer's instructions, equipped with a 500 N load cell and calibrated with the correct clamps and surfaces installed. (INSTRON Clamps with Model 2702-032 Rubber Coated 25mm Width Edge Clamps, or equivalent) Specimens are installed in a tensile tester and analyzed to determine the 100% elastic modulus (i.e. the stress required to achieve 100% elongation film) and tensile strength (i.e. the stress required to break the film).

[00180] In general, higher PR values are desirable because they correspond to stronger pouch seals when the film is the limiting or weakest element of the seal.

[00181] Generally, higher MOR values are desirable because they correspond to bags that have greater rigidity and are less likely to warp and stick to each other when loaded on top of each other during production or in the final consumer package.

[00182] Without being limited by theory, it is believed that the change in modulus of elasticity over time can be used to predict whether a package containing liquid laundry detergent will remain elastic over time or whether the package will lose elasticity and take on a loose and saggy appearance and sensation. In particular, without being limited by theory, it is believed that a film having a greater positive change in elastic modulus (modulus) over time will remain more taut for at least 12 weeks at ambient conditions or at temperatures up to 38°C and relative humidity up to 80% compared to films with a modulus of about 0, and will remain significantly more taut than films with a negative modulus.

Liquid release test

[00183] A water-soluble film and/or pouch characterized or subject to delayed solubility testing in accordance with the liquid release test is analyzed as follows using the following materials:

• 2 L glass and 1.2 L glass of deionized (DI) water

• Tested water-soluble package; the film has a thickness of 76 microns; the bag is pre-conditioned for two weeks at 38°C.

• Thermometer

• Wire cage

• Timer

[00184] Before performing the experiment, ensure that enough deionized water is available to repeat the experiment five times, and ensure that the wire cage and beaker are clean and dry.

[00185] A wire cage is a plastic-coated wire mesh cage (4" X 3.5" X 2.5" or about 10 cm x 9 cm x 6 cm) without sharp edges or the like. The wire gauge should be about 1.25 mm and have 0.5 inch (1.27 cm) square holes. An exemplary representation of cage 28 with test packets 30 is shown in FIG. 1.

[00186] To prepare for the test, carefully place the water-soluble pouch into the cage without scratching the pouch on the cage and leaving room for the pouch to move. Do not attach the bag tightly with the wire cage, but make sure that it is securely fastened and will not fall out of the cage. The orientation of the bag in the cage should be such that the natural buoyancy of the bag, if any, is allowed (ie, the side of the bag that will float on top should be facing up). If the package is symmetrical, the orientation of the package usually does not matter.

[00187] Then fill a 2 L beaker with 1200 milliliters of deionized water at 20 °C.

[00188] Then lower the wire cage with the enclosed bag into the water. Make sure the cage is 1 inch (2.54 cm) from the bottom of the glass. Be sure to completely submerge the bag on all sides. Make sure the cage is stable and does not move, and start the timer as soon as the bag is lowered into the water. The position of the cell in relation to the water in the beaker can be adjusted and maintained by any suitable means, for example, by using a clamp fixed above the beaker and a rod attached to the top of the cell. The clamp can hook onto the rod to secure the position of the cage, and the tension of the clamp can be released to lower the cage into the water. As an alternative to the clamp, other means of frictional engagement may be used, such as a clamp with a set screw, as shown in FIG. 2 (set screw not shown). In FIG. 2 shows a beaker 30 mounted on a stand 40 that holds a rod 50 for lowering a cage 10 (not shown) into the beaker 30, which rod 50 can be held in a fixed vertical position by the use of a cuff 60 having a set screw (not shown) that engages the rod 50, for example, by friction or by engagement with an opening (not shown) in the rod 50.

[00189] Release of liquid contents is defined as the first visual evidence that liquid is leaving the immersed package.

[00190] Use a timer to record when the liquid contents enter the surrounding water (release time) with a stop point of 45 seconds.

[00191] Each bag will be given a pass or fail rating. A "pass" rating is given if the dissolvable pouch holds liquid for 30 seconds or longer. A “fail” rating is given if the dissolvable pouch does not hold liquid for at least 30 seconds.

[00192] Repeat this process with new deionized water and a new water-soluble pack five times for each film tested.

[00193] For each type of film sample, test at least 15 bags unless otherwise specified.

Measurement in Compression Test

[00194] A water-soluble film and/or package characterized or to be tested for the ability of a water-soluble capsule to withstand a mechanical compressive force of at least 300 N as measured in a compression test is analyzed as follows using the following materials:

Instron model 5544 (or equivalent)

At least 15 water-soluble pouches or capsules to be tested have a film thickness of 76 µm; The bags are pre-conditioned for at least 24 hours at a temperature of 23±1°C and a relative humidity of 50±4%.

Zip bags

Two flat plates (top plate: max. load 10 kN T1223-1022/bottom plate: max. load 100 kN T489-74)

Load cell (static load ±2 kN, maximum spindle torque 20 Nm, bolt torque 25 Nm and weight 1.2 kg)

Marker

Hex key (6mm)

[00195] Inspect the bag for leaks and then place in a ziplock bag (about 57 microns thick on each side). Close the bag so that there is minimal air inside. Label the bag with the name and number of the sample.

[00196] Open compression test method. The slew rate should be 4 mm/s.

[00197] Carefully place the sample, thermoformed side down, between the two plates, making sure the pouch is centered on the bottom plate. Move the capsule inside the bag away from the edges.

[00198] Press start to start the test. As the two plates come closer together, the bag will burst. Record the compression force (for example, in Newtons) and the location on the bag where the rupture occurred. Repeat this process for all samples.

[00199] Suitable behavior of water-soluble films according to this description is determined by packages having compressive force values of at least about 300 N and less than about 2000 N, as measured in an elastic test.

Measurement in Film Swelling Test

[00200] A water-soluble film and/or pouch characterized or tested for resistance to swelling in the presence of a liquid composition is analyzed as follows.

[00201] Three film samples are taken from different sections of film from a roll on a larger film sample. Using a punch, cut out three squares measuring 2 by 2 inches (about 5x5 cm). Measure and record the mass and caliber of each sample.

[00202] For each sample, weigh a Petri dish and add 12 g of test liquid to it. A film sample is added to the Petri dish at the center of the base. Add additional test liquid until there is 20 g of test liquid in the Petri dish and the film sample is completely covered and immersed in the test liquid. Place a lid on the Petri dish.

[00203] Each Petri dish is wrapped in parafilm and placed in a conditioning oven at 38°C and 80% relative humidity for 24 hours.

[00204] Place the measuring grid on a horizontal surface. After conditioning, the Petri dishes are unpacked and film samples are removed. Place film samples on the measuring grid. Record the length and width of the film sample along with the machine direction. Wipe the test liquid from the surface of the film sample using a KimWipe® or equivalent. Record the mass and thickness of the film sample.

[00205] The swelling ratio is the ratio of the mass added to the film to the initial mass (eg, (final mass - initial mass)/original mass)).

[00206] For the water-soluble films of this disclosure comprising a blend of PVA resins, the performance of the water-soluble films of this disclosure is characterized in comparison to an identical water-soluble film containing only the first PVA copolymer. In particular, the suitable behavior of water-soluble films according to this description is characterized by a swelling coefficient value, as measured in a film swelling test, that does not exceed 60% of the swelling coefficient value of a comparative film that is identical, but differs by a second PVA copolymer that is an individual resin, and the amount of this second PVA copolymer in the comparative film is equal to the total amount of resins in the water-soluble film of the present invention.

[00207] Swelling causes the film to change dimensions, which can result in looser packaging because the final film area is larger but contains the same volume of liquid.

Measurement in Crystallinity Test

[00208] A water-soluble film and/or package characterized or subject to film crystallinity testing is analyzed as follows.

[00209] Film samples are maintained at 22°C and 40% relative humidity for at least 24 hours. A 3 mm by 3 mm sample of the wetted film is then placed in a sealed cell. A WAXD measurement is then performed using a D8 Discover X-ray diffractometer or equivalent equipped with a 2D detector (Bruker AXS Co., Ltd.) using an exposure time of 600 seconds.

[00210] A one-dimensional profile (Intensity from 2 theta) is obtained by averaging the annular diffraction data of a photographic image. A background profile is obtained, which is subtracted from the sample profile to obtain a background-subtracted profile. A straight line connecting the diffraction angle intensity values at 15 degrees and 25 degrees is subtracted from the background-subtracted profile to provide a baseline.

[00211] The Gaussian function reproduces intensity values in the range of diffraction angles from 15 degrees to 17.6 degrees and intensity values in the range from 21 degrees to 21.6 degrees as a function of the scattering of amorphous PVA. Find the peak position, peak width and peak height of the Gaussian function by least squares approximation. Diffraction signals at 19.5 degrees and 23 degrees are reproduced, which are attributed to diffraction 110 and diffraction 200 of the PVA crystal with two Gaussian functions. Find the peak position, peak width and peak height by least squares approximation. The parameters of the Gaussian function assigned to amorphous PVA are fixed. The fitting parameters of the Gaussian functions considered as crystals are fixed, and the three parameters of the Gaussian function assigned to the amorphous PVA are again approximated by the least squares method. Find the integral intensity values of the three Gaussian functions. Apparent crystallinity is calculated as a percentage of the sum of the integrated intensity values of the two Gaussian functions assigned to the PVA crystal, in the total integrated intensity values.

[00212] Without being limited by theory, it is believed that the crystallinity of a water-soluble film can be reduced by increasing the level of anionic monomer unit contained in the resin, reducing the degree of hydrolysis of the resin, increasing the amount of plasticizer contained in the film composition, and/or rapidly cooling the water-soluble film after casting . Moreover, without being limited by theory, it is believed that, in general, the lower the crystallinity of the film, the more the film swells upon contact with the liquid composition.

[00213] Water-soluble films according to this specification may be better understood in light of the following examples, which are intended to be illustrative of water-soluble films only and are in no way intended to limit the scope of the invention.

Examples

Example 1: Customized Resin Film

[00214] Example 1 is a water-soluble film that was formed with a custom PVA copolymer, Resin A. Resin A was a commercially available PVA copolymer with a degree of hydrolysis ranging from 89% to 93%, having a comonomer content (eg, modification) specification 1.75 mol. % maleic anhydride (sodium salt) and 3.5 mol. % side groups, and having a specified viscosity of a 4% solution at 20°C of 23 cP. Said film contained (i) Resin A (100 parts by weight), (ii) glycerin plasticizer (24.67 parts by weight per hundred parts resin (ppm)), (iii) sorbitol plasticizer (13.02 ppm). ), (iv) trimethylolpropane plasticizer (5.33 ppm), (v) propylene glycol plasticizer (0.49 ppm), (vi) filler (4.85 ppm bulking agent and inhibitory agent). adhesion), (vii) surfactants and other processing aids (3.15 ppm, including antioxidant, defoamer, amine oxide surfactant and cationic surfactant) and residual water (about 5- 12 m.h.). The aqueous compositions of the above were cast and dried to form film samples of 76 μm thickness, which were tested for residual CR values in the above manner. The resin and film properties for the film samples of Example 1 at ambient conditions (eg, 23°C and 35% relative humidity (RH)) prior to exposure to liquid laundry detergent are shown in Table 1. In Table 1, side group content (P) for films is presented in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and other non-resin components), and the P value additionally indicates that the side group corresponds to the maleic anhydride comonomer unit (M ).

Example 2: Customized Resin Film

[00215] Example 2 is a water-soluble film that is formed with a custom PVA copolymer, Resin B. Resin B was a commercially available PVA copolymer with a degree of hydrolysis in the range of 88-92% having a level of (eg, modification) maleic anhydride comonomer 4 .0 mol. % (sodium salt) and 8.0 mol. % side groups, and having a specified viscosity of a 4% solution at 20°C nominally 15-20 cP. This film contained Resin B (100 parts by weight) and non-resin components in the amounts and types as described in Example 1. Films were prepared and tested as described in Example 1. Resin and Film Properties for Film Samples of Example 2 at ambient conditions (e.g. 23°C and 35% RH) prior to exposure to liquid laundry detergent are given in Table 1. In Table 1, the anionic pendant (P) content of the film is presented in terms of moles relative to the PVA resins in film (i.e., excluding plasticizers and their other non-resin components), and the P value additionally indicates that the anionic monomer corresponds to the maleic anhydride comonomer unit (M).

Table 1. Resin and Film Data for Examples 1 and 2

Resin Film Example Type μ (cP) SG (%) P (mol %) KR (%) P (mol %) 1 A 23 91.0 3.50 (M) 22.51 3.50(M) 2 IN 17.5 90.0 8.00 (M) 0.87 8.00 (M)

[00216] Thus, Table 1 shows that water-soluble films prepared from a PVA-maleate copolymer having a modification level ranging from about 1.5 to about 2 mol. % (Resin A) have higher residue values (CR values) compared to a water-soluble film prepared from a PVA-maleate copolymer having a modification level ranging from about 3 to about 5 mol. % (Resin B).

Example 3: Customized Resin Film

[00217] Example 3 is a water-soluble film that is formed with Resin A as described in Example 1. Said film contained (i) Resin A (100 parts by weight), (ii) glycerin plasticizer (6.66 parts by weight) , (iii) sorbitol plasticizer (6.24 ppm), (iv) 2-methyl-1,3-propanediol plasticizer (13.32 ppm), (v) filler (2.67 ppm . bulking agent and anti-blocking agent), (vi) surfactants and other processing aids (0.83 ppm, including antioxidant, defoamer and non-ionic surfactant) and residual water (about 5-12 m .ch.). Films were prepared and tested as described in Example 1. The resin and film properties for the film samples of Example 3 under ambient conditions (eg, 23°C and 35% RH) prior to exposure to liquid laundry detergent are shown in Table 2. Table 2, the side group content (P) for films is presented in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and other non-resin components), and the P value additionally indicates that the side group corresponds to the maleic anhydride copolymer unit (M).

Example 4: Customized Resin Film

[00218] Example 4 represents water-soluble films that were prepared containing a single PVA copolymer, Resin B, as described above in Example 2. Said film contained Resin B (100 parts by weight) and non-resin components in amounts and types as described in Example 3. Films were prepared and tested as described in Example 1. Resin and film properties for the film samples of Example 4 under ambient conditions (eg, 23°C and 35% RH) prior to exposure to liquid laundry detergent are shown in Table 2. In Table 2, the anionic side group (P) content of the film is presented in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and other non-resin components), and the P value additionally indicates that the anionic monomer corresponds to the maleic anhydride comonomer unit (M).

Table 2. Resin and Film Data for Examples 3 and 4

Resin Film Example Type μ (cP) SG (%) P (mol %) KR (%) P (mol %) 3 A 23 91.0 3.50(M) 31.59 3.50(M) 4 IN 17.5 90.0 8.00 (M) 0.86 8.00 (M)

[00219] Thus, Table 2 shows that water-soluble films prepared from a PVA-maleate copolymer having a modification level ranging from about 1.5 to about 2 mol. % (Resin A) have higher residue values (CR values) compared to a water-soluble film prepared from a PVA-maleate copolymer having a modification level ranging from about 3 to about 5 mol. % (Resin B). In addition, comparison of Examples 1 and 2 with Examples 3 and 4 shows that films prepared from a PVA-maleate copolymer having from about 1.5 to about 2 mol. % modification (Resin A), had higher residue values compared to films prepared from a PVA-maleate copolymer having from about 3 to about 5 mol. % modification (Resin B), at both high plasticizer levels (e.g., greater than 30 ppm total, Examples 1 and 2) and low plasticizer levels (e.g., less than 30 ppm total, Examples 3 and 4).

Examples 5-8: Dual Resin Blend Films

[00220] Examples 5-8 are formed water-soluble films, each of which contains a mixture of two copolymers of Resins A and B, as described in Examples 1-4 above. Specific mixtures contain 80 wt.% Resin A and 20 wt.% Resin B (Example 5), 60 wt.% Resin A and 40 wt.% Resin B (Example 6), 40 wt.% Resin A and 60 wt.% Resin B (Example 7) and 20 wt.% Resin A and 80 wt.% Resin B (Example 8). These blend films contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. The films were prepared and tested as described in Example 1. Table 3 shows the resin and film properties for Examples 5-8. The first and last entries in Table 3 represent the individual resin limit for the film composition (ie, Examples 1 and 2), while the remaining values represent the compositions of mixtures of the two resins. In Table 3, the pendant group (P) content for the films is presented in terms of moles relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other non-resin components), and the values P further indicates that said anionic comonomer unit corresponds to the maleic anhydride comonomer unit (M).

Table 3. Resin and Film Data for Examples 5-8

Resins Film Example Type Col. (wt.%) Type Col. (wt.%) KR (%) % Crystallinity P (mol %) 1 A 100 IN 0 22.51 20.4* 3.50(M) 5 A 80 IN 20 17.28* 18.4* 4.4 (M) 6 A 60 IN 40 10.42* 17.3* 5.3 (M) 7 A 40 IN 60 8.32* 15.9* 6.2 (M) 8 A 20 IN 80 1.83* 14.9* 7.1 (M) 2 A 0 IN 100 0.87* 14.7 8.00 (M)

[00221] Examples 5-8 show that water-soluble films containing mixtures of PVA resins containing a first copolymer containing a first level of modification with an anionic monomer and a second copolymer containing a second level of modification with an anionic monomer, as described herein, can exhibit a combination the inherently advantageous, but competing, physical and chemical properties when selecting PVA resin blends based on their specific blend components, the relative amounts of blend components, or both. For example, as noted above, films that are particularly suitable for composition delivery applications in a pouch satisfy at least one of the following thresholds: (a) a CR residue value of about 20 wt.% or less to reduce or eliminate film residue on articles in laundering and (b) crystallinity of at least 15% to create rigid packages with less likelihood of softening and sagging when forming packages containing liquid compositions. It is desirable that the film meets the Raman residue criterion (a) and the crystallinity criterion (b).

[00222] As illustrated in the custom resin film data in Examples 1 and 2, desired Raman values often degrade the desired PR and/or MOD values. For example, the film of Example 2 (Resin B) had a desirably low residual Raman value, but at the same time a crystallinity value.

[00223] As shown in Examples 5-8, it was unexpectedly discovered that certain water-soluble films containing mixtures of PVA resins of a first PVA copolymer having a first level of anionic monomer as described herein and a second PVA copolymer having a second level of anionic monomer as described herein meet criteria (a) and/or (b). In Table 3, film properties marked with an “*” satisfy criteria (a) and/or (b). It is apparent from the data that films containing PVA resin blends comprising two anionic PVA copolymers, as shown in Examples 5-8, generally meet both criteria (a) and (b) for A/B blend ratios ranging from about 20/ 80 to about 80/20 (w/w, respectively).

[00224]

Examples 9-12: Two Resin Blend Films

[00225] Examples 9-12 are formed water-soluble films, each containing a mixture of two copolymers, Resin A and Resin B. Specific mixtures contain 80 wt.% Resin A and 20 wt.% Resin B (Example 9), 60 wt. .% Resin A and 40 wt.% Resin B (Example 10), 40 wt.% Resin A and 60 wt.% Resin B (Example 11) and 20 wt.% Resin A and 80 wt.% Resin B (Example 12 ). These blend films contained two resins that constituted 100% of the resin in the film, while plasticizers and other additives were present in the amounts and types as described in Example 3. The films were prepared and tested as described in Example 1. Table 4 shows the properties of the resin and film for Examples 9-12. The first and last entries in Table 4 represent the individual resin limit for the film composition (ie, Examples 3 and 4), while the remaining values represent the compositions of mixtures of the two resins. In Table 4, the pendant group (P) content for the film is presented in terms of moles relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other non-resin components), and the values P is additionally indicated that they correspond to the maleic anhydride comonomer unit (M).

Table 4. Resin and Film Data for Examples 3, 4 and 9-12

Resins Film Example Type Col. (wt.%) Type Col. (wt.%) KR (%) % Crystallinity P (mol %) 3 A 100 IN 0 31.59 18.5* 3.5 (M) 9 A 80 IN 20 22.89 18.8* 4.4 (M) 10 A 60 IN 40 14.19* 19.0* 5.3 (M) eleven A 40 IN 60 5.34* 17.8* 6.2 (M) 12 A 20 IN 80 4.29* 17.3* 7.1 (M) 4 A 0 IN 100 0.89* 14.7 8.00 (M)

[00226] Examples 9-12 show that water-soluble films containing mixtures of PVA resins containing a first copolymer containing a first level of modification with an anionic monomer and a second copolymer containing a second level of modification with an anionic monomer, as described herein, can exhibit a combination the inherently advantageous, but competing, physical and chemical properties when selecting PVA resin blends based on their specific blend components, the relative amounts of blend components, or both. For example, as noted above, films that are particularly suitable for pouch composition delivery applications satisfy at least one of the criteria set forth in Examples 5-8. It is desirable that the film meets the Raman residue criterion (a) and the crystallinity criterion (b).

[00227] As illustrated in the custom resin film data in Examples 3 and 4, desired Raman values often degrade desired crystallinity values. For example, the film of Example 3 (Resin A) had an undesirably low CR residue but an acceptable crystallinity value.

[00228] As shown in Examples 9-12, it was unexpectedly discovered that certain water-soluble films containing mixtures of PVA resins of a first PVA copolymer having a first level of anionic monomer as described herein and a second PVA copolymer having a second level of anionic monomer as described herein meet criteria (a) and/or (b). In Table 4, film properties marked with an “*” satisfy criteria (a) and/or (b). It is apparent from the data that films containing PVA resin blends comprising two anionic PVA copolymers, as shown in Examples 9-12, generally meet both criteria for A/B blend ratios ranging from about 20/80 to about 80/20 ( w/w, respectively).

Examples 13-18: Individual resin film exposed to LMS

[00229] Films prepared with Resin A as described in Example 1 were exposed to liquid laundry detergent one (LML 1) as described herein. Films were tested for residual CR values by the above methods after storage in contact with LMS 1 for 3, 6, 9 or 12 weeks at ambient (23 °C, 35% RH) or high load, 38 °C ambient and RH conditions. humidity 80%. The average values of CR, PR and MOD are given in Table 5. In Table 5, the content of side groups (P) for films is presented in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and their other components, not related to resins), and the P value additionally indicates that the side group corresponds to a maleic anhydride comonomer unit (M). The first entry in Table 5 represents the individual resin limit for the film composition (ie, Example 1).

Table 5. Resin and Film Data for Examples 1 and 13-18

Example Type Weeks of storage Environmental conditions KR (%) P (mol %) 1 A 0 23 °C, RH 35% 22.51 3.5 (M) 13 A 3 23 °C, RH 35% 25.24 3.5 (M) 14 A 6 23 °C, RH 35% 32.05 3.5 (M) 15 A 12 23 °C, RH 35% 29.21 3.5 (M) 16 A 3 38 °C, RH 80% 24.40 3.5 (M) 17 A 6 38 °C, RH 80% 20.66 3.5 (M) 18 A 12 38 °C, RH 80% 20.05* 3.5 (M)

[00230] Thus, Table 5 demonstrates that for a custom resin film containing a PVA copolymer having from about 1.5 to about 2 mol. % modification with maleate, CR residue values typically increase after exposure to liquid laundry detergent and after storage at ambient temperature and humidity. In Table 5, the film properties marked with "*" satisfy criterion (a) as described in Examples 5-8.

Examples 19-24: Individual resin film exposed to LMS

[00231] Films prepared with Resin A as described in Example 3 were exposed to liquid laundry detergent one (LML 1) as described herein. These films were tested for Raman residue values as described in Examples 13-18. The average KP values are given in Table 6. In Table 6, the side group content (P) for the films is presented in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and other non-resin components). , and the P value additionally indicates that the side group corresponds to a maleic anhydride comonomer unit (M). The first entry in Table 6 represents the individual resin limit for the film composition (ie, Example 3).

Table 6. Resin and Film Data for Examples 3 and 19-24

Example Type Weeks of storage Environmental conditions KR (%) P (mol %) 3 A 0 23 °C, RH 35% 31.59 3.5 (M) 19 A 3 23 °C, RH 35% 29.88 3.5 (M) 20 A 6 23 °C, RH 35% 32.88 3.5 (M) 21 A 12 23 °C, RH 35% 36.92 3.5 (M) 22 A 3 38 °C, RH 80% 27.10 3.5 (M) 23 A 6 38 °C, RH 80% 22.16 3.5 (M) 24 A 12 38 °C, RH 80% 32.06 3.5 (M)

[00232] Thus, Table 6 demonstrates that for a custom resin film containing a PVA copolymer having from about 1.5 to about 2 mol. % modification with maleate, CR residue values generally remain unchanged after exposure to liquid laundry detergent and after storage at ambient temperature and humidity at 38°C and 85% RH. In Table 6, the film properties marked with "*" satisfy criterion (a) as described in Examples 5-8.

Examples 25-30: Individual resin film exposed to LMS

[00233] Films were prepared with Resin B as described in Example 2. The resulting films were exposed to liquid laundry detergent one (LML 1) as described herein and tested for KR residue values as described in Examples 13-18 . The average KP values are given in Table 7. In Table 7, the side group content (P) for the film is presented in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and other non-resin components). , and the P value additionally indicates that the side group corresponds to a maleic anhydride comonomer unit (M).

Table 7. Resin and Film Data for Examples 2 and 25-30

Example Type Weeks of storage Environmental conditions KR (%) P (mol %) 2 IN 0 23 °C, RH 35% 1.94* 8.00 (M) 25 IN 3 23 °C, RH 35% 8.47* 8.00 (M) 26 IN 6 23 °C, RH 35% 6.33* 8.00 (M) 27 IN 12 23 °C, RH 35% 13.75* 8.00 (M) 28 IN 3 38 °C, RH 80% 6.19* 8.00 (M) 29 IN 6 38 °C, RH 80% 5.72* 8.00 (M) thirty IN 12 38 °C, RH 80% 11.95* 8.00 (M)

[00234] Thus, Table 7 demonstrates that for a custom resin film containing a PVA copolymer comprising about 3 mol. % to about 5 mol. % modification with maleate, CR residue values generally increase after exposure to liquid laundry detergent and storage. In Table 7, the film properties marked with "*" satisfy criterion (a) as described in Examples 5-8.

[00235] In addition, the combined data of Table 5 and Table 7 show that water-soluble films exposed to liquid laundry detergent and stored for 3, 6 or 12 weeks prepared from a PVA copolymer having from about 1.5 to about 2 mol. % modification with maleate (Resin A), have higher residue values (CR values) compared to water-soluble films that were exposed to liquid laundry detergent and stored for 3, 6 or 12 weeks, prepared from a PVA copolymer having approx. 3 to about 5 mol. % modification with maleate (Resin B).

Examples 31-36: Individual resin film exposed to LMS

[00236] Films were prepared with Resin B as described in Example 4. The resulting films were exposed to Liquid Laundry Detergent One (LML 1) as described herein and tested for KR residue values as described in Examples 13-18 . The average KP values are given in Table 8. In Table 8, the side group content (P) for the film is presented in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and other non-resin components). , and the P value additionally indicates that the side group corresponds to a maleic anhydride comonomer unit (M).

Table 8. Resin and Film Data for Examples 4 and 31-36

Example Type Weeks of storage Environmental conditions KR (%) P (mol %) 4 IN 0 23 °C, RH 35% 0.86* 8.00 (M) 31 IN 3 23 °C, RH 35% 7.94* 8.00 (M) 32 IN 6 23 °C, RH 35% 4.46* 8.00 (M) 33 IN 12 23 °C, RH 35% 9.10* 8.00 (M) 34 IN 3 38 °C, RH 80% 3.94* 8.00 (M) 35 IN 6 38 °C, RH 80% 2.69* 8.00 (M) 36 IN 12 38 °C, RH 80% 6.12* 8.00 (M)

[00237] Thus, Table 8 demonstrates that for a custom resin film containing a PVA copolymer comprising about 3 mol. % to about 5 mol. % modification with maleate and side groups, KR residue values generally increase after exposure to liquid laundry detergent and storage, although at a much slower rate than for an individual resin film containing a PVA copolymer having from about 1.5 mol. % to about 3 mol. % modification with maleate (ie, Examples 19-24 in Table 6). In Table 8, the film properties marked with "*" satisfy criterion (a) as described in Examples 5-8.

Examples 37-42: Two Resin Blend Films

[00238] Examples 37-42 are formed water-soluble films, each of which contains a mixture of two copolymers of Resins A and B. Each of these films contained 80 wt.% Resin A and 20 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. Films were prepared as described in Example 1 and tested as described in Examples 13-18. The average KP values are given in Table 9. In Table 9, the pendant group (P) content for the films is presented on a mole basis relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 9. Resin and Film Data for Examples 37-42

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 37 80/20 3 23 °C, RH 35% 19.72* 4.4 (M) 38 80/20 6 23 °C, RH 35% 28.41 4.4 (M) 39 80/20 12 23 °C, RH 35% 20.97 4.4 (M) 40 80/20 3 38 °C, RH 80% 16.75* 4.4 (M) 41 80/20 6 38 °C, RH 80% 19.03* 4.4 (M) 42 80/20 12 38 °C, RH 80% 15.52* 4.4 (M)

[00239] In Table 9, the film properties marked with "*" satisfy criterion (a), as described in Examples 5-8. As shown in Examples 37-42, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with 80 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and 20 wt.% of the second copolymer PVA having a second level of anionic monomer content, as described herein, generally meets criteria (a) up to at least 12 weeks of storage at 38°C and 80% relative humidity.

Examples 43-48: Two Resin Blend Films

[00240] Examples 43-48 are formed water-soluble films, each of which contains a mixture of two copolymers of Resins A and B. Each of these films contained 80 wt.% Resin A and 20 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 3. Films were prepared as described in Example 1 and tested as described in Examples 13-18. The average KP values are given in Table 10. In Table 10, the pendant group (P) content for the film is presented on a mole basis relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 10. Resin and Film Data for Examples 43-48

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 43 80/20 6 23 °C, RH 35% 16.46* 4.4 (M) 44 80/20 9 23 °C, RH 35% 25.57 4.4 (M) 45 80/20 12 23 °C, RH 35% 17.5* 4.4 (M) 46 80/20 6 38 °C, RH 80% 18.54* 4.4 (M) 47 80/20 9 38 °C, RH 80% 21.53 4.4 (M) 48 80/20 12 38 °C, RH 80% 19.57* 4.4 (M)

[00241] In Table 10, the film properties marked with "*" satisfy criterion (a), as described in Examples 5-8. As shown in Examples 43-48, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with 80 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and 20 wt.% of the second copolymer PVA having a second level of anionic monomer content as described herein generally meets criteria (a) up to at least 12 weeks of storage at ambient conditions of 38° C. and 80% relative humidity.

Examples 49-54: Two Resin Blend Films

[00242] Examples 49-53 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 60 wt.% Resin A and 40 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. Films were prepared as described in Example 1 and tested as described in Examples 13-18. The average KP values are given in Table 11. In Table 11, the pendant group (P) content for the film is presented on a mole basis relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 11. Resin and Film Data for Examples 49-54

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 49 60/40 3 23 °C, RH 35% 22.79 5.3 (M) 50 60/40 6 23 °C, RH 35% 26.34 5.3 (M) 51 60/40 12 23 °C, RH 35% 15.23* 5.3 (M) 52 60/40 3 38 °C, RH 80% 15.14* 5.3 (M) 53 60/40 6 38 °C, RH 80% 19.91* 5.3 (M) 54 60/40 12 38 °C, RH 80% 12.56* 5.3 (M)

[00243] In Table 11, the film properties marked with "*" satisfy criterion (a), as described in Examples 5-8. As shown in Examples 49-54, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 60 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 40 wt.% a second PVA copolymer having a second level of anionic monomer content as described herein generally meets criteria (a)-(c) up to at least 12 weeks of storage at 38° C. and 80% relative humidity.

Examples 55-60: Two Resin Blend Films

[00244] Examples 55-60 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 60 wt.% Resin A and 40 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 3. Films were prepared as described in Example 1 and tested as described in Examples 13-18. The average KP values are given in Table 12. In Table 12, the pendant group (P) content for the film is presented on a mole basis relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values further indicate that said comonomer corresponds to a maleic anhydride comonomer unit (M).

Table 12. Resin and Film Data for Examples 55-60

Example Type
(A′′/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 55 60/40 6 23 °C, RH 35% 19.71* 5.3 (M) 56 60/40 9 23 °C, RH 35% 10.69* 5.3 (M) 57 60/40 12 23 °C, RH 35% 16.51* 5.3 (M) 58 60/40 6 38 °C, RH 80% 15.43* 5.3 (M) 59 60/40 9 38 °C, RH 80% 13.80* 5.3 (M) 60 60/40 12 38 °C, RH 80% 10.78* 5.3 (M)

[00245] In Table 12, the film properties marked with "*" satisfy criterion (a), as described in Examples 5-8. As shown in Examples 55-60, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 60 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 40 wt.% a second PVA copolymer having a second level of anionic monomer content, as described herein, meets criteria (a) up to at least 12 weeks of storage at ambient conditions and up to at least 12 weeks of storage at 38° C. and relative humidity 80%.

Examples 61-66: Two Resin Blend Films

[00246] Examples 61-66 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 40 wt.% Resin A and 60 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. Films were prepared as described in Example 1 and tested as described in Examples 13-18. The average KP values are given in Table 13. In Table 13, the pendant group (P) content for the film is presented on a mole basis relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 13. Resin and Film Data for Examples 61-66

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 61 40/60 3 23 °C, RH 35% 15.94* 6.2 (M) 62 40/60 6 23 °C, RH 35% 24.93 6.2 (M) 63 40/60 12 23 °C, RH 35% 5.23* 6.2 (M) 64 40/60 3 38 °C, RH 80% 3.78* 6.2 (M) 65 40/60 6 38 °C, RH 80% 3.62* 6.2 (M) 66 40/60 12 38 °C, RH 80% 7.98* 6.2 (M)

[00247] In Table 13, the film properties marked with "*" satisfy criterion (a), as described in Examples 5-8. As shown in Examples 61-66, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 40 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 60 wt.% a second PVA copolymer having a second level of anionic monomer content as described herein generally meets criteria (a) up to at least 12 weeks of storage at ambient conditions and up to at least 12 weeks of storage at 38° C. and relative humidity 80%.

Examples 67-72: Two Resin Blend Films

[00248] Examples 67-72 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 40 wt.% Resin A and 60 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 3. Films were prepared as described in Example 1 and tested as described in Examples 13-18. The average KP values are given in Table 14. In Table 14, the pendant group (P) content for the film is presented on a mole basis based on the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 14. Resin and Film Data for Examples 67-72

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 67 40/60 6 23 °C, RH 35% 8.62* 6.2 (M) 68 40/60 9 23 °C, RH 35% 13.10* 6.2 (M) 69 40/60 12 23 °C, RH 35% 16.68* 6.2 (M) 70 40/60 6 38 °C, RH 80% 9.46* 6.2 (M) 71 40/60 9 38 °C, RH 80% 8.08* 6.2 (M) 72 40/60 12 38 °C, RH 80% 13.55* 6.2 (M)

[00249] In Table 14, the film properties marked with "*" satisfy criterion (a), as described in Examples 5-8. As shown in Examples 67-72, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 40 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 60 wt.% a second PVA copolymer having a second level of anionic monomer content as described herein generally meets criteria (a) up to at least 12 weeks of storage at ambient conditions and up to at least 12 weeks of storage at 38° C. and relative humidity 80%.

Examples 73-78: Two Resin Blend Films

[00250] Examples 73-78 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 20 wt.% Resin A and 80 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. Films were prepared as described in Example 1 and tested as described in Examples 13-18. The average KP values are given in Table 15. In Table 15, the pendant group (P) content for the film is presented on a mole basis relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 15. Resin and Film Data for Examples 73-78

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 73 20/80 3 23 °C, RH 35% 12.22* 7.1 (M) 74 20/80 6 23 °C, RH 35% 20.35* 7.1 (M) 75 20/80 12 23 °C, RH 35% 9.66* 7.1 (M) 76 20/80 3 38 °C, RH 80% 12.99* 7.1 (M) 77 20/80 6 38 °C, RH 80% 6.44* 7.1 (M) 78 20/80 12 38 °C, RH 80% 4.80* 7.1 (M)

[00251] In Table 15, the film properties marked with "*" satisfy criterion (a), as described in Examples 5-8. As shown in Examples 73-78, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 20 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 80 wt.% a second PVA copolymer having a second level of anionic monomer content as described herein generally meets criteria (a) up to at least 12 weeks of storage at ambient conditions and up to at least 12 weeks of storage at 38° C. and relative humidity 80%.

Examples 79-84: Dual Resin Blend Films

[00252] Examples 79-84 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 20 wt.% Resin A and 80 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 3. Films were prepared as described in Example 1 and tested as described in Examples 13-18. The average KP values are given in Table 16. In Table 16, the pendant group (P) content for the film is presented on a mole basis relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 16. Resin and Film Data for Examples 79-84

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 79 20/80 6 23 °C, RH 35% 10.76* 7.1 (M) 80 20/80 9 23 °C, RH 35% 7.83* 7.1 (M) 81 20/80 12 23 °C, RH 35% 6.58* 7.1 (M) 82 20/80 6 38 °C, RH 80% 6.12* 7.1 (M) 83 20/80 9 38 °C, RH 80% 8.25* 7.1 (M) 84 20/80 12 38 °C, RH 80% 4.25* 7.1 (M)

[00253] In Table 16, the film properties marked with "*" satisfy criterion (a), as described in Examples 5-8. As shown in Examples 79-84, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 20 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 80 wt.% a second PVA copolymer having a second level of anionic monomer content, as described herein, meets criteria (a) up to at least 12 weeks of storage at ambient conditions and up to at least 12 weeks of storage at 38° C. and relative humidity 80%.

Example 85 : Film Swelling

[00254] Water-soluble films were formed from individual resins or mixtures of two copolymers of Resins A and B. Films were prepared with weight ratios of Resin A to Resin B of 100/0, 80/20, 60/40, 40/60, 30/70 , 20/80 and 0/100. Resin A, B, or a combination of Resin A and Resin B constituted 100% of the resin in the films produced herein, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. The films were tested on the swelling ratio in each of propylene glycol, polyethylene glycol (PEG) 200, glycerol and diglycerol according to the film swelling test described herein. Average swelling ratios are given in Table 17.

Table 17 : Average swelling coefficients of films in various solvents

Resin A/Ratio
Resin B Propylene glycol PEG 200 Glycerol Diglycerin 100/0 0.1587 -0.0187 0.4040 0.0834 80/20 0.2006 -0.0269 0.6630 0.1408 60/40 0.2247 -0.0092 0.9705 0.1304 40/60 0.4304 0.0194 1.5743 0.1955 20/80 0.6054 0.0479 6.1284 0.3437 0/100 1.7167 0.1293 10.6665 0.7266

[00255] As shown in Table 17, as the amount of PVA-maleate copolymer having 3 to 5 mol. % modification with maleate (Resin B), the swelling value of a water-soluble film generally increases, and a significant increase is observed for films that do not contain a PVA-maleate copolymer having from 1.5 to 2 mol. % modification with maleate (Resin A) (for example, at an A/B ratio of 0/100). Without being limited by theory, it is believed that when a film exhibits a swelling ratio value that is no more than 60% of the swelling ratio value of a comparative film that is identical but differs in the second PVA copolymer being an individual resin, and the amount of that second PVA copolymer in the comparative film equal to the total amount of resins in the water-soluble film of this invention (eg, A/B ratio of 0/100), the film is less likely to soften and sag (ie remain taut) when molded into bags containing liquid compositions.

Examples 86-92: Individual resin film exposed to LMS

[00256] Films were prepared with Resin B as described in Example 4. The aqueous compositions of the above were cast and dried to form 76 μm thick film samples. The resulting films were exposed to liquid laundry detergent two (LML 2) as described herein. Films were tested for residual CR values by the above methods before storage in contact with LMS 2 and after storage in contact with LMS 2 for 3, 6 or 12 weeks under ambient conditions (23 °C, 35% relative humidity) or high load ambient conditions. environment 38°C and relative humidity 80%. The average KP values are given in Table 18. In Table 18, the side group content (P) for the film is presented in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and other non-resin components). , and the P value additionally indicates that the side group corresponds to a maleic anhydride comonomer unit (M).

Table 18. Resin and Film Data for Examples 86-92

Example Type Weeks of storage Environmental conditions KR (%) P (mol %) 86 IN 0 23 °C, RH 35% 2.28* 8.00 (M) 87 IN 3 23 °C, RH 35% 1.22* 8.00 (M) 88 IN 6 23 °C, RH 35% 1.80* 8.00 (M) 89 IN 12 23 °C, RH 35% 0.81* 8.00 (M) 90 IN 3 38 °C, RH 80% 2.14* 8.00 (M) 91 IN 6 38 °C, RH 80% 0.19* 8.00 (M) 92 IN 12 38 °C, RH 80% 1.77* 8.00 (M)

[00257] In Table 18, residue values marked with "*" satisfy the criteria for a CR residue of 20 wt.% or less. Table 18 demonstrates that water-soluble films containing a single PVA resin can have acceptable residue values. In particular, Table 18 demonstrates that a water-soluble film containing an individual PVA resin containing a maleic anhydride comonomer having from about 3 to about 5 mol. % maleate modification, shows good residue values.

Examples 93-99: Individual resin film exposed to LMS

[00258] Films were prepared with Resin A and non-resin components as described in Example 1. These films were prepared and tested as described in Examples 86-92. The average KP values are given in Table 19. In Table 19, the side group content (P) for the film is presented in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and other non-resin components). , and the P value additionally indicates that the side group corresponds to a maleic anhydride comonomer unit (M).

Table 19. Resin and Film Data for Examples 93-99

Example Type Weeks of storage Environmental conditions KR (%) P (mol %) 93 A 0 23 °C, RH 35% 24.05 3.50(M) 94 A 3 23 °C, RH 35% 22.45 3.50(M) 95 A 6 23 °C, RH 35% 20.74 3.50(M) 96 A 12 23 °C, RH 35% 17.48* 3.50(M) 97 A 3 38 °C, RH 80% 23.86 3.50(M) 98 A 6 38 °C, RH 80% 12.95* 3.50(M) 99 A 12 38 °C, RH 80% 12.30* 3.50(M)

[00259] In Table 19, the residue values marked with "*" satisfy the KR residue criteria as described in Examples 86-92. Table 19 demonstrates that water-soluble films containing a single PVA resin can have poor residue values. In particular, Table 19 demonstrates that a water-soluble film containing an individual PVA resin containing a maleic anhydride comonomer having from about 1.5 to about 2 mol. % maleate modification, may exhibit poor residue values when stored in contact with liquid laundry detergent.

Examples 100-106: Two Resin Blend Films

[00260] Examples 100-106 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 80 wt.% Resin A and 20 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. These films were prepared and tested as described in Examples 86-92. The average KP values are given in Table 20. In Table 20, the pendant group (P) content for the film is presented on a mole basis based on the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 20. Resin and Film Data for Examples 100-106

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 100 80/20 0 23 °C, RH 35% 19.68* 4.4 (M) 101 80/20 3 23 °C, RH 35% 23.41 4.4 (M) 102 80/20 6 23 °C, RH 35% 22.42 4.4 (M) 103 80/20 12 23 °C, RH 35% 14.08* 4.4 (M) 104 80/20 3 38 °C, RH 80% 17.54* 4.4 (M) 105 80/20 6 38 °C, RH 80% 15.18* 4.4 (M) 106 80/20 12 38 °C, RH 80% 14.18* 4.4 (M)

[00261] In Table 20, the residue values marked with "*" satisfy the KR residue criteria as described in Examples 86-92. As shown in Examples 100-106, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 80 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 20 wt.% a second PVA copolymer having a second level of anionic monomer content as described herein generally meets the criteria for acceptable residue and resilience values for A/B blend ratios of about 80/20 (w/w, respectively) up to at least 12 weeks storage at 38°C and 80% relative humidity.

Examples 107-113: Two Resin Blend Films

[00262] Examples 107-113 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 60 wt.% Resin A and 40 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. These films were prepared and tested as described in Examples 86-92. The average KP values are given in Table 21. In Table 21, the pendant group (P) content for the film is presented on a mole basis based on the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 21. Resin and Film Data for Examples 107-113

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 107 60/40 0 23°C, RH 35% 11.48* 5.3 (M) 108 60/40 3 23°C, RH 35% 23.13 5.3 (M) 109 60/40 6 23°C, RH 35% 14.95* 5.3 (M) 110 60/40 12 23°C, RH 35% 23.5 5.3 (M) 111 60/40 3 38°C, RH 80% 16.89* 5.3 (M) 112 60/40 6 38°C, RH 80% 15.26* 5.3 (M) 113 60/40 12 38°C, RH 80% 14.95* 5.3 (M)

[00263] In Table 21, the residue values marked with "*" satisfy the KR residue criteria as described in Examples 86-92. As shown in Examples 107-113, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 60 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 40 wt.% a second PVA copolymer having a second level of anionic monomer content as described herein generally meets the criteria for acceptable residue values up to at least 12 weeks of storage at 38° C. and 80% relative humidity.

Examples 114-120: Two Resin Blend Films

[00264] Examples 114-120 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 40 wt.% Resin A and 60 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. These films were prepared and tested as described in Examples 86-92. The average KP values are given in Table 22. In Table 22, the pendant group (P) content for the film is presented on a mole basis based on the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components, non-resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 22. Resin and Film Data for Examples 114-120

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 114 40/60 0 23 °C, RH 35% 3.76* 6.2 (M) 115 40/60 3 23 °C, RH 35% 11.20* 6.2 (M) 116 40/60 6 23 °C, RH 35% 11.19* 6.2 (M) 117 40/60 12 23 °C, RH 35% 10.96* 6.2 (M) 118 40/60 3 38 °C, RH 80% 6.58* 6.2 (M) 119 40/60 6 38 °C, RH 80% 9.27* 6.2 (M) 120 40/60 12 38 °C, RH 80% 6.33* 6.2 (M)

[00265] In Table 22, the residue values marked with "*" satisfy the KR residue criteria as described in Examples 86-92. As shown in Examples 114-120, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 40 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 60 wt.% a second PVA copolymer having a second level of anionic monomer content as described herein generally meets the criteria for acceptable residue values up to at least 12 weeks of storage at ambient conditions and up to at least 12 weeks of storage at 38° C. and relative humidity 80%.

Examples 121-127: Two Resin Blend Films

[00266] Examples 121-127 are formed water-soluble films, each containing a mixture of two copolymers of Resins A and B. Each of these films contained 20 wt.% Resin A and 80 wt.% Resin B. These films of the mixture contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in the amounts and types as described in Example 1. These films were prepared and tested as described in Examples 86-92. The average values of KP and elasticity are given in Table 23. In Table 23, the pendant group (P) content for the film is presented in terms of moles relative to the total polymer resin in the film (i.e., including both resins present, but excluding plasticizers and other components other than resins), and the P values additionally include the maleic anhydride comonomer unit (M).

Table 23. Resin and Film Data for Examples 121-127

Example Type
(A/B ratio) Weeks of storage Environmental conditions KR (%) P (mol %) 121 20/80 0 23 °C, RH 35% 0.98* 7.1 (M) 122 20/80 3 23 °C, RH 35% 1.25* 7.1 (M) 123 20/80 6 23 °C, RH 35% 3.95* 7.1 (M) 124 20/80 12 23 °C, RH 35% 5.99* 7.1 (M) 125 20/80 3 38 °C, RH 80% 2.26* 7.1 (M) 126 20/80 6 38 °C, RH 80% 5.96* 7.1 (M) 127 20/80 12 38 °C, RH 80% 3.02* 7.1 (M)

[00267] In Table 23, the residual values marked with "*" satisfy the KR residual value criteria as described in Examples 86-92. As shown in Examples 121-127, it was unexpectedly discovered that some water-soluble films containing mixtures of PVA resins with about 20 wt.% of the first PVA copolymer having a first level of anionic monomer content, as described herein, and about 80 wt.% a second PVA copolymer having a second level of anionic monomer content as described herein generally meets the criteria for acceptable residue values up to at least 12 weeks of storage at ambient conditions and up to at least 12 weeks of storage at 38° C. and relative humidity 80%.

[00268] The foregoing description is provided for clarity of understanding only, and is not intended to be unduly limiting, since modifications within the scope of the invention may be obvious to those skilled in the art.

[00269] All patents, publications and references mentioned herein are incorporated herein by reference in their entirety. In the event of any conflict between this document and the incorporated patents, publications and references, this document shall control.

Claims (34)

1. Water-soluble film for packaging, containing: a mixture of polyvinyl alcohol (PVA) resins containing: a first PVA copolymer containing a first anionic monomer unit comprising maleic anhydride or an alkali metal salt of maleic anhydride, where said first anionic monomer unit is present in the first PVA copolymer in an amount of 1 mol. % up to 3 mol. %; And a second PVA copolymer containing a second anionic monomer unit comprising maleic anhydride or an alkali metal salt of maleic anhydride present in the second PVA copolymer in an amount of from 3 mol. % up to 8 mol. %; where the first PVA copolymer is contained in the specified mixture in an amount ranging from 10 wt. % up to 70 wt. % based on the total weight of the PVA resin mixture, and the said number of first anionic monomer units present in the first PVA copolymer is different from the second number of anionic monomer units present in the second PVA copolymer, wherein the first and second PVA copolymers contain side groups, and the first PVA copolymer has a first level of side groups (a ₁ ) derived from the first anionic monomer unit; said second PVA copolymer has a second level of side groups (a ₂ ) derived from a second anionic monomer unit; and the difference between a ₁ and a ₂ is in the range of 4 mol. % up to 10 mol. %; and having a crystallinity of at least 15%. 2. Water-soluble film according to claim 1, characterized in that said first PVA copolymer is present in an amount ranging from 10 wt. % up to 40 wt. % of the total mass of the mixture of PVA resins. 3. Water-soluble film according to any one of paragraphs. 1, 2, characterized in that said second PVA copolymer is present in an amount ranging from 30 wt. % up to 90 wt. % of the total mass of the PVA polymer in the specified film. 4. Water-soluble film according to any one of paragraphs. 1-3, characterized in that said first PVA copolymer is a maleic anhydride copolymer having a first level of anionic monomer content (b ₁ ), and the second said PVA copolymer is a maleic anhydride copolymer having a second level of anionic monomer content (b ₂ ) , where the difference between b ₁ and b ₂ is in the range of 2 mol. % up to 7 mol. %. 5. Water-soluble film according to any one of paragraphs. 1-3, characterized in that said first PVA copolymer has a viscosity of 4% solution at 20°C in the range from 4 cP to 30 cP. 6. Water-soluble film according to any one of paragraphs. 1-3, characterized in that said second PVA copolymer has a viscosity of 4% solution at 20°C in the range from 12 cP to 30 cP. 7. Water-soluble film according to any one of paragraphs. 1-3, characterized in that the residue has a value of 20 wt. % or less as measured in the dissolution chamber test. 8. Water-soluble film according to any one of paragraphs. 1-3, characterized in that said mixture of PVA resins consists of a first PVA copolymer and a second PVA copolymer. 9. Water-soluble film according to any one of paragraphs. 1-3, further containing at least a third water-soluble polymer that is different from the PVA polymer. 10. The water-soluble film of claim 9, wherein said third water-soluble polymer is selected from one or more of: polyethylenimine, polyvinylpyrrolidone, polyalkylene oxide, polyacrylamide, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polyamide, gelatin, methylcellulose , carboxymethylcellulose, carboxymethylcellulose salt, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, starch, modified starch, guar gum, acacia gum, xanthan gum, carrageenan, polyacrylate, polyacrylate salt and a copolymer of any of the above. 11. Water-soluble film according to any one of paragraphs. 1-3, characterized in that said first PVA copolymer and said second PVA copolymer independently of each other have a degree of hydrolysis in the range from 75% to 99%. 12. Water-soluble film according to any one of paragraphs. 1-3, further comprising an auxiliary agent selected from one or more of a plasticizer, a plasticizer compatibilizer, a lubricant, an anti-blocking agent, a filler, a diluent, a cross-linking agent, an anti-blocking agent, an antioxidant, a tack-reducing agent, an antifoaming agent, nanoparticles, whitening agent and surfactant. 13. Water-soluble film according to any one of paragraphs. 1-3, additionally containing one or more plasticizers in an amount of 30 parts by weight. or more. 14. Water-soluble film according to any one of paragraphs. 1-3, additionally containing one or more plasticizers in an amount of less than 30 parts by weight. 15. Water-soluble film according to any one of paragraphs. 1-3, containing a first plasticizer having a molecular weight of 92 g/mol or more, and a second plasticizer having a molecular weight of 150 g/mol or more. 16. Water-soluble film according to claim 15, additionally containing a third plasticizer. 17. Water-soluble film according to any one of paragraphs. 1-3, additionally containing a filler in an amount of at least 2 parts by weight. 18. The water-soluble film of claim 17, wherein said filler includes a bulking agent and an anti-blocking agent, or a combination thereof. 19. Water-soluble film according to claim 1, characterized in that: the second PVA copolymer is present in an amount ranging from 30 wt. % up to 90 wt. % of the total mass of the mixture of PVA resins; And a ₁ is in the range from 3 mol. % up to 6 mol. %; a ₂ is in the range from 7 mol. % up to 9 mol. %. 20. Product for storing a liquid composition, containing: water-soluble film according to any one of paragraphs. 1-19 in the form of a package, defining the internal volume of the package. 21. Product according to claim 20, characterized in that the composition is contained in the internal volume of the package. 22. The product according to claim 20, characterized in that said liquid composition is a liquid detergent. 23. The product according to claim 20, characterized in that said liquid composition contains a low molecular weight polyol. 24. Product according to any one of paragraphs. 20-23, characterized in that it has a delayed release time of at least 30 seconds as measured in a liquid release test.

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