RU2783026C2 - Water-soluble film of mixture of polyvinyl alcohol, related methods and related products - Google Patents

Abstract

FIELD: packaging.

SUBSTANCE: invention relates to water-soluble film for the manufacture of packages. Film contains: a plasticizer and a mixture of resins of polyvinyl alcohol (hereinafter – PVA). The mixture of PVA resins contains: the first PVA copolymer containing the first anionic monomeric link selected from a group including alkylacrylates, alkylalkacrylates, hydrolyzed salts of alkaline metals of the above-mentioned, and combinations of the above-mentioned; and the second PVA copolymer containing the second anionic monomeric link selected from one or more of maleic anhydride and salt of alkaline metal of maleic anhydride. In this case, the first PVA copolymer is contained in amount in the range from about 10 wt. % to about 40 wt. % per the total weight of the mixture of PVA resins, and the first anionic monomeric link differs from the second anionic monomeric link, where the plasticizer is present in amount from about 5 wt.pts. to less than 30 wt.pts. per 100 wt.pts. of PVA (phr), and it includes glycerin and sorbitol. Water-soluble film has a residue value of about 35 wt. % or less according to data on measurement in testing a dissolution chamber and crystallinity of at least 15%. The invention also relates to a product.

EFFECT: proposed film can be formed into packages, which save film rigidity and remain elastic, saving transparency without deterioration of final solubility of water-soluble film.

24 cl, 4 dwg, 23 tbl, 127 ex

Description

FIELD OF TECHNOLOGY

[0001] This description generally refers to water-soluble films and related packages. More specifically, this disclosure relates to water-soluble polyvinyl alcohol based films that contain a blend of polyvinyl alcohol (PVA) resins and that can be used in contact with liquids, solids, or combinations thereof with one or more of the advantages of maintaining film rigidity and maintaining bag tension when enclosing liquid formulations such as low molecular weight polyols.

BACKGROUND OF THE INVENTION

[0002] Water-soluble polymeric films are typically used as packaging materials to facilitate dispersion, pouring, dissolving, and dosing of delivered material. For example, bags made from water-soluble film are typically used to package home care compositions such as laundry and dish detergents. The consumer may directly add the composition in the bag 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. The packaged composition can also reduce the mess that can be associated with dispensing a similar composition from a container, such as when pouring liquid laundry detergent from a bottle. In general, pre-measured soluble polymer film pouches provide consumer convenience in a variety of applications.

[0003] Some of the water-soluble polymeric films that are used to make bags currently on the market interact with the components of the bag (eg, detergents), which affects the properties of the bag, for example, the ability to maintain the rigidity of the film. For example, the bags may exhibit film softening over time upon contact with their contents, such as liquid solvents typically used in liquid detergent compositions, and low molecular weight polyols. Such softening may, for example, reduce tension on the pouch and give the pouch a loose and droopy look and feel. In another type of problem, the transparency of the film may be affected by the clouding effect of the components of the package 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 undesirable residue left after washing. In another type of problem, the mechanical properties of the film may change over time in contact with its contents, resulting in an undesirable increase in film stiffness or increased film brittleness.

[0004] In addition, COMMISSION REGULATION (EC) 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 of 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 soluble packaging. Among these provisions were the requirement that the instant pack retain a liquid content for at least 30 seconds when the instant pack is placed in water at 20°C. Naturally, the film must then break down and preferably completely dissolve in order 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 shaped, that maintain film rigidity 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 specification, there is provided a water-soluble film comprising a polyvinyl alcohol (PVA) resin blend comprising a first PVA copolymer containing a first anionic monomer unit selected from the group consisting of alkyl acrylates, alkyl alkacrylates, hydrolysed alkali metal salts of the foregoing, and combinations of the foregoing, and a second PVA copolymer containing a second anionic monomeric unit, where the first anionic monomeric unit is different from the second anionic monomeric unit and, optionally, the first PVA copolymer is present in an amount ranging from about 10 wt. % to about 40 wt. % based on the total weight of the PVA resin mixture.

[0007] Another aspect of this description relates to an article containing a water-soluble film according to this description in the form of a package, defining the internal volume of the package and optionally containing the composition in the internal volume of the package, for example, a liquid composition.

[0008] Additional aspects and advantages will become apparent to those of ordinary skill in the art upon reading the following detailed description. While said film, bag, and methods for making the same allow for embodiments of the invention 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 present invention to the specific embodiments of the invention described herein. .

BRIEF DESCRIPTION OF GRAPHICS

[0009] FIG. 1 illustrates a wireframe cage (shown with an open top to better illustrate the water soluble packets it contains) for use in the fluid release test described herein.

[0010] FIG. 2 illustrates a fluid release test apparatus comprising a beaker mounted on a stand, a stand holding a rod for lowering the cage into the beaker, the rod being fixed with a collar with a set screw (not shown).

[0011] FIG. 3a and 3b are plots of RC residual values over time for films stored at ambient temperature (FIG. 3a) and at 38°C and 80% relative humidity (FIG. 3b) for films made from PVA resin blends, comprising a PVA-acrylate copolymer and a PVA-maleate copolymer. The percentage of PVA-acrylate copolymer in the mixture is indicated in the legend, and the rest of the resin is the maleate copolymer.

[0012] FIG. 4a and 4b are graphs of film dissolution at 10°C over time for films stored at ambient temperature (FIG. 4a) and at 38°C and 80% relative humidity (FIG. 4b) for films made from blends PVA resins comprising a PVA-acrylate copolymer and a PVA-maleate copolymer. The percentage of PVA-acrylate copolymer in the mixture is indicated in the legend, and the rest of the resin is the maleate copolymer.

DETAILED DESCRIPTION OF THE INVENTION

[0013] In one aspect of this specification, there is provided a water-soluble film comprising a polyvinyl alcohol (PVA) resin blend comprising a first PVA copolymer containing a first anionic monomer unit selected from the group consisting of alkyl acrylates, alkyl alkacrylates, hydrolysed alkali metal salts of the foregoing, and combinations of the foregoing, and a second PVA copolymer containing a second anionic monomer unit, where the first PVA copolymer is present in an amount ranging from about 10 wt. % to about 40 wt. % based on the total weight of the PVA resin mixture and the first anionic monomer unit is different from the second anionic monomer unit.

[0014] 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 60 wt. % to about 90 wt. % or from about 60 wt. % to about 80 wt. % of the total weight of the mixture of PVA resins.

[0015] In embodiments of the invention, the first and second PVA copolymers contain pendant groups provided by an anionic monomer unit. The pendant group as used herein includes pendant groups from any vinyl ester copolymerized monomer and does not include residual ester groups or hydrolysed ester groups from the vinyl ester. For example, acetate groups resulting from the polymerization of vinyl acetate and hydroxyl groups formed from the 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 ), while the difference between a ₁ and a ₂ is from about 2 mol. % to about 10 mol. %. The first side group and the second side group may be present together in a combined amount ranging from about 2 to 15 mol. % or from about 2 to 10 mol. %. In embodiments of the invention, the first PVA copolymer is an alkyl acrylate copolymer having a first anionic monomer content (b ₁ ), the second PVA copolymer is a maleic anhydride copolymer having a second anionic monomer content (b ₂ ), wherein the difference between b ₁ and b ₂ is from about 0.2 to 2 mol. %. In embodiments of the invention, the first PVA copolymer has a viscosity of a 4% solution at 20° C. in the range of about 4 centipoise to about 24 centipoise. In embodiments of the invention, the second PVA copolymer has a viscosity of a 4% solution at 20° C. in the range of about 12 centipoise to about 30 centipoise.

[0016] In embodiments of the invention, the specified water-soluble film has a residue value of about 35 wt. % or less as measured in the dissolution chamber test ("CR Residue"). In embodiments of the invention, said water-soluble film may have a swell factor value according to a film swelling test that is no more than 60% of the swell factor value of a comparative film that is identical to but differs from the second PVA copolymer, which is an individual resin, and the amount of this second of the PVA copolymer in the comparative film is equal to the total amount of resins in the water-soluble film of this invention.

[0017] In embodiments of the invention, said mixture of PVA resins 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, said first PVA copolymer and the second PVA copolymer independently have a degree of hydrolysis in the range of about 75% to about 99%.

[0018] In embodiments of the invention, said first PVA copolymer contains an alkyl acrylate monomer unit, 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, the second PVA copolymer contains a second anionic monomer unit selected from the group consisting of maleic anhydride, its alkali metal salts and combinations of the above, the second PVA copolymer is present in an amount ranging from about 60 wt. % to about 90 wt. % of the total weight of the mixture of PVA resins, in which the difference between a1 and a2 is from about 2 mol. % to about 6 mol. %, a1 is in the range from about 4 mol. % to about 6 mol. %, a2 is in the range from about 7 mol. % to about 9 mol. %, and the first side group and the second side group together are present in a combined amount in the range from about 10 mol. % up to 15 mol. %.

[0019] In embodiments of the invention, said first PVA copolymer contains an alkyl acrylate monomer unit and is present in an amount ranging from about 10 wt. % to about 40 wt. % of the total mass of the mixture of PVA resins, and the water-soluble film additionally contains a plasticizer in an amount of at least 30 m.h.

[0020] In embodiments of the invention, said first PVA copolymer contains an alkyl acrylate monomer unit and is present in an amount ranging from about 10 wt. % to about 40 wt. % of the total weight of the mixture of PVA resins, and the water-soluble film additionally contains the first plasticizer having a molar mass of more than or equal to 92 g/mol, and the second plasticizer having a molar mass of more than or equal to 150 g/mol. Optionally, said water-soluble film may further comprise a third plasticizer.

[0021] In embodiments of the invention, said first PVA copolymer contains an alkyl acrylate monomer unit and is present in an amount ranging from about 10 wt. % to about 40 wt. % of the total mass 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.

[0022] In another aspect of the invention, there is provided an article of manufacture 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 internal volume 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 internal volume of the bag is solid.

[0023] In embodiments of the invention, the composition contained in the interior of the pouch is a liquid, and said article has a delayed release time of at least 30 seconds as measured by the liquid release test. In embodiments of the invention, the composition contained in the internal volume of the package is a liquid, and the specified product has a compressive strength of more than 300 N as measured in a compression test. In embodiments of the invention, the composition contained in the interior of the bag is a liquid and said article has a compressive strength of less than 2000 N as measured in a compressive test.

[0024] As used herein, the term "comprising" or "comprising" means various components, ingredients, or steps that can be used together in the practice of this description. Accordingly, the term "comprising" encompasses 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 bag may "consist essentially of" the film described herein to apply its thermoforming characteristics, also including a non-thermoformed film (eg, part of the lid) and additional markings on the film, such as by inkjet printing. The invention illustratively described herein can be suitably practiced in the absence of any element or step not specifically described herein.

[0025] All percentages, parts and ratios mentioned herein are based on the total dry weight of the film composition or the total weight of the package content composition as described herein, as the case may be, and all measurements made are taken at about 25°C, unless otherwise indicated. All weights referring to ingredients listed are active level based and therefore do not include carriers or by-products that may be found in commercially available materials unless otherwise noted.

[0026] All ranges specified herein include all possible subsets of ranges and any combination of such subsets of ranges. By default, ranges include the specified endpoints unless otherwise specified. If a range of values is proposed, it is understood that every intermediate value between the upper and lower limit of this range and any other declared or intermediate value in this specified range is covered in this description. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also included herein, subject to any specifically excluded limit within the specified range. If a specified range includes one or both of the limits, ranges excluding one or both of the included limits are also considered part of this specification.

[0027] It is specifically contemplated that for any numerical value described herein, for example, as a parameter of the described subject matter or as 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 numeric value (for example, for a size listed as "40 mm", an intended alternate embodiment of the invention is "about 40 mm").

[0028] As used herein, the terms "package(s)" and "bag(s)" should be considered interchangeable. In certain embodiments, the terms package(s) and bag(s), respectively, are used to refer to a container made using a film and a fully sealed container, preferably containing material sealed therein, such as in the form of a metered dose delivery system. The sealed bags can be made by any suitable method, including methods and features such as heat sealing, solvent sealing, and gluing (eg, using a water-soluble adhesive).

[0029] As used in this document, and unless otherwise indicated, the terms "wt. %" are intended to indicate the composition of the identified element of the "dry" (not containing water) parts by weight of the entire film, including residual moisture. in a film (if applicable) or parts by weight of the entire composition enclosed in a bag (if applicable).

[0030] As used herein, and unless otherwise indicated, the term "m.h." is intended to indicate the composition of an identified element in parts per hundred parts of a water-soluble polymer resin (whether PVA or other polymer resins, unless otherwise indicated) in a water-soluble film or solution used to make that film.

[0031] The specified film can be made by any suitable method, including the method of casting from a solution. Said film may be used to form the container (pouch) by any suitable method, including vertical forming, filling and sealing (VFFS) or thermoforming. Said film may 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 to be delivered to a bulk aqueous medium.

[0032] The film, pouches, and associated methods of making and uses are intended 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.

[0033] In any embodiment of the invention, the specified water-soluble package may contain (enclose) the 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 fluids include agricultural compositions, automotive compositions, aviation compositions, food and nutrition 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 treatment, including cleaning and washing compositions applicable to 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 can provide technical benefits including, but not limited to, laundry benefits, pretreatment benefits, and/or aesthetic effects.

[0034] In any of the laundry-oriented embodiments of the invention, said composition may be selected from the group of, for example, liquid detergent compositions for mild conditions and liquid detergent compositions for hard conditions, powdered detergent compositions, fabric enhancers, washing gels, as a rule used for washing, and bleaches (for example, organic or inorganic bleaches) and additives for washing.

[0035] Water Soluble Film

[0036] The film and associated packages 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. Said film may be of any suitable thickness, and a film thickness of about 76 microns (μm) is typical and especially 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 about 40 to about 90 microns, or about 50 to 80 microns, or about 60 to 65 µm, such as 65 µm, 76 µm or 88 µm.

[0037] PVA RESIN

[0038] Polyvinyl alcohol is a synthetic resin typically obtained by alcoholysis, commonly referred to as hydrolysis or saponification, of polyvinyl acetate. Fully hydrolyzed PVA, in which virtually all of the acetate groups have been converted to alcohol groups, is a highly crystalline polymer with strong hydrogen bonds that only dissolves in hot water - above 140°F (about 60°C). If sufficient acetate groups remain after hydrolysis of the polyvinyl acetate, that is, the PVA polymer is partially hydrolyzed, then said polymer is more weakly hydrogen bonded, less crystalline, and generally cold water soluble—less than about 50°F (about 10 °C). As such, said partially hydrolysed polymer is a copolymer of vinyl alcohol and vinyl acetate, which is a copolymer of PVA, but is generally referred to as PVA.

[0039] In particular, 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.

[0040] Water-soluble polymer films based on PVA can be subject to changes in solubility characteristics. The acetate group in a co-poly(vinyl acetate-vinyl alcohol) copolymer is known to those skilled in the art to be hydrolysable by acid or alkaline hydrolysis. As the degree of hydrolysis increases, the polymer composition made from the PVA homopolymer resin will have increased mechanical strength, but reduced solubility at lower temperatures (eg, requiring hot water temperature for complete dissolution). Accordingly, exposing a PVA resin homopolymer to an alkaline environment (for example, by using a laundry bleach additive) can convert said resin from a resin that dissolves rapidly and completely in a given aqueous environment (for example, cold water environment) to a resin that dissolves slowly and/or incompletely in a given aqueous environment, which can lead to the formation of undissolved polymer residue at the end of the wash cycle. This is a natural disadvantage when using only vinyl acetate/vinyl alcohol copolymer based films, typified by commercial PVA homopolymer resins.

[0041] 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 water solubility of the PVA copolymer resin. In the presence of a strong base, such as a laundry detergent, lactone rings can open within a few weeks under relatively warm (ambient) conditions and high humidity (e.g. via lactone ring opening reactions to form the corresponding pendent 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 bag during storage. Therefore, as they age, these bags may become increasingly prone to premature dissolution during the hot wash cycle (40°C nominal) and may in turn reduce the effectiveness of some laundry actives due to the presence of the bleaching agent and the effect of the resultant pH.

[0042] When creating a suitable film for a given application (eg, a pouch for laundry), many factors must be considered. These factors include: (1) film strength, where higher strength desirably translates into greater bag sealing when the film is the weak link in the seal; (2) change in the elastic modulus of the film after exposure to a liquid, where a positive change in the modulus desirably provides a lower chance of softening, loosening and sagging when forming a bag encapsulating the liquid composition, and/or deformation and sticking to other films when loaded on top of each other during production or in final consumer packaging; (3) the value of the swelling coefficient of the film after exposure to the liquid solution, with a lower value of the coefficient of swelling desirably providing greater rigidity of the film, less change in the area of the film (length x width) after exposure to the liquid solution and a greater density of the package and less chance of softening, loosening and sagging when compiling a package encapsulating a liquid composition; (4) a dissolution residue, where a lower residue value desirably reduces the likelihood of residual film remaining after harsh washing conditions (eg, low water (eg, washing machine overload) and cold water wash 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 bag encapsulating a liquid composition. Often, water-soluble polymer resins, whether PVA or otherwise, may perform well with respect to some of these factors, but they may perform poorly with respect to other of these factors. Accordingly, it is desirable to provide a water-soluble film in which many, if not all, of these factors would have favorable properties in said film.

[0043] In view of these factors, this description includes a water-soluble film containing a mixture of polyvinyl alcohol (PVA) resin 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, which is a PVA copolymer ("first PVA copolymer") containing one or more types of anionic monomer units (e.g., a ternary (or higher) PVA copolymer) and a second PVA resin. which is a PVA copolymer ("second PVA copolymer") containing one or more types of anionic monomer units (for example, a three-component (or higher-component) PVA copolymer). In some aspects, said PVA resin blend contains only a first PVA copolymer and a second PVA copolymer (eg, a binary blend of two polymers). Alternatively or additionally, the PVA resin mixture, the water-soluble film, or both can be characterized as free or substantially free of other polymers (eg, generally other water-soluble polymers, in particular other PVA-based polymers, or both). As used herein, the term "substantially free" means that the first and second PVA copolymers are at least 95 wt. %, at least 97 wt. % or at least 99 wt. % of the total amount of water-soluble polymers in the water-soluble film. In other aspects, the specified 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).

[0044] 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 it is not fully hydrolyzed), and the individual type of anionic monomer unit (eg, where 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 the PVA copolymer include vinyl polymerization units corresponding to vinyl monocarboxylic acid 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 vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, fumaric anhydride, taconic acid, monoalkyl itaconate, dialkyl itaconate, itaconic anhydride, , 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 alkali metal salts of the above, and combinations of the above.

[0045] In one type of embodiments of the invention, the specified PVA is a copolymer modified with carboxyl groups. In another aspect, said PVA may be modified with a dicarboxylic 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 linked to an unsaturated bond, and said unsaturated bond is further substituted, for example, with 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 another carbonyl are linked to an unsaturated bond (eg, itaconic acid, cis-glutaconic acid, trans-glutaconic acid). Monomers are contemplated which contain alkyl carboxyl groups. The maleate type comonomer (eg, dialkyl maleate or monoalkyl maleate, including monomethyl maleate) is especially contemplated.

[0046] In embodiments, the first PVA copolymer comprises a first anionic monomer selected from the group consisting of alkyl acrylates, alkyl alkacrylates, hydrolysed alkali metal salts of the foregoing, and combinations of the foregoing. In embodiments of the invention, the second PVA copolymer contains a second anionic monomer selected from the group consisting of maleic anhydride, its alkali metal salts, and combinations of the above.

[0047] The content level of one or more anionic monomer units in the PVA copolymers 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 mole % 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).

[0048] 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. The lactone-containing polymer can be treated with alkali such that all or only some of the lactone rings are opened. For example, PVA-methyl acrylate copolymers form lactone rings and can be processed such that, for example, 70% of the lactone rings are opened. Accordingly, the level of side groups is 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 neighboring 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, said copolymer contains two pendant groups per anionic monomer unit contained in said copolymer.

) в диапазоне от около 2 мол. % до около 20 мол. %. То есть, первая боковая группа и вторая боковая группа вместе присутствуют в объединенном количестве в диапазоне от около 2 мол. % до около 20 мол. %, от около 2 мол. % до около 15 мол. %, от около 5 мол. % до около 15 мол. %, от около 5 мол. % до около 10 мол. %, от около 5 мол. % до около 8 мол. % или от около 10 мол. % до около 15 мол. %. Средневзвешенное арифметическое значение боковых групп

рассчитывают по формуле

, где

представляет собой процент по массе соответствующего сополимера ПВС и

представляет собой соответствующий мол. % боковых групп в указанном сополимере ПВС. [0049] The level of side groups in the 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 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, 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 mole % in various embodiments). A mixture of PVA resins may have an arithmetic mean number of side groups (

) in the range of about 2 mol. % to about 20 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 20 mol. %, from about 2 mol. % to about 15 mol. %, from about 5 mol. % to about 15 mol. %, from about 5 mol. % to about 10 mol. %, from about 5 mol. % to about 8 mol. % or from about 10 mol. % to about 15 mol. %. Arithmetic weighted mean of the side groups

calculated according to the formula

, where

is the percentage by weight of the corresponding PVA copolymer and

is the corresponding mol. % side groups in the specified PVA copolymer.

[0050] The specified 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. % mixture of PVA resins. 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 40 wt. % (or from about 15 wt.% to about 35 wt.%, or from about 20 wt.% to about 30 wt.%) of the total amount of PVA polymers and PVA copolymers in the specified film (i.e., relative to the weight of the mixture of PVA resins ). 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. % or 35 wt. % and/or up to about 25 wt. %, 30 wt. %, 35 wt. % or 40 wt. % of the total amount of PVA polymers and PVA copolymers in the specified film. In embodiments of the invention, the above concentrations of the first PVA copolymer, alternatively or additionally, may refer to the total content of water-soluble polymer in the film, PVA or other. Of course, the first water-soluble resin may be more than 40 wt. % of the total amount of PVA polymers and PVA copolymers in the film, however, when the amount of the first water-soluble resin increases above 40 wt. %, the decrease in the value of the swelling ratio is not significant, as shown in the examples, while the values of the residue undesirably increase with the increase in the amount of the first water-soluble resin.

[0051] In embodiments of the invention, the second PVA copolymer is present in the water-soluble film in an amount of from about 60 wt. % to about 90 wt. % (or about 65 wt. % to about 85 wt. %, or from about 70 wt. ). For example, the second PVA copolymer may be present in an amount of at least 60 wt. %, 65 wt. %, 70 wt. %, 75 wt. %, 80 wt. % or 85 wt. % and/or up to about 70 wt. %, 75 wt. %, 80 wt. %, 85 wt. % or 90 wt. % of the total amount of PVA polymers and PVA copolymers in the specified film. In another aspect, the above concentrations of the second PVA copolymer, alternatively or additionally, may refer to the total content of water-soluble polymer in the film, PVA or other.

[0052] In the aspect of the water-soluble film, the first PVA copolymer contains one or more first anionic monomer units, and the second PVA copolymer contains one or more second anionic monomer units. The first and second anionic monomer units in the two PVA copolymers may be the same or different in various embodiments of the invention. For reference, the first PVA copolymer is designated as having a first level of side groups (a ₁ ) and a first level (b ₁ ) of first anionic monomer units, and the second PVA copolymer is designated as having a second level of side groups (a ₂ ) and a second level of ( b ₂ ) second anionic monomer units.

[0053] In a refinement of this aspect, the first and second PVA copolymers are selected so that the difference between a1 and a2 is in the range of about 0.5 mol. % to about 12 mol. % (or from about 1 mol.% to about 11 mol.%, from about 2 mol.% to about 10 mol.%, from about 3 mol.% to 6 mol.%, or from about 2 mol.% to about 6 mol.%), and more generally may be at least 0.5, 1 or 2 mol. % and/or up to about 1, 2, 3, 4, 5, 10 or 12 mol. %. Individually, the level of side groups (a1) for the first PVA copolymer may range from about 2 mol. % to about 6 mol. % (or 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 (a2) for the second anionic monomer units may be in the range from about 6 mol. % to about 12 mol. % (or from about 6 mol.% to about 10 mol.%, or from about 7 mol.% to about 9 mol.%, or about 6 mol.%, 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 %.

[0054] In embodiments of the invention, the first and second PVA copolymers are selected so that the difference between b ₁ and b ₂ is in the range from about 0.2 mol. % to about 2 mol. % (or from about 0.3 mol.% to about 1.5 mol.%, from about 0.4 mol.% to about 1.5 mol.% or from about 0.5 mol.% to about 1.5 mol.%), and more generally can be at least 0.2, 0.3, 0.4 mol. % or 0.5 mol. % and/or up to about 1.0, 1.5 or 2.0 mol. %. Individually, the level of content (b ₁ ) of the first anionic monomer units (ie, the amount of anionic modification of the PVA copolymer) can range from about 3 mol. % to about 8 mol. % (or from about 4 mol.% to about 6 mol.%, for example, about 5 mol.%) in the first PVA copolymer. Alternatively or additionally, the level of content (b ₂ ) of the second anionic monomer units (ie, the amount of anionic modification of the PVA copolymer) can be in the range from about 2 mol. % to about 6 mol. % (or from about 3 mol.% to about 5 mol.%, for example about 4 mol.%) in the second PVA copolymer.

[0055] The degree of hydrolysis (DH) of the PVA homopolymers and PVA copolymers contained in the water-soluble films of this disclosure 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%, or 92%, for example, for compositions soluble in cold water; from about 90% to about 99%, from about 92% to about 99%, about 95% to about 99%, about 98%, about 99%, or more than 99%). As the degree of hydrolysis decreases, a film made from resin will have reduced mechanical strength but faster dissolution at temperatures less than about 20°C. As the degree of hydrolysis increases, a film made from said polymer will tend to become mechanically stronger and thermoformability will decrease. The degree of hydrolysis of PVA can be chosen so that the solubility of the polymer in water depends on the 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), cold water soluble film, water soluble at less than 10°C, may contain PVA with a degree of hydrolysis in the range of about 75% to about 90%, or in the range of about 80% to about 90%, or in the range of 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%.

. Например,

для смолы ПВС, содержащей два или более полимера ПВС, рассчитывается по формуле

, где Wi представляет собой процент по массе соответствующего полимера ПВС, а H _i представляет собой соответствующие степени гидролиза.[0056] The degree of hydrolysis of a mixture of resins can also be characterized by the weighted arithmetic degree of hydrolysis

. For example,

for a PVA resin containing two or more PVA polymers, is calculated by the formula

where Wi is the percent by weight of the respective PVA polymer and H _i are the respective degrees of hydrolysis.

[0057] PVA polymer viscosity (µ) is determined by measuring a fresh solution using a Brookfield LV viscometer with UL adapter as described in 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 given herein in centipoise (cP) are to be understood as referring to the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20°C, unless otherwise indicated. Similarly, when a resin is described as having (or not having) a particular viscosity, unless otherwise indicated, said viscosity is intended to be the average viscosity for a resin that inherently has an appropriate molecular weight distribution.

смолы ПВС, и часто вязкость используется как показатель

. Таким образом, среднемассовая молекулярная масса водорастворимых полимеров, включающих первый сополимер ПВС и второй сополимер ПВС, может находиться в диапазоне, например, от около 30000 до около 175000, от около 30000 до около 100000 или от около 55000 до около 80000. Что касается средней вязкости смеси смол ПВС, используют средневзвешенное натуральнологарифмическое вязкости

.

для смолы ПВС, которая содержит два или более полимеров ПВС, рассчитывают по формуле

, где µι представляет собой вязкость соответствующих полимеров ПВС.[0058] For reference, the first PVA copolymer is referred to as having the viscosity of the first 4% solution at 20°C (µ ₁ ), and the second PVA copolymer is referred to as having the viscosity of the second 4% solution at 20°C (µ ₂ ). In various embodiments, the first viscosity µ1 may range from about 4 centipoise to about 30 centipoise (e.g., at least about 4, 8, 10, 12, or 16 centipoise and/or up to about 12, 16, 20, 24 or 30 cps, such as about 4 cps to about 24 cps, about 10 cps to about 16 cps, about 10 cps to about 20 cps, or about 20 cps to about 30 cps). Alternatively or additionally, the second viscosity µ2 may range from about 4 centipoise to about 30 centipoise (e.g., at least about 4, 8, 10, 12, or 16 centipoise and/or up to about 12, 16, 20, 24 or 30 cps, for example, about 12 cps to about 30 cps, about 10 cps to about 16 cps, about 10 cps to about 20 cps, or about 20 cps to about 30 cps). When the mixture of PVA resins 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

PVA resins, and often viscosity is used as an indicator

. 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 regard to the average viscosity mixtures of PVA resins, use a weighted average of the natural logarithmic viscosity

.

for a PVA resin that contains two or more PVA polymers, is calculated by the formula

, where µι is the viscosity of the corresponding PVA polymers.

[0059] 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 retains film rigidity and retains the resilience of the bag (e.g., is less likely to loosen and sag) upon contact with the liquid contents of the bag and preferably maintaining or improving dissolution, residue and mechanical properties. In some embodiments of the invention, the specified water-soluble film has the property that (a) the water-soluble film has a residue value of 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 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 to about 45 wt % or from about 25 wt % to about 40 wt % as measured in the dilution 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%, 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 the crystallinity test (described below). In some embodiments of the invention, said water-soluble film has the property that (c) the water-soluble film is resistant to the effect of haze, as determined by visual inspection of the opacity of the film of the bag material relative to the opacity of the film during manufacture. In some embodiments of the invention, said water-soluble film has the property that (d) the water-soluble film has a swelling ratio value that is no more than 60% of the swelling ratio value of the comparative film, which is identical to but different from the second PVA copolymer, which 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 this invention as measured in the film swelling test (described below). It should be appreciated that not every one of properties (a)-(d) must be satisfied to provide a water-soluble film having retained film stiffness and retained bag resilience (e.g., less likely to loosen and sag) upon contact with the liquid contents of the bag, 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 retained film rigidity and retained pouch resilience can be developed, for example, by changing the type and/or amount of plasticizer contained in the film. In various embodiments of the invention, the specified water-soluble film has the 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 aforementioned properties exhibit those properties prior to exposure to a liquid composition (eg, liquid laundry detergent) and retain the aforementioned properties after exposure to the liquid composition. Water-soluble films as described herein "retain" a property after exposure to a liquid composition if that property has a value after exposure to the liquid composition that is within the ranges described herein for said property. Water soluble films as described herein need not retain exactly the same property value after exposure to the liquid composition that the film exhibited prior to exposure to the liquid composition. For example, in one type of embodiment 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.

[0060] PVA resin blends as described herein surprisingly produce water soluble films having a combination of desirable 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 blend has at least one undesirable feature for a particular property, but a water-soluble film comprising said blend provides a desired feature for a particular property of each PVA copolymer. For example, the PVA resin blend may comprise first and second PVA copolymers such 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 the 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 the 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 the 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). The corresponding PVA copolymer means a water-soluble film containing only the first PVA copolymer or the second PVA copolymer as a water-soluble polymer resin, but otherwise containing the same type and amounts of plasticizers and other additives, having the same thickness, etc.

[0061] OTHER WATER-SOLUBLE POLYMERS

[0062] 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, polyethyleneimine, 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 above 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 their salts, dextrins, ethylcelluloses, hydroxyethylcelluloses, hydroxypropylmethylcelluloses, maltodextrins, polymethacrylates, and combinations of any of the above. Such water-soluble polymers, whether PVA or otherwise, are commercially available from a variety of sources.

[0063] In embodiments of the invention, said mixture of PVA resins 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.

[0064] The specified water-soluble film may contain other auxiliary agents and processing agents, such as, but not limited to, plasticizers, agents that improve compatibility with plasticizers, 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 metabisulphite, sodium bisulfite or others), aversive agents such as bitter substances (e.g. 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 (e.g. capsaicin, piperine, allyl isothiocyanate and resinferatoxin) and other functional ingredients in amounts fit for the intended purposes. Embodiments of the invention containing plasticizers are preferred. The amount of such agents can 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. % individually or together.

[0065] PLASTICIZERS

[0066] A plasticizer is a liquid, solid, or semi-solid that is added to a material (typically a resin or elastomer) to make 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 chemical modification of said polymer or monomer. Additionally or alternatively, the specified polymer can be plasticized from the outside 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 (resistance) to various environmental conditions, including low and high relative humidity.

[0067] The specified 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, trimethylol propane, polyester 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, trimethylol propane, 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 film weight. 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. %, for example, 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. %, for example 6 wt. %. Optionally, sorbitol can be used in an amount of from about 1 wt. % to about 20 wt. % or from about 2 wt. % to about 10 wt. %, for example, about 5 wt. %. Specific amounts of plasticizers may be selected in a particular embodiment of the invention based on the desired flexibility of the film and processability features of the water-soluble film. At low levels of plasticizer, films can become brittle, difficult to process, or prone to breakage. At elevated levels of plasticizer, films may be too soft, brittle, or difficult to process for the desired application.

[0068] In some embodiments of the invention, the specified plasticizer may include glycerin, sorbitol and trimethylolpropane. Optionally, the plasticizer may be present in an amount greater than or equal to 30 ppm. or more than 40 m.h., for example, in the range from about 30 m.h. up to about 75 m.h., from about 30 m.h. up to about 70 m.h., from about 30 m.h. up 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.

[0069] In some embodiments of the invention, the specified plasticizer may include glycerin, sorbitol and 2-methyl-1,3-propanediol. Optionally, the plasticizer may be present in an amount of less than 30 ppm. or less than 25 m.h., for example, in the range from about 5 m.h. up to about 30 m.h., from about 10 m.h. up to about 30 m.h., from about 15 m.h. up to about 30 m.h., from about 5 m.h. up to about 29 m.h., from about 5 m.h. up 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.

[0070] In some embodiments of the invention, the specified 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 in the range of about 150 g/mol to 200 g/mol, e.g., about 150 g/mol to about 190 g/mol, about 160 g/mol to about 190 g/mol, about 170 g/mol to about 190 g/mol or from about 180 g/mol to about 190 g/mol.

[0071] It is understood that individual plasticizers may have Hansen solubility parameters that are outside the defined Hansen range, but that when the plasticizers are mixed, the resulting combination or ratio may then fall within the defined Hansen range. Accordingly, when more than one plasticizer is used for a polymer resin, the combination will be chosen to have the Hansen Solubility Parameters (HSP) described herein.

[0072] The solubility characteristics of a material can be characterized by three separate forces: dispersion forces (δ _D ), polar forces (δ _P ), and hydrogen bonding forces (δ _H ). Individual forces can be combined into a total cohesive energy (δ _T ) as shown in Equation 1: (δ _T ) ² = (δ _D ) ² + (δ _P ) ² + (δ _H ) ² . (1) In addition to the representative solubility parameters for a single component, the Hansen region can be defined in Hansen space as a sphere with the individual solubility parameters (δ _D ), (δ _P ) and (δ _H ) as the center and the radius RAD defining the volume spheres.

[0073] In another aspect, the definition of the Hansen area may further include "basic" values. The principal values determine how much the center of the sphere (defined by δ _D , δ _P , δ _H and RAD) can move in some sense in the directions δ _D , δ _P and δ _H (+ or -) to expand the Hansen domain. Thus, the larger the fundamental values, the less accurately the Hansen region approaches a truly spherical region.

[0074] Calculations to estimate various HSP values can be performed using a commercially available software package such as HSPIP (available from the Hansen Solubility Parameters website, currently in 4th edition). Good plasticizers and poor plasticizers can be tested experimentally, and the HSP coordinates δ _D , δ _P and δ _H for a material can be determined experimentally. Alternatively, the individual HSP coordinates δ _D , δ _P and δ _H can be calculated using the Y-MB methodology (included in the HSPIP software). Regardless of the method chosen to evaluate the HSP parameters, it is advisable to use a consistent method for all plasticizers and polymer components of interest.

[0075] 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

[0076] SURFACTANTS

[0077] Surfactants for use in water-soluble films are well known in the art. Optionally, surfactants are added to aid dispersion of the resin solution during casting. Suitable surfactants for water-soluble films as described herein include, but are not limited to, dialkyl sulfosuccinates, glycerol-propylene glycol lactic acid esters, lactic acid fatty acid esters, 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, alkylbenzenesulfonates, monoethanolamine, lauryl alcohol ethoxylate, propylene glycol, diethylene glycol, salts thereof, and combinations of any of the above.

[0078] Suitable surfactants may include nonionic, cationic, anionic and zwitterionic classes. Suitable surfactants include, but are not limited to, propylene glycols, diethylene glycols, monoethanolamine, polyoxyethylene polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides (nonionic), polyoxyethylene amines, quaternary ammonium salts, and quaternized polyoxyethylene amines (cationic), alkali metal salts of higher fatty acids containing from 8 to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylate sulfates and alkylbenzenesulfonates (anionic), and amine oxides, N-alkyl betaines and sulfo betaines (zwitterionic). Other useful surfactants include sodium dioctyl sulfosuccinate, glycerol and propylene glycol lactic acid esters, 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 of the invention, the amount of surfactant in the water-soluble film is in the range from about 0.1 wt. % up to 2.5 wt. %, optionally from about 1.0 wt. % up 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 the total water-soluble polymer (m.p.) in the water-soluble film, and it is present in the range from about 0.5 m.h. up to about 4 m.h., from about 0.75 m.h. up to about 3.0 m.h., from about 1.0 m.h. up 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.

[0079] Surfactants can be characterized in terms of hydrophilic-lipophilic balance (HLB). The Griffin 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 as follows: HLB=20*Mh/M, where Mh is the molecular weight of the hydrophilic portion of the molecule and M is the molecular weight of the entire molecule, giving an HLB value on a scale of 0 to 20. An HLB value of 0 corresponds completely lipophilic/hydrophobic molecule, and a value of 20 corresponds to a fully hydrophilic/lipophobic molecule.

[0080] 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 comprises an anionic monomer selected from the group consisting of maleic acid, maleic anhydride, monoalkyl maleates, dialkyl maleates, and combinations thereof, and the water-soluble film further comprises a nonionic surfactant, a surfactant based on an amine oxide, an anionic surfactant, a cationic surfactant, or combinations thereof. In refinements of the above aspect, the nonionic surfactant is selected from the group consisting of polyoxyethylene polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols, alkanolamides, and combinations thereof. In 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 foregoing. It should be understood that commercially available amine oxide surfactants may be mixtures of the above, as the amine source may contain a distribution of amines with different chain lengths. Accordingly, by way of example, in some embodiments of the invention, "dimethyldodecylamine oxide" may include a distribution of amine oxides, in which the average amine oxide and/or the main fraction of the amine oxide includes a dodecyl chain. In refinements, said anionic surfactant may include sodium dioctylsulfosuccinate. In refinements, said cationic surfactant may be selected from the group consisting of polyoxyethylene amines, quaternary ammonium salts, quaternized polyoxyethylene amines, and combinations thereof. In embodiments of the invention, the total amount of combined surfactants in the water-soluble film is in the range from about 0.5 m.h. up to about 4 m.h., from about 0.75 m.h. up to about 3.0 m.h., from about 1.0 m.h. up 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.

[0081] In refinements of 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. %.

[0082] 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 embodiments of the invention, the amount of lubricant/release agent in the specified water-soluble film is in the range from about 0.02 wt. % to about 1.5 wt. %, optionally from about 0.1 wt. % to about 1 wt. %.

[0083] Fillers may be contained in water soluble films and may include bulking agents, diluents, antiblocking agents, tackifiers, and combinations thereof. Suitable fillers/bulking agents/diluents/anti-caking agents/anti-tack agents include, but are not limited to, starches, modified starches, cross-linked polyvinylpyrrolidone, cross-linked cellulose, microcrystalline cellulose, silicon dioxide, 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 embodiments of the invention, the amount of filler/diluent/agent that prevents blocking/agent that reduces stickiness in a water-soluble film can be in the 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 m.h. up 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.

[0084] In some embodiments of the invention, the specified water-soluble film may contain 2 or more m.h. (for example, from 2 m.h. to 6 m.h. or from 2 m.h. to 4 m.h.) of the filler. In some embodiments of the invention, the specified film contains 2 or more m.ch. (eg, 2 ppm to 6 ppm or 2 ppm to 4 ppm) filler, and said filler comprises a bulking agent, an anti-caking agent, or a combination thereof. Without being limited by theory, it is believed that the content of 2 or more m.h. (e.g., 2 ppm to 6 ppm or 2 ppm to 4 ppm) filler may be useful in preventing seepage or migration of plasticizer from the film when the plasticizer is present in an amount greater than or equal to equal to 30 m.h., for example, in the range from 30 m.h. up to 50 m.h.

[0085] The release agent (e.g., SiO2 and/or stearic acid) may be present in the film in an amount of at least 0.1 ppm, at least 0.5 ppm, or at least 1 ppm, or in the range of about 0.1 to 5.0 ppm, about 0.1 to about 3.0 ppm, about 0.4 to 1.0 ppm, about 0, 5 to about 0.9 ppm, about 0.5 to about 2 ppm, about 0.5 to about 1.5 ppm, 0.1 to 1.2 ppm . or from 0.1 to 2.7 m.h., for example, 0.5 m.h., 0.6 m.h., 0.7 m.h., 0.8 m.h. or 0.9 m.h.

[0086] Suitable average particle sizes for the release agent include an average particle size in the range of about 3 microns to about 11 microns, about 4 microns to about 11 microns, about 4 microns to about 8 microns, or about 5 microns to about 6 microns. eg 5, 6, 7, 8 or 9 microns. Suitable SiO2 is untreated synthetic amorphous silica intended for use in aqueous systems.

[0087] The water-soluble film may optionally have a residual moisture content of at least 4 wt. %, for example, in the range from about 4 to about 10 wt. % as measured by Karl Fischer titration.

[0088] To be considered a water-soluble film as used herein, a film about 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

[0089] One contemplated class of embodiments of the invention is characterized in that said water-soluble film is formed by dipping into a solution. Solution dip molding methods for PVA 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, dispensed onto the surface, allowed to substantially dry (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 intermittently, but it is more efficient to perform continuously.

[0090] When forming continuous films of polyvinyl alcohol, it is common practice to dispense the solution onto a moving casting surface, such as a continuously moving metal drum or tape, substantially remove the solvent from the liquid, whereby a self-supporting cast film is formed, and then the resulting cast film is removed from casting surface.

[0091] Optionally, said water-soluble film may be a free-standing film consisting of a single layer or a plurality of such layers.

[0092] PACKAGES

[0093] the Film described in this document is suitable for the manufacture of packages containing the composition. The package composition may be in any form such as powders, gels, pastes, liquids, tablets, or any combination thereof. Said film is also suitable for any other application where improved liquid resistance and low residue in cold water are desired. Said film forms at least one side wall of the bag, optionally the entire bag and preferably the outer surface of at least one side wall.

[0094] The film described herein can also be used to make a bag with two or more compartments made from the same film, or in combination with films of other polymeric materials. Additional films can be obtained, for example, by casting, blow molding, extrusion or blow extrusion of the same or 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, said polymers may be selected from polyacrylates and water-soluble copolymers of acrylate, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and combinations thereof, or selected from polyvinyl alcohols, copolymers of polyvinyl alcohols and hydroxypropyl methylcellulose (HPMC), and their combinations. One intended class of embodiments of the invention is characterized by the level of polymer in the bag material, such as the PVA copolymer described above, as described above, ranging from at least 60 wt. % and up to 99 wt. %.

[0095] The packages of this description may contain at least one sealed compartment. Thus, said packages may contain one or more compartments. The water soluble bag can be formed from two layers of water soluble polymeric 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 pouch that contains any desired composition for release into an aqueous medium. The specified composition is not specifically limited, for example, including any of the many compositions described below. In embodiments of the invention containing multiple compartments, each compartment may contain identical and/or different compositions. In turn, these compositions may take any suitable form, including, but not limited to, liquid, solid, and combinations thereof (eg, a solid suspended in a liquid). In embodiments of the invention, these packages contain the first, second and third compartments, each of which respectively contains a different first, second and third composition.

[0096] These multi-compartment pouch compartments may have the same or different sizes and/or volume. Said compartments of the 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 envisaged that the first, second and optionally third and subsequent compartments can be attached to each other side by side. These compartments can be packed in a tape, with each compartment separated separately by a perforation line. Therefore, each compartment can be individually torn away from the remainder of the tape by the end user, for example, to pre-treat or post-treat the fabric with the 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 pouch in pouch configuration.

[0097] In embodiments of the invention, multi-compartment bags comprise 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 so 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 the third compartment are arranged in a structure on the first compartment. Said design may be decorative, educational, or illustrative, such as to illustrate a concept or instruction and/or use to indicate the origin of a product. In embodiments, the first compartment is the largest compartment having two large perimeter sealed surfaces, and the second compartment is smaller covering less than about 75% or less than about 50% of the surface area of one side of the first compartment. In embodiments that include 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.

[0098] The packages as described herein may contain one or more different films. For example, in single-compartment embodiments, said pouch may consist of a single wall that folds over on itself and seals at the edges, or alternatively two walls that seal at the edges. In embodiments of the invention with multiple compartments, the specified package may consist of one or more films, so that any given compartment of the package may contain walls made from one film or several films having different compositions. In one embodiment of the invention, the multi-compartment bag 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 bag. The specified partition is inside the package and is attached to, as a rule, opposite outer walls along the line of seal. Said partition divides the interior of the multi-compartment bag into at least a first compartment and a second compartment.

[0099] The bags can be made using any suitable equipment and in any way. For example, single compartment bags can be made by vertical mold filling, horizontal mold filling, or rotary drum filling methods well known in the art. Such methods may be either continuous or discontinuous. The specified film can be moistened and/or heated to increase its plasticity. Said method may also include the use of vacuum to draw the film into a usable mold. Vacuum stretching of said film into a mold may be carried out 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 moment 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.

[00100] Molds in which bags can be made can be of any shape, length, width, and depth depending on the required bag sizes. If desired, these molds may also vary in size and shape. For example, the volume of finished pouches 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 mold sizes are adjusted accordingly.

[00101] In one embodiment of the invention, the specified package contains the first and second sealed compartment. The second compartment is generally aligned with the first sealed compartment, so that the second sealed compartment and the first sealed compartment have a common inner septum of the bag.

[00102] In one embodiment of the invention, said bag containing the first and second compartments further comprises a third sealed compartment. The third sealed compartment is generally aligned with the first sealed compartment, so that the third sealed compartment and the first sealed compartment share a common internal baffle of the bag.

[00103] 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.

[00104] In some embodiments, said first, second, and third compositions are selected from one of the following combinations: solid, liquid, liquid and liquid, liquid, liquid.

[00105] 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.

[00106] In one embodiment of the invention, said composition may be selected from the group of, for example, liquid detergent compositions for mild conditions and liquid detergent compositions for harsh conditions, powder detergent compositions, hand dishwashing detergents and/or dishwashers; hard surface cleaning compositions, fabric enhancers, washing gels typically used for laundry and laundry detergents and additives, shampoos and body washes, agricultural compositions, automotive compositions, aviation compositions, food and nutrition compositions, industrial compositions, compositions for livestock, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office compositions and compositions for recreation areas and parks, compositions for pets, compositions for water treatment, including cleaning and washing compositions applicable to any such application .

Vertical Form, Filling and Sealing

[00107] One of the traditional automated processes includes a vertical form, fill and seal (VFFS) process. The VFFS includes a device such as an assembly machine that winds one piece of film around a vertically oriented feed tube. Said machine heat seals or otherwise seals opposite edges of the film together to create a side seal and form a hollow tube of the film. Said machine then heat seals or otherwise creates a bottom seal, thereby forming part of the open top container where the top seal will later be formed. Said machine introduces a certain 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 sealer, for example to create a top seal. Finally, said machine advances the film to a cutter which cuts the film just above the top seal to produce a filled package.

[00108] 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 machine and not stick to the machine assembly or be so brittle as to break during processing.

Forming, sealing and thermoforming

[00109] A thermoformable film is a film that can be shaped by the application of heat and force. In general, films as described herein are thermoformable.

[00110] As is known in the art, film thermoforming is the process of heating the film, shaping it (e.g., in a mould), and then cooling the film so that the film retains its shape, e.g., the shape of the 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 brought to the surface or already on the surface. Alternatively, it can be heated indirectly, for example by surface heating or by applying a hot object to the film. In embodiments of the invention, said film is heated using infrared light. Said film may be heated to a temperature in the range of about 50 to about 150°C, about 50 to about 120°C, about 60 to about 130°C, about 70 to about 120°C, or about 60 to about 90 °C. Thermoforming can be performed by any one or more of the following methods: manually wrapping a thermally softened film onto a mold, molding a softened film onto a mold under pressure (e.g. trimming station, or automatic placement, insertion and/or pneumatic stretching and forming of the film under pressure.

[00111] Alternatively, said film can 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 of the above) onto the film prior to its application to the surface already on the surface, or indirectly , by wetting the surface or by applying a wet object to the film.

[00112] Once the film has been heated and/or wetted, it can be drawn into a usable 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 shape of the product and the desired filling rate. In embodiments of the invention, said cast film is filled with current filling technologies. The filled open pouches are then closed 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 carried out by continuously applying a second film, preferably a water-soluble film, over and on the open pouches, and then preferably bonding the first and second film together, typically in the region between the molds and thus between the pouches.

[00113] 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 welding, solvent sealing or wet sealing, and combinations thereof. Typically, only the area that is to form a seal is treated with heat or a solvent. Heat or solvent may be applied in any manner, generally to the closure material and generally only to the areas that are to form a seal. If wet or solvent sealing or welding is used, heat co-application may be preferred. Preferred wet or solvent sealing/welding methods include selectively applying the solvent to the area between the 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, sealing rolls and belts can be used as described above (optionally also providing warmth).

[00114] The formed pouches can then be cut with a cutting device. The cutting can be done in any suitable manner. It may be preferred 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, in which case said hot object or laser "burns through" the film/sealing area.

[00115] The various compartments of the multi-compartment pouches may be made together in a side-by-side fashion, with the resulting joint pouches may or may not be separated by cutting. Alternatively, these compartments can be made separately.

[00116] In embodiments of the invention, the bags can be made in accordance with the method, including the following steps: a) the formation of the first office (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 bag. Said recess formed in step (b) can be achieved by applying a vacuum to the compartment made in step (a).

[00117] In embodiments, the second and/or third compartment(s) may be made 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.

[00118] In embodiments of the invention, bags can be made 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 a third molded compartment; d) filling in the second and optionally third compartments; e) sealing the second and optionally the third compartment 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 form a multi-compartment bag.

[00119] Said 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 rotary drum molding machine, preferably positioned above the first molding machine.

[00120] It should be understood that by using appropriate dispensing stations, multi-compartment pouches can be produced containing a number of different or distinct compositions and/or different or distinct liquid, gel, or paste compositions.

[00121] In embodiments of the invention, said 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, the specified film and/or package are printed, for example, using ink and/or an active agent.

Package Contents

[00122] These products (eg, in the form of packages) may contain various compositions, for example, compositions for home care. A multi-compartment package may contain the same or different compositions in each individual compartment. The specified composition is close to the water-soluble film. Said composition may be 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 bag or compartment containing the composition.

[00123] This feature of this specification 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 shelf 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.

[00124] The fabric care or home care composition includes fabric, hard surface, air care, car care, dishwashing, fabric conditioning and softening agents, detergents, additive and/or agent for washing and rinsing care, hard surface cleaners and/or treatments and other types of cleaners for consumer or institutional use. Compositions not related to home care are intended for other purposes.

[00125] Non-limiting examples of suitable compositions (e.g., home care compositions) include liquid detergent compositions for mild and harsh conditions, compositions for cleaning hard surfaces, washing gels typically used for laundry, bleaches and laundry additives, enhancer compositions fabrics (such as fabric softeners), shampoos, body gels 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 a solid. 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 benefits in laundering or as a pre-treatment, sustained or sequential release component; additionally or alternatively, it can provide an aesthetic effect.

[00126] Non-limiting examples of other suitable compositions (e.g., non-homecare compositions) include agricultural compositions, automotive compositions, aviation compositions, food and nutrition compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office compositions and compositions for recreation areas and parks, compositions for pets, compositions for water treatment, including cleaning and washing compositions applicable to any such application, excluding compositions for fabric care and home care. Compositions for use in these packages may be in the form of a liquid, solid or powder. Liquid compositions may contain a solid. 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 benefits in laundering or as a pre-treatment, sustained or sequential release component; additionally or alternatively, it can provide an aesthetic effect.

[00127] The compositions encapsulated in the films described herein may have any suitable viscosity depending on such factors as the ingredients of the composition and the purpose of the composition. In one embodiment of the invention, said composition has a high shear viscosity at a shear rate of 20 s ^-1 and a temperature of 20 °C, from 100 to 3000 cps, alternatively from 300 to 2000 cps, alternatively from 500 to 1000 cps and low shear viscosity at a shear rate of 1 s ^-1 and a temperature of 20°C from 500 to 100,000 centipoise, alternatively from 1000 to 10,000 centipoise, alternatively from 1300 to 5000 centipoise. Methods for measuring viscosity are known in the art. In accordance with this description, measurements of shear viscosity of compositions other than solutions of PVA polymers are carried out using a rotary rheometer, for example, TA instruments AR550. This instrument includes a 40 mm 2° or 1° taper fixture with a gap of about 50-60 µm for isotropic liquids or a 40 mm flat steel plate with a 1000 µm gap for liquids containing particles. The measurement is performed using a flow technique that includes a conditioning step, a peak hold, and a continuous ramp step. This conditioning step includes setting the measurement temperature to 20°C, pre-shifting for 10 seconds at a shear rate of 10 s ^-1 , and equilibrating for 60 seconds at the selected temperature. Specified peak retention includes applying a shear rate of 0.05 s ^-1 at 20°C for 3 minutes with sampling every 10 seconds. This continuous ramping step is performed at a shear rate of 0.1 to 1200 s ^-1 for 3 minutes at 20° C. to obtain a complete flow profile.

[00128] As described above, said composition may be a non-home care composition. For example, said non-homecare composition may be selected from agricultural compositions, automotive compositions, aviation compositions, food and nutrition compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office compositions and compositions for recreation areas and parks, compositions for pets, compositions for water treatment, including cleaning and washing compositions applicable to any such application, excluding compositions for fabric care and home care.

[00129] In one type of embodiment of the invention, the specified 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 patent No. 6204223 and 4681228 and EP 0989803 A1. For example, suitable herbicides include paraquat salts (e.g. paraquat dichloride or paraquat bis(methylsulfate), diquat salts (e.g. diquat dibromide or diquat alginate) and glyphosate or a salt or ester thereof (e.g. isopropylammonium glyphosate, sesquin sodium glyphosate or glyphosate-trimesium , also known as sulfosate.) Incompatible crop protection chemical pairs can be used in separate chambers, for example, as described in US Pat. No. 5,558,228. Incompatible plant protection chemical pairs 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; tralometrin and any organophosphate such as monocrotophos or dimethoate; bromoxynil and N-[[4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide; bromoxynil and methyl 2-[[[[[(4-methyl-6-methoxy)-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate; bromoxynil and methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]sulfonyl]benzoate. In another related 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 the types of embodiments of the invention described in US patent No. 8333033.

[00130] In another type of embodiments of the invention, the composition is a water treatment agent. Such agents include harsh oxidizing chemicals, such as those described in US Patent Application Publication No. 2014/0110301 and US Patent No. 8,728,593. For example, disinfecting agents may include hypochlorite salts such as sodium hypochlorite, calcium hypochlorite, and lithium hypochlorite; chlorinated isocyanurates such as dichloroisocyanuric acid (also referred to as "dichlor" or dichloro-s-triazinetrione, 1,3-dichloro-1,3,5-triazinane-2,4,6-trione) and trichloroisocyanuric acid (also referred to as " trichlor" or 1,3-trichloro-1,3,5-triazinan-2,4,6-trione). Salts and hydrates of said disinfectant compounds are also contemplated. 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- bromine-3-chloro-5,5-dimethylhydantoin; and 2-bromo-2-nitro-1,3-propanediol, among others. The specified oxidizing agent may be an agent described in US patent No. 7476325, 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 adjusts pH 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.

[00131] 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-methylamidopropyltrimethylammonium chloride (MAPTAC), or acrylic acid; cationic polyacrylamide; anionic polyacrylamide; neutral polyacrylamide; polyamine; polyvinylamine; polyethyleneimine; polydimethyldiallylammonium chloride; polyoxyethylene; polyvinyl alcohol; polyvinylpyrrolidone; polyacrylic acid; polyphosphoric acid; polystyrenesulfonic acid; or any combination of them. 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.

[00132] Said composition may be a lime scale remover, eg citric or maleic acid or their sulfate salt, or any mixture thereof, eg as described in US Patent Application No. 2006/0172910.

[00133] Various other types of compositions are contemplated for the pouch applications described herein, including particles such as down feathers, for example as described in US RE29059 E; superabsorbent polymers, for example, as described in US Patent Application Publication Nos. 2004/0144682 and 2006/0173430; pigments and dyes, for example, as described in US patent No. 3580390 and in the publication of the application for US patent 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.

[00134] In packs containing laundry compositions, laundry additives, and/or fabric enhancers, said compositions may contain one or more of the following non-limiting list of ingredients: a fabric care agent; detergent enzyme; means for deposition; rheology modifier; modifier; bleach; bleaching agent; bleach precursor; whitening enhancer; bleaching catalyst; fragrances and/or fragrance microcapsules (see, for example, US Pat. No. 5,137,646); zeolite loaded with perfume; a combination of fragrances encapsulated with starch; esters of polyglycerol; bleaching agent; pearlescent agent; enzyme stabilization systems; scavengers, 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 soil repellant polymer and/or a soil suspending polymer; dispersants; defoamers; non-aqueous solvent; fatty acid; suds suppressors, for example, silicone suds suppressors (see: US Patent Application Publication No. 2003/0060390 A1, paras. 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; clouding agent; antioxidant; hydrotropes such as toluenesulfonates, cumenesulfonates and naphthalenesulfonates; colored blotches; colored granules, spheres or extrudates; clay-based softening agents; 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, said 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 structure NR4 ⁺ where R is an alkyl group or an aryl group.

Surfactants

[00135] Detergent compositions may contain from about 1% to 80% by weight of a 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 a surfactant. The second and third compositions may contain a surfactant in an amount of from 0.1 to 99.9%.

[00136] The detergent surfactants used may be of the 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 are substantially free of betaine surfactants. Detergent surfactants used in this document are described in US patent No. 3664961; 3919678; 4222905; and 4,239,659. Anionic and nonionic surfactants are preferred.

[00137] Suitable anionic surfactants can be of several different types per se. 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 alkylammonium salts of higher fatty acids having from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soaps can be obtained 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 derived from coconut oil and animal fat, ie sodium or potassium animal and coconut soap.

[00138] 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 part _{of acyl} groups.) Examples of this group of synthetic surfactants include: animal or coconut oil glycerides; 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 alkylbenzene sulfonates wherein 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. in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated C ₁₁ -C ₁₃ LAS.

[00139] 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 3 to about 80. Particularly preferred are the condensates of C ₁₂ -C ₁₅ alcohols with about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g. C ₁₂ -C ₁₃ alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol .

[00140] Solvent System

[00141] The solvent system in detergent compositions can be a solvent system containing only water or mixtures of organic solvents with water. Preferred organic solvents include 1,2-propanediol, ethanol, glycerol, 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 embodiments of this disclosure of anhydrous solid detergents, 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, such as about 0.1% to 25% propylene glycol, 0.5% to 20% propylene glycol, or 5% to 15% propylene glycol. propylene glycol by weight of the composition.

[00142] The specified cleaning composition in this document can usually be obtained by mixing the ingredients together. If a pearlescent material is used, it should be added in the later stages of mixing. If a rheology modifier is used, it is preferred to first form a premix in which the rheology modifier is dispersed in a portion of the water and optionally other ingredients eventually used for inclusion in detergent compositions. This premix is shaped to form a structured liquid. The surfactant(s) and primary laundry adjuvants, as well as water and any additional detergent composition additives to be applied, can then be added to this structured premix while the premix is under agitation.

[00143] The pH of said detergent composition may be from about 2 to about 12, from about 4 to about 12, from about 5.5 to about 9.5, from about 6 to about 8.5, or from about 6.5 to about 8.2. Laundry detergent compositions may have a pH of about 6 to about 10, about 6.5 to about 8.5, about 7 to about 7.5, or about 8 to about 10. Automatic dishwashing compositions may have a pH about 8 to about 12. Laundry detergent additive compositions can have a pH of about 4 to about 8. Fabric enhancers can have a pH of about 2 or 4 to about 8, about 2 to about 4, about 2.5 to about 3.5 or from about 2.7 to about 3.3.

[00144] Detergent pH is defined as the pH of a 10% (w/v) aqueous solution of detergent at 20 °C ± 2 °C; for solids and detergent powder, it is defined as the pH of a 1% (w/v) detergent solution in water at 20 °C ± 2 °C. Any meter capable of measuring pH to within ± 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 must be equipped with a suitable glass calomel or silver chloride reference electrode. An example includes Mettler DB 115. The electrode should be stored in the electrolyte solution recommended by the manufacturer.

[00145] A 10% aqueous detergent solution is prepared according to the following procedure. A sample of 10 ± 0.05 grams is weighed using a balance capable of measuring to the nearest ± 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 appropriate if the water conductivity is <5 µS/cm) and mixed thoroughly. About 50 ml of the resulting solution is poured into a beaker, the temperature is brought to 20 °C ± 2 °C, and the pH is measured according to the standard method of the pH meter manufacturer (it is also extremely important to follow the manufacturer's instructions for setting up and calibrating the pH meter).

[00146] For solid and powder detergents, a 1% aqueous detergent solution is prepared in accordance with the following procedure. A sample of 10 ± 0.05 grams is weighed using a balance capable of measuring to the nearest ± 0.02 grams. Transfer the sample to a 1000 ml volumetric flask, dilute to volume with purified water (deionized and/or distilled water is appropriate if the water conductivity is <5 µS/cm) and mix thoroughly. About 50 ml of the resulting solution is poured into a beaker, the temperature is brought to 20 °C ± 2 °C, and the pH is measured according to the standard method of the pH meter manufacturer (it is also extremely important to follow the manufacturer's instructions for setting up and calibrating the pH meter).

[00147] It is known in the art that when forming a bag with an enclosed composition, some components of the film (for example, plasticizers) may in some cases migrate from the film into the enclosed composition and, additionally or alternatively, some components of the enclosed composition (e.g. plasticizer, solvent) may migrate into the film. Without being limited by theory, it is believed that this migration of components into/out of the film can lead to changes in the amount of swelling of the film.

[00148] Bleaches

[00149] 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.

[00150] Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates for use in the detergent composition described herein. Said percarbonate is most preferably incorporated into the products in coated and/or encapsulated form to provide stability within the product. A suitable coating material to provide 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 1466799 and US Pat. Nos. 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 of 1:99 to 1:9 and preferably 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 0.1 to 3, preferably 0.3 to 1.0 and , more preferably from 0.2 to 0.5. Another suitable coating material for internal stability 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 applied.

[00151] Organic bleaches may contain organic peroxyacids, including diacyl and tetraacyl peroxides, especially diperoxytetradecanedioic acid, diperoxytetradecanedioic acid, and diperoxyhexadecanedioic acid. Dibenzoyl peroxide is the preferred organic peroxyacid in this document. 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 less than 10 µm, preferably less than 6 µm.

[00152] Other organic bleaches include peroxy acids, specific examples of which are alkyl peroxy acids and aryl peroxy acids. Preferred representatives are: (a) peroxybenzoic acid and ring-substituted derivatives thereof, such as alkyl peroxybenzoic 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-nonenylamidoperadipic acid, and N-nonenylamidopersuccinates; and (c) aliphatic and arylaliphatic peroxydicarboxylic acids such as 1,12-diperoxyazelaic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassilic acid, diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-N-dioic acid, N, N-terephthaloyldi(6-aminopercaproic acid).

[00153] Bleaching activators may contain organic peracid precursors that enhance the bleaching effect during cleaning at temperatures of 60°C and below. Bleach activators suitable for use herein include compounds which, under perhydrolysis conditions, give 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 with 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 tetraacetyl glycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isonanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, as well as triethylacetyl citrate (TEAC).

[00154] Preferred bleaching catalysts 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 pentaminacetate cobalt (III) and related complexes (US patent No. 4810410). A full description of bleach catalysts suitable for use herein can be found in US Pat. No. 6,599,871, incorporated herein by reference.

[00155] Dishwashing Liquids

[00156] A preferred surfactant for use in automatic dishwashing detergents is a low sudsing surfactant alone or in combination with other components (eg, suds suppressors). Preferred for use herein are low and high cloud point nonionic surfactants and mixtures thereof, including nonionic alkoxylated surfactants (especially ethoxylates derived from C ₆ -C ₁₈ primary alcohols), ethoxylated-propoxylated alcohols ( e.g. POLY-TERGENT® SLF18 from Olin Corporation), epoxy terminated poly(oxyalkylated)alcohols (e.g. POLY-TERGENT® SLF18B from Olin Corporation - see WO-A-94/22800), surfactants based on ether-terminated poly(oxyalkylated)alcohol and block-polyoxyethylene-polyoxypropylene polymeric compounds such as PLURONIC®, REVERSED PLURONIC® and TETRONIC® from BASF-Wyandotte Corp., Wyandotte, Michigan; amphoteric surfactants such as C ₁₂ -C ₂₀ alkylamine oxides (preferred amine oxides for use herein include lauryl dimethylamine oxide and hexadecyldimethylamine oxide) and alkylamphocarboxylic surfactants such as MIRANOL ^™ C2M; and zwitterionic surfactants such as betaines and sultaines; and their mixtures. Surfactants suitable for use herein are described, for example, in US Pat. Surfactants may be present in the detergent at levels 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 of the detergent composition.

[00157] Other Compositions and Additives

[00158] Modifiers suitable for use in the detergent composition described herein include water-soluble modifiers including citrates, carbonates, silicates, and polyphosphates, such as sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate, and mixed salts of sodium and potassium tripolyphosphate.

[00159] Enzymes suitable for use in the detergent composition described herein include bacterial and fungal cellulases, including CAREZYME and CELLUZYME (Novo Nordisk A/S); peroxidase; 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); α and β amylases including PURAFECT OX AM (Genencor) and TERMAMYL, BAN, FUNGAMYL, DURAMYL and NATALASE (Novo); pectinases; and their mixtures. Enzymes may be added to the composition as granules, granulates, or cogranulates at levels typically in the range of about 0.0001% to about 2% pure enzyme by weight of the cleaning composition.

[00160] 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 nonionic surfactants, which results from the fact that the surfactant becomes less soluble with increasing temperature, the temperature at which the appearance of the second phase is observed is called the "temperature turbidity." As used herein, a "low cloud point" nonionic surfactant is defined as an ingredient in 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 ethoxylates derived from a primary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse type block copolymers. In addition, such low cloud point nonionic surfactants may include, for example, ethoxylated-propoxylated alcohol (for example, BASF POLY-TERGENT SLF18) and epoxy-terminated poly(oxyalkylated) alcohols (for example, the BASF POLY- TERGENT SLF18B, as described, for example, in US-A-5576281).

[00161] Other suitable components for use in the detergent composition described herein include cleaning polymers having anti-scaling, soil release, or other cleaning properties. Anti-deposit polymers for use herein include polymers containing acrylic acid 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). Soil-repellent polymers for use herein include alkyl and hydroxyalkyl celluloses (US-A-4000093), polyoxyethylenes, polyoxypropylenes and their copolymers, as well as nonionic and anionic polymers based on ethylene glycol terephthalate ethers, propylene glycol and mixtures thereof.

[00162] Heavy metal sequestrants and crystal growth inhibitors are also suitable for use in these detergents, e.g. ethylenediaminetetracetate, ethylenediamine-N, N'-disuccinate in their salt and free acid forms.

[00163] A corrosion inhibitor is also suitable for use in the cleaning composition described herein, for example, organic silver plating agents (especially paraffins such as WINOG 70 available from Wintershall, Salzbergen, Germany), nitrogen containing compounds for example benzotriazole and benzimidazole - see GB-A-1137741) and Mn(II) compounds, especially Mn(II) salts of organic ligands.

[00164] Other suitable ingredients for use in the detergent composition described herein include enzyme stabilizers such as calcium ion, boric acid, and propylene glycol.

[00165] Other suitable ingredients for use in the detergent composition described herein include humectants, for example, as described in US Patent Application Publication No. 2015/0329807.

[00166] Suitable rinse aids are known in the art. Commercial dishwashing rinses are typically blends 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 rinse aids is to influence the surface tension of the water so that it can run off the rinsed surfaces in the form of a thin adhesive film so that no water droplets, streaks or films remain after the subsequent drying process. EP 0197434 B1 describes rinse aids which contain mixed ethers as surfactants. Rinse additives such as fabric softeners and the like are also contemplated and are suitable for film encapsulation as described herein.

[00167] 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:

JMS 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%

JMS 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%

[00168] Methods of use

[00169] The films and articles described herein, as well as the compositions contained therein, can be used to treat a substrate, such as a fabric or a hard surface, for example, by bringing the substrate into contact with the film, article, and/or composition contained in them. Said contacting can 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 the present invention are particularly suitable for dissolving in cold water and therefore provide advantages in cold water laundering (e.g., about 1°C to about 30°C or 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 content contained therein.

Dissolution Chamber Residue Test

[00170] The water-soluble film, characterized or to be tested for the presence of undissolved residue in accordance with the test of the dissolution chamber (CR), is analyzed as follows using the following materials: 1. Beaker (4000 ml); 2. Stainless steel washers (OD 3.5" (88.9 mm), ID 1.875" (47.6 mm), thickness 0.125" (3.18 mm)); 3. Styrene butadiene rubber gaskets (3.375" (85.7 mm) OD, 1.91" (48.5 mm) ID, 0.125" (3.18 mm) thick); 4. Stainless steel screens (3.0" OD, 200x200 mesh, 0.0021" OD wire, 304SS mesh); 5. Thermometer (from 0°C to 100°C, accuracy +/-1°C); 6. Die-cutting die (diameter 1.5 inches (38.1 mm)); 7. Timer (up to a second); 8. Reverse osmosis water (RO); 9. Clamps (size #5 or equivalent); 10. Aluminum trays (outside diameter 2.0 inches (50.8 mm)); and 11. Sonicator.

[00171] For each film to be tested, three test specimens are cut using a punch die from a selected test film having a thickness of 76 microns. When cutting from a continuous film web, these specimens shall be cut from portions of the web evenly spaced along the transverse direction of the web (i.e., perpendicular to the machine direction). Each test piece is then analyzed by the following procedure: 1. Weigh the film sample and follow the sample during the test. Record the initial film weight (Fo). 2. Weigh a set of two sonicated clean and dry sieves for each sample and monitor them during the test. Record the initial masses of sieves (in the aggregate So for the total mass of two sieves). 3. Assemble the sample dissolving chamber by placing the film sample evenly between the center of two sieves, then applying two rubber spacers (one spacer on each side between the sieve and washer) and then applying two washers. 4. Secure the dissolution chamber assembly with four clamps evenly spaced around the washers, with handles bent away from the screens. 5. Fill the beaker with 1500 ml reverse osmosis water at laboratory room temperature (72 +/- 3 °F, 22 +/- 2 °C) and record the room temperature. 6. Set the timer to the prescribed dive time of 5 minutes. 7. Place the dissolving chamber assembly into the beaker and immediately start the timer by placing the dissolving chamber assembly at an angle of approximately 45 degrees to the surface of the water. This entry angle helps to remove air bubbles from the chamber. The dissolution chamber assembly rests on the bottom of the beaker so that the film of the test sample is horizontal about 10 mm from the bottom. The four backward-curved clamps of the dissolution chamber assembly allow a gap of about 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 has elapsed, 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 drip tray, and carefully remove the fastening clips, washers, and spacers. Do not disassemble jammed sieves. 10. Place the pinched sieves (i.e. sieve/residual undissolved film/sieve) on an aluminum tray and in an oven at 100°C for 30 minutes to dry. 11. Weigh the dried set of clamped sieves containing all residual undissolved film in it. Measure and add to this mass of dried sieves any drops of dried film captured and removed from the tray (eg by scraping) when the dissolution chamber assembly was first removed from the beaker and during drying. Record the final weight of the clamped sieves (collectively Sf, including the dried film droplets). 12. Calculate the % residue ("RC residue") remaining for the film sample: % RC residue=100*((Sf - So)/Fo). 13. Clear pinched screens by soaking them in a glass of reverse osmosis water for about 20 minutes. Then separate them and perform a final rinse in the sonicator (on and filled with reverse osmosis water) for at least 5 minutes or until no residue is left on the screens.

[00172] Suitable behavior of water-soluble films in accordance with this description is characterized by the values of the balance of the CD 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 test. Generally, lower CR residue values are desirable to reduce the likelihood of film residue remaining on the washed garment after aggressive washing conditions (e.g., low water conditions (e.g., overloading a washing machine) and cold water wash conditions). In various embodiments of the invention, the specified water-soluble film has a value of the remainder of the CD, equal to 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., about 3% to about 48%, about 5% to about 48%, about 12% to about 48%, about 25% 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 wt%, from about 3 wt% to about 40 wt%, or from about 3 wt% to about 35 wt%.

Dissolution and Disintegration Test (MSTM 205)

[00173] Said 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.

Appliance and Materials

Glass 600 ml

Magnetic Stirrer (Labline Model #1250 or equivalent)

Magnetic stirring 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 glass slide (or equivalent)

Slide holder 35 mm MonoSol (or equivalent)

Distilled water

[00174] For each film to be tested, three test pieces are cut from the film sample, which is a 3.8 cm x 3.2 cm sample. canvases. Each test piece is then analyzed by the following procedure.

[00175] Fix each sample on a separate 35 mm glass slide.

[00176] Fill the beaker with 500 ml of distilled water. Measure the temperature of the water with a thermometer and, if necessary, heat or cool the water to maintain the temperature at 20°C (about 68°F).

[00177] Mark the height of the water column. Place the magnetic stirrer on the holder base. Place the beaker on a magnetic stirrer, add a magnetic stirring stick to the beaker, turn on the stirrer and adjust the stirring speed until a swirl is formed that is about one-fifth of the height of the water column. Mark the depth of the swirl.

[00178] Attach a 35 mm slide to 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's depth adjuster must 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 beaker wall and the other should be placed directly over the center of the stirring stick so that the surface of the film is perpendicular to the water flow.

[00179] In one motion, lower the fixed slide and clamp into the water and start the timer. Decomposition occurs when the film breaks. When all visible film has been released from the slide, lift the slide from 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.

[00180] The results should include the following: complete identification of the sample; individual and average decay and dissolution time; and the water temperature at which the specimens were tested.

[00181] The disintegration time of the film (I) and the dissolution time of the film (I) can be corrected to a standard or reference film thickness using the exponential algorithms shown below in Equation 1 and Equation 2, respectively.

I _corr = I _meas x (reference thickness/measured thickness) ^1.93 [1]

_Scorr =S _meas x (reference thickness/measured thickness) ^1.83 [2]

Tensile Strength Test and Modulus Test

[00182] A water-soluble film characterized or to be tested for tensile strength according to the tensile strength (TS) test and modulus (or tensile stress) according to the elastic modulus (MOD) test was analyzed as follows. This procedure includes the determination of tensile strength and determination of modulus of elasticity 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 robust cutting tools to ensure dimensional stability and reproducibility. The 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 prepare samples of one sheet of film with a width of 1 inch (2.54 cm) and a thickness of 76 microns. 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. The correct clamps and surfaces are installed (INSTRON clamps with model 2702-032 rubber coated edges and 25mm width or equivalent). Samples are placed in a tensile tester and analyzed to determine 100% modulus (i.e. stress required to achieve 100% elongation of the film) and tensile strength (i.e. stress required to break the film).

[00183] Higher IR values are generally desirable because they correspond to a stronger seal on the bags when the film is the limiting or weakest seal element.

[00184] Higher MOD values are generally desirable because they correspond to pouches having greater rigidity and less chance of warping and sticking to each other when stacked on top of each other during manufacture or in final consumer packaging. In addition, the MOD values at 100% elongation correspond to the ability of the film to maintain the rigidity and tension of the package when in contact with the liquid contents of the package.

[00185] Without being limited by theory, it is believed that the change in elastic modulus over time can be used to predict whether a bag containing liquid laundry detergent will remain taut over time or the bag will lose density and take on a loose and saggy appearance and feeling. In particular, without being limited by theory, it is believed that a film having a greater positive change in modulus of elasticity (∆ modulus) (positive slope or increase in modulus of elasticity) over time will remain more taut for at least 12 weeks under ambient or at temperatures up to 38°C and relative humidity up to 80% compared to films having a Δ modulus of about 0, and will remain significantly more stretched than films with a negative Δ modulus.

Liquid release test

[00186] A water-soluble film and/or pouch characterized or to be tested for delayed solubility in accordance with the liquid release test is analyzed as follows using the following materials: • 2 L beaker and 1.2 L of deionized (DI) water

Tested water soluble sachet; the film has a thickness of 88 microns; the bag is preconditioned for two weeks at 38°C.

Thermometer

wire cage

Timer

[00187] Before conducting 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.

[00188] A wire frame cage is a plastic coated wire mesh cage (4 inches X 3.5 inches X 2.5 inches or about 10 cm x 9 cm x 6 cm) without sharp edges or similar. The gauge of the wire should be about 1.25 mm and it should have 0.5 inch (1.27 cm) square holes. An exemplary image of cage 28 with test bags 30 is shown in FIG. one.

[00189] 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 to the wire cage, but make sure it is secure and will not fall out of the cage. The orientation of the bag in the cage must be such that the bag's natural buoyancy, if any, is allowed (i.e. the side of the bag that will float on top must be facing up). If the package is symmetrical, the orientation of the package generally does not matter.

[00190] Then fill a 2 L beaker with 1200 ml of deionized water at 20°C.

[00191] 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 fully submerge the package 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 cage with respect to the water in the beaker can be adjusted and maintained by any suitable means, such as a clamp attached over the beaker and a rod attached to the top of the cage. The clamp can catch on the rod to fix the position of the cage, and the tension of the clamp can be reduced to lower the cage into the water. As an alternative to the clip, other frictional engagement means can be used, such as a collar with a set screw, as shown in FIG. 2 (set screw not shown). On FIG. 2 shows cup 30 mounted on a stand 40 which holds a rod 50 for lowering a cage 10 (not shown) into the cup 30, the rod 50 being able to maintain a fixed vertical position through the use of a cuff 60 having a set screw (not shown) which engages with the stem 50, for example by friction or by engaging with a hole (not shown) in the stem 50.

[00192] The release of the liquid content is defined as the first visual evidence that the liquid is leaving the submerged package.

[00193] Use a timer to record when the liquid content enters the surrounding water (release time) with a stop point of 45 seconds.

[00194] Each bag will be assigned a pass or fail score. A pass is awarded if the instant sachet retains liquid for 30 seconds or longer. A Fail score is awarded if the instant pouch does not retain liquid for at least 30 seconds.

[00195] Repeat this process with new deionized water and a new water soluble bag five times for each film tested.

[00196] For each type of film sample, test at least 15 bags, unless otherwise noted.

Measurement in Compression Test

[00197] A water-soluble film and/or pouch characterized or to be tested for the ability of the water-soluble capsule to withstand a mechanical compression force of at least 300 N as measured in the compression test is analyzed as follows using the following materials:

Instron Model 5544 (or equivalent)

In at least 15 water-soluble bags or capsules to be tested, the film has a thickness of 88 microns; the package is preliminarily kept for at least 24 hours at a temperature of 23±1°C and a relative humidity of 50±4%.

Zip bags

Two flat plates (upper 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)

[00198] Inspect the bag for leaks and then place in a zipper bag (about 57 microns thick on each side). Close the bag so that there is a minimum of air inside. Mark the name and number of the sample on the bag.

[00199] Open compression test method. The slew rate should be 4 mm/s.

[00200] Carefully place the sample cavity down between the two plates, making sure the bag is centered on the bottom plate. Move the capsule inside the bag away from the edges.

[00201] Press start to start the test. As the two plates approach each other, the bag will burst. Write down the compression force and the place on the package where the rupture occurred. Repeat this process for all samples.

[00202] Suitable behavior of water-soluble films in accordance with this description is determined by compression values of at least about 300 N and less than about 2000 N, as measured in a compression test.

Measurement in Film Swell Test

[00203] A water soluble film and/or pouch characterized or to be tested for swelling resistance in the presence of a liquid composition is analyzed as follows.

[00204] Three film samples are taken from different areas of the film from the roll on the larger film sample. Use a punch to cut out three squares measuring 2 by 2 inches (about 5 x 5 cm). Measure and record the mass and caliber of each sample.

[00205] For each sample, a petri dish is weighed and 12 g of the test liquid is added to it. A film sample is added to the Petri dish in the center of the base. Add more test liquid until there are 20 g of test liquid in the Petri dish and the film sample is completely covered and immersed in the test liquid. Put a lid on the Petri dish.

[00206] Each Petri dish is wrapped in parafilm and placed in a conditioning oven at 38° C. and 80% relative humidity for 24 hours.

[00207] Lay the measuring grid on a horizontal surface. After conditioning, unpack the Petri dishes and remove the film samples. Place the 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 KimWipe® or equivalent. Record the weight and thickness of the film sample.

[00208] The swelling ratio is the ratio of the weight added to the film to the original weight (eg, (final weight - original weight)/original weight)).

[00209] For the water soluble films of this disclosure comprising a blend of PVA resins, the useful behavior of the water soluble films of this disclosure is characterized in comparison to a comparative film that is identical to but different from the second PVA copolymer being an individual resin and the amount of this second copolymer The PVA in the comparative film is equal to the total amount of resins in the water soluble film of this invention. In particular, the suitable behavior of the water-soluble films according to this specification is characterized by a swell value that does not exceed 60% of the swell value of the comparative film, which is identical to but different from the second PVA copolymer being 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 this invention as measured in the film swelling test.

[00210] Swelling causes the film to change dimensions, which can result in a less stretched package because the final area of the film is larger but holds the same volume of liquid.

Measurement in the Crystallinity Test

[00211] The water-soluble film and/or package characterized or to be tested for film crystallinity is analyzed as follows.

[00212] The film samples are kept at 22°C and 40% relative humidity for at least 24 hours. Then a 3 mm by 3 mm sample of the moistened film is placed in a sealed cell. WAXD is then measured using a D8 Discover X-ray diffractometer or equivalent equipped with a two-dimensional detector (Bruker AXS Co., Ltd.) using an exposure time of 600 seconds.

[00213] A one-dimensional profile (Intensity from 2theta) 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 intensity values of the diffraction angles at 15 degrees and 25 degrees is subtracted from the background-subtracted profile to provide a baseline.

[00214] Using the Gaussian function, intensity values are reproduced 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 amorphous PVA scattering. The peak position, peak width, and peak height of the Gaussian function are found by least squares approximation. The diffraction signals at 19.5 degrees and 23 degrees are reproduced, which are attributed to the diffraction 110 and diffraction 200 of the PVA crystal with two Gaussian functions. The peak position, peak width, and peak height are found by least squares fit. The parameters of the Gaussian function assigned to amorphous PVA are fixed. The Gaussian fit parameters, considered as crystals, are fixed, and the three Gaussian fit parameters attributed to amorphous PVA are again fitted by least squares. Find integral intensity values of three Gaussian functions. Apparent crystallinity is calculated as a percentage of the sum of the integrated intensity values of the two Gaussian functions attributed to the PVA crystal in the total integrated intensity values.

[00215] Without being limited by theory, it is believed that the crystallinity of the water soluble film can be reduced by increasing the level of the 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. . In addition, without being limited by theory, it is believed that, as a rule, the lower the crystallinity of the film, the more the film swells upon contact with the liquid composition.

[00216] Water soluble films as described herein may be better understood in light of the following examples, which are intended to be illustrative of water soluble films only and are not intended to limit the scope of the invention in any way.

Examples

Example 1: Individual Resin Film

[00217] Example 1 is a water soluble film that is formed with an individual PVA copolymer, Resin A. Resin A was a fully hydrolyzed (99% hydrolysis degree) PVA polymer having a methyl acrylate comonomer level of 5 mol %. %, which had 70% open rings, with a level of side groups of 5 mol. % and viscosity of a 4% solution at 20°C 20 cP. Said film contained (i) Resin A (100 mass parts), (ii) glycerol plasticizer (24.67 mass parts per hundred parts of resin (m.h.)), (iii) sorbitol plasticizer (13.12 m.h. ), (iv) trimethylol propane plasticizer (5.33 ppm), (v) propylene glycol plasticizer (0.50 ppm), (vi) filler (4.85 ppm bulking agent and release agent, together), (vii) surfactants and other processing aids (3.15 ppm including antioxidant, defoamer, amine oxide surfactant and cationic surfactant) and residual water (about 5- 12 hours). The aqueous compositions of the above were cast and dried to form 76 µm thick film samples which were tested for residual CR values in the manner described above. The resin and film properties for the film samples of Example 1 at ambient conditions (i.e., 23°C and 35% relative humidity (RH)), prior to exposure to liquid laundry detergent, are shown in Table 1. In Table 1, the content of side groups (P) for the film is given in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and their other non-resin components), and the value of P additionally indicates that the side group corresponds to the methyl acrylate comonomer unit (A).

Example 2: Individual Resin Film

[00218] Example 2 are water-soluble films that were formed with the individual PVA copolymer, Resin B. Resin B was a commercially available PVA copolymer with a hydrolysis degree of 88-92% having a maleic anhydride comonomer level of 4.0 mol %. % (sodium salt) and 8.0 mol. % side groups, and having the specified viscosity of a 4% solution at 20°C 15-20 cP. This film contained (i) Resin B (100 mass parts), (ii) glycerol plasticizer (23.9 mass parts per hundred parts of resin (m.h.)), (iii) sorbitol plasticizer (17.46 m.h. ), (iv) trimethylol propane plasticizer (4.05 ppm), (v) propylene glycol plasticizer (0.47 ppm), (vi) filler (1.78 ppm anti-caking agent), (viii) surfactants and other processing aids (3.06 ppm including antioxidant, defoamer, amine oxide surfactant and cationic surfactant) and residual water (about 5-12 ppm). h.). Films were prepared and tested as described in Example 1. The resin and film properties for film samples according to Example 2 at ambient conditions (i.e., 23°C and 35% RH) prior to exposure to liquid laundry detergent are shown in Table 1 In Table 1, the content of anionic side groups (P) for the film is presented in terms of moles in relation to the PVA resins in the film (i.e., excluding plasticizers and other components that are not related to resins), and in the P value additionally it is indicated that the anionic monomer corresponds to the comonomer unit of maleic anhydride (M).

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

Resin Film Example Type of µ (cP) SG (%) P (mole %) CR (%) P (mole %) one A twenty 99 5.00 (A) 9.01 5.00 (A) 2 AT 17.5 90 8.00 (M) 1.94 8.00 (M)

[00219] Thus, Table 1 shows that water-soluble films made from PVA-alkyl acrylate copolymer (Resin A) have higher residue values (CR values) compared to water-soluble films made from PVA-maleate copolymer (Resin B ).

Example 3 Individual Resin Film

[00220] Example 3 is a water-soluble film that was formed with Resin A and non-resin components in the amounts and types as described in Example 1. Films were made and tested as described in Example 1. Resin and film properties for samples films according to Example 3 at ambient conditions (i.e., 23°C and 35% RH) before exposure to liquid laundry detergent are given in Table 2. In Table 2, the content of side groups (P) for the film is presented in terms of moles with respect to PVA resins in the film (i.e., excluding plasticizers and their other non-resin components), and in the P value it is additionally indicated that the side group corresponds to the unit of the methyl acrylate copolymer (A).

Example 4 Individual Resin Film

[00221] Example 4 are water-soluble films that contain the individual PVA copolymer, Resin B, and non-resin components in the amounts and types as described above in Example 2. Films were made and tested as described in Example 1. Properties resins and films for film samples according to Example 4 at ambient conditions (i.e., 23°C and 35% RH) before exposure to liquid laundry detergent are shown in Table 2. In Table 2, the content of anionic side groups (P) for films are expressed in terms of moles relative to the PVA resins in the film (i.e., excluding plasticizers and their other components that are not related to resins), and in the P value it is additionally indicated 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 of µ (cP) SG (%) P (mole %) CR (%) P (mole %) 3 A twenty 99 5.00 (A) 21.2 5.00 (A) four AT 17.5 90 8.00 (M) 0.86 8.00 (M)

[00222] Thus, Table 2 shows that water-soluble films made from PVA-alkyl acrylate copolymer (Resin A) have higher residue values (CR values) compared to water-soluble films made from PVA-maleate copolymer (Resin B ). In addition, a comparison of Examples 1 and 2 with Examples 3 and 4 shows that the films made from the PVA-alkyl acrylate copolymer (Resin A) had higher residue values compared to the films made from the PVA-maleate copolymer (Resin B), both at high levels of plasticizer (eg, more than 30 ppm in total, 1 and 2) and at low levels of plasticizer (eg, less than 30 ppm in total, 3 and 4).

Examples 5-8: Dual Resin Blend Films

[00223] Examples 5-8 are formed water-soluble films, each of which contains a mixture of two copolymers, Resin A and Resin B. 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 blended films contained two resins that were 100% resin in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 1. Films were made and tested as described in Example 1. 1. Table 3 lists 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 mixture compositions of the two resins. In Table 3, the side group content (P) 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 in terms of P further indicates whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

Table 3 Resin and Film Data for Examples 5-8

resins Film Example Type of Qty. (wt %) Type of Qty. (wt %) CR (%) % Crystallinity P (mole %) one A 100 AT 0 9.01* 18.9* 5.00 (A) 5 A 80 AT twenty 9.67* 18.7* 5.6 (A/M) 6 A 60 AT 40 17.62* 20.1* 6.2 (A/M) 7 A 40 AT 60 12.32* 18.4* 6.8 (A/M) eight A twenty AT 80 3.06* 15.2* 7.4 (A/M) 2 A 0 AT 100 1.94* 13.8 8.00 (M)

[00224] Examples 5-8 show that water-soluble films containing PVA resin blends containing a first copolymer containing a first anionic monomer unit and a second copolymer containing a second anionic monomer unit, as described herein, can exhibit a combination of substantially 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 delivery applications satisfy at least one of (a) a CR residue value of about 35 wt. % or less to reduce or eliminate film residue on products in the wash; or (b) at least 15% crystallinity to create rigid bags less likely to soften and sag when forming bags containing liquid compositions. It is desirable that the film meet criteria (a) and (d).

[00225] However, as illustrated in the individual resin film data in Examples 1 and 2, desirable CR values often degrade crystallinity values. For example, the film from Example 2 (Resin B) had a desirably low CR residue value, but at the same time a low crystallinity value.

[00226] As shown in Examples 5-8, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins of a first PVA copolymer containing a first anionic monomer, as described herein, and a second PVA copolymer containing a second anionic monomer, as described in this document meet criteria (a) and (b). In Table 3, film properties marked with "*" satisfy criteria (a) or (b). It can be seen from the data that films containing PVA resin blends comprising two anionic PVA copolymers as shown in Examples 5-8 generally meet criteria (a) and (b) for A/B blend ratios ranging from about 20/80 up to about 80/20 (by weight, respectively).

Examples 9-12: Dual Resin Blend Films

[00227] Examples 9-12 are formed water-soluble films, each of which contains 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 blended films contained two resins that were 100% resin in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 3. Films were made and tested as described in Example 3. 1. Table 4 lists the resin and film properties 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 mixture compositions of the two resins. In Table 4, the side group content (P) for the film is given 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 in terms of P further indicates whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

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

resins Example Type of Qty. (wt %) Type of Qty. (wt %) CR (%) % Crystallinity (≥ 15%) P (mole %) 3 A 100 AT 0 21.20* Undefined 5.0 (A) 9 A 80 AT twenty 18.63* Undefined 5.6 (A/M) ten A 60 AT 40 19.35* Undefined 6.2 (A/M) eleven A 40 AT 60 16.16* 18.1* 6.8 (A/M) 12 A twenty AT 80 14.3* 19.3* 7.4 (A/M) four A 0 AT 100 0.86* 14.7 8.00 (M)

[00228] Examples 9-12 show that water soluble films containing PVA resin blends containing a first copolymer containing a first anionic monomer unit and a second copolymer containing a second anionic monomer unit as described herein can exhibit a combination of substantially 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.

[00229] However, as illustrated in the individual resin film data in Examples 3 and 4, desirable CR values often degrade crystallinity values. For example, the film from Example 4 (Resin B) had a desirably low CR residue value, but at the same time a low crystallinity value.

[00230] As shown in Examples 9-12, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins of a first PVA copolymer containing a first anionic monomer, as described herein, and a second PVA copolymer containing a second anionic monomer, as described herein meet one or both of criteria (a) and (b). In Table 4, film properties marked with "*" satisfy criteria (a) or (b). It can be seen from the data that films containing PVA resin blends comprising two anionic PVA copolymers as shown in Examples 9-12 generally meet criteria (a) and (b) for A/B blend ratios ranging from about 20/80 up to about 80/20 (w/w, respectively).

Examples 13-18 Individual Resin Film Exposed to GMS

[00231] Films made with Resin A and non-resin components in the types and amounts described in Example 1 were exposed to liquid laundry detergent 1 (LMC 1) as described herein. These films were prepared as described in Example 1 and tested for residual CR values by the above method after storage in contact with GMS 1 for 3, 6, or 12 weeks at ambient (23°C, 35% r.h.) or high load, ambient 38°C and relative humidity 80%. The average values of SC are shown in Table 5. In Table 5, the content of side groups (P) for the film is given in terms of moles in relation to the PVA resins in the film (i.e., excluding plasticizers and their other non-resin components) , and the P value additionally indicates that the side group corresponds to the methyl acrylate comonomer unit (A). The first entry in Table 5 is the individual resin limit for film composition (eg, as similarly presented in Example 1).

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

Example Type of weeks storage Environmental conditions CR (%) P (mole %) one A 0 23°C, RH 35% 9.01* 5.0 (A) 13 A 3 23°C, RH 35% 33.36* 5.0 (A) fourteen A 6 23°C, RH 35% 32.13* 5.0 (A) fifteen A 12 23°C, RH 35% 48.45 5.0 (A) 16 A 3 38°C, RH 80% 46.97 5.0 (A) 17 A 6 38°C, RH 80% 42.95 5.0 (A) eighteen A 12 38°C, RH 80% 43.17 5.0 (A)

[00232] In summary, Table 5 demonstrates that, for a single resin film containing a PVA copolymer comprising an acrylate modification and pendant groups, CR residue values increase when stored at ambient temperature and humidity and further increase when stored at 38° C and relative humidity 80%. In addition, by comparing the values of the CR residue in Example 1 with the values of the CR residue in Examples 13-18, it can be seen that for a film made from an individual resin containing a PVA copolymer comprising a modification and acrylate side groups, the film residue generally increases after exposure to liquid detergent. powder and storage. In Table 5, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12.

Examples 19-24 Individual Resin Film Exposed to GMS

[00233] Films made with Resin A and non-resin components in the types and amounts described in Example 3 were exposed to liquid laundry detergent 1 (LMC 1) as described herein. These films were prepared as described in Example 1 and tested as described in Examples 13-18. The average values of SC are given in Table 6. In Table 6, the content of side groups (P) for the film is given in terms of moles in relation to the PVA resins in the film (i.e., excluding plasticizers and their other non-resin components) , and the P value additionally indicates that the side group corresponds to the methyl acrylate comonomer unit (A). The first entry in Table 6 is the individual resin limit for the film composition (ie, Example 3).

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

Example Type of weeks storage Environmental conditions CR (%) P (mole %) 3 A 0 23°C, RH 35% 21.20* 5 (A) 19 A 3 23°C, RH 35% 32.61* 5 (A) twenty A 6 23°C, RH 35% 28.21* 5 (A) 21 A 12 23°C, RH 35% 36.57 5 (A) 22 A 3 38°C, RH 80% 29.91* 5 (A) 23 A 6 38°C, RH 80% 41.45 5 (A) 24 A 12 38°C, RH 80% 40.09 5 (A)

[00234] In summary, Table 6 demonstrates that for a single resin film containing a PVA copolymer comprising an acrylate modification and pendant groups, CR residue values increase when stored at ambient temperature and humidity and further increase when stored at 38° C and relative humidity 80%. In addition, by comparing the CR residue values in Example 3 with the CR residue values in Examples 19-24, it can be seen that for an individual resin film containing a PVA copolymer comprising a modification and acrylate pendant groups, the film residue generally increases after exposure to liquid detergent. powder and storage. In Table 6, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12.

[00235] In addition, by comparing the data in Table 5 and Table 6, it can be seen that films made from PVA-alkyl acrylate copolymer (Resin A) having a high level of plasticizer (for example, more than 30 ppm, Examples 13-18 ) showed higher CR residue values compared to films made from PVA-alkyl acrylate copolymer (Resin A) having a low level of plasticizer (eg, less than 30 ppm in total, Examples 19-24).

Examples 25-30 Individual Resin Film Exposed to GMS

[00236] Films were prepared with Resin B and non-resin components in amounts and types as described in Example 2. Films prepared as described in Example 1 were exposed to liquid laundry detergent alone (LMS 1) as described in this document. These films were tested as described in Examples 13-18. The average values of SC are given in Table 7. In Table 7, the content of side groups (P) for the film is given in terms of moles in relation to the PVA resins in the film (i.e., excluding plasticizers and their other non-resin components) , and the value of P additionally indicates that the side group corresponds to a unit of maleic anhydride comonomer (M).

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

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

[00237] In summary, Table 7 demonstrates that for a single resin film containing a PVA copolymer comprising a modification and maleate pendant groups, CR residue values generally increase when stored at ambient temperature and humidity (23°C and relative humidity 35%) and when stored at 38°C and 80% relative humidity. In addition, comparing the values of the residue of the CR in Example 2 with the values of the residue of the CR in Examples 25-30, it can be seen that for a film of an individual resin containing a PVA copolymer containing a modification and maleate side groups, the film residue generally increases after exposure to liquid detergent powder and storage, albeit at a much slower rate than for an individual resin film containing a PVA copolymer comprising modification and acrylate pendant groups (i.e., Examples 13-18 in Table 5). In Table 7, film properties marked with "*" meet criterion (a) as described in Examples 5-12.

[00238] 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, obtained from a copolymer of PVA and acrylate (Resin A), have more high residue values (CR values) compared to water-soluble films that have been exposed to liquid laundry detergent and stored for 3, 6, or 12 weeks, made from a copolymer of PVA and maleate (Resin B).

Examples 31-36 Individual Resin Film Exposed to GMS

[00239] Films were prepared with Resin B and non-resin components in amounts and types as described in Example 4. Films prepared as described in Example 1 were exposed to liquid laundry detergent alone (LMS 1) as described in this document. These films were tested as described in Examples 13-18. The average values of SC are given in Table 8. In Table 8, the content of side groups (P) for the film is given in terms of moles in relation to the PVA resins in the film (i.e., excluding plasticizers and their other non-resin components) , and the value of P additionally indicates that the side group corresponds to a unit of maleic anhydride comonomer (M).

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

Example Type of weeks storage Environmental conditions CR (%) P (mole %) four AT 0 23 °C, RH 35% 0.86* 8.00 (M) 31 AT 3 23 °C, RH 35% 7.94* 8.00 (M) 32 AT 6 23 °C, RH 35% 4.46* 8.00 (M) 33 AT 12 23 °C, RH 35% 9.10* 8.00 (M) 34 AT 3 38 °C, RH 80% 3.94* 8.00 (M) 35 AT 6 38 °C, RH 80% 2.69* 8.00 (M) 36. AT 12 38 °C, RH 80% 6.12* 8.00 (M)

[00240] In summary, Table 8 demonstrates that for a single resin film containing a PVA copolymer comprising a modification and maleate pendant groups, CR residue values generally remain relatively stable when stored at ambient temperature and humidity (23°C and relative humidity 35%) and when stored at 38°C and relative humidity 80%. In addition, by comparing the values of the residue CR in Example 4 with the values of the residue CR in Examples 31-36, it can be seen that for a film of an individual resin containing a PVA copolymer containing a modification and maleate side groups, the film residue generally increases after exposure to liquid detergent. powder and storage, albeit at a much slower rate than for a single resin film containing a PVA copolymer comprising modification and acrylate pendant groups (i.e., Examples 19-24 in Table 6). In Table 8, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12.

[00241] In addition, the combined data of Table 6 and Table 8 show that water-soluble films exposed to liquid laundry detergent and stored for 3, 6 or 12 weeks, obtained from a copolymer of PVA and acrylate (Resin A), have more high residue values (CR values) compared to water-soluble films that have been exposed to liquid laundry detergent and stored for 3, 6, or 12 weeks, made from a copolymer of PVA and maleate (Resin B).

Examples 37-42: Dual Resin Blend Films

[00242] Examples 37-42 are formed water-soluble films, each containing a mixture of 80 wt. % Resin A and 20 wt. % Resin B. These films from the blend contained two resins that made up 100% of the resins in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 1. Films were prepared as described in Example 1. The resulting films were exposed to liquid laundry detergent one (LMS 1) as described herein and tested as described in Examples 13-18. Average FR values are shown in Table 9. In Table 9, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

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

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 37 80/20 3 23 °C, RH 35% 23.67* 5.6 (A/M) 38 80/20 6 23 °C, RH 35% 25.52* 5.6 (A/M) 39 80/20 12 23 °C, RH 35% 35.53 5.6 (A/M) 40 80/20 3 38 °C, RH 80% 34.28* 5.6 (A/M) 41 80/20 6 38 °C, RH 80% 33.71* 5.6 (A/M) 42 80/20 12 38 °C, RH 80% 43.76 5.6 (A/M)

[00243] In Table 9, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12. As shown in Examples 37-42, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with 80 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and 20 wt. % of a second PVA copolymer containing a second anionic monomer as described herein generally meets criteria (a) for A/B blend ratios of about 80/20 (w/w, respectively) up to at least 6 weeks storage at ambient conditions and up to at least 6 weeks storage at 38°C and 80% relative humidity.

Examples 43-48: Dual Resin Blend Films

[00244] Examples 43-48 are formed water-soluble films, each containing a mixture of 80 wt. % Resin A and 20 wt. % Resin B. These films from the blend contained two resins that made up 100% of the resins in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 3. Films were prepared as described in Example 1. The resulting films were exposed to liquid laundry detergent one (LMS 1) as described herein and tested as described in Examples 13-18. Average FR values are shown in Table 10. In Table 10, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

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

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 43 80/20 3 23 °C, RH 35% 31.02* 5.6 (A/M) 44 80/20 6 23 °C, RH 35% 24.53* 5.6 (A/M) 45 80/20 12 23 °C, RH 35% 27.0* 5.6 (A/M) 46 80/20 3 38 °C, RH 80% 35.33* 5.6 (A/M) 47 80/20 6 38 °C, RH 80% 35.17* 5.6 (A/M) 48 80/20 12 38 °C, RH 80% 34.91* 5.6 (A/M)

[00245] In Table 10, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12. As shown in Examples 43-48, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with 80 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and 20 wt. % of the second PVA copolymer containing the second anionic monomer, as described herein, meet the criteria of (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 80 relative humidity %.

Examples 49-54: Dual Resin Blend Films

[00246] Examples 49-53 are formed water-soluble films, each containing a mixture of 60 wt. % Resin A and 40 wt. % Resin B. These films from the blend contained two resins that were 100% resin in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 1. Films prepared as described in Example 1, exposed to liquid laundry detergent one (LMS 1) as described herein. These films were tested as described in Examples 13-18. Average FR values are shown in Table 11. In Table 11, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

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

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 49 60/40 3 23 °C, RH 35% 20.50* 6.2 (A/M) fifty 60/40 6 23 °C, RH 35% 23.31* 6.2 (A/M) 51 60/40 12 23 °C, RH 35% 34.1* 6.2 (A/M) 52 60/40 3 38 °C, RH 80% 34.84* 6.2 (A/M) 53 60/40 6 38 °C, RH 80% 36.85 6.2 (A/M) 54 60/40 12 38 °C, RH 80% 23.62* 6.2 (A/M)

[00247] In Table 11, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12. As shown in Examples 49-54, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 60 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 40 wt. % of the second PVA copolymer containing the second anionic monomer as described herein generally meet the criteria for (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 55-60: Dual Resin Blend Films

[00248] Examples 55-60 are formed water-soluble films, each containing a mixture of 60 wt. % Resin A and 40 wt. % Resin B. These films from the blend contained two resins that made up 100% of the resins in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 3. Films prepared as described in Example 1, exposed to liquid laundry detergent one (LMS 1) as described herein. These films were tested as described in Examples 13-18. Average FR values are shown in Table 12. In Table 12, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

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

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 55 60/40 3 23 °C, RH 35% 28.61* 6.2 (A/M) 56 60/40 6 23 °C, RH 35% 34.66* 6.2 (A/M) 57 60/40 12 23 °C, RH 35% 25.83* 6.2 (A/M) 58 60/40 3 38 °C, RH 80% 37.30 6.2 (A/M) 59 60/40 6 38 °C, RH 80% 31.91* 6.2 (A/M) 60 60/40 12 38 °C, RH 80% 28.46* 6.2 (A/M)

[00249] In Table 12, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12. As shown in Examples 55-60, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 60 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 40 wt. % of the second PVA copolymer containing the second anionic monomer as described herein generally meet the criteria for (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: Dual Resin Blend Films

[00250] Examples 61-66 are formed water-soluble films, each containing a mixture of 40 wt. % Resin A and 60 wt. % Resin B. These films from the blend contained two resins that were 100% resin in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 1. Films prepared as described in Example 1, exposed to liquid laundry detergent one (LMS 1) as described herein. These films were tested as described in Examples 13-18. Average FR values are shown in Table 13. In Table 13, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

Table 13 Resin and Film Data for Examples 61-66

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 61 40/60 3 23 °C, RH 35% 21.02* 6.8 (A/M) 62 40/60 6 23 °C, RH 35% 17.97* 6.8 (A/M) 63 40/60 12 23 °C, RH 35% 33.31* 6.8 (A/M) 64 40/60 3 38 °C, RH 80% 20.14* 6.8 (A/M) 65 40/60 6 38 °C, RH 80% 21.38* 6.8 (A/M) 66 40/60 12 38 °C, RH 80% 32.08* 6.8 (A/M)

[00251] In Table 13, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12. As shown in Examples 61-66, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 40 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 60 wt. % of the second PVA copolymer containing the second anionic monomer, as described herein, meet the criteria of (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 80 relative humidity %.

Examples 67-72: Dual Resin Blend Films

[00252] Examples 67-72 are formed water-soluble films, each containing a mixture of 40 wt. % Resin A and 60 wt. % Resin B. These films from the blend contained two resins that made up 100% of the resins in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 3. Films prepared as described in Example 1, exposed to liquid laundry detergent one (LMS 1) as described herein. These films were tested as described in Examples 13-18. Average FR values are shown in Table 14. In Table 14, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

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

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 67 40/60 3 23 °C, RH 35% 32.05* 6.8 (A/M) 68 40/60 6 23 °C, RH 35% 25.38* 6.8 (A/M) 69 40/60 12 23 °C, RH 35% 29.89* 6.8 (A/M) 70 40/60 3 38 °C, RH 80% 28.14* 6.8 (A/M) 71 40/60 6 38 °C, RH 80% 31.05* 6.8 (A/M) 72 40/60 12 38 °C, RH 80% 26.19* 6.8 (A/M)

[00253] In Table 14, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12. As shown in Examples 67-72, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 40 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 60 wt. % of the second PVA copolymer containing the second anionic monomer, as described herein, meet the criteria of (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 80 relative humidity %.

Examples 73-78: Dual Resin Blend Films

[00254] Examples 73-78 are formed water-soluble films, each containing a mixture of 20 wt. % Resin A and 80 wt. % Resin B. These films from the blend contained two resins that were 100% resin in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 1. Films prepared as described in Example 1, exposed to liquid laundry detergent one (LMS 1) as described herein. These films were tested as described in Examples 13-18. Average FR values are shown in Table 15. In Table 15, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

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

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 73 20/80 3 23 °C, RH 35% 20.61* 7.4 (A/M) 74 20/80 6 23 °C, RH 35% 19.25* 7.4 (A/M) 75 20/80 12 23 °C, RH 35% 19.37* 7.4 (A/M) 76 20/80 3 38 °C, RH 80% 14.41* 7.4 (A/M) 77 20/80 6 38 °C, RH 80% 17.59* 7.4 (A/M) 78 20/80 12 38 °C, RH 80% 6.99* 7.4 (A/M)

[00255] In Table 15, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12. As shown in Examples 73-78, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 20 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 80 wt. % of the second PVA copolymer containing the second anionic monomer, as described herein, meet the criteria of (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 80 relative humidity %.

Examples 79-84: Dual Resin Blend Films

[00256] Examples 79-84 are formed water-soluble films, each containing a mixture of 20 wt. % Resin A and 80 wt. % Resin B. These films from the blend contained two resins that made up 100% of the resins in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 3. Films prepared as described in Example 1, exposed to liquid laundry detergent one (LMS 1) as described herein. These films were tested as described in Examples 13-18. Average FR values are shown in Table 16. In Table 16, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

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

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 79 20/80 3 23 °C, RH 35% 7.40* 7.4 (A/M) 80 20/80 6 23 °C, RH 35% 39.70 7.4 (A/M) 81 20/80 12 23 °C, RH 35% 20.49* 7.4 (A/M) 82 20/80 3 38 °C, RH 80% 17.75* 7.4 (A/M) 83 20/80 6 38 °C, RH 80% 14.67* 7.4 (A/M) 84 20/80 12 38 °C, RH 80% 12.77* 7.4 (A/M)

[00257] In Table 16, film properties marked with "*" satisfy criterion (a) as described in Examples 5-12. As shown in Examples 79-84, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 20 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 80 wt. % of the second PVA copolymer containing the second anionic monomer, as described herein, generally meet the criteria (a) up to at least 12 weeks of storage at 38°C and 80% relative humidity.

Example 85 Film Swelling

[00258] Water soluble films were formed from individual resins or mixtures of two copolymers of Resins A and B. Films were made with a weight ratio 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 was 100% resin in the films produced herein, while plasticizers and other non-film components were present in the amounts and types as described in Example 1. The films were tested for swell factor in each of propylene glycol, polyethylene glycol (PEG) 200, glycerin and diglycerin according to the film swelling test described herein. Average swelling ratios are shown in Table 17.

Table 17. Average swelling coefficients of films in various solvents

Resin A/Resin B ratio propylene glycol PEG 200 Glycerol Diglycerin 100/0 0.0793 -0.015 0.7478 0.0599 80/20 0.1825 -0.0605 0.7425 0.1327 60/40 0.1599 -0.0558 0.6189 0.1451 40/60 0.2067 -0.0153 0.9806 0.1678 30/70 0.2105 Undefined 1.1194 Undefined 20/80 0.4744 0.0179 1.6723 0.3428 0/100 1.7167 0.3367 10.6665 0.7266

[00259] As shown in Table 17, as the amount of PVA-maleate copolymer (Resin B) increases, the amount of swelling of the water-soluble film generally increases, and a significant increase is observed for films not containing PVA-alkyl acrylate copolymer (Resin A) (for example, when ratio 0/100). Without being limited by theory, it is believed that when the film exhibits an increase in the swelling ratio value that is less than 60% of the swelling ratio value of the comparative film which is identical but different to the second PVA copolymer being an individual resin, and the amount of this second PVA copolymer in Comparative film is equal to the total amount of resins in the water soluble film of this invention (e.g. A/B ratio 0/100), said film is less likely to soften and sag (i.e., remain taut) when forming bags containing liquid compositions.

[00260] In Fig. 3 and 4 are graphical representations of the data from Examples 5, 7, 9, 11, 13 and 15 above. FIG. 3 shows the evolution of CR residual values over time for films stored at ambient temperature (FIG. 3a) and at 38°C and 80% relative humidity (FIG. 3b) for films made from PVA resin blends comprising a PVA copolymer -acrylate and PVA-maleate copolymer. The percentage of acrylate in the mixture is indicated in the legend, and the rest of the resin is a maleate copolymer.

[00261] FIG. 4 is a graphical representation of film dissolution at 10°C measured by MSTM-205 over time for films stored at ambient temperature (Fig. 4a) and at 38°C and 80% relative humidity (Fig. 4b) for films made from PVA resin blends, including PVA-acrylate copolymer and PVA-maleate copolymer. The percentage of acrylate in the mixture is indicated in the legend, and the rest of the resin is a maleate copolymer.

Examples 86-92 Individual Resin Film Exposed to GMS

[00262] Films were made with Resin B, including plasticizers and other non-resin components, in amounts and types as described in Example 2. Aqueous compositions from the above were cast and dried to form 76 µm thick film samples. The resulting films were subjected to liquid laundry detergent two (LMS 2) as described herein. The films were tested for residual CR values by the above methods before storage in contact with GMS 2 and after storage in contact with GMS 2 for 3, 6, or 12 weeks under ambient conditions (23 °C, 35% r.h.) or high load, ambient environment 38°C and relative humidity 80%. Table 18 shows the average values of SC. In Table 18, the content of side groups (P) for the film is given in terms of moles in relation to the PVA resins in the film (i.e., excluding plasticizers and their other non-resin components) , and the value of P additionally indicates that the side group corresponds to a unit of maleic anhydride comonomer (M).

Table 18 Resin and Film Data for Examples 86-92

Example Type of weeks storage Environmental conditions CR (%) P (mole %) 86 AT 0 23 °C, RH 35% 0.73* 8.00 (M) 87 AT 3 23 °C, RH 35% 1.78* 8.00 (M) 88 AT 6 23 °C, RH 35% 3.87* 8.00 (M) 89 AT 12 23 °C, RH 35% 2.97* 8.00 (M) 90 AT 3 38 °C, RH 80% 3.28* 8.00 (M) 91 AT 6 38 °C, RH 80% 1.11* 8.00 (M) 92 AT 12 38 °C, RH 80% 2.20* 8.00 (M)

[00263] In Table 18, residue values marked with "*" meet the criteria for good CR residue values, i.e., less than 35 wt. %. Table 18 demonstrates that water-soluble films containing a single PVA resin containing maleic anhydride comonomer can exhibit good residue values.

Examples 93-99 Individual Resin Film Exposed to GMS

[00264] Films were made with Resin A and non-resin components in amounts and types as described in Example 1. Films were formed and tested as described in Examples 86-92. Table 19 shows the average values of SC. In Table 19, the content of side groups (P) for the film is given in terms of moles in relation to the PVA resins in the film (i.e., excluding plasticizers and their other non-resin components) , and the P value additionally indicates that the side group corresponds to the methyl acrylate comonomer unit (A).

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

Example Type of weeks storage Environmental conditions CR (%) P (mole %) 93 A 0 23 °C, RH 35% 11.43* 5.00 (A) 94 A 3 23 °C, RH 35% 27.08* 5.00 (A) 95 A 6 23 °C, RH 35% 25.20* 5.00 (A) 96 A 12 23 °C, RH 35% 30.55* 5.00 (A) 97 A 3 38 °C, RH 80% 30.59* 5.00 (A) 98 A 6 38 °C, RH 80% 40.35 5.00 (A) 99 A 12 38 °C, RH 80% 58.15 5.00 (A)

[00265] In Table 19, residue values marked with "*" meet the criteria for a KR residue, as described in Examples 86-92. Table 19 demonstrates that water-soluble films containing a single PVA resin containing methacrylate comonomer can show poor residue values when stored in contact with liquid laundry detergent under high load conditions (eg, 38°C, 80% RH).

Examples 100-106 Two Resin Blend Films

[00266] Examples 100-106 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 from the blend contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 1. These films were prepared and tested as described in Examples 86-92. Average FR values are shown in Table 20. In Table 20, the side group content (P) for films is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

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

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 100 80/20 0 23 °C, RH 35% 3.86* 5.6 (A/M) 101 80/20 3 23 °C, RH 35% 12.63* 5.6 (A/M) 102 80/20 6 23 °C, RH 35% 14.81* 5.6 (A/M) 103 80/20 12 23 °C, RH 35% 15.30* 5.6 (A/M) 104 80/20 3 38 °C, RH 80% 13.79* 5.6 (A/M) 105 80/20 6 38 °C, RH 80% 20.11* 5.6 (A/M) 106 80/20 12 38 °C, RH 80% 03.22* 5.6 (A/M)

[00267] In Table 20, residue values marked with "*" satisfy the criteria for a KR residue value, as described in Examples 86-92. As shown in Examples 100-106, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 80 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 20 wt. % of a second PVA copolymer containing a second anionic monomer as described herein generally meets the stated criteria for acceptable residue values up to at least 12 weeks storage at ambient conditions and up to at least 12 weeks storage at 38°C and relative humidity of 80%.

Examples 107-113 Two Resin Blend Films

[00268] Examples 107-113 are formed water-soluble films, each of which contains 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 from the blend contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 1. These films were prepared and tested as described in Examples 86-92. Average FR values are shown in Table 21. In Table 21, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

Table 21 Resin and Film Data for Examples 107-113

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 107 60/40 0 23 °C, RH 35% 6.31* 6.2 (A/M) 108 60/40 3 23 °C, RH 35% 10.07* 6.2 (A/M) 109 60/40 6 23 °C, RH 35% 7.88* 6.2 (A/M) 110 60/40 12 23 °C, RH 35% 7.80* 6.2 (A/M) 111 60/40 3 38 °C, RH 80% 10.74* 6.2 (A/M) 112 60/40 6 38 °C, RH 80% 13.14* 6.2 (A/M) 113 60/40 12 38 °C, RH 80% 7.48* 6.2 (A/M)

[00269] In Table 21, residue values marked with "*" satisfy the criteria for a KR residue value, as described in Examples 86-92. As shown in Examples 107-113, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 60 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 40 wt. % of a second PVA copolymer containing a second anionic monomer as described herein generally meets the stated criteria for acceptable residue values up to at least 12 weeks storage at ambient conditions and up to at least 12 weeks storage at 38°C and relative humidity of 80%.

Examples 114-120: Dual Resin Blend Films

[00270] Examples 114-120 are formed water-soluble films, each of which contains 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 from the mixture contained two resins that were 100% resin in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 1. These films were prepared as described in Examples 86-92. Average FR values are shown in Table 22. In Table 22, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

Table 22 Resin and Film Data for Examples 114-120

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 114 40/60 0 23 °C, RH 35% 3.96* 6.8 (A/M) 115 40/60 3 23 °C, RH 35% 9.05* 6.8 (A/M) 116 40/60 6 23 °C, RH 35% 13.93* 6.8 (A/M) 117 40/60 12 23 °C, RH 35% 12.96* 6.8 (A/M) 118 40/60 3 38 °C, RH 80% 9.78* 6.8 (A/M) 119 40/60 6 38 °C, RH 80% 12.95* 6.8 (A/M) 120 40/60 12 38 °C, RH 80% 6.55* 6.8 (A/M)

[00271] In Table 22, residue values marked with "*" meet the criteria for a KR residue value, as described in Examples 86-92. As shown in Examples 114-120, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 40 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 60 wt. % of a second PVA copolymer containing a second anionic monomer as described herein generally meets the stated criteria for acceptable residue values up to at least 12 weeks storage at ambient conditions and up to at least 12 weeks storage at 38°C and relative humidity of 80%.

Examples 121-127: Dual Resin Blend Films

[00272] Examples 121-127 are formed water-soluble films, each of which contains 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 from the blend contained two resins that constituted 100% of the resin in the film, while plasticizers and other non-resin components were present in amounts and types as described in Example 1. These films were prepared and tested as described in Examples 86-92. Average FR values are shown in Table 23. In Table 23, the side group content (P) for the film is given 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 indicate whether they correspond to a methyl acrylate comonomer unit (A) or a maleic anhydride comonomer unit (M).

Table 23 Resin and Film Data for Examples 121-127

Example Type of
(A/B ratio) weeks storage Environmental conditions CR (%) P (mole %) 121 20/80 0 23 °C, RH 35% 3.09* 7.4 (A/M) 122 20/80 3 23 °C, RH 35% 12.13* 7.4 (A/M) 123 20/80 6 23 °C, RH 35% 13.02* 7.4 (A/M) 124 20/80 12 23 °C, RH 35% 9.67* 7.4 (A/M) 125 20/80 3 38 °C, RH 80% 12.82* 7.4 (A/M) 126 20/80 6 38 °C, RH 80% 11.75* 7.4 (A/M) 127 20/80 12 38 °C, RH 80% 7.35* 7.4 (A/M)

[00273] In Table 23, residue values marked with "*" meet the criteria for a KR residue value, as described in Examples 86-92. As shown in Examples 121-127, it was unexpectedly found that some water-soluble films containing mixtures of PVA resins with about 20 wt. % of the first PVA copolymer containing the first anionic monomer, as described in this document, and about 80 wt. % of a second PVA copolymer containing a second anionic monomer as described herein generally meets the stated criteria for acceptable residue values up to at least 12 weeks storage at ambient conditions and up to at least 12 weeks storage at 38°C and relative humidity of 80%.

[00274] The foregoing description is provided for clarity of understanding only, and should not introduce any undue restrictions as modifications within the scope of the invention may be apparent to those skilled in the art.

[00275] All patents, publications and references mentioned in this document are incorporated into this description in their entirety by reference. In the event of any conflict between this document and incorporated patents, publications, and references, this document shall govern.

Claims (39)

1. Water-soluble film for the manufacture of packaging, containing: a plasticizer and a mixture of polyvinyl alcohol (PVA) resins, where the mixture of polyvinyl alcohol (PVA) resins contains: a first PVA copolymer containing a first anionic monomer unit selected from the group consisting of alkyl acrylates, alkyl alkacrylates, hydrolysed alkali metal salts of the foregoing, and combinations of the foregoing; and a second PVA copolymer containing a second anionic monomer unit selected from one or more of maleic anhydride and an alkali metal salt of maleic anhydride; where the first PVA copolymer is contained in an amount in the range from about 10 wt. % to about 40 wt. % based on the total weight of the mixture of PVA resins, and the first anionic monomer unit is different from the second anionic monomer unit, where the plasticizer is present in an amount of from about 5 m.h. up to less than 30 m.h. per 100 m.h. PVA (phr) and includes glycerin and sorbitol; and where the water-soluble film has a residue value of about 35 wt. % or less as measured in a dissolution chamber test and a crystallinity of at least 15%. 2. Water-soluble film according to claim 1, characterized in that said second anionic monomer is selected from the group consisting of vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, fumaric anhydride, taconic acid, monoalkyl itaconate, dialkyl itaconate, itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkyl citraconic acid, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconate, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations of the foregoing. 3. Water-soluble film according to claim 1 or 2, characterized in that said first PVA copolymer has a first level of side groups (a ₁ ) derived from the first anionic monomer unit; and said second PVA copolymer has a second level of side groups (a ₂ ) derived from the second anionic monomer unit; where the difference between a ₁ and a ₂ is in the range of about 2 mol. % to about 10 mol. %. 4. Water-soluble film according to any one of paragraphs. 1-3, characterized in that said first PVA copolymer is present in an amount ranging from about 20 wt. % to about 40 wt. % of the total weight of the mixture of PVA resins. 5. Water-soluble film according to any one of paragraphs. 1-3, characterized in that said second PVA copolymer is present in an amount ranging from about 60 wt. % to about 90 wt. % of the total weight of the PVA polymer in the specified film. 6. Water-soluble film according to any one of paragraphs. 1-5, characterized in that said first PVA copolymer has a level of first side groups derived from the first anionic monomer, and said second PVA copolymer has a level of second side groups derived from the second anionic monomer, and the level of the first and second side groups together is arithmetic weighted average value in the range of about 2 mol. % up to 15 mol. %. 7. Water-soluble film according to any one of paragraphs. 1-6, characterized in that said first PVA copolymer is an alkyl acrylate copolymer having a first level of anionic monomer content (b ₁ ), and said second 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 about 0.2 mol. % up to 2 mol. %. 8. Water-soluble film according to any one of paragraphs. 1-7, characterized in that said first PVA copolymer has a viscosity of a 4% solution at 20°C in the range from about 4 centipoise to about 24 centipoise. 9. Water-soluble film according to any one of paragraphs. 1-8, characterized in that said second PVA copolymer has a 4% solution viscosity at 20°C in the range of about 12 centipoise to about 30 centipoise. 10. Water-soluble film according to any one of paragraphs. 1-9, characterized in that said mixture of PVA resins consists essentially of a first PVA copolymer and a second PVA copolymer. 11. Water-soluble film according to any one of paragraphs. 1-9, further comprising at least a third water-soluble polymer that is different from the PVA polymer. 12. Water-soluble film according to claim 11, characterized in that said third water-soluble polymer is selected from one or more of: polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxide, polyacrylamide, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polyamide, gelatin, methylcellulose , carboxymethylcellulose, salts of carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, starch, modified starch, guar gum, acacia gum, xanthan gum, carrageenan, polyacrylate, salt of polyacrylate and a copolymer of any of the above. 13. Water-soluble film according to any one of paragraphs. 1-12, 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 about 75% to about 99%. 14. Water-soluble film according to any one of paragraphs. 1-13, further comprising an auxiliary agent selected from one or more of a plasticizer, an agent that improves compatibility with plasticizers, a lubricating agent, an anti-adhesive agent, a filler, a diluent, a cross-linking agent, an anti-blocking agent, an antioxidant, an agent that reduces stickiness, a defoamer, nanoparticles, bleaching agent and surfactant. 15. Water-soluble film according to any one of paragraphs. 1-14, additionally containing a third plasticizer. 16. Water-soluble film according to any one of paragraphs. 1-15, additionally containing a filler in an amount of at least 2 m.h. 17. A water-soluble film according to claim 16, characterized in that said filler comprises a bulking agent, an anti-blocking agent, or a combination thereof. 18. Water-soluble film according to any one of paragraphs. 1-17, characterized in that: the first PVA copolymer contains an alkyl acrylate monomer unit; the first PVA copolymer is present in an amount ranging from about 10 wt. % to about 40 wt. % of the total mass of the mixture of PVA resins; the second PVA copolymer contains a second anionic monomer unit selected from one or more of maleic anhydride and an alkali metal salt of maleic anhydride; the second PVA copolymer is present in an amount ranging from about 60 wt. % to about 90 wt. % of the total mass of the mixture of PVA resins; where the difference between a ₁ and a ₂ is in the range of about 2 mol. % to about 6 mol. %; a ₁ is in the range from about 2 mol. % to about 6 mol. %; a ₂ is in the range of about 7 mol. % to about 9 mol. %; and the level of the first side groups and the level of the second side groups together constitute a weighted arithmetic value in the range of about 2 mol. % up to 15 mol. %. 19. Product for the content of the composition, containing: water-soluble film according to any one of paragraphs. 1-18 in the form of a package defining the internal volume of the package. 20. The product according to claim 19, additionally containing a composition enclosed in the internal volume of the package. 21. The product according to claim 20, characterized in that said composition is a liquid composition. 22. The product according to claim 21, characterized in that said liquid composition is a liquid detergent. 23. The product according to claim 21 or 22, characterized in that said liquid composition contains a low molecular weight polyol. 24. The product according to any one of paragraphs. 20-23, characterized in that the composition contained in the internal volume of the package is a liquid, and the specified product has a delayed release time of at least 30 s as measured in the liquid release test.

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