Hybrid starch / PVOH water-soluble film

Abstract

Provided herein are water-soluble films comprising a water-soluble polymer, such as polyvinyl alcohol (PVOH), and a high content of water-soluble starch, as well as related water-soluble film-forming solutions, articles made therefrom, such as pouches or packets, and methods for their preparation and use.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS The benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 477,561, filed December 28, 2022, the entire disclosure of which is incorporated herein by reference.

[0002] The present disclosure relates generally to water-soluble films and related water-soluble film-forming solutions, articles comprising pouches or packets made therefrom, and methods of preparing and using them. More specifically, the present disclosure relates to water-soluble films comprising a water-soluble polymer such as polyvinyl alcohol (PVOH) and a high content of starch, and related water-soluble film-forming solutions, articles, e.g., pouches or packets, made therefrom, and methods of preparing and using them. [Background technology]

[0003] Water-soluble polymer films are commonly used as packaging materials to simplify the dispersion, injection, dissolution, and dosage of the composition to be dispensed.For example, packets made of water-soluble films are commonly used to package pouches containing household care compositions, such as laundry detergent or dish detergent.Consumers can directly add the packaged composition in the pouch to a mixing container, such as a bucket, sink, or any container suitable for holding water.Advantageously, this provides accurate dosage while eliminating the need for consumers to measure the composition.Packaged compositions can also reduce the mess associated with dispensing compositions from product containers, such as pouring or drawing materials.In short, dissolvable pre-measured polymer film pouches provide the convenience of consumer use in various applications.

[0004] Currently, consumers are increasingly inclined to use environmentally friendly or renewable products.However, one problem with conventional water-soluble films is that such films are generally not environmentally friendly or renewable, and typically have a low renewable carbon index (RCI).In addition, many renewable components are inherently very rigid and are not miscible or compatible with other polymer components in conventional water-soluble films, so their use in these films is limited by the need to maintain suitable mechanical properties for conversion to and use as packaging, such as high levels of elongation, deformation recovery, and strength properties. Summary of the Invention

[0005]

[0006] The embodiments disclosed herein address the aforementioned needs by providing sustainable water-soluble films for use with consumer compositions, such as liquid detergents, and sustainable consumer compositions packaged in the sustainable water-soluble films to result in highly sustainable and environmentally friendly consumer products. The water-soluble films can have a high Renewable Carbon Index (RCI), of 50% or greater, and also desirable physical properties.

[0006] One aspect of the present disclosure provides a water-soluble film comprising a water-soluble polyvinyl alcohol (PVOH) and a water-soluble starch, wherein the water-soluble starch has a cook percentage of at least about 5% by weight, the water-soluble starch may be present in an amount of about 5-65% by weight of the water-soluble film, and the PVOH and the water-soluble starch are miscible or have phase domains of less than 2000 μm in the water-soluble film. The water-soluble polyvinyl alcohol may be soluble in water within about 60 minutes at a temperature of about 60°C or less, or may be soluble in water within about 60 minutes at a temperature of about 60°C, about 40°C, about 20°C, or about 10°C. The water-soluble polyvinyl alcohol may comprise an anionic group-modified polyvinyl alcohol. The water-soluble starch may comprise a cationic group-modified starch. The water-soluble starch may include neutral group-modified starch.

[0007] Another aspect of the present disclosure provides an aqueous solution suitable for forming the water-soluble film of the present disclosure, the aqueous solution comprising a water-soluble polyvinyl alcohol (PVOH), a water-soluble starch, and water, wherein the water-soluble starch has a Cook % of at least about 5% by weight, the aqueous solution has a total solids content of at least 15% by weight of the aqueous solution, and the water-soluble starch may be present in an amount of about 5 to 65% by weight of the total solids, and wherein the water-soluble polyvinyl alcohol (PVOH) and the water-soluble starch are miscible in the aqueous solution or do not exhibit bulk phase separation, as determined by visual inspection at a temperature ranging from about 20°C to 100°C, for at least 24 hours.

[0008] Another aspect of the present disclosure provides a method of forming the water-soluble film of the present disclosure, the method comprising casting an aqueous solution of the present disclosure onto a substrate at a specified thickness and drying water from the cast aqueous solution to form the water-soluble film.

[0009] Another aspect of the present disclosure provides an article comprising a pouch or packet made from the water-soluble film of the present disclosure defining an interior pouch volume. The article may further comprise a consumer or chemical composition contained in the interior pouch volume and enclosed within the pouch.

[0010] For the water-soluble films, aqueous solutions for forming the water-soluble films, and articles described herein, it is contemplated that optional features, including but not limited to, ingredients and their composition ranges, film-forming materials, film-forming solution compositions and characteristics, and / or mechanical properties, may be selected from the various aspects and embodiments provided herein.

[0011] Further aspects and advantages will be apparent to those skilled in the art from a review of the following detailed description. While the water-soluble films, aqueous solutions, and articles of the present disclosure are capable of embodiment in a variety of forms, the following description includes specific embodiments with the understanding that the disclosure is exemplary and is not intended to limit the disclosure to the specific embodiments described herein. [Brief explanation of the drawings]

[0012] To facilitate a better understanding of the present disclosure, drawings are attached hereto. The drawings described herein are for illustrative purposes only of selected embodiments, not all possible implementations, and are not intended to limit the scope of the present disclosure.

[0013] [Figure 1A] Shown are images of a single-phase aqueous solution Sample 2 with Starch A and Resin A at a starch loading level of 55 PHR, and an image of the solution phase separation of an aqueous solution Sample 6 with Starch E and Resin A at a starch loading level of 49 PHR, respectively. [Figure 1B] 1 shows an image of a single-phase aqueous solution Sample 2 with Starch A and Resin A at a starch loading level of 55 PHR, and an image of the solution phase separation of an aqueous solution Sample 6 with Starch E and Resin A at a starch loading level of 49 PHR, respectively. [Figure 2]1 is a plot of cold water dissolution and disintegration times of films according to Example 1. [Figure 3A] 1 is a photomicrograph of the stretched and unstretched films described in Example 2. [Figure 3B] 1 is a photomicrograph of the stretched and unstretched films described in Example 2. [Figure 3C] 1 is a photomicrograph of the stretched and unstretched films described in Example 2. [Figure 4] 10 is an illustration of film moisture content as a function of ambient humidity, as described in Example 8. [Figure 5] 10 is an illustration of dynamic vapor sorption test results, as described in Example 8. DETAILED DESCRIPTION OF THE INVENTION

[0014] The following description of the technology is merely exemplary in nature of the subject matter, manufacture, and use of one or more inventions and is not intended to limit the scope, application, or uses of any particular invention claimed in this application, or in such other application that may be filed claiming priority to this application, or in any patent issuing therefrom. A non-limiting discussion of terms and phrases intended to aid in the understanding of the technology is provided at the end of this Detailed Description.

[0015] Conventional water-soluble films have high raw material costs due to the high loading content of water-soluble polymers, such as polyvinyl alcohol (PVOH), in the formulation. PVOH is typically a petroleum-derived polymer product. Rising oil prices and associated petroleum-derived products result in price and supply fluctuations for many polymer products. The present invention can be used in methods to replace petroleum-derived polymers with polymers derived from renewable sources, such as plants, because such materials are relatively inexpensive and more environmentally friendly, thus benefiting both economically and socially. Previously, achieving the desired miscibility between water-soluble polymers and renewable components, such as starch, at high loading levels in aqueous solutions for water-soluble film formation processes, such as solution casting, was difficult, resulting in phase separation between the water-soluble polymer and the renewable component, resulting in either an inability to form a film or an unacceptable degree of phase separation between the water-soluble polymer and the renewable component in the resulting water-soluble film. Conventional water-soluble films using high levels of renewable components, such as starch, also had one or more negative aspects, including poor processability, high brittleness, limited flexibility, and poor water solubility, low pouch compression strength, and poor mechanical strength properties.

[0016] The present disclosure provides water-soluble films comprising water-soluble polyvinyl alcohol and water-soluble starch at high loading levels of starch, as well as related water-soluble solutions, pouches or packets for forming the water-soluble films, and methods for preparing and using the same.

[0017] One aspect of the present disclosure is a water-soluble film comprising a water-soluble polyvinyl alcohol (PVOH) and a water-soluble starch, wherein the water-soluble starch has a cook percentage of at least about 5% by weight, the water-soluble starch is present in an amount of about 5-65% by weight of the water-soluble film, and the PVOH and the water-soluble starch are miscible or each has a thickness of about 2000 μm, about 15 μm, or more in the water-soluble film. The present invention provides a water-soluble film having an average phase domain size of less than about 1000 μm, about 1000 μm, about 900 μm, about 800 μm, about 700 μm, about 600 μm, about 500 μm, about 400 μm, about 300 μm, about 200 μm, about 100 μm, about 90 μm, about 80 μm, about 70 μm, about 60 μm, about 50 μm, about 40 μm, about 30 μm, about 20 μm, about 10 μm, or even less than about 1 μm. The domain size can be measured by various methods, such as atomic force microscopy (AFM), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and refractometry, including optical refraction and X-ray refraction. In one embodiment, the domain size can be measured by AFM.

[0018] As used herein, and unless otherwise specified, the term "water-soluble polyvinyl alcohol" refers to polyvinyl alcohol that is soluble in water within about 60 minutes, about 50 minutes, about 40 minutes, about 30 minutes, about 20 minutes, about 10 minutes, about 5 minutes, or about 3 minutes at a temperature of about 60° C. The water-soluble polyvinyl alcohol may be soluble in water within about 60 minutes, about 50 minutes, about 40 minutes, about 30 minutes, about 20 minutes, about 10 minutes, about 5 minutes, or about 3 minutes at a temperature of about 40° C. The water-soluble polyvinyl alcohol may be soluble in water within about 60 minutes, about 50 minutes, about 40 minutes, about 30 minutes, about 20 minutes, about 10 minutes, about 5 minutes, or about 3 minutes at a temperature of about 10° C.

[0019] The water-soluble polyvinyl alcohol may comprise one or more polyvinyl alcohol homopolymers and / or copolymers, such as one or more selected from unmodified polyvinyl alcohol, nonionic group-modified polyvinyl alcohol, anionic group-modified polyvinyl alcohol, and cationic group-modified polyvinyl alcohol. The water-soluble polyvinyl alcohol may comprise anionic group-modified polyvinyl alcohol. The water-soluble starch may comprise one or more starches selected from unmodified starch, nonionic group-modified starch, anionic group-modified starch, and cationic group-modified starch. The water-soluble starch may comprise cationic group-modified starch. The water-soluble polyvinyl alcohol may comprise an anionic group-modified polyvinyl alcohol, and the water-soluble starch may comprise cationic group-modified starch.

[0020] The water-soluble film may be a free-standing film, i.e., a film that does not require a substrate to maintain the integrity of the film structure, and optionally may be a film that is free of such a substrate.

[0021] The water-soluble film can have any renewable carbon index (RCI), and optionally, for example, at least about 30%, 40%, 50%, 55%, 60%, 65%, 70%, or 80%, or in the range of about 50-90%, or about 50-80%.

[0022] The water-soluble starch may comprise substantially gelatinized starch.

[0023] The water-soluble starch can have a cook% of, for example, at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 11%, at least about 12%, at least about 13%, at least about 14%, at least about 15%, at least about 16%, at least about 17%, at least about 18%, at least about 19%, at least about 20%, at least about 21%, at least about 22%, at least about 23%, at least about 24%, at least about 25%, at least about 26%, at least about 27%, at least about 28%, at least about 29%, or at least about 30%, or a related range, e.g., at least 10% up to 40%, or at least 10% up to 30%, by weight. The water-soluble starch can have a cook% of at least about 15% by weight.

[0024] Water-soluble starch has a concentration of about 10 3 ~10 7 g / mol, or about 10 3 ~10 6 g / mol, or about 10 4 ~10 5 The polymer may have an average molecular weight in the range of g / mol.

[0025] The water-soluble starch may have an amylose content ranging from about 0 to 50%, about 0 to 40%, about 0 to 30%, or about 0 to 25% by weight of the water-soluble starch.

[0026] The water-soluble starch may have a Brookfield viscosity in a 5 wt % aqueous solution in the range of about 1 to 2000 cP, about 1 to 1500 cP, about 1 to 1000 cP, about 1 to 900 cP, about 1 to 800 cP, about 1 to 700 cP, about 1 to 600 cP, about 1 to 500 cP, about 2 to 400 cP, about 2 to 300 cP, about 2 to 200 cP, or about 2 to 100 cP at a shear rate of about 20 rpm and a temperature of about 87.8°C.

[0027] The water-soluble starch may be present in an amount of about 10-65%, 15-65%, 20-60%, about 25-60%, about 30-60%, about 30-55%, about 30-50%, or about 30-45% by weight of the water-soluble film.

[0028] The water-soluble film may be soluble in water at a temperature of about 15° C., leaving behind a residue of less than about 10%, about 5.0%, about 4.0%, about 3.0%, about 2.5%, or about 2.0% by weight of the water-soluble film, according to the Accelerated Quantitative Residue Evaluation Test Method described below. The residue may be measured at a temperature of about 15° C., for example, leaving behind a residue of less than 5.0% by weight of the water-soluble film.

[0029] The water-soluble starch may include unmodified starch.

[0030] The water-soluble starch may optionally include neutral or non-ionic group modified starch having a modification level of about 0.1 to 10 mole %, or about 1 to 5 mole %.

[0031] The water-soluble starch may optionally include cationic group-modified starch having a degree of modification of about 0.01 to 10 mol%, about 0.1 to 5 mol%, about 0.1 to 2 mol%, or about 0.1 to 0.5 mol%.

[0032] Cationic group modified starches can include cationic quaternary ammonium group modified starches, such as those having the structure of Formula A, wherein R1, R2, and R3 are each independently H or C1-C 10 Alkyl or C1-C 10 hydroxyalkyl group, and R4 is a linear or branched C1-C1 alkyl group optionally substituted with one or more heteroatom-containing groups. 10 Alkylene or C1-C 10 is a hydroxyalkylene group, and X is an ether or ester linkage connecting R4 to the starch, or an oxygen-, nitrogen-, or sulfur-containing hydrocarbon group. [ka]

[0033] R1, R2, and R3 can be the same C1-C4 alkyl group, and R4 can be a linear or branched C1-C6 hydroxyalkylene group. In another embodiment, R4 can be a C3-C6 hydroxyalkylene group. In another embodiment, R1, R2, and R3 can each be a methyl group, and R4 can be a C3-C6 hydroxyalkylene group.

[0034] The cationic quaternary ammonium groups can be quaternary 2-hydroxy-3-(trimethylammonium)propyl, 2-diethylaminoethyl, or 2,3-epoxypropyltrimethylammonium groups, or combinations thereof.

[0035] The cationic group modified starch may include cationic trimethylammonium group modified starch.

[0036] Cationic group modified starch can include starch modified with 2-diethylaminoethyl salts, 2,3-epoxypropyltrimethylammonium salts, or 2-hydroxy-3-(trimethylammonium)propyl salts, or combinations thereof.

[0037] The 2-diethylaminoethyl salts may include 2-diethylaminoethyl halide, the 2,3-epoxypropyltrimethylammonium salts may include 2,3-epoxypropyltrimethylammonium halide, and the 2-hydroxy-3-(trimethylammonium)propyl salts may include 2-hydroxy-3-(trimethylammonium)propyl halide.

[0038] The 2-diethylaminoethyl salts may include 2-diethylaminoethyl chloride, the 2,3-epoxypropyltrimethylammonium salts may include 2,3-epoxypropyltrimethylammonium chloride, and the 2-hydroxy-3-(trimethylammonium)propyl salts may include 2-hydroxy-3-(trimethylammonium)propyl chloride.

[0039] The water-soluble starch may further comprise unmodified starch and / or nonionic group-modified starch having a modification level of about 0.05-5 mol %, or about 0.5-5 mol %, or about 1-5 mol %.

[0040] The water-soluble polyvinyl alcohol may include unmodified polyvinyl alcohol, anionic group-modified polyvinyl alcohol, cationic group-modified polyvinyl alcohol, or a combination thereof.

[0041] The polyvinyl alcohol may contain anionic group-modified polyvinyl alcohol having a degree of modification in the range of about 0.1 to 10 mol %, or about 1.0 to 5.0 mol %.

[0042] The anionic group modified polyvinyl alcohol may include polyvinyl alcohol modified with one or more groups derived from itaconic acid, monomethyl maleate (MMM), methyl acrylate (MA), aminopropyl sulfonate, maleic acid, maleic anhydride, vinylpyrrolidone, n-vinylpyrrolidone, n-vinylcaprolactam, derivatives of any of the foregoing, or combinations thereof.

[0043] The anionic group-modified polyvinyl alcohol may include polyvinyl alcohol modified with monomethyl maleate, methyl acrylate, or a combination thereof.

[0044] The water-soluble film may further comprise a plasticizer present in the range of about 5.0-50.0 wt.%, about 5.0-40.0 wt.%, or 10.0-40.0 wt.%, by weight of the water-soluble film.

[0045] The plasticizer may include sorbitol, glycerin, glycerol, diglycerol, propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols up to MW 400, 2-methyl-1,3-propanediol, ethanolamine, trimethylolpropane (TMP), polyether polyols, isomalt, maltitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol, mannitol, sugar alcohols, or combinations thereof.

[0046] The plasticizer may include a bio-derived plasticizer. The bio-derived plasticizer may include glycerin and / or sorbitol.

[0047] The water-soluble film may further include a surfactant.

[0048] The surfactant may comprise a linear aliphatic ethoxylated surfactant, such as laureth-6 carboxylic acid, C9-C 15 ethylene oxide, or a combination thereof.

[0049] The water-soluble film may further comprise one or more adjuvants in the group of anti-foaming agents, antioxidants, disinfectants, anti-blocking agents, fillers, sodium metabisulfite, sodium hydroxide, matting agents, slip agents, dispersing agents, or combinations thereof.

[0050] The water-soluble film may have a dissolution time in water according to MSTM-205 of 300 seconds or less, or in the range of 30 to 300 seconds, at a temperature of about 40° C. The dissolution time in water may be 300 seconds or less, or in the range of 30 to 300 seconds, at a temperature of about 30° C., or about 20° C., or about 15° C. The dissolution time in water may be in the range of 30 to 300 seconds at a temperature of about 10° C., or alternatively about 5° C.

[0051] The water-soluble film may have a maximum stress of at least about 10 MPa, about 11 MPa, about 12 MPa, about 13 MPa, about 14 MPa, about 15 MPa, about 16 MPa, about 17 MPa, about 18 MPa, about 19 MPa, or about 20 MPa. The maximum stress is the stress at break of the water-soluble film.

[0052] The water-soluble film may have a strain at break of at least about 100%, about 150%, about 160%, about 170%, about 180%, about 190%, about 200%, about 210%, about 220%, about 230%, about 240%, or about 250%.

[0053] The weight ratio of polyvinyl alcohol to water-soluble starch can be in the range of about 10:1 to about 1:8, about 9:1 to about 1:7, about 6:1 to about 1:6, about 5:1 to about 1:6, about 4:1 to 1:2, or about 4:1 to about 1:1.

[0054] The polyvinyl alcohol can have a degree of hydrolysis ranging from about 74 mol % to about 99 mol %, or from about 74 mol % to about 91 mol %.

[0055] The water-soluble film may comprise a water-soluble anionic group-modified polyvinyl alcohol having a degree of modification of about 1 to 5 mol % and a water-soluble cationic group-modified starch having a degree of modification of 0.05 to 5 mol %, and has a Brookfield viscosity in a 5 wt % aqueous solution of about 1 to 200 cP at about 20 rpm and about 87.8°C, the cationic group-modified starch having a Cook % of at least about 5 wt %, and the cationic group-modified starch is present in an amount of about 20 to 60 wt % by weight of the water-soluble film. and the anionic group-modified PVOH and the cationic group-modified starch are miscible or have phase domains in the water-soluble film that are less than about 2000 μm, about 1500 μm, about 1000 μm, about 900 μm, about 800 μm, about 700 μm, about 600 μm, about 500 μm, about 400 μm, about 300 μm, about 200 μm, about 100 μm, about 90 μm, about 80 μm, about 70 μm, about 60 μm, about 50 μm, about 40 μm, about 30 μm, about 20 μm, about 10 μm, or about 1 μm.

[0056] Another aspect of the present disclosure provides an aqueous solution for forming the water-soluble film of the present disclosure, the aqueous solution comprising a water-soluble polyvinyl alcohol (PVOH), a water-soluble starch, and water, the water-soluble starch having a Cook % of at least about 5% by weight, the aqueous solution having a total solids content of at least 15% by weight of the aqueous solution, the water-soluble starch being present in an amount of about 5-65% by weight of the total solids, and the water-soluble polyvinyl alcohol and the water-soluble starch being miscible in the aqueous solution or not exhibiting bulk phase separation upon visual inspection at a temperature ranging from about 5-100° C. for at least 24 hours. Various aspects of such film-forming solutions are described.

[0057] The water-soluble polyvinyl alcohol may be soluble in water within about 60, about 50, about 40, about 30, about 20, about 10, about 5, or about 3 minutes at a temperature of about 60° C. The water-soluble polyvinyl alcohol may be soluble in water within about 60, about 50, about 40, about 30, about 20, about 10, about 5, or about 3 minutes at a temperature of about 40° C. The water-soluble polyvinyl alcohol may be soluble in water within about 10 minutes at a temperature of about 40° C. The water-soluble polyvinyl alcohol may be soluble in water within about 60, about 50, about 40, about 30, about 20, about 10, about 5, or about 3 minutes at a temperature of about 20° C.

[0058] The total solids content may have a Renewable Carbon Index (RCI) of at least about 30%, or about 40%, or about 50%, or about 60%, or about 70%, or about 80%, or about 85%, or about 60%, or in the range of about 50-90%, or about 50-80%.

[0059] The water-soluble starch may comprise substantially gelatinized starch.

[0060] The water soluble starch can have a cook% of at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 11%, at least about 12%, at least about 13%, at least about 14%, at least about 15%, at least about 16%, at least about 17%, at least about 18%, at least about 19%, at least about 20%, at least about 21%, at least about 22%, at least about 23%, at least about 24%, at least about 25%, at least about 26%, at least about 27%, at least about 28%, at least about 29%, or about 30% by weight. The water soluble starch has a cook% of at least about 15% by weight.

[0061] Water-soluble starch has a concentration of about 10 3 ~10 6 g / mol, or about 10 4 ~10 5 The polymer may have an average molecular weight in the range of g / mol.

[0062] The water-soluble starch may have an amylose content ranging from about 0 to 50%, about 0 to 40%, or about 0 to 30% by weight of the water-soluble starch.

[0063] The water-soluble starch may have a Brookfield viscosity in a 5 wt % aqueous solution in the range of about 1 to 2000 cP, about 1 to 1500 cP, about 1 to 1000 cP, about 1 to 900 cP, about 1 to 800 cP, about 1 to 700 cP, about 1 to 600 cP, about 1 to 500 cP, about 2 to 400 cP, about 2 to 300 cP, about 2 to 200 cP, or about 2 to 100 cP at a shear rate of about 20 rpm and a temperature of about 87.8°C.

[0064] The aqueous solution may have a total solids content of at least about 20%, about 25%, or about 32% by weight, or in the range of about 15-45%, about 20-40%, about 25-38%, or about 28-35% by weight of the aqueous solution. The total solids content may be in the range of about 25-40% or about 28-35% by weight of the aqueous solution.

[0065] The water-soluble starch may be present in an amount of about 10-65%, about 15-65%, about 20-60%, about 25-60%, about 30-55%, about 30-50%, or about 30-45% by weight of the total solids.

[0066] The water-soluble starch may include unmodified starch, nonionic group modified starch, anionic group modified starch, and / or cationic group modified starch.

[0067] The water-soluble starch may comprise cationic group-modified starch having a degree of modification in the range of about 0.01 to 10 mol%, about 0.1 to 5 mol%, about 0.1 to 3 mol%, about 0.1 to 2 mol%, about 0.1 to 1 mol%, or about 0.1 to 0.5 mol%.

[0068] Cationic group modified starches can include cationic quaternary ammonium group modified starches, such as those having the structure of Formula A, wherein R1, R2, and R3 are each independently H or C1-C 10 Alkyl or C1-C 10 hydroxyalkyl group, and R4 is a linear or branched C1-C1 alkyl group optionally substituted with one or more heteroatom-containing groups. 10 Alkylene or C1-C 10 is a hydroxyalkylene group, and X is an ether or ester linkage connecting R4 to the starch, or an oxygen-, nitrogen-, or sulfur-containing hydrocarbon group. [ka]

[0069] R1, R2, and R3 can be the same C1-C4 alkyl group, and R4 can be a C1-C6 hydroxyalkylene group. Alternatively, R4 can be a C3-C6 hydroxyalkylene group. Alternatively, R1, R2, and R3 can each be a methyl group, and R4 can be a C3-C6 hydroxyalkylene group.

[0070] The cationic quaternary amine groups can be quaternary 2-hydroxy-3-(trimethylammonium)propyl, 2-diethylaminoethyl, 2,3-epoxypropyltrimethylammonium groups, or combinations thereof.

[0071] The cationic group modified starch may include a cationic trimethylammonium group modified starch.The cationic group modified starch may include a starch modified with a cationic trimethylammonium salt.

[0072] Cationic group modified starch can include starch modified with 2-diethylaminoethyl salts, 2,3-epoxypropyltrimethylammonium salts, or 2-hydroxy-3-(trimethylammonium)propyl salts, or combinations thereof.

[0073] The 2-diethylaminoethyl salts may include 2-diethylaminoethyl halide, the 2,3-epoxypropyltrimethylammonium salts may include 2,3-epoxypropyltrimethylammonium halide, and the 2-hydroxy-3-(trimethylammonium)propyl salts may include 2-hydroxy-3-(trimethylammonium)propyl halide.

[0074] The 2-diethylaminoethyl salts may include 2-diethylaminoethyl chloride, the 2,3-epoxypropyltrimethylammonium salts may include 2,3-epoxypropyltrimethylammonium chloride, and the 2-hydroxy-3-(trimethylammonium)propyl salts may include 2-hydroxy-3-(trimethylammonium)propyl chloride.

[0075] The water-soluble starch may include a combination of cationic group-modified starch and unmodified starch.

[0076] The polyvinyl alcohol (PVOH) may include unmodified polyvinyl alcohol, nonionic group-modified polyvinyl alcohol, anionic group-modified polyvinyl alcohol, cationic group-modified polyvinyl alcohol, or a combination thereof.

[0077] The polyvinyl alcohol may contain anionic group-modified polyvinyl alcohol having a modification degree of about 0.1 to 10 mol%, about 0.5 to 8 mol%, about 1 to 6 mol%, about 1 to 5 mol%, about 1 to 4 mol%, or about 1 to 3.5 mol%.

[0078] The anionic group modified polyvinyl alcohol may include polyvinyl alcohol modified with one or more groups derived from itaconic acid, monomethyl maleate (MMM), methyl acrylate (MA), aminopropyl sulfonate, maleic acid, maleic anhydride, vinyl pyrrolidone, n-vinyl pyrrolidone, n-vinyl caprolactam, derivatives of any of the foregoing, or combinations thereof.

[0079] The anionic group-modified polyvinyl alcohol may include polyvinyl alcohol modified with monomethyl maleate, methyl acrylate, or a combination thereof.

[0080] The aqueous solution may further include a plasticizer present in the range of about 5-40% by weight by weight of the total solids.

[0081] The plasticizer may include sorbitol, glycerin, glycerol, diglycerol, propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols up to MW 400, 2-methyl-1,3-propanediol, ethanolamine, trimethylolpropane (TMP), polyether polyols, isomalt, maltitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol, mannitol, sugar alcohols, or combinations thereof. The plasticizer may not include trimethylolpropane (TMP).

[0082] The plasticizer may include a bio-derived plasticizer. The bio-derived plasticizer may include glycerin and / or sorbitol.

[0083] The aqueous solution may further comprise a surfactant.

[0084] The surfactant may comprise a linear aliphatic ethoxylated surfactant, such as laureth-6 carboxylic acid, C9-C 15 ethylene oxide, or a combination thereof.

[0085] The aqueous solution may further comprise at least one adjuvant in the group of antifoaming agents, antioxidants, disinfectants, antiblocking agents, fillers, sodium metabisulfite, sodium hydroxide, matting agents, slip agents, dispersing agents, or combinations thereof.

[0086] The weight ratio of polyvinyl alcohol to water-soluble starch can be in the range of about 10:1 to about 1:8, about 9:1 to about 1:7, about 6:1 to about 1:6, or about 5:1 to about 1:6.

[0087] Another aspect of the present disclosure provides a method of forming the water-soluble film of the present disclosure, the method comprising casting an aqueous solution of the present disclosure onto a substrate at a specified thickness and drying water from the cast aqueous solution to form the water-soluble film.

[0088] Another aspect of the present disclosure provides an article comprising a pouch or packet made from a water-soluble film of the present disclosure and defining an interior pouch volume.

[0089] The article may further include a consumer or chemical composition contained within the internal pouch volume and enclosed within the pouch. The chemical composition may be a household care composition. The household care composition may be in either liquid or solid form, for example, a laundry detergent or dishwashing detergent in liquid form.

[0090] The pouch may have a compressive strength of at least about 300N, at least about 600N, at least about 800N, or at least about 1000N.

[0091] The pouch may have a matte-to-matte, matte-to-gloss, or gloss-to-gloss seal, for example, a matte-to-matte seal.

[0092] The pouch may have a release time of the chemical composition of 300 seconds or less after mixing the pouch in water at a temperature of about 20° C. according to the Liquid Release Test described herein. The release time may range from about 30 to 300, about 30 to 200, or about 30 to 150 seconds after mixing the pouch in water at about 20° C., or alternatively about 5° C. or about 15° C. according to the Liquid Release Test described herein.

[0093] Water-soluble film The present disclosure provides water-soluble films containing a water-soluble polymer and a bio-derived polysaccharide at a high loading level. Such films can have desirable physical properties. The bio-derived polysaccharides can include homopolysaccharides and heteropolysaccharides. The bio-derived polysaccharides can include starch, glycogen, galactogen, inulin, cellulose, chitin, hyaluronic acid, heparin, chondroitin-4-sulfate, gamma globulin, or combinations thereof. The bio-derived polysaccharides can be water-soluble bio-derived polysaccharides. The water-soluble bio-derived polysaccharides can include water-soluble starch. The water-soluble starch can be present in an amount of about 5-65 wt%, about 10-65 wt%, about 10-60 wt%, about 15-60 wt%, about 20-60 wt%, about 20-55 wt%, about 20-50 wt%, or about 25-45 wt% by weight of the water-soluble film.

[0094] As used herein, and unless otherwise specified, the term "water-soluble film" refers to a film having a dissolution time of 300 seconds or less at a temperature of about 40°C according to MSTM-205, as described herein. For example, the dissolution time can optionally be 200 seconds or less, 100 seconds or less, 60 seconds or less, or 30 seconds or less at temperatures of about 80°C, about 70°C, about 60°C, about 50°C, about 40°C, about 20°C, about 10°C, or about 5°C. As used herein, and unless otherwise specified, the term "cold water-soluble" refers to any film having a dissolution time of 300 seconds or less at 10°C, as determined according to MSTM-205. For example, the dissolution time can optionally be 200 seconds or less, 100 seconds or less, 60 seconds or less, or 30 seconds at 10°C. A 1.5 mil thick "water-soluble film" can dissolve in 300 seconds or less at a temperature of 80°C. Optionally, a 1.5 mil (about 38 μm) thick water-soluble film can have a dissolution time of 300 seconds or less, 200 seconds or less, 100 seconds or less, 60 seconds or less, 30 seconds or less, or 20 seconds or less at a temperature of about 70°C, about 60°C, about 50°C, about 40°C, about 30°C, about 20°C, about 10°C, or about 5°C.

[0095] As used herein, the term "water-soluble starch" refers to a starch having a cook percentage of at least about 5% by weight, e.g., at least about 6%, or at least about 7%, or at least about 8%, or at least about 9%, or at least about 10%, or at least about 11%, or at least about 12%, or at least about 13%, or at least about 14%, at least about 15%, at least about 16%, or at least about 17%, at least about 18%, at least about 19%, or at least about 20% by weight. To dissolve in water, starch must first be gelatinized in water. Gelatinization is the process by which water swells starch granules, breaking the intermolecular bonds between starch molecules and destroying the semicrystalline regions of the starch in the presence of heat. The inventors have surprisingly found that starches having the unique combination of low molecular weight, low amount of amylose, and / or chemical modifications of the present disclosure can more easily gelatinize and dissolve in water to achieve a cook% of at least about 5%, or about 10%, or about 15% by weight after heating and mixing at about 95°C for about 30 minutes, resulting in useful water-soluble film-forming solutions and related useful water-soluble films and articles made therefrom.

[0096] The water-soluble starch can be a starch that is substantially gelatinized in a water-soluble film.

[0097] Water-soluble starch may include water-soluble unmodified starch, water-soluble modified starch, or a combination thereof. Water-soluble unmodified starch may include naturally occurring polysaccharides consisting of anhydroglucose units with 1-4α and 1-6α glycosidic linkages resulting in linear or branched chains. Linear chains are known as amylose, and branched chains are known as amylopectin. Generally, starches with lower molecular weights and lower amylose contents are more likely to gelatinize and dissolve in water. Water-soluble unmodified starch may include starches that do not have chemical moieties added to the polysaccharide. For example, unmodified starch may include starches with reduced molecular weights by techniques such as acid hydrolysis.

[0098] The water-soluble modified starch may include physically modified starch, enzyme modified starch, and chemically modified starch. The chemically modified starch may include chemically degraded starch such as acid-treated starch, hypochlorite-oxidized starch, or dialdehyde starch; nonionic group-modified starch, including esterified starch and etherified starch; and / or ionic group-modified starch, including anionic group-modified starch and cationic group-modified starch. The water-soluble starch may include unmodified or modified starch disclosed herein, which has one or more characteristics, including a desired molecular weight, amylose to amylopectin ratio, and type and level of modification, so that it achieves a cook percentage of at least about 5% by weight, or about 10% by weight, or at least about 15% by weight under batch cooking conditions (heating and stirring in water at about 95°C for about 30 minutes).

[0099] The molecular weight, amylose / amylopectin ratio, and type and level of modification of starch can significantly affect the cooked percentage (the maximum weight percentage of starch dissolved in water after heating and mixing in 95°C water for 30 minutes, often referred to as the cooked percentage in the starch industry), the rheology of the resulting starch solution, and even its interaction and miscibility with polyvinyl alcohol. Unmodified starch extracted directly from plants often has a cooked percentage of only 1-2%. The molecular weight of starch can be reduced through acid hydrolysis, which increases the maximum cooked percentage. Certain types of chemical modifications to starch can increase the cooked percentage, inhibit retrogradation, and reduce the viscosity of starch solutions. Chemical modifications are typically located at the second and third carbons of glucose units and can occur through reaction with secondary alcohols at these sites. Examples of chemical modifications include nonionic (eg, hydroxyethyl, hydroxypropyl), anionic (eg, carboxyl), and cationic (eg, trimethylammonium) modifications of starch.

[0100] The water-soluble starch of the present disclosure may have a desired combination of low molecular weight, amylose / amylopectin ratio, and type and level of modification, may have a Cook % of at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 16 wt%, at least about 17 wt%, at least about 18 wt%, at least about 19 wt%, at least about 20 wt%, or even 25 wt%, may have good miscibility with the PVOH of the present disclosure, and may not have phase separation from the PVOH in PVOH-based aqueous film-forming solutions having total solids amounts in the range of about 5-50 wt%, about 10-40 wt%, about 15-35 wt%, about 20-35 wt%, about 25-35 wt%, about 25-32 wt%, or even about 32-35 wt%.

[0101] Water-soluble modified starches may include physically modified starches such as discrete amylose or amylopectin, or heat-moisture treated starches; enzyme-modified starches such as hydrolyzed dextrin, enzymatically degraded dextrin or amylose; and / or chemically degraded starches such as acid-treated starch, hypochlorite-oxidized starch, or dialdehyde starch.

[0102] The water-soluble modified starch may include chemically modified starches, including nonionic group-modified starches such as esterified starches and etherified starches, and / or ionic group-modified starches such as anionic group-modified starches and cationic group-modified starches. Esterified starches may include acetate-esterified starch, succinate-esterified starch, nitrate-esterified starch, phosphate-esterified starch, urea-phosphate-esterified starch, xanthate-esterified starch, acetoacetate-esterified starch, etc. Etherified starches may include allyl-etherified starch, methyl-etherified starch, carboxymethyl-etherified starch, hydroxyethyl-etherified starch, hydroxypropyl-etherified starch, etc. Non-limiting examples of nonionic group-modified starches may include hydroxyethyl- or hydroxypropyl-group-modified starch.

[0103] The water-soluble modified starch may include ionic group-modified starch, including cationic group-modified starch or anionic group-modified starch. The modified starch may include anionic group-modified starch. Non-limiting examples of anionic group-modified starch may include carboxyl group-modified starch.

[0104] The modified starch may include cationic group-modified starch. The cationic group-modified starch may include cationic amine or ammonium group-modified starch, including primary amine group-modified starch, secondary amine group-modified starch, tertiary amine group-modified starch, or quaternary amine or ammonium group-modified starch. The cationic group-modified starch may include quaternary ammonium group-modified starch. Non-limiting examples of quaternary ammonium group-modified starch may include trimethylammonium group-modified starch, starch modified with 2-diethylaminoethyl halide salt, starch modified with 2,3-epoxypropyltrimethylammonium halide salt, etc.

[0105] The modified starch may include chemically modified starch, and the degree of modification of the starch may be in the range of about 0.01 to 10 mol%, about 0.05 to 5 mol%, about 0.05 to 4 mol%, about 0.05 to 3 mol%, about 0.05 to 2 mol%, about 0.05 to 1 mol%, about 0.1 to 1 mol%, about 0.1 to 0.5 mol%, about 0.1 to 0.3 mol%, about 0.05 to 3.5 mol%, about 1.0 to 5.0 mol%, or about 1 to 3.5 mol%, for example, about 0.18 mol% or 0.21 mol%.

[0106] The modified starch may include cationic group-modified starch, and the degree of modification of the starch may be in the range of about 0.01 to 10 mol%, about 0.05 to 5 mol%, about 0.05 to 4 mol%, 0.05 to 3.5 mol%, about 0.05 to 3 mol%, about 0.05 to 2 mol%, about 0.05 to 1 mol%, about 0.1 to 1 mol%, about 0.1 to 0.5 mol%, or about 0.1 to 0.3 mol%.

[0107] The loading level of water-soluble starch in the water-soluble film can be relatively high, for example, at least about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, or even greater than about 65% by weight, or in the range of about 5-70%, about 10-65%, about 10-60%, about 15-60%, about 20-55%, about 25-50%, or about 25-45% by weight, by weight of the dry water-soluble film.

[0108] The water-soluble films can exhibit desirable physical properties for use in pouches and packets for packaging liquid detergent compositions, even at high loading levels of water-soluble starch.

[0109] The water-soluble film may further include one or more plasticizers, optionally at least one of which is bio-based. The water-soluble film may have a high renewable carbon index (RCI), which may be greater than about 50%. The water-soluble film may further include one or more of a disinfectant, an antioxidant or preservative, a defoamer or defoaming agent, a surfactant, an antiblocking agent, a filler, and a matting agent.

[0110] The water-soluble film can have a Renewable Carbon Index (RCI) of about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or even greater than about 85%, or in the range of about 30-85%, 40-75%, 45-70%, about 50-75%, or about 50-70%. The water-soluble film can include a bio-based plasticizer.

[0111] The water-soluble film may be soluble in water at a temperature of about 15°C with a residue (undissolved film) of about 10% by weight or less, e.g., about 9%, 8%, 7%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, or 0.5% by weight or less, or even 0% by weight (completely dissolved with no undissolved film) by weight of the water-soluble film, according to the Accelerated Quantitative Residue Evaluation Test Method described herein. The water-soluble film may have a residue of about 7% or less, about 6.0% or less, about 5.0% or less, about 4.0% or less, about 3.0% or less, or about 3.5% or less by weight of the film at temperatures of about 90° C., about 80° C., about 70° C., about 60° C., about 50° C., about 40° C., about 30° C., about 20° C., about 10° C., or about 5° C. The water-soluble film may have a residue of about 5.0% or less by weight of the film at temperatures ranging from about 5 to 95° C., at cold water temperatures of about 5° C. or about 10° C., or at about room temperature.

[0112] Water-soluble polyvinyl alcohol (PVOH) Water-soluble polymers may include, but are not limited to, polyvinyl alcohol (PVOH), polyacrylamide, poly(acrylic acid), poly(methacrylic acid), polyvinylpyrrolidone, polyacrylates, water-soluble acrylate copolymers, vinylpyrrolidone-modified PVOH, polyethyleneimine, pullulan, cellulose ethers, copolymers of the foregoing, and combinations of any of the foregoing. Such water-soluble polymers, whether PVOH or otherwise, are commercially available from a variety of sources.

[0113] The water-soluble polymer may be or include water-soluble polyvinyl alcohol (PVOH).

[0114] As used herein, and unless otherwise specified, the term "water-soluble polyvinyl alcohol" refers to polyvinyl alcohol that is soluble in water within about 60, 50, 40, 30, 20, 10, 5, or 3 minutes at a temperature of about 60°C. The water-soluble polyvinyl alcohol may be soluble in water at a temperature of about 40°C within about 60, 50, 40, 30, 20, 10, 5, or 3 minutes. The water-soluble polyvinyl alcohol may be soluble in cold water at about room temperature within about 60, 50, 40, 30, 20, 10, 5, or 3 minutes. The water-soluble polyvinyl alcohol may be soluble in cold water at a temperature of about 10°C within about 60, 50, 40, 30, 20, 10, 5, or 3 minutes.

[0115] The water-soluble polyvinyl alcohol in the film of the present disclosure may include bio-derived polyvinyl alcohol. Bio-derived polyvinyl alcohol includes polyvinyl alcohol in which at least a portion of the carbon constituting the polyvinyl alcohol is derived from biomass. In particular, bio-derived polyvinyl alcohol may include polyvinyl alcohol produced by hydrolysis or saponification of bio-derived polyvinyl acetate or a blend of polyvinyl acetates containing bio-derived polyvinyl acetate. In turn, bio-derived polyvinyl acetate may include polyvinyl acetate produced by polymerizing bio-derived vinyl acetate or a blend of vinyl acetates containing bio-derived vinyl acetate. Generally, bio-derived vinyl acetate includes vinyl acetate in which at least a portion of the carbon constituting the vinyl acetate is derived from biomass. Vinyl acetate can be obtained, for example, by the gas-phase reaction of ethylene, acetic acid, and oxygen, and bio-derived vinyl acetate can refer to vinyl acetate in which at least a portion of the ethylene and / or acetic acid is derived from biomass. For example, bio-derived vinyl acetate includes vinyl acetate obtained by the reaction of ethylene, acetic acid, and oxygen, where at least a portion of the ethylene and / or at least a portion of the acetic acid is bio-derived. Therefore, examples of bio-derived polyvinyl alcohol include polyvinyl alcohol in which part of the carbon constituting the polyvinyl alcohol is derived from bio-derived ethylene and / or bio-derived acetic acid.

[0116] Plants that can be sources of biogenic ethylene and / or biogenic acetic acid include, but are not limited to, potato, sweet potato, sugar beet, rice, wheat, palm oil, algae, corn, sugarcane, sorghum, and cassava. Similarly, biogenic acetic acid can be produced through a bioethanol route.

[0117] Bio-based polyvinyl alcohol is a type of carbon-14( 14 C) content. Generally, biomass-derived resources can be characterized by: 14The greater abundance of C (i.e., as a percentage of the total carbon content) 14 In particular, bio-derived ethylene and acetic acid generally have a higher content of ethylene and acetic acid than petroleum-derived ethylene and acetic acid. 14 The C content is higher, and secondly, bio-based polyvinyl alcohols are generally more biodegradable than fully petroleum-derived polyvinyl alcohols. 14 Therefore, in polymers such as polyvinyl alcohol resins, 14 The C content can serve as a marker of the bio-based content of the polymer. 14 The C content can be measured by known means, for example, mass spectrometry.

[0118] The films of the present disclosure may include bio-based polyvinyl alcohols, such as those described in U.S. Patent Application Publication Nos. 2023 / 0257491 A1, 2023 / 0070770 A1, and WO2022 / 034906 A1, which are incorporated by reference in their entireties. The polyvinyl alcohol resin comprising the films of the present disclosure may include only petroleum-based polyvinyl alcohol, only bio-based polyvinyl alcohol, or a blend of petroleum-based and bio-based polyvinyl alcohols. In the case of a film comprising a blend of petroleum-derived (i.e., non-biologically derived) polyvinyl alcohol and bio-derived polyvinyl alcohol, the ratio (by weight) of the amounts of bio-derived polyvinyl alcohol to non-biologically derived polyvinyl alcohol is not particularly limited and can be, for example, in the range of about 99:1 to about 1:99, or about 95:5 to about 5:99, or about 80:20 to about 20:80, or about 70:30 to about 30:70, or about 60:40 to about 40:60.

[0119] Generally speaking, polyvinyl alcohol often has chemical incompatibility with starch. However, the present inventors have discovered that phase separation between water-soluble polyvinyl alcohol (PVOH) and water-soluble starch can be eliminated or minimized by selectively controlling one or more aspects of the film and film-forming solution, such as the properties of the water-soluble PVOH and water-soluble starch, the type of plasticizer and other film components, the relative amounts of the film components, and the process for making the water-soluble film.

[0120] The present inventors have surprisingly found that the phase separation problem of water-soluble PVOH and water-soluble starch in the final water-soluble film and / or aqueous film-forming solution during the preparation process can be completely eliminated or minimized by selectively using a combination of an ionically group-modified water-soluble polymer, such as ionically group-modified polyvinyl alcohol (PVOH), and an ionically group-modified starch to prepare a water-soluble film, even at high solids and / or high starch loading levels. For example, a combination of an anionic group-modified polyvinyl alcohol (PVOH) and a cationic group-modified starch can be used, and the resulting water-soluble film does not have a phase separation problem in both the water-soluble film and the aqueous film-forming solution. The anionic group-modified PVOH and the cationic group-modified starch were characterized by a single glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) testing, as shown in Table 11 of Example 7. In another embodiment, a water-soluble film can be prepared without a phase separation problem using a combination of cationic group-modified polyvinyl alcohol (PVOH) and an anionic group-modified starch.

[0121] The water-soluble polymer may comprise a polyvinyl alcohol (PVOH) resin present in an amount of about 10% to about 95% by weight, about 20% to about 95% by weight, about 25% to about 85% by weight, about 30% to about 75% by weight, about 30% to about 65% by weight, about 30% to about 55% by weight, about 30% to about 50% by weight, about 35% to about 45% by weight, or about 35% to about 55% by weight, based on the total weight of the water-soluble film.

[0122] The polyvinyl alcohol (PVOH) resin may include modified polyvinyl alcohol (PVOH) resin and / or unmodified polyvinyl alcohol (PVOH) resin. The water-soluble polymer may include modified PVOH, including anionic group-modified polyvinyl alcohol (PVOH) resin or cationic group-modified polyvinyl alcohol (PVOH) resin.

[0123] The modified (PVOH) may include anionic group-modified polyvinyl alcohol (PVOH) resins modified with an anionic group selected from the group consisting of itaconic acid, monomethyl maleate (MMM), maleic anhydride, methyl acrylate (MA), aminopropyl sulfonate, maleic acid, n-vinylpyrrolidone, n-vinylcaprolactam, derivatives of any of the foregoing, or combinations of any of the foregoing. The degree of modification of the PVOH may be about 0.01 to 10 mol%, about 0.05 to 9 mol%, about 0.1 to 8 mol%, about 0.2 to 7 mol%, about 0.3 to 6 mol%, about 0.4 to 5 mol%, about 0.5 to 5 mol%, about 1 to 5 mol%, about 1 to 4 mol%, or about 1 to 3.5 mol%. The modified PVOH may be present in the water-soluble film in an amount of about 10 to 95 wt%, about 15 to 95 wt%, about 20 to 85 wt%, about 25 to 75 wt%, about 30 to 65 wt%, about 30 to 55 wt%, about 35 to 55 wt%, or about 30 to 50 wt%, based on the total weight of the water-soluble film.

[0124] Polyvinyl alcohol is a synthetic polymer generally prepared by alcoholysis, commonly referred to as hydrolysis or saponification, of polyvinyl acetate. Fully hydrolyzed PVOH, in which substantially all acetate groups have been converted to alcohol groups, is a strongly hydrogen-bonded, highly crystalline polymer that is soluble only in hot water above about 140°F (about 60°C). If a sufficient number of acetate groups remain after hydrolysis of polyvinyl acetate, i.e., the PVOH polymer is partially hydrolyzed, the polymer is more weakly hydrogen-bonded, less crystalline, and generally soluble in cold water below about 50°F (about 10°C). Thus, partially hydrolyzed polymers are vinyl alcohol-vinyl acid copolymers, which are PVOH copolymers, but are commonly referred to as homopolymer PVOH or unmodified polyvinyl alcohol (PVOH). As used herein, the term "unmodified polyvinyl alcohol" refers to PVOH that is fully or partially hydrolyzed polyvinyl acetate and has vinyl alcohol monomer units and, optionally, vinyl acetate monomer units (if partially hydrolyzed), but no third monomer units.

[0125] Polyvinyl alcohols include modified polyvinyl alcohols, such as copolymers. As used herein, the term "modified polyvinyl alcohol" refers to polyvinyl alcohol resins that are chemically modified with chemical groups and may include copolymers or higher polymers (e.g., terpolymers) containing one or more monomers in addition to vinyl acetate / vinyl alcohol groups. The modification may be provided by neutral, e.g., ethylene, propylene, N-vinylpyrrolidone, or other uncharged monomer species. In other embodiments, the modification may be cationic, e.g., provided by positively charged monomer species. In other embodiments, the modification may be anionic, e.g., provided by negatively charged monomer species.

[0126] Pyrrolidone comonomers may include compounds having a polymerizable carbon-carbon double bond and a pyrrolidone ring substituent represented by the following formula: [ka] wherein R1, R2, R3, R4, R5, and R6 are each independently selected from a hydrogen atom or an alkyl group, such as an alkyl group having 1 to 8 carbon atoms. Examples of groups represented by general formula (I) include 2-oxopyrrolidin-1-yl, 3-propyl-2-oxopyrrolidin-1-yl, 5-methyl-2-oxopyrrolidin-1-yl, 5,5-dimethyl-2-oxopyrrolidin-1-yl, and 3,5-dimethyl-2-oxopyrrolidin-1-yl. The carbon-carbon double bond contained in the pyrrolidone comonomer may include vinyl, allyl, styryl, acryloxyl, methacryloxyl, vinyloxyl, allyloxyl, and other groups that are copolymerizable with the vinyl esters of the above fatty acids and that form vinyl alcohol copolymers with high alkali resistance upon copolymer hydrolysis. Examples of pyrrolidone comonomers may include, among others, N-vinyl-2-pyrrolidone, N-vinyl-3-propyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,5-dimethyl-2-pyrrolidone, and N-allyl-2-pyrrolidone.

[0127] As used herein, the term "cationic group-modified polyvinyl alcohol" refers to a polyvinyl alcohol resin that has been chemically modified with cationic groups and may include partially or fully hydrolyzed PVOH copolymers containing cationic monomer units, vinyl alcohol monomer units, and optionally vinyl acetate monomer units (i.e., if not fully hydrolyzed). Examples of cationic polyvinyl alcohols include glycidyltrimethylammonium chloride-modified polyvinyl alcohols and those derived from cationic monomers of acrylamide and methacrylamide derivatives, such as N-(1,1-dimethyl-dimethylaminopropyl)acrylamide and N-(dimethylaminopropyl)methacrylamide, and their quaternary ammonium salts.

[0128] Polyvinyl alcohol (PVOH) resins may include anionically modified polyvinyl alcohols. As used herein, the terms "anionic group-modified polyvinyl alcohol" or "anionically modified polyvinyl alcohol" refer to polyvinyl alcohol resins that have been chemically modified with anionic groups and may include partially or fully hydrolyzed PVOH copolymers containing anionic monomer units, vinyl alcohol monomer units, and optionally vinyl acetate monomer units (i.e., if not fully hydrolyzed). PVOH copolymers may contain two or more types of anionic monomer units. Common types of anionic monomer units that can be used in PVOH copolymers include vinyl polymerized units corresponding to sulfonic acid vinyl monomers and their esters, monocarboxylic acid vinyl monomers and their esters and anhydrides, dicarboxylic acid monomers having a polymerizable double bond and their esters and anhydrides, and alkali metal salts of any of the foregoing.Examples of suitable anionic monomer units include vinyl acetic acid, maleic acid, monoalkyl maleates, dialkyl maleates, monomethyl maleate (MMM), maleic anhydride, dimethyl maleate, methyl acrylate (MA), fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, itaconic acid, monoalkyl itaconate, dialkyl itaconate, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, carboxylic acid, aminopropyl sulfonate, n-vinylpyrrolidone, n-vinylcaprolactam, citraconic acid, monoalkyl citraconic acid, dialkyl citraconic acid, citraconic anhydride, mesaconic acid, monoalkyl mesaconic acid, dialkyl mesaconic acid, glutaconic acid, monoalkyl glutaconate, glutaconic acid ... Included are polymerized vinyl units corresponding to vinyl anionic monomers such as dialkyl glutaconic acid, glutaconic anhydride, alkyl acrylates, alkyl acrylates, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the foregoing (e.g., sodium, potassium, or other alkali metal salts), esters of the foregoing (e.g., methyl, ethyl, or other C1-C4 or C6 alkyl esters), and combinations of the foregoing (e.g., multiple types of anionic monomers, or equivalent forms of the same anionic monomer).

[0129] Polyvinyl alcohol (PVOH) may be modified with an anionic group selected from one or more of maleic acid, monoalkyl maleates, dialkyl maleates, monomethyl maleate (MMM), maleic anhydride, dimethyl maleate, methyl acrylate (MA), alkali metal salts of any of the foregoing, esters of any of the foregoing, and combinations of any of the foregoing. Polyvinyl alcohol may be modified with an anionic group consisting of maleic acid, monomethyl maleate, dimethyl maleate, maleic anhydride, alkali metal salts of any of the foregoing, esters of any of the foregoing, and combinations of any of the foregoing. The anionic monomer may include one or more of monomethyl maleate and its alkali metal salt (e.g., sodium salt).

[0130] The PVOH copolymer may include two or more types of monomer units selected from neutral, anionic, and cationic monomer units.

[0131] The incorporation level of one or more anionic monomer units in the PVOH copolymer can range from about 0.1 mol % to about 10 mol %, or from about 1 mol % to about 5 mol % (e.g., at least about 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, or 4.0 mol %, and / or up to about 3.0, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, or 10 mol %, for example).

[0132] The anionic group-modified polyvinyl alcohol may contain at least about 0.5 mol% of modification. The anionic group-modified polyvinyl alcohol may contain about 1.0 mol% to about 5.0 mol% of modification. The anionic group-modified polyvinyl alcohol may contain about 1.0 mol% to about 3.5 mol% of modification.

[0133] The amount of anionic group-modified PVOH resin present in the water-soluble film can be in the range of at least about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, or about 90% by weight, and / or up to about 60%, about 70%, about 80%, about 90%, about 95%, or about 99% by weight, by weight of the water-soluble film. The amount of the anionic group-modified PVOH resin present in the water-soluble film may be in the range of about 10 to 80 wt %, about 15 to 75 wt %, about 20 to 70 wt %, about 25 to 65 wt %, about 30 to 55 wt %, about 30 to 50 wt %, or about 30 to 45 wt %, based on the weight of the water-soluble film.

[0134] The total PVOH resin content of the water-soluble film, whether present as unmodified PVOH or anionic group-modified PVOH, can have a degree of hydrolysis (DH or DH) of about 60 mol%, at least about 70 mol%, about 74 mol%, about 80 mol%, about 84 mol%, about 85 mol%, about 88 mol%, about 90 mol%, about 91 mol%, or about 94 mol%, and up to about 99 mol%, about 98 mol%, about 96 mol%, about 95 mol%, about 94 mol%, about 93 mol%, about 92 mol%, or about 91 mol%, for example, from about 74 mol% to about 99 mol%, or from about 74 mol% to about 91 mol%. As used herein, the degree of hydrolysis is expressed as the mole percentage of vinyl acetate units converted to vinyl alcohol units. The PVOH can have a degree of hydrolysis of at least about 74 mol%. The PVOH can have a degree of hydrolysis of up to 99 mol%. The PVOH may have a degree of hydrolysis of up to about 91 mole %. The PVOH may have a degree of hydrolysis ranging from about 74 to 99 mole %, or from about 74 to 91 mole %.

[0135] Polyvinyl alcohol may undergo changes in solubility characteristics. Those skilled in the art know that acetate groups in copoly(vinyl acetate vinyl alcohol) polymers (PVOH homopolymers) can be hydrolyzed by either acid or alkaline hydrolysis. With increasing degree of hydrolysis, polymer compositions made from PVOH homopolymers exhibit increased mechanical strength at lower temperatures and decreased solubility (e.g., requiring warmer water temperatures for complete dissolution). Therefore, exposure of PVOH homopolymers to an alkaline environment (e.g., resulting from laundry bleach additives) can convert the polymer from one that dissolves quickly and completely in a given aqueous environment (e.g., cold water medium) to one that dissolves slowly and / or incompletely in the aqueous environment, potentially resulting in undissolved polymer residue at the end of the wash cycle.

[0136] For example, PVOH copolymers with pendant carboxyl groups, such as vinyl alcohol / hydrolyzed methyl acrylate (MA) sodium salt polymers, may form lactone rings between adjacent pendant carboxyl and alcohol groups, thus reducing the water solubility of the PVOH copolymer. In the presence of a strong base, the lactone rings can open over the course of several weeks under relatively warm (ambient), humid conditions (e.g., via a lactone ring-opening reaction to form corresponding pendant carboxyl and alcohol groups with increased water solubility). Therefore, contrary to the effects observed with PVOH homopolymers, it is believed that such PVOH copolymers may become more soluble during storage due to chemical interactions between the polymer and the alkaline composition inside the pouch. As a result, as the product ages, packets may tend to dissolve more quickly during high-temperature wash cycles (nominally 40°C), which in turn may reduce the effectiveness of certain laundry actives due to the presence of bleach and the resulting drop in pH.

[0137] Certain sulfonic acids and their derivatives having polymerizable vinyl bonds can be copolymerized with vinyl acetate to provide cold-water-soluble PVOH polymers that are stable in the presence of strong base. The base-catalyzed alcoholysis products of these copolymers used in water-soluble film formulations are rapidly soluble vinyl alcohol sulfonate copolymers. Although the sulfonate groups in the PVOH copolymer can revert to sulfonic acid groups in the presence of hydrogen ions, the sulfonic acid groups still provide the polymer with excellent cold-water solubility. Optionally, the vinyl alcohol sulfonate copolymer may contain no residual acetate groups (i.e., be fully hydrolyzed) and therefore not be capable of further hydrolysis by either acidic or alkaline hydrolysis.

[0138] Generally, increasing the amount of modification increases water solubility, so sufficient modification via sulfonate or sulfonic acid groups suppresses hydrogen bonding and crystallinity, allowing for solubility in cold water. In the presence of acidic or basic species, the copolymers are generally unaffected, with the possible exception of sulfonate or sulfonic acid groups, which maintain excellent cold water solubility even in the presence of acidic or basic species. Examples of suitable sulfonic acid comonomers (and / or their alkali metal salt derivatives) include vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, and 2-sulfoethyl acrylate, with the sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) being a preferred comonomer.

[0139] Water-soluble polymers, whether polyvinyl alcohol polymers or not, can be blended. When the polymer blend includes a blend of polyvinyl alcohol polymers, the PVOH polymer blend can include a first PVOH polymer ("first PVOH polymer"), which can include a PVOH homopolymer or a PVOH copolymer containing one or more types of anionic monomer units (e.g., a PVOH terpolymer (or higher copolymer)), and a second PVOH polymer ("second PVOH polymer"), which can include a PVOH homopolymer or a PVOH copolymer containing one or more types of anionic monomer units (e.g., a PVOH terpolymer (or higher copolymer)). In some embodiments, the PVOH polymer blend includes only a first PVOH polymer and a second PVOH polymer (e.g., a binary blend of the two polymers). Alternatively or additionally, the PVOH polymer blend or a water-soluble film made therefrom can be characterized as being free or substantially free of other polymers (e.g., other water-soluble polymers in general, other PVOH-based polymers in particular, or both). As used herein, "substantially free" means that the first and second PVOH polymers constitute at least 95%, at least 97%, or at least 99% by weight of the total amount of water-soluble polymers in the water-soluble fiber or film.

[0140] In other embodiments, the water-soluble film may include one or more additional water-soluble polymers. For example, a PVOH polymer blend may include a third PVOH polymer, a fourth PVOH polymer, a fifth PVOH polymer, etc. (e.g., one or more additional PVOH homopolymers or PVOH copolymers, with or without anionic monomer units). For example, the water-soluble film may include at least a third (or fourth, fifth, etc.) water-soluble polymer that is other than a PVOH polymer (e.g., other than a PVOH homopolymer or PVOH copolymer, with or without anionic monomer units).

[0141] The degree of hydrolysis (DH) of the PVOH homopolymers and modified PVOH copolymers included in the water-soluble films of the present disclosure can range from about 60% to about 99%, or from about 74% to about 99% (e.g., from about 74% to about 91%, from about 79% to about 92%, from about 80% to about 90%, from about 88% to 92%, from about 86.5% to about 89%, or from about 88%, 90%, or 92% for cold water-soluble compositions; and from about 90% to about 99%, from about 92% to about 99% for hot water-soluble compositions). %, about 95% to about 99%, about 98% to about 99%, about 98% to about 99.9%, about 96%, about 98%, about 99%, or greater than 99%. As the degree of hydrolysis decreases, water-soluble films made from the polymer tend to have reduced mechanical strength but dissolve more quickly at temperatures below about 20°C. As the degree of hydrolysis increases, water-soluble films made from the polymer tend to be mechanically stronger but dissolve more slowly at temperatures below about 20°C. The degree of hydrolysis of PVOH is related to the polymer The water solubility of the polymer and additional components can be selected to be temperature dependent, thus affecting the solubility of films made from the polymer and additional components. In one option, the film is cold water soluble. For co-poly(vinyl acetate vinyl alcohol) polymers that do not contain any other monomers (e.g., homopolymers not copolymerized with anionic monomers), cold water soluble films that are soluble in water at temperatures below 10°C can contain PVOH with a degree of hydrolysis ranging from about 74% to about 91%, or from about 80% to about 90%, or from about 85% to about 90%. In another option, the film is hot water soluble. For co-poly(vinyl acetate vinyl alcohol) polymers that do not contain any other monomers (e.g., homopolymers not copolymerized with anionic monomers), hot water soluble films that are soluble in water at temperatures of at least about 60°C can contain PVOH with a degree of hydrolysis of at least about 98%.

[0142] When a PVOH polymer is referred to as having a particular degree of hydrolysis, the PVOH polymer is understood to be a single polyvinyl alcohol polymer having the particular degree of hydrolysis; a blend of polyvinyl alcohol polymers having a specified average degree of hydrolysis is generally represented by the average (e.g., weight average) degree of hydrolysis.

[0143] The viscosity (μ) of PVOH polymers is determined by measuring freshly made solutions using a Brookfield LV-type viscometer equipped with a UL adapter, as described in BS EN ISO 15023-2:2006 Annex E Brookfield Test Method. It is international practice to state the viscosity of a 4% aqueous polyvinyl alcohol solution at 20°C. Unless otherwise specified, all viscosities specified herein in centipoise (cP) should be understood to refer to the viscosity of a 4% aqueous polyvinyl alcohol solution at 20°C. Similarly, when a polymer is described as having (or not having) a particular viscosity, it is intended that the specified viscosity is the average viscosity of a polymer essentially having the corresponding molecular weight distribution, unless otherwise specified. Additionally, when a resin comprises a blend of one or more PVOH polymers and the resin / blend is described as having (or not having) a particular viscosity, it is intended that the specified viscosity is the weighted average viscosity of a resin / blend essentially having the corresponding weighted average molecular weight distribution, unless otherwise specified.

[0144] In embodiments where the water-soluble film comprises PVOH, the PVOH has a viscosity of at least about 4 cP, about 5 cP, about 6 cP, about 8 cP, about 10 cP, about 12 cP, about 13 cP, about 13.5 cP, about 14 cP, about 15 cP, about 16 cP, about 17 cP, about 18 cP, about 19 cP, or about 20 cP, and up to about 30 cP, about 28 cP, about 27 cP, about 26 cP, about 24 cP, about 22 cP, about 26 cP, about 28 cP, about 29 cP, about 30 cP, about 31 cP, about 32 cP, about 33 cP, about 34 cP, about 35 cP, about 36 cP, about 37 cP, about 38 cP, about 39 cP, about 40 cP, about 41 cP, about 42 cP, about 43 cP, about 44 cP, about 45 cP, about 46 cP, about 47 cP, about 48 cP, about 49 cP, about 50 cP, about 51 cP, about 52 cP, about 53 cP, about 54 cP, about 55 cP, about 56 cP, about 57 cP, about 58 cP, about 59 cP, about 60 cP, about 61 cP, about 62 cP, about 63 cP, about 64 cP, about 65 cP, about 66 cP, about 67 cP, about 68 cP, about 69 cP, about 70 cP, about 71 cP, about 72 cP, about 73 cP, about 74 cP, about 7 The viscosity may be in the range of 0 cP, about 19 cP, about 18 cP, or about 17.5 cP, e.g., about 10 cP to about 30 cP, or about 13 cP to about 27 cP, or about 13.5 cP to about 20 cP, or about 18 cP to about 22 cP, or about 14 cP to about 19 cP, or about 16 cP to about 18 cP, or about 17 cP to about 16 cP, e.g., 23 cP, or 20 cP, or 16.5 cP. It is well known in the art that the viscosity of a PVOH polymer correlates with the weight average molecular weight of the PVOH polymer, and that viscosity is often used as a proxy for weight average molecular weight.

[0145] Other water-soluble polymers that can be used in the water-soluble film can include, but are not limited to, polyvinyl acetate, ethylene vinyl alcohol, polyacrylates, poly(meth)acrylates, water-dispersible acrylate copolymers, polyvinylpyrrolidone, polyethyleneimine, polyalkylene oxides, polyacrylamides, polyacrylic acids and their salts, polymethacrylic acids, polycarboxylic acids and their salts, polyamino acids, polyamides, gelatin, quaternary ammonium polymers, polymethacrylates, and combinations of any of the foregoing. Water-soluble polymers, whether PVOH or otherwise, are commercially available from a variety of sources.

[0146] Water-soluble starch The water-soluble starch of the present disclosure may include modified and / or unmodified starches. Starches have various molecular weights and amylose / amylopectin contents depending on their source. These starches may be further processed to reduce molecular weight (e.g., via acid hydrolysis) and by chemical modification. These factors affect the ease of gelatinization (the process of starch granules dissolving in water during mixing) and the maximum solubility (cook %) of the starch in water after gelatinization. For example, a low molecular weight starch that dissolves at a high weight percent in water with a high weight percent of PVOH present is required.

[0147] Examples of unmodified starches include raw starches such as corn starch, potato starch, sweet potato starch, wheat starch, cassava starch, sago starch, tapioca starch, rice starch, pea starch, arrowroot starch, bracken starch, lotus starch, and horse chestnut starch. Unmodified starch is a naturally occurring polysaccharide composed of anhydroglucose units with 1-4α and 1-6α glycosidic bonds resulting in linear or branched chains. Linear chains are known as amylose, and branched chains are known as amylopectin. Amylopectin branching generally occurs at about 1 / 25 repeating units. Unmodified starch can also include starches without chemical moieties added to the polysaccharide. For example, unmodified starch can include starches with reduced molecular weights by techniques such as acid hydrolysis.

[0148] The water-soluble starch may have an amylose content of about 0 to 50%, about 0 to 30%, or about 0 to 25%, or about 1% to about 30%, or about 5% to about 30% by weight based on the weight of the water-soluble starch.

[0149] The water-soluble starch can include starch that is substantially gelatinized in the water-soluble film and in the aqueous solution used to form the water-soluble film. The water-soluble starch can be substantially or completely amorphous in the water-soluble film and in the aqueous solution, with substantially no crystalline or semi-crystalline regions of the starch.

[0150] Water-soluble starch, for example, has a viscosity of about 10 3 ~10 6 g / mol, 10 3 ~5×10 5 g / mol, 10 3 ~10 5 g / mol, approximately 10 3 ~5×10 4 g / mol, or about 10 3 ~10 4The water-soluble starch may have a low molecular weight, with an average molecular weight in the range of 1000 to 2000 cP, 1000 to 1500 cP, 1000 to 500 cP, 1000 to 400 cP, 1000 to 300 cP, 1000 to 200 cP, or 1000 to 200 cP, at about 20 rpm and about 87.8°C. It is well known in the art that the viscosity of water-soluble starch correlates with the weight-average molecular weight of the water-soluble starch, and that viscosity is often used as a proxy for the weight-average molecular weight of the water-soluble starch. Examples of Brookfield viscosities of two exemplary water-soluble cationic group-modified starches (Starch A and Starch B) at different weight percents of starch at 150°F and 190°F (87.8°C) are shown in Table 1 below. Starch A is a cationic group modified starch having about 25% by weight amylose and a degree of modification of about 0.18 mole %. [Table 1]

[0151] The modified starch may include ionic group-modified starches, including cationic group-modified starches or anionic group-modified starches. The cationic group-modified starches may include cationic ammonium group-modified starches, including quaternary ammonium or amine group-modified starches, such as trimethylammonium group-modified starches (reaction products of starch with trimethylammonium salts), reaction products of starch with 2-diethylaminoethyl chloride, reaction products of starch with 2,3-epoxypropyltrimethylammonium chloride, and reaction products of starch with trimethylammonium.

[0152] The water-soluble film may include unmodified starch, which may have a low molecular weight. The water-soluble film may include neutrally modified starch (non-ionic group modified starch), such as hydroxyethyl starch or hydroxypropyl starch. The water-soluble film may include one or more of unmodified starch, neutrally modified starch, anionic group modified starch, cationic group modified starch, or a combination thereof. The unmodified starch or neutrally modified starch may have a molecular weight of about 10 3~10 6 g / mol, approximately 10 3 ~10 5 g / mol, approximately 10 4 ~10 5 g / mol, or about 10 3 ~10 4 It may have a low average molecular weight in the g / mol range. The unmodified starch or neutral modified starch may have an amylose content of about 0 to 50% by weight, about 0 to 40% by weight, about 0 to 30% by weight, or about 0 to 25% by weight, or about 1% to about 40%, or about 5% to about 40%.

[0153] Aqueous starch solution is intended to mean a starch solution in which the solvent contains water as the major component, or in which water is present at least 90%, or at least 95%, or entirely in the starch solvent. As is known in the art, starch is a carbohydrate composed of many glucose units linked by glycosidic bonds. The starch of the present disclosure can be obtained from seeds, roots, or tubers by wet milling, washing, sieving, and drying. Starch is primarily obtained from corn, wheat, and potato, and to a lesser extent from sources such as rice, sweet potato, sago, and mung bean. The starch can be left unmodified or chemically modified to enable the starch to be functional under the conditions encountered during the processing of the present disclosure, for example, upon interaction with the PVOH polymer through ionic and / or hydrogen bonding interactions. Such modifications include, but are not limited to, acid treatment, alkali treatment, bleaching, oxidation, enzyme treatment, acetylation, phosphorylation, or a combination thereof. Modified starches may include cationic starch, hydroxyethyl starch, hydroxypropyl starch, and carboxymethylated starch. The starch may include modified starch. The starch may be or may include cationic group modified starch.

[0154] The inventors tested various starches and polysaccharides and found that many combinations of starch and PVOH were incompatible and had phase separation problems in the film-forming solution. However, Starch A, a cationic group-modified starch, was highly miscible with anionic group-modified PVOH resins (e.g., monomethyl maleate-modified PVOH and methyl acrylate-modified PVOH). Starch A is a low-molecular-weight cationic quaternary ammonium group-modified starch with approximately 25% amylose by weight and approximately 0.18 mol % modification. The following polyvinyl alcohol (PVOH) resins were used in the various examples: Resin A is an anionic group-modified polyvinyl alcohol (PVOH) modified with monomethyl maleate (MMM) and having a degree of modification of approximately 1.5-2.0 mol % and hydrolysis of 89-91 mol %. Resin B is an anionic-modified polyvinyl alcohol (PVOH), which is a polyvinyl alcohol modified with methyl acrylate (MA) and has a degree of modification of about 1-10 mol % and a hydrolysis level of 80-99 mol %. Without intending to be bound by any particular theory, the observed high miscibility is believed to be the result of ionic attraction between the anionic-modified PVOH and the cationic-modified starch, making it possible to prepare aqueous film-forming solutions at high solids levels, in which the total solids by weight of the film-forming solution can exceed 32 wt %, and achieve an RCI of greater than 50%, at high loading levels of starch ranging from about 5-65 wt % or about 25-60 wt % by weight of the total solids in the aqueous solution. Previous mixtures of starch and PVOH have been aqueous dispersions or suspensions, or mixtures of modified starch at very low loading levels with homopolymer PVOH, or where the starch and PVOH phase-separated in the mixture. Additionally, high molecular weight starches that are not or only slightly soluble are often used in polyvinyl alcohol films to reduce film blocking and modify the coefficient of friction of such films; similarly, larger particle sizes of such starches are preferred for such purposes.

[0155] The starch may include a neutrally modified starch such as Starch C, a hydroxyethyl-modified starch with a low molecular weight, about 25% amylose by weight, and a degree of modification of less than about 3 mol%. Starch C has high miscibility with anionic PVOH. Water-soluble films have been successfully prepared using Starch C as the base starch in formulations with an RCI greater than 50%. However, it has been shown that the miscibility between PVOH and Starch C, while good, is not as good as that of cationic modified starches (such as Starch A) at very high starch loading levels. PVOH and the neutrally modified starch, Starch C, phase separate in film-forming solutions when the weight ratio of Starch C to PVOH is greater than about 45:55 at total solids contents of about 10% by weight or greater.

[0156] Modified starches may include anionic group-modified starches or cationic group-modified starches. Modified starches include cationic group-modified starches. Cationic group-modified starches may include starches modified with amino or ammonium groups, such as quaternary amine or ammonium groups, primary amino groups, secondary amino groups, or tertiary amino groups. Cationic group-modified starches may include starches modified with quaternary ammonium groups. Cationic group-modified starches such as those described herein may have a degree of modification in the range of 0.05 to 10 mol%, about 0.1 to 8 mol%, 0.1 to 5 mol%, 0.1 to 4 mol%, 0.1 to 3.5 mol%, 0.1 to 2 mol%, 0.1 to 1 mol%, 0.2 to 5 mol%, 0.2 to 0.5 mol%, about 0.1 to 0.3%, about 0.18 mol%, or about 0.21 mol%.

[0157] A non-limiting example of a cationic group modified starch can have the structure of Formula A, discussed hereinabove.

[0158] Non-limiting examples of cationic group-modified starches can have a structure according to Formulas B-I shown below, wherein R1, R2, R3, R5, and R6 are each independently hydrogen (H), a C1-C6 alkyl, or a C1-C6 hydroxyalkyl group; R4 and R7 are independently linear or branched C1-C6 alkyl groups;10 Alkylene or C1-C 10 A is a hydroxyalkylene group, or a linear or branched C1-C6 alkylene or C1-C6 hydroxyalkylene group optionally substituted with one or more heteroatom-containing groups, and A is a C1-C6 alkylene or C1-C6 hydroxyalkylene group, or an oxygen-, nitrogen-, or sulfur-containing hydrocarbon group. [ka] [ka] [ka]

[0159] A can be a hydrocarbon group containing one or more heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur. The oxygen, nitrogen, or sulfur-containing hydrocarbon group can have one of the following formulas: -(CR8R9) n , —O—, where n is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; (i) -[(CR8R9) n O] m wherein n and m are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; (ii) -(CR8R9) n -S-, where n is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; (iii) -[(CR8R9) n S] m wherein n and m are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; (iv) -(CR8R9) n- NR 10 wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; (v) -[(CR8R9) n NR 10 ] mwherein n and m are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; (vi) In the formula, R8, R9, and R 10 are each independently hydrogen, a C1-C6 alkyl, a C1-C6 cycloalkyl, or an aryl group.

[0160] As used herein, the terms "cationic group-modified starch" and "cationic starch" are used in the broadest sense. In one aspect of the present invention, cationic starch refers to starch that has been chemically modified to provide the starch with a net positive charge in aqueous solution under acidic conditions (a pH of less than 7, e.g., pH 3). This chemical modification may include, but is not limited to, the addition of amino and / or ammonium groups to the starch molecule. Non-limiting examples of these ammonium groups may include those previously discussed herein, or substituents such as trimethylhydroxypropylammonium salts (such as halide or chloride salts), dimethylstearylhydroxypropylammonium salts (such as halide or chloride salts), dimethyldodecylhydroxypropylammonium salts (such as halide or chloride salts), 2-diethylaminoethyl salts (such as halide or chloride salts), or 2,3-epoxypropyltrimethylammonium salts (such as halide or chloride salts). Non-limiting examples of these ammonium groups may include those previously discussed herein or substituents such as trimethylhydroxypropylammonium chloride, dimethylstearylhydroxypropylammonium chloride, dimethyldodecylhydroxypropylammonium chloride, 2-diethylaminoethyl chloride, or 2,3-epoxypropyltrimethylammonium chloride.

[0161] Non-limiting examples of quaternary ammonium group modified starches can include reaction products of starch with one or more of trimethylhydroxypropylammonium salts, dimethylstearylhydroxypropylammonium salts, dimethyldodecylhydroxypropylammonium salts, 2-diethylaminoethyl salts, or 2,3-epoxypropyltrimethylammonium salts.

[0162] The water-soluble starch may be present in the water-soluble film in an amount ranging from about 5 to 75 wt%, about 5 to 70 wt%, about 10 to 65 wt%, about 10 to 60 wt%, about 10 to 55 wt%, about 10 to 50 wt%, about 15 to 50 wt%, about 20 to 50 wt%, about 20 to 45 wt%, about 25 to 45 wt%, about 30 to 55 wt%, about 35 to 55 wt%, or about 30 to 50 wt% by weight of the water-soluble film. The weight ratio of water-soluble starch to polyvinyl alcohol (PVOH) can be about 5:95 to about 95:5, about 10:90 to about 90:10, about 15:85 to about 85:15, about 20:80 to about 80:20, about 30:70 to about 70:30, about 35:65 to about 65:35, about 40:60 to about 60:40, about 45:55 to about 55:45, about 30:70 to about 80:20, or about 50:50.

[0163] The starch can have an amylose content in the range of about 0-50%, about 0-40%, about 0-30%, or about 0-25% by weight of the starch.

[0164] The film may be free or substantially free of octenyl succinic anhydride modified starch.

[0165] plasticizer The water-soluble film may further include one or more plasticizers.

[0166] Plasticizers are liquid, solid, or semi-solid substances added to materials (usually resins or elastomers) to make them softer, more flexible, and easier to process (by decreasing the polymer's glass transition temperature and crystallinity). Alternatively, polymers can be internally plasticized by chemically modifying the polymer or monomer. Additionally, or alternatively, polymers can be externally plasticized by the addition of a suitable plasticizer. While water is recognized as a very efficient plasticizer for PVOH and other polymers, including but not limited to water-soluble polymers, the volatility of water limits its usefulness because polymer films must be at least somewhat resistant (robust) to a variety of ambient conditions, including low and high relative humidity.

[0167] Suitable non-aqueous plasticizers include, but are not limited to, glycerine (also called glycerol or glycerin), diglycerin (also called diglycerol), sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols up to 400 MW, neopentyl glycol, trimethylolpropane (TMP), polyether polyols, 2-methyl-1,3-propanediol (e.g., MP Diol®), ethanolamine, isomalt, maltitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol, mannitol, and combinations of the foregoing.

[0168] The non-aqueous plasticizer may include a bio- or plant-derived plasticizer. The plasticizer may include a water-soluble bio-derived plasticizer. The plasticizer may include one or more water-soluble bio-derived plasticizers selected from the group consisting of sorbitol, glycerin, ethylene glycol, xylitol, ethanolamine, mannitol, polyethylene glycols up to 400 MW, and propylene glycol. The plasticizer may include a mixture of sorbitol and glycerin.

[0169] If present, the total amount of plasticizer present in the water-soluble film can be up to about 50% by weight of the water-soluble film, for example, in the range of about 0.01% to about 50%, about 0.1% to about 45%, about 1% to about 40%, about 2% to about 30%, about 3% to about 20%, or about 3% to about 15%, e.g., about 5% by weight. The total amount of plasticizer can also be expressed in parts per 100 parts of polymer, both polyvinyl alcohol (PVOH) and water-soluble starch. Thus, the total amount of plasticizer can range from about 2 phr to about 70 phr, from about 5 phr to about 65 phr, from about 10 phr to about 60 phr, from about 15 phr to about 50 phr, from about 20 phr to about 55 phr, from about 25 phr to about 50 phr, from about 30 phr to about 45 phr, or from about 30 phr to about 40 phr.

[0170] Glycerin can be used in an amount of about 1% to about 40%, about 5% to about 30%, about 10% to about 25%, about 15% to about 25%, or about 16% to about 20%, for example, about 18% by weight based on the weight of the water-soluble film. Sorbitol can be used in an amount of about 1% to about 30%, about 1% to about 20%, about 2% to about 15%, about 3% to about 13%, or about 4% to about 10%, for example, about 5% by weight based on the weight of the water-soluble film. The plasticizer can include a mixture of sorbitol and glycerin in a weight ratio ranging from about 1:10 to about 3:1, about 1:8 to about 2:1, about 1:6 to about 1:1, about 1:5 to about 1:2, or about 1:4 to about 1:2. Plasticizer levels consistent with those of the examples described herein are specifically contemplated both as representative levels for water-soluble film formulations with the various other components described herein, and as various upper and lower limits of ranges. The specific type and amount of plasticizer can be selected in particular embodiments based on the desired film plasticity and processability characteristics of the water-soluble film. At low plasticizer levels, the film may be brittle, difficult to process, or prone to breakage. At high plasticizer levels, the film may be too soft, weak, or difficult to process for the desired use.

[0171] surfactants Surfactants for use in water-soluble films are well known in the art. Surfactants may be included to aid in the dispersion of the resin solution during casting. Suitable surfactants for the water-soluble films of the present disclosure include linear aliphatic ethoxylated surfactants, laureth-6 carboxylic acid, C9-C 15 Examples of suitable oleic acid surfactants include, but are not limited to, ethylene oxide, C10-Guerbet alcohol, C10-Guerbet alcohol ethoxylate POE(8), laureth-3, laureth-5, laureth-7, oleth-10 carboxylic acid, dialkyl sulfosuccinates, lactylated fatty acid esters of glycerin and propylene glycol, lactyl esters of fatty acids, sodium alkyl sulfate, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, alkyl polyethylene glycol ethers, lecithin, acetylated fatty acid esters of glycerin and propylene glycol, sodium lauryl sulfate, acetylated esters of fatty acids, myristyl dimethylamine oxide, trimethyl tallow alkyl ammonium chloride, quaternary ammonium compounds, alkali metal salts of higher fatty acids containing about 8 to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylate sulfates, alkyl benzene sulfonates, monoethanolamine, lauryl alcohol ethoxylate, propylene glycol, diethylene glycol, salts thereof, and combinations of any of the foregoing. Linear fatty ethoxylated surfactants include laureth-6 carboxylic acid, C9-C 15 ethylene oxide, or a combination thereof.

[0172] Suitable surfactants may include nonionic, cationic, anionic, and zwitterionic types. Suitable surfactants include, but are not limited to, propylene glycol, diethylene glycol, monoethanolamine, polyoxyethylated polyoxypropylene glycol, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylene glycols, and alkanolamides (nonionic), polyoxyethylated amines, quaternary ammonium salts, and quaternized polyoxyethylated amines (cationic), alkali metal salts of higher fatty acids containing about 8 to 24 carbon atoms, alkyl sulfates, alkyl polyethoxylate sulfates, and alkyl benzene sulfonates (anionic), and amine oxides, N-alkyl betaines, and sulfobetaines (zwitterionic). Other suitable surfactants include dioctyl sodium sulfosuccinate, lactylated fatty acid esters of glycerin and propylene glycol, lactyl esters of fatty acids, sodium alkyl sulfate, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerin and propylene glycol, and acetylated esters of fatty acids, and combinations thereof.

[0173] The amount of surfactant in the water-soluble film can be in the range of about 0.05 wt.% to about 10.0 wt.%, about 0.05 wt.% to about 5.0 wt.%, about 0.1 wt.% to about 2.5 wt.%, about 0.1 wt.% to about 2.0 wt.%, about 0.1 wt.% to about 1.5 wt.%, about 0.1 wt.% to about 1.0 wt.%, about 0.1 wt.% to about 0.8 wt.%, about 0.2 wt.% to about 0.8 wt.%, or about 0.2 wt.% to about 0.4 wt.% by weight of the water-soluble film. The amount of surfactant in the water-soluble film can be expressed in parts per 100 parts (phr) of total polymer of polyvinyl alcohol (PVOH) and water-soluble starch in the water-soluble film, and can be present in the range of about 0.1 phr to about 5 phr, about 0.1 phr to about 4 phr, about 0.2 phr to about 3.0 phr, about 0.3 phr to about 2.0 phr, about 0.4 phr to about 1.5 phr, about 0.4 phr to about 1.0 phr, about 0.4 phr to about 0.8 phr, about 0.5 to about 0.7 phr, or about 0.3 phr to about 1.0 phr.

[0174] A blend of surfactants has been found to be advantageous for water-soluble films containing an anionic monomer selected from the group consisting of maleic acid, maleic anhydride, monoalkyl maleates, dialkyl maleates, and combinations thereof. Thus, in embodiments of the present disclosure, the PVOH may contain an anionic monomer selected from the group consisting of maleic acid, maleic anhydride, monoalkyl maleates, monomethyl maleate (MMM), dialkyl maleates, methyl acrylate (MA), and combinations thereof, and the total level of anionic pendant groups from the PVOH may be at least about 1 mol%, about 2 mol%, about 3 mol%, at least about 3.5 mol%, at least about 4.0 mol%, at least about 6 mol%, or at least about 8 mol%, or in the range of about 1-10 mol%, about 2-8 mol%, or about 3-5 mol%, and the water-soluble film may further contain a nonionic surfactant, an amine oxide surfactant, an anionic surfactant, a cationic surfactant, or a combination thereof.

[0175] Nonionic surfactants may be selected from the group consisting of polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylene glycols, alkanolamides, C10-Guerbet alcohols, and combinations thereof. Amine oxide surfactants may be selected from the group consisting of dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyldodecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide, dimethyloctadecylamine oxide, and combinations of the foregoing. It will be understood that commercially available amine oxide surfactants may be blends of the foregoing, as the amine source may contain a distribution of amines of various chain lengths. Thus, by way of example, "dimethyldodecylamine oxide" may contain a distribution of amine oxides in which the average amine oxide and / or a major portion of the amine oxide may contain dodecyl chains. Anionic surfactants may include dioctyl sodium sulfosuccinate. The cationic surfactant may be selected from the group of polyoxyethylenated amines, quaternary ammonium salts, quaternized polyoxyethylenated amines, and combinations thereof.

[0176] Each surfactant present in the water-soluble film may be present in an amount ranging from about 1% to about 98% by weight, or from about 10% to about 80% by weight, or from about 15% to about 70% by weight, or from about 16% to about 68% by weight, or from about 17% to about 42% by weight, or from about 30% to about 40% by weight of the total amount of surfactant.

[0177] Other additives Suitable lubricants / release agents may include, but are not limited to, fatty acids and their salts, fatty alcohols, fatty esters, fatty amines, fatty amine acetates, and fatty amides. Preferred lubricants / release agents are fatty acids, fatty acid salts, and fatty acid amine acetates. The amount of lubricant / release agent in the water-soluble film may range, for example, from about 0.02% to about 1.5% by weight, optionally from about 0.1% to about 1% by weight, based on the weight of the water-soluble film.

[0178] Fillers may be included in the water-soluble film and may include bulking agents, extenders, antiblocking agents, anti-adhesion agents, and combinations thereof. Suitable fillers / bulking agents / extenders / anti-blocking agents / anti-adhesion agents include, but are not limited to, water-insoluble starch, water-insoluble modified starch, crosslinked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, mica, stearic acid and its metal salts, such as magnesium stearate. Preferred materials are water-insoluble starch, water-insoluble modified starch, silica, and talc. The starch and modified starch used as fillers are particulate starches and are not water-soluble starches as defined in this disclosure. In one type of embodiment, the amount of filler / bulking agent / antiblocking agent / tack reducer in the water-soluble film can range from about 0.5 wt. % to about 6 wt. %, about 0.6 wt. % to about 5 wt. %, about 0.7 wt. % to about 4 wt. %, about 0.8 wt. % to about 3 wt. %, about 0.9 wt. % to about 2 wt. %, about 1 wt. % to about 1.8 wt. %, or about 1 wt. % to about 1.5 wt. %, or, for example, from about 1 phr to about 6 phr, or from about 1 phr to about 5 phr, or from about 1 phr to about 4 phr, or from about 2 phr to about 4 phr, per 100 parts of the total of PVOH and water-soluble starch.

[0179] In some embodiments, the water-soluble film can include 1 phr or more (e.g., 2 phr to 6 phr, or 2 phr to 4 phr) of filler. In some embodiments, the film can include 2 phr or more (e.g., 2 phr to 6 phr, or 2 phr to 4 phr) of filler, which can include a bulking agent, an antiblocking agent, or a combination thereof. Without intending to be bound by theory, it is believed that including 2 phr or more (e.g., 2 phr to 6 phr, or 2 phr to 4 phr) of filler can be useful in preventing leaching or migration of plasticizer from the film when the plasticizer is included in an amount of 30 phr or more, for example, in the range of 30 phr to 50 phr.

[0180] The antiblocking agent (e.g., SiO2 and / or stearic acid) can be present in the film in an amount of at least 0.1 PHR, at least 0.5 PHR, or at least 1 PHR, or in a range of about 0.1 to 5.0 PHR, about 0.5 to about 5.0 PHR, about 1.0 to 4.0 PHR, about 1.5 to about 4.0 PHR, about 2.0 to about 4.0 PHR, about 2.5 to about 4.0 PHR, about 3.0 to about 4.0 PHR, or about 3.0 to 3.5 PHR, per 100 parts of the combined PVOH and water-soluble starch.

[0181] Suitable median particle sizes of the antiblocking agent include ranges of about 3 to about 11 microns, or about 4 microns to about 11 microns, or about 4 to about 8 microns, or about 5 to about 6 microns, e.g., median values ​​of 5, 6, 7, 8, or 9 microns. The preferred SiO2 is an untreated synthetic amorphous silica designed for use in aqueous systems.

[0182] The water-soluble film may further have a residual moisture content of at least 4% by weight, such as in the range of about 4% to about 10% by weight, as measured by Karl Fischer titration.

[0183] The water-soluble films of the present disclosure may have a Renewable Carbon Index (RCI) of greater than about 30%, about 40%, about 50%, about 55%, about 60%, about 70%, about 80%, or about 90%, or in the range of about 30-90%, about 40-80%, about 40-70%, about 45-70%, about 45-65%, or about 50-60%.

[0184] Method for preparing an aqueous solution for forming a water-soluble film The present disclosure provides a method for preparing an aqueous solution suitable for forming a water-soluble film, as discussed above. The method for preparing the aqueous solution includes the following steps: 1) heating water in a container to a temperature in the range of about 60-95°C, e.g., about 85°C; 2) adding water-soluble starch to the water; 3) continuing heating and mixing at a temperature in the range of about 60-95°C, e.g., about 85°C, for about 0.5-20 hours, e.g., about 0.5-3 hours, or about 1 hour, to form a gelatinized starch liquid solution; 4) adding water-soluble polyvinyl alcohol (PVOH) to the starch liquid solution; and 5) continuing heating and mixing at a temperature in the range of about 60-95°C, e.g., about 85°C, for about 0.5-20 hours to form a gelatinized starch liquid solution. and forming a water-soluble starch and PVOH solution, wherein the water-soluble starch has a cook percentage of at least about 5%, at least about 10%, or at least about 15% by weight under batch cooking conditions (heating and mixing in water at about 95° C. for about 30 minutes), the aqueous solution has a total solids content of at least 15% by weight of the aqueous solution, the water-soluble starch is present in an amount of about 5-65% by weight of the total solids, and the water-soluble polyvinyl alcohol (PVOH) and the water-soluble starch are miscible and do not phase separate in the aqueous solution by visual inspection at about room temperature for at least 24 hours.

[0185] In preparing an aqueous solution of PVOH and water-soluble starch, it is desirable to provide sufficient time, heat, and shear for the starch to gelatinize and completely dissolve in the warm water, and to further mix uniformly with the PVOH to form a miscible solution, thus preventing phase separation between the PVOH and the water-soluble starch.

[0186] Generally, the aqueous solution can be prepared by either first adding polyvinyl alcohol (PVOH) to the warm water before adding the water-soluble starch, or alternatively by first adding the water-soluble starch to the warm water before adding the polyvinyl alcohol. The order in which the polyvinyl alcohol and the water-soluble starch are added to the warm water is not particularly limited.

[0187] In certain situations, when starch is added to a hopper of a hot water container, there may be a problem of starch clumping due to steam from the hot water. To avoid starch clumping, the starch can be added to cold water at about ambient conditions to first form a cold slurry, which is then mixed and heat-treated to gelatinize and completely dissolve the water-soluble starch. Thus, the method may include adding water-soluble starch to water at ambient conditions or cold water at about 5°C to about 30°C to first form a cold slurry, and then mixing and heat-treating the water-soluble starch at a temperature of about 60°C to 95°C, for example, about 85°C, to gelatinize and completely dissolve the starch before adding PVOH.

[0188] Alternatively, the starch slurry can be gelatinized with the aid of steam injection, or jet-cooked, i.e., the slurry can be passed through a jet cooker to heat the starch and apply high shear. Jet cooking can increase starch gelatinization, improve starch solvation, and reduce retrogradation. In a jet cooker, steam is continuously injected into the flowing starch slurry through an injector coaxial with the starch stream.

[0189] After heat treatment and mixing in warm water at a temperature in the range of about 60 to 95°C, for example about 85°C, for about 0.5 to 20 hours or about 0.5 to 5 hours, the water-soluble starch is gelatinized and completely dissolved in water.

[0190] PVOH and water-soluble starch may each be completely soluble in an aqueous solution, may be miscible in the aqueous solution, or may not have phase or bulk phase separation. The phase miscibility between PVOH and water-soluble starch in the aqueous solution of the present disclosure is advantageous for improving processability when forming or casting a water-soluble film. Furthermore, the resulting aqueous solution may be stable for a longer period of time, allowing for a longer holding time of the aqueous solution before forming a film. Generally, if PVOH and starch are not miscible in a liquid mixture, once the PVOH and water-soluble starch phase separate (e.g., liquid-liquid phase separation), it is impractical to remix them into a miscible solution.

[0191] The PVOH may include an anionic group-modified PVOH modified with monomethyl maleate (MMM) having a degree of modification of about 1 to 5 mol %, and the water-soluble starch is added to the water before the PVOH. When the MMM-modified starch is used to prepare the aqueous solution, the starch may be added and dissolved in warm water at a temperature in the range of about 60 to 95°C before adding the PVOH.

[0192] The method may further include adding a plasticizer and an antifoaming agent to the water while mixing before adding the water-soluble starch, adding an antiblocking agent to the water with the water-soluble starch, adding an additive (antioxidant) to the gelatinized starch liquid solution after adding the water-soluble starch and before adding the PVOH, and adding a surfactant to the aqueous solution and mixing for about 5 to 60 minutes. Alternatively, any one or more of the plasticizer, antifoaming agent, antiblocking agent, and other additives may be added to the solution after dissolving the PVOH.

[0193] A method for preparing the aqueous solution may include the following steps: 1) heating water in a container to a temperature in the range of about 60-95°C, e.g., about 85°C; 2) adding water-soluble polyvinyl alcohol (PVOH) to the water; 3) continuing heating and mixing at a temperature in the range of about 60-95°C, e.g., about 85°C, for about 0.5-20 hours, e.g., about 0.5-3 hours, or about 1 hour, to form a liquid solution; 4) adding water-soluble starch to the liquid solution; and 5) heating and mixing at a temperature in the range of about 60-95°C for about 0.5-20 hours to form an aqueous solution, wherein the water-soluble starch is added by batch cooking. The aqueous solution has a cook percentage of at least about 10% by weight under conditions (heating and mixing, such as using direct steam injection, in water at about 95°C for about 30 minutes), the aqueous solution has a total solids content of at least 15% by weight of the aqueous solution, the water soluble starch is present in an amount of about 5-65% by weight of the total solids, and the water soluble polyvinyl alcohol (PVOH) and the water soluble starch are miscible and do not phase separate in the aqueous solution upon visual inspection at about room temperature to about 90°C for at least 24 hours, at least 36 hours, at least 48 hours, at least 60 hours, at least 1 week, or at least 2 weeks, or even more than 2 weeks.

[0194] The viscosity of the aqueous solution can be, for example, at least about 2,000 or 3,000 cps at 185°F (85°C), and up to about 20,000 cps, about 15,000 cps, or about 10,000 cps at 185°F, e.g., about 3,000 cps to about 10,000 cps at 185°F (85°C).

[0195] The PVOH may include an anionic group-modified PVOH modified with methyl acrylate (MA) having a degree of modification of about 1 to 5 mol %, and optionally, the PVOH is added to the water before the water-soluble starch.

[0196] PVOH and water-soluble starch are completely soluble and miscible in aqueous solution, and there is no phase separation in the aqueous solution.

[0197] The method may further include adding a plasticizer and an antifoaming agent to the water while mixing before adding the PVOH; adding additives (antioxidants and caustic soda) to the water before adding the PVOH; adding an antiblocking agent to the liquid solution along with the water-soluble starch; and adding a surfactant to the aqueous solution and mixing for about 5 to 60 minutes.

[0198] The aqueous solution formulation is mixed and cast. Mixing is performed in a container while heating. The order of component addition can be plasticizer, antifoaming agent, water-soluble starch, additive, PVOH, and finally surfactant. It is desirable to have sufficient time, heat, and shear for the water-soluble starch to gelatinize, completely dissolve in the warm water, and be uniformly mixed with the PVOH resin. After mixing, the resulting aqueous solution can be stored overnight in a 90°C oven and optionally degassed under vacuum. For the control PVOH / starch solution described below, if the formulation is not phase stable or miscible, the PVOH and starch will phase separate during this storage time. A phase-separated solution will either be uncastable or castable, resulting in large PVOH-rich domains and large starch-rich domains, resulting in poor mechanical properties in the starch-rich regions. Thus, the miscible and phase-stable PVOH and water-soluble starch solutions of the present disclosure have the advantages of good processability to form films and excellent physical properties of the resulting films.

[0199] In a non-limiting example, an aqueous solution containing the cationic group-modified starch (starch A) and PVOH modified with monomethyl maleate (MMM) (resin A) of the present disclosure is prepared according to the following steps: heat water to about 85°C; then, while the water is heating, add a plasticizer (e.g., glycerin and sorbitol) and an antifoaming agent; add water-soluble starch to gelatinize and mix for about 1 hour (optional water-insoluble starch particles as an antiblocking agent can be added along with the water-soluble starch); add other additives and mix for about 20 minutes (sodium metabisulfite); add resin A and mix for about 1 hour; add a surfactant and mix for about 10 minutes to form an aqueous solution. After mixing, the resulting aqueous solution can be stored in a 90°C oven overnight and optionally degassed under reduced pressure.

[0200] Method for preparing a water-soluble film The present disclosure provides a method for forming the water-soluble film discussed above. The method may include casting an aqueous solution discussed above onto a substrate at a specified thickness and drying the water from the casting solution to form a water-soluble film. The viscosity of the casting solution may be, for example, at least about 2,000 or about 3,000 cps at 185°F (85°C), and up to about 20,000, about 15,000, or about 10,000 cps at 185°F (85°C), for example, from about 3,000 cps to about 10,000 cps at 185°F (85°C).

[0201] One type of embodiment considered is characterized by a water-soluble film formed by solvent casting of the aqueous solution discussed herein above.The process for solvent casting of aqueous film-forming solution is known in the art and will be described in detail below.For example, in the film-forming process, water-soluble polyvinyl alcohol, water-soluble starch, and secondary additives are dissolved in a solvent, typically water, to form the aqueous solution discussed herein above, metered onto a surface, spread on the surface, and then dried (or forced dried) to form a cast film, and then the resulting cast film is removed from the casting surface.The process can be carried out batchwise, or more efficiently in a continuous process.

[0202] In forming the continuous water-soluble films discussed earlier herein, it is conventional practice to meter an aqueous solution onto a moving casting surface, such as a continuously moving metal drum or belt, allow the solvent to be substantially removed from the liquid, thereby forming a self-supporting cast film, and then peel the resulting cast film from the casting surface.

[0203] Optionally, the water-soluble film can be a free-standing film consisting of one layer or multiple similar layers.

[0204] In a non-limiting example, a water-soluble film is prepared by the following steps: casting a phase-stable aqueous solution of the present disclosure onto a heated steel substrate and drying the water from the cast aqueous solution to form a water-soluble film, wherein the temperature of the substrate can be heated and the target thickness of the dried film can be any desired thickness, for example, in the range of 5 μm to 200 μm, or 20 μm to 100 μm, or 40 μm to 90 μm, or 50 μm to 80 μm, e.g., 76 μm.

[0205] Pouch The present disclosure provides an article including a pouch made from the water-soluble film discussed hereinabove, the pouch defining an internal pouch volume. The article may further include a chemical composition contained in the internal pouch volume. The chemical composition may be a household care composition. The household care composition may be a liquid laundry detergent. The pouch of the present disclosure may have the advantage of improved pouch compression strength of at least about 300 N, at least about 600 N, or at least about 800 N, or at least about 1000 N, or at least about 1200 N.

[0206] An article including a pouch and a chemical composition may have a residue of about 10% by weight or less, about 5% by weight or less, or about 2.5% by weight or less after mixing in water for about 8.5 minutes at a temperature of about 15° C. The article may have a residue of about 10% by weight or less, about 5% by weight or less, or about 2.5% by weight or less, by weight of the pouch after mixing in water for about 8.5 minutes at a temperature of about 15° C. The article may have a residue of about 10% by weight or less, about 5% by weight or less, or about 2.5% by weight or less after mixing in water for about 8.5 minutes at a temperature of about 10° C. The article may have a residue of about 10% by weight or less, about 5% by weight or less, or about 2.5% by weight or less after mixing in water for about 8.5 minutes at a temperature of about 5° C.

[0207] The pouch of the present disclosure may include at least one sealed compartment. Thus, the pouch may include a single compartment or multiple compartments. The water-soluble pouch may be formed from two layers of water-soluble film sealed at their interfaces, or from a single film folded over and sealed on itself. The film defines an internal pouch volume that contains any desired composition for release into an aqueous environment. The composition is not particularly limited and may include, for example, any of the various compositions described below.

[0208] The pouch may have a matte-to-matte seal type. The water-soluble film prepared by the film casting method may have two surfaces. One surface contacts the casting substrate and is generally matte. The other surface that does not contact the casting substrate may be smoother, glossier, and have a more attractive appearance to customers. Therefore, the pouch seal may match the matte surfaces, so that both exposed film surfaces of the pouch are smooth and glossy. Optionally, the pouch made from the water-soluble film with a matte-to-matte seal type exhibits good sealing, and the article may have a compressive strength of greater than about 300 N, about 600 N, about 800 N, about 1000 N, or about 1200 N.

[0209] The water-soluble films disclosed herein can be useful for making pouches for containing chemical compositions therein. The chemical composition can be a detergent or a household care composition such as a liquid laundry detergent. The pouch composition can be in any form, such as a powder, gel, paste, liquid, tablet, or any combination thereof. Films according to the present disclosure can also be useful in any other application where improved wet handling and low cold water residue are desirable. The film forms at least one sidewall of the pouch, optionally the entire pouch, and preferably the outer surface of at least one sidewall.

[0210] The water-soluble films described herein can also be used to make packets with two or more compartments made from the same film or in combination with films of other polymeric materials. The additional films can be obtained, for example, by casting, blown film, extrusion, or blown extrusion of the same or different polymeric materials as known in the art.

[0211] In embodiments comprising multiple compartments, each compartment may contain the same and / or different compositions. The compositions may then be in any suitable form, including, but not limited to, liquids, solids, and combinations thereof (e.g., solids suspended in liquids). The pouch may comprise first, second, and third compartments, each containing a different first, second, and third composition, respectively.

[0212] Pouches and packets can be made using any suitable equipment and methods. For example, single-compartment pouches can be made using vertical form-fill, horizontal form-fill, or rotary drum-fill techniques commonly known in the art. Such processes can be either continuous or intermittent. The film can be moistened and / or heated to increase its malleability. The method can also involve the use of a vacuum to draw the film into a suitable mold. The vacuum to draw the film into the mold can be applied for about 0.2 to about 5 seconds, or about 0.3 to about 3, or about 0.5 to about 1.5 seconds once the film is placed on a horizontal portion of a surface. The vacuum can be such as to provide a negative pressure in the range of 10 mbar to 1000 mbar, or in the range of 100 mbar to 600 mbar, for example.

[0213] The mold from which the packet can be made can have any shape, length, width, and depth depending on the required dimensions of the pouch. The molds can also vary in size and shape as needed. For example, the volume of the final pouch can be about 5 ml to about 300 ml, or about 10 to 150 ml, or about 20 to about 100 ml, and the size of the mold will be adjusted accordingly.

[0214] The compositions may be selected from the group of light and heavy duty liquid detergent compositions, powder detergent compositions, dish detergents for hand and / or machine washing, including cleaning compositions and detergent compositions applicable for any such use; hard surface cleaning compositions, fabric enhancers, detergent gels commonly used in laundry, as well as bleaches and laundry additives, shampoos and body washes, agricultural compositions, automotive compositions, aviation compositions, food and nutritional compositions, industrial compositions, livestock compositions, marine compositions, medical compositions, commercial compositions, military and paramilitary compositions, office compositions, and recreational and park compositions, pet compositions, water treatment compositions.

[0215] Any suitable method of sealing the packet and / or its individual compartments may be utilized. Non-limiting examples of such means include heat sealing, solvent welding, solvent or wet sealing, and combinations thereof. Optionally, only the area where the seal will be formed is treated with heat or solvent. Heat or solvent may be applied by any method, typically only onto the sealant material, and optionally only onto the area where the seal will be formed. When solvent or wet sealing or welding is used, it may be preferable to also apply heat. Wet or solvent sealing / welding methods may include selectively applying solvent onto the areas between the dies or onto the sealant material, for example, by spraying or printing on these areas, and then applying pressure onto these areas to form the seal. For example, sealing rolls and sealing belts (optionally also providing heat), as described above, may be used.

[0216] The formed pouch can then be cut by a cutting device. Cutting can be accomplished using any suitable method. Cutting can also be done in a continuous manner, optionally at a constant speed and optionally in a horizontal position. The cutting device can be, for example, a sharp article, or a hot article, or a laser, in the latter case, where the hot article or laser "burns" through the film / seal area.

[0217] Dissolution and Disintegration Test (MSTM-205) The films can be characterized by or tested for dissolution time and disintegration time according to MonoSol Test Method 205 (MSTM205), a method known in the art. See, for example, U.S. Patent No. 7,022,656. Equipment and Materials: 600mL beaker Magnetic stirrer (Labline model number 1250 or equivalent) Magnetic stirring bar (5cm) Thermometer (0~100℃±1℃) Template, stainless steel (3.8cm x 3.2cm) Timer (0-300 seconds, second accuracy) Polaroid 35mm slide mount (or equivalent) MonoSol 35mm Slide Mount Holder (or equivalent) Distilled water

[0218] All films tested were conditioned for a minimum of 24 hours in a 23°C / 35% relative humidity environment. For each film tested, three test specimens were cut from the film sample, representing 3.8 cm x 3.2 cm specimens. When cutting from a film web, specimens should be cut from equally spaced areas of the web along the cross direction of the web. Each test specimen was then analyzed using the following procedure.

[0219] Each specimen is mounted in a separate 35 mm slide mount.

[0220] Fill a beaker with 500 mL of distilled water. Measure the water temperature with a thermometer and, if necessary, heat or cool the water to maintain the temperature at approximately 5°C (approximately 41°F).

[0221] Mark the height of the water column. Place a magnetic stirrer on the base of the holder. Place the beaker on the magnetic stirrer, add a magnetic stir bar to the beaker, turn on the stirrer, and adjust the stirring speed until a vortex is created that is approximately one-fifth the height of the water column. Mark the depth of the vortex.

[0222] Secure the 35 mm slide mount in the alligator clamp of the 35 mm slide mount holder so that the long end of the slide mount is parallel to the water surface. The depth adjuster on the holder should be set so that the end of the clip is 0.6 cm below the water surface when dropped. One of the short sides of the slide mount should be next to the side of the beaker, and the other should be directly above the center of the stir bar, so that the film surface is perpendicular to the water flow.

[0223] In one motion, drop the secured slide and clip into the water and start the timer. Disintegration occurs when the film breaks. Once all visible film has been released from the slide mount, raise the slide out of the water while continuing to monitor the solution for undissolved film fragments. Once dissolution has occurred, all film fragments will no longer be visible and the solution will be clear.

[0224] Results should include the following: complete sample identification, individual and average disintegration and dissolution times, and the water temperature at which the sample was tested.

[0225] The film disintegration time (I) and film dissolution time (S) can be corrected for a standard or reference film thickness using the exponential algorithm shown below in Equation 1 and Equation 2, respectively. I 補正 =I 実測 × (reference thickness / measured thickness) 1.93 [1] S 補正 =S 実測 × (reference thickness / measured thickness) 1.83 [2]

[0226] Tensile Strength Test Water-soluble films characterized by or tested for tensile strength (i.e., maximum stress, the stress required to break the film) are analyzed as follows. The procedure involves determining tensile strength in accordance with ASTM D 882 ("Standard Test Method for Tensile Properties of Thin Plastic Sheeting") or equivalent. An INSTRON tensile testing device (Model 5544 Tensile Tester or equivalent) is used to collect film data. A minimum of three test specimens, each cut with a reliable cutting tool to ensure dimensional stability and repeatability, are tested in the machine direction (MD) (if applicable) for each measurement. The film to be tested is conditioned for a minimum of 24 hours in an environment of 23±2.0°C and 35±5% relative humidity, and tensile strength testing is also performed in an environment of 23±2.0°C and 35±5% relative humidity. For tensile strength, a 1-inch (2.54 cm) wide sample of a single film sheet with a thickness of 76 μm is prepared. The sample is then transferred to an Instron tensile tester for testing while minimizing exposure to a 35% relative humidity environment. The tensile tester is equipped with a 500 N load cell and calibrated according to the manufacturer's instructions. The correct grips and faces are installed (Instron grips with model number 2702-032 faces, rubber coated, 25 mm wide, or equivalent). The sample is attached to the tensile tester and analyzed to determine the tensile strength (i.e., the stress required to break the film).

[0227] Young's modulus was determined as the slope of the linear fit of the stress-strain data over the range of 1 to 10% strain.

[0228] Strain at break test Determination of strain at break (i.e., maximum strain, or elongation at break) is based on ASTM D 882 ("Standard Test Method for Tensile Properties of Thin Plastic Sheeting") or equivalent. An INSTRON® tensile testing device (Model 5544 Tensile Tester or equivalent) is used to collect film data. A minimum of three test specimens, each cut with a reliable cutting tool to ensure dimensional stability and repeatability, are tested in the machine direction (MD) (if applicable) for each measurement. The film being tested is conditioned for a minimum of 24 hours in an environment of 23±2.0°C and 35±5% relative humidity, and elongation at break testing is also performed in an environment of 23±2.0°C and 35±5% relative humidity. For determination of elongation at break, a 1-inch (2.54 cm) wide specimen is prepared from a single film sheet having a thickness of 1.4±0.15 mils (approximately 35.6±3.8 μm). The sample is then transferred to an INSTRON® tensile tester for testing while minimizing exposure to a 35% relative humidity environment. The tensile tester is equipped with a 500 N load cell and calibrated according to the manufacturer's instructions. The correct grips and faces are installed (INSTRON® grips with model number 2702-032 faces, rubber coated, 25 mm wide, or equivalent). The sample is mounted in the tensile tester and analyzed to determine the strain at break (i.e., Young's modulus is applied).

[0229] Differential scanning calorimetry (DSC) To avoid weight loss during the temperature increase, tests were performed using a TA Instruments Q2000 Differential Scanning Calorimeter (DSC), or equivalent, equipped with a 50 mL / min nitrogen purge and TZERO aluminum hermetic pans (available from TA Instruments). The film specimens to be tested were cut into small pieces to provide approximately 3-5 mg of total sample that would fit in the pan (e.g., approximately three stacked cut film pieces). DSC testing is performed by equilibrating the sample at -80°C, followed by (1) heating the sample to 75°C at a rate of 10°C / min to initiate the first DSC heating curve, (2) holding the sample at 75°C for 15 minutes, (3) heating the sample from 75°C to 200°C at a rate of 10°C / min and holding the sample at 200°C for 1 minute to complete the first DSC heating curve, (4) cooling the sample to -80°C at a rate of -5°C / min to generate a DSC cooling curve, and optionally (5) reheating the sample to 200°C at a rate of 10°C / min to generate a second DSC heating curve. Once the curves are generated, transitions due to glass transition, melting, and crystallization are assigned, and the glass transition, melting, and crystallization temperatures (Tg, Tm, and Tc, respectively) are determined, and the enthalpy of melting or crystallization is determined according to standard calorimetric analysis.

[0230] Water uptake Water uptake was measured using a DVS (Dynamic Vapor Sorption) instrument. The instrument used was a ProUmid SPS-DVS (Model SPSx-1μ-High load equipped with a permeability kit). The DVS uses a gravimetric method for determining water uptake / desorption and is fully automated.

[0231] The accuracy of the system is ±0.6% for RH (relative humidity) over a range of 0 to 98% and ±0.3°C at a temperature of 25°C. Temperatures can range from +5 to +60°C. A microbalance within the instrument allows for mass change accuracy of 0.1 m. Two replicates of each film are measured, and the average water capacity value is reported.

[0232] For the specific conditions of the test, a six-pan carousel was used (one pan was used as a reference for the microbalance and had to be left empty) allowing five films to be tested simultaneously.

[0233] Each pan had a threaded aluminum ring designed to hold the film in place. A piece of film was placed on the pan and gently stretched. The ring was then placed on top, the film was firmly secured with screws, and excess film was removed. The film covering the pan surface had a diameter of 80 mm.

[0234] The temperature was fixed at 20°C. The relative humidity (RH) was set at 35% for 6 hours and then gradually increased to 50% over 5 minutes. The RH remained at 50% for 12 hours. The total duration of the measurements was 18 hours.

[0235] The cycle time (= time between measuring each pan) was set to 10 minutes and the DVS recorded each weight result versus time and automatically calculated the % moisture in the film as the relative mass change to the starting weight of the film, i.e., 10% reflects a 10% film weight increase relative to the starting film weight.

[0236] Capsule compression test Water-soluble films and / or pouches characterized by or tested for their ability to withstand a minimum mechanical compression strength of 300 N according to a compression test measurement are analyzed as follows, using the following materials: Instron model 5544 (or equivalent); At least five water-soluble pouches or capsules must be tested, the film having a thickness of 76 μm and the pouches preconditioned for at least 24 hours at 23±1° C. and 50±4% relative humidity. Zipper-type bags; Two flat plates (top plate: 10kN maximum load T1223-1022 / bottom plate: 100kN maximum load T489-74); Load cell (static load ±2kN, maximum spindle torque 20Nm, bolt torque 25Nm, and weight 1.2kg); marker Allen wrench (6mm)

[0237] The pouch is inspected for leaks and then placed in a zip lock bag (approximately 57 microns thick on each side). The bag is sealed with minimal air inside. The bag is labeled with the sample name and number.

[0238] Start the method for the compression test. The ramp rate should be 4 mm / sec.

[0239] Carefully place the sample, thermoformed side down, between the two plates, ensuring the pouch is centered on the bottom plate. Move the capsule inside the bag away from the edges.

[0240] Press Start to run the test. When the two plates come together, the pouch will burst. Record the compressive strength and location on the pouch where the burst occurs. Repeat this process for all samples.

[0241] Suitable performance of the water-soluble films according to the present disclosure is characterized by pouches having a compressive strength value of at least about 300N and less than about 2000N.

[0242] Liquid Release Time Test MSTM-126 Water-soluble films and / or pouches characterized by or tested for delayed dissolution according to the Liquid Release Test are analyzed as follows, using the following materials: A 2 L beaker and 1.2 L of deionized (DI) water; The water-soluble pouches to be tested, the film has a thickness of 76 μm, and the pouches are preconditioned at 38° C. for 2 weeks. thermometer; Wire cage; timer.

[0243] Before conducting the experiment, ensure that enough DI water is available to repeat the experiment five times and that the wire cage and beaker are clean and dry.

[0244] The wire frame cage is a plastic-coated wire cage (4 in x 3.5 in x 2.5 in, or approximately 10 cm x 9 cm x 6 cm) without sharp edges, or equivalent. The wire gauge should be approximately 1.25 mm, and the wire should have openings 0.5 in (1.27 cm) square in size.

[0245] To set up for testing, carefully place the water-soluble pouch in the cage, allowing free space for the pouch to move without scratching the pouch on the cage. Securely fasten the pouch to the wire cage without tying it down too tightly, preventing it from leaving the cage. The orientation of the pouch in the cage should be set up to allow the pouch's natural buoyancy (if any) to come into play (i.e., the pouch should be placed face up, with the floating side facing up). If the pouch is symmetrical, the orientation of the pouch will generally not be important.

[0246] Next, fill a 2 L beaker with 1200 milliliters of DI water at 20° C. Other water temperatures may be used in alternative methods.

[0247] The wire frame cage containing the pouch is then lowered into the water. Ensure the cage is 1 inch (2.54 cm) from the bottom of the beaker. Ensure the pouch is completely submerged on all sides. Ensure the cage is stable and does not move, and start a timer as soon as the pouch is lowered into the water. The position of the cage relative to the water in the beaker can be adjusted and maintained by any suitable means, for example, by using a clamp fixed on top of the beaker and a rod attached to the top of the cage. The clamp can engage the rod to fix the cage's position, reducing tension on the clamp to lower the cage into the water. Other means of frictional engagement can be used instead of a clamp, for example, a collar with a set screw.

[0248] Liquid content release refers to the first visual evidence of liquid leaving the immersed pouch.

[0249] A timer is used to record the point at which the pouch breaks (liquid release) and the liquid contents are released into the surrounding water (release time).

[0250] This process is repeated five times with fresh DI water and a new water-soluble pouch for each film tested.

[0251] Unless otherwise reported, a total of at least three pouches are tested for each film sample type.

[0252] Accelerated Quantitative Residue Assessment This test method is for quantitatively assessing film residue and includes the steps detailed below.

[0253] Sample cleaning and calibration

[0254] Cut the film sample into 2" x 2" strips and immerse directly into a glass bottle containing the desired liquid laundry detergent (LLD). Ensure the LLD completely covers the film sample. Multiple film samples of the same type can be conditioned together in the same LLD container. Cover the bottle and add to the conditioned environment for the desired amount of time. n = 3 for each film type investigated, and each n should contain two film squares.

[0255] Remove the film / LLD from the conditioned environment. Remove the film sample from the LLD with tweezers, allow the LLD to drain, and then rinse briefly with methanol. Immediately wipe the film gently with a Kimwipe™ to remove any residual LLD and methanol (the film should not have a greasy appearance).

[0256] This test requires a 9cm diameter espresso colored 100% cotton fabric. The fabric circle and film combination is assigned a sample identification number (ABC).

[0257] Label and use weigh boats to both weigh and transport between testing steps. Use address labels to label the film, detergent used, sample age (7, 14...70 days, etc.), conditions collected (38°C, 80% RH), and sample identifier. Create duplicate labels for each sample, labeling one "front" and the other "back" for photographic purposes after the samples have dried.

[0258] Weigh and record the weight of the weigh boat. Weigh and record the weight of the washed film. Weigh and record the dry weight of the fabric circles. Ensure fabric and film are kept separate while in the weigh boat.

[0259] Sample testing Fill four 1000 ml beakers with 800 ml of 15°C tap water.

[0260] Place a stir bar in the beaker and place it on top of the hot plate with a timer set nearby.

[0261] Set stirring on hot plate to 300 RPM.

[0262] Two 2 inch by 2 inch strips of film are cut into four approximately equal strips each by first cutting them in half, stacking the two strips on top of each other, and cutting them in half again.

[0263] Eight strips of film (1 inch x 1) are dropped into the water and a count-up timer is started at the same time.

[0264] Prepare a Büchner funnel with a rubber collar (9 cm inner diameter), a vacuum flask, and a vacuum pump.

[0265] Place the fabric circle inside the Buchner funnel, making sure all holes are covered. Water may be used to wet and stabilize the edges of the fabric.

[0266] When the count-up timer approaches 8 minutes, approximately 7:50, start the vacuum pump. When the timer approaches 8 minutes, stop the stirring function and begin slowly pouring the liquid into the Büchner funnel.

[0267] Pour the dissolved film solution from the 1000 ml beaker directly onto the fabric and center of the funnel, not pouring in so much that it displaces the bottom fabric filter or the liquid is no longer filtered through the fabric.

[0268] After all the liquid has filtered, inspect the beaker and stir bar for any visible residue. Using water from a squirt bottle, squirt water down the sides of the beaker and stir bar, swirl the beaker several times, and pour it back into the Buchner funnel.

[0269] If there is a lot of visible residue, run the vacuum pump for a longer period of time to extract as much water as possible.

[0270] After the vacuum pump is turned off, tweezers are used to lift one end of the fabric, then the other end, clamp the ends together with the tweezers, transfer to a weigh boat, weigh it, and transfer back.

[0271] Remove the hose from the vacuum flask and transfer the filtered liquid from the vacuum flask to the sink. Reattach the hose.

[0272] Dry the sample in an oven at 38°C and 25% RH overnight (minimum 6 hours).

[0273] Sample preparation and testing After the sample has dried, it is weighed and the weight of the weigh boat and film is recorded. The weight of the original weigh boat and the weight of the fabric are subtracted to obtain the residue weight.

[0274] Reporting test results After the sample has dried, it is weighed and the weight of the weigh boat and film is recorded. The weight of the original weigh boat and the weight of the fabric are subtracted to obtain the residue weight.

[0275] These calculations describe the results. Residue = Final - {Fabric (Initial) + Calibration Boat (Initial)} Residue % = (residue / film (initial))*100 Dissolution%=100-Residue%

[0276] A correction factor of 0.03 is added to the residue results to account for typical fabric losses during the filtration process.

[0277] Various embodiments of the present disclosure are described in more detail below. [Example]

[0278] The following examples further illustrate the present disclosure.

[0279] material Water-soluble films of the present disclosure and related aqueous solutions for forming the water-soluble films were prepared using different water-soluble polyvinyl alcohol (PVOH) resins and water-soluble starches at different weight ratios and total solids loading levels. Control films were also prepared in these studies.

[0280] The following starches were used in the various examples: Starch A was approximately 10 3 ~10 6 The cationic quaternary ammonium group modified starch had a low average molecular weight in the range of g / mol, about 25% by weight amylose, and a modification level of 0.18 mol%. The properties of Starch A and the other starches used in this study are shown in Table 2 below. Starch B had a low average molecular weight in the range of g / mol, about 25% by weight amylose, and a modification level of 0.18 mol%. 3 ~10 6 Starch C is a cationic quaternary ammonium group-modified starch with a low average molecular weight in the g / mol range, no amylose (100% amylopectin), and a modification level of 0.18 mol%. Starch D is a hydroxyethylated corn starch (neutral modified starch) with about 25% amylose by weight and a modification level of less than about 3.0 mol%. Starch E is an unmodified starch with about 25% amylose by weight and no modification. Starch F is an octenyl succinate-modified wax starch. Starch G is a hydroxyethylated corn starch (neutral modified starch) with about 25% amylose by weight and a modification level of less than about 3.0 mol%, and the average molecular weight of Starch G is higher than that of Hydroxyethylated Starch C. Starch H is a cationically modified starch with about 25% amylose by weight. Starch J is a cationically modified starch with no amylose (100% amylopectin) and a modification level of about 0.37 mol%. [Table 2]

[0281] The following polyvinyl alcohol (PVOH) resins were used in the various examples. Resin A is an anionic group-modified polyvinyl alcohol (PVOH) modified with monomethyl maleate (MMM) and having a degree of modification of approximately 1.5-2.0 mol% and a hydrolysis level of 89-91 mol%. Resin B is an anionic group-modified polyvinyl alcohol (PVOH) modified with methyl acrylate (MA) and having a degree of modification of approximately 1-10 mol% and a hydrolysis level of 80-99 mol%. Resin C is an anionic group-modified polyvinyl alcohol (PVOH) modified with monomethyl maleate (MMM) and having a degree of modification of approximately 3.8-4.2 mol% and a hydrolysis level of 89-91 mol%.

[0282] Two polyvinyl alcohol homopolymers (Resin D and Resin E) were also investigated. Resin D is a commercially available polyvinyl alcohol homopolymer with a specified degree of hydrolysis of 86.7% to 88.7%, a pH of 4.5 to 7, and a specified viscosity of a 4% solution at 20°C of 11.4 to 14.5 cP. Resin E is a commercially available polyvinyl alcohol homopolymer with a specified degree of hydrolysis of 87% to 89%, a pH of 5 to 7, and a specified viscosity of a 4% solution at 20°C of 20.5 to 24.5 cP. However, we found that these PVOH homopolymers had poor miscibility and phase separation with all starches tested at total solids in the aqueous film-forming solution of 10 wt% or more, and at starch loading levels exceeding 15 wt% of the total solids. At high starch loading levels, films could not be cast for Resin D or E.

[0283] Example 1 Water-soluble film containing anionic polyvinyl alcohol (resin A) In this study, different water-soluble films were prepared using anionic group-modified polyvinyl alcohol, Resin A (polyvinyl alcohol modified with monomethyl maleate (MMM)), and different types of starch, Starches A-E (each shown in Table 2, each with a different PVOH / starch weight ratio). The formulations of the different water-soluble films with different weight ratios of PVOH to starch are shown in Table 3 below and are described by their "PHR" starch. PHR starch is based on 100 parts of the total amount of PVOH and starch in the formulation, where PHR starch = 100 x starch. 重量% / (starch 重量% +PVOH 重量% The polyvinyl alcohol used in each of the formulations in Table 3 was Resin A.

[0284] Methods for preparing water-soluble films and the associated aqueous solutions for forming these films are described below. The phase stability, physical properties, and solubility of these water-soluble films were investigated. The phase stability of the associated aqueous solutions for forming each of the water-soluble films was also investigated. The test results are shown in Table 4 below.

[0285] All percentages are percentages by dry weight of the film. A 33 PHR starch formulation was prepared with two polyvinyl alcohol resins, 37.33 wt. % Resin A and 15.64 wt. % Resin C, by weight of the dry film. The remaining formulations (with 41, 45, 49, 55, and 80 PHR starch) were prepared with an anionic polyvinyl alcohol resin, Resin A. [Table 3]

[0286] In this study, a 50:50 weight ratio blend of Starch A and Starch B was also used to prepare water-soluble films. The A:B blends were evaluated in 41 PHR and 49 PHR formulations (Samples 12 and 23 in Table 4, respectively). The phase stability of the aqueous solutions, the physical properties of the water-soluble films, and the water dissolution times were tested, and the test results are shown in Table 4 and are detailed below.

[0287] Method for preparing an aqueous solution for forming a water-soluble film Aqueous solutions for forming water-soluble films were prepared by the following steps: 1) heating water in a container to a temperature of about 85°C, 2) adding plasticizers (glycerin and sorbitol) and antifoaming agents while maintaining the water temperature at about 85°C, 3) adding one of the starches in Table 2 to the water and mixing for about 1 hour to gelatinize and dissolve the starch while simultaneously adding an antiblocking agent such as Hylon-V starch particles, 4) adding an additive (e.g., sodium metabisulfite) and mixing for about 20 minutes, 5) adding Resin A (and Resin C for the 33 PHR starch formulation) and mixing for about 1 hour, and 6) adding a surfactant and mixing for about 10 minutes. The water was maintained at a constant temperature of about 85°C throughout the preparation process.

[0288] In preparing the aqueous solution, sufficient time, heat, and shear were applied for the starch to gelatinize and completely dissolve in the warm water and to homogeneously mix with the PVOH to form a miscible solution, or at least to prevent bulk phase separation between the PVOH and the water-soluble starch in the aqueous solution and the resulting water-soluble film.

[0289] After mixing, the aqueous solutions were stored overnight in an oven at 90°C to degas. This also allowed time for the solutions to phase separate if the formulation was not phase stable. The phase stability of each of the aqueous solutions was evaluated by visual inspection after 24 hours of storage at 90°C, and the test results are shown in Table 4.

[0290] The aqueous solutions each had a total solids content ranging from 28 to 35 wt. % by weight of the aqueous solution. The total solids content of each of the aqueous solution formulations tested in this study is detailed in Table 4.

[0291] Method for preparing a water-soluble film In this study, the samples in Table 4 that formed either single-phase aqueous solutions or gels were subsequently cast to form films for further testing of the physical properties of the resulting films. The method of forming the water-soluble film involves casting the aqueous solution or gel discussed previously herein onto a substrate at a specified thickness and drying the water from the cast aqueous solution or gel to form the water-soluble film.

[0292] In this study, water-soluble films were formed by the following steps: setting the casting bed at a temperature of approximately 205°F (96°C); setting the doctor blade to the desired width (which varied for each formulation, as the width was significantly affected by viscosity); spraying a 1 wt. % release agent solution over the surface of the casting bed using a spray bottle; metering the aqueous solution or gel into the casting trough; activating a mechanical arm and moving the doctor blade across the bed to cast the aqueous solution onto the surface and spread it over the surface of the casting bed; drying to form a cast film; and removing the resulting cast film from the casting surface to form a free-standing film. Drying times ranged from approximately 7 to 12 minutes, or from approximately 8.5 to 9.5 minutes. The resulting films were further tested for their mechanical and solubility properties after standard conditioning at approximately 35% RH and 23°C for 24 hours.

[0293] Phase stability of aqueous solutions with anionic polyvinyl alcohol (resin A) The phase stability of liquid solution mixtures of all formulations in Table 3 was tested and the test results are shown in Table 4 below. [Table 4-1] [Table 4-2]

[0294] As shown in Table 4, Starch A (cationically modified starch) at all starch loading levels tested in this study (41, 45, 49, 55, and 80 PHR) formed single-phase aqueous solutions with no phase or bulk phase separation between Starch A and Resin A (anionic group-modified PVOH) by visual inspection, and no formation of highly viscous gels. The aqueous solutions also had no phase or bulk phase separation between the polyvinyl alcohol and the starch by visual inspection when initially prepared, and during and after storage at about 90°C for at least 24 hours and at least about 48 hours. The test results indicate that Resin A and Starch A are miscible, or at least have no bulk phase separation, in the resulting aqueous solutions at starch loading levels up to about 80 PHR. Further testing by differential scanning calorimetry (DSC) showed a single Tg for the resulting water-soluble films with Starch A at 41 PHR and 45 PHR, respectively.

[0295] An image of the single-phase solution of Sample 2 is shown in Figure 1A, which is a representative image of a single-phase solution without phase or bulk phase separation for all stable single-phase formulations described in this disclosure. The image was taken using a hot plate as a light box and a monochrome filter on the camera. This method allowed for easy identification of phase separation by the opacity of the solution. Solutions with different opacities are non-homogeneous and therefore have phase separation using a monochromatic color filter, and the light box behind the sample makes it easy to distinguish the phases when taking images.

[0296] Cationic starch B has the same type and degree of cationic quaternary ammonium group modification as starch A and a similar molecular weight, but contains no amylose. Starch A, on the other hand, contains approximately 25% amylose by weight. Single-phase aqueous solutions were formed only at slightly lower starch loading levels of 41 PHR (Sample 20) and 45 PHR (Sample 15), respectively, which are still usefully higher than those achievable with conventional starch. When the starch loading level was increased to 49 PHR, slight phase separation was observed in the resulting liquid solution mixture (Sample 10). When the starch loading was further increased to 55 PHR, clear phase separation was observed in the resulting solution (Sample 4). Thus, the test results indicated that the amylose content of the cationic starch also affected the phase stability of the resulting liquid solution mixture with anionic resin A.

[0297] A 50:50 weight ratio blend of cationic starch A and starch B, having a resulting average amylose content of about 12.5 wt % based on the total weight of starch, was used to prepare aqueous solutions at loading levels of 41 PHR and 49 PHR, respectively. In contrast, as noted above, for liquid solution mixtures with starch B at both loading levels, the resulting aqueous solutions had a single phase and no phase separation was observed.

[0298] Nonionic group-modified starch C (hydroxyethyl group-modified starch with a degree of modification less than 3.0 mol%) formed stable aqueous solutions with resin A at the relatively low starch loading levels tested of 41 PHR (sample 19) and 45 PHR (sample 14), respectively. At higher starch loading levels of 49 PHR (sample 8) and 55 PHR (sample 3), these liquid solution mixtures with starch C were not stable and the phase separated into two layers. An image of the solution phase separation for sample 8 is shown in Figure 1B, which is a representative image of the solution phase separation for all unstable and phase-separated formulations described in this disclosure.

[0299] For unmodified starch D, which had 25% by weight amylose, formulations with starch D only formed stable aqueous solutions with resin A at relatively low starch loading levels of 41 PHR and 45 PHR, respectively. However, formulations at higher loading levels of starch D, 49 PHR and 55 PHR, respectively, were observed to form gels that had high viscosities and therefore made subsequent film formation difficult. Without wishing to be bound by theory, it is believed that gel formation may be caused by the amount of unmodified amylose in unmodified starch D (25%). Given that gel formation dramatically increases the viscosity of the solution, this indicates that unmodified high-amylose starches such as starch D are not suitable for film formation.

[0300] For Starch E, an unmodified starch with no amylose, formulations with Starch D only formed stable aqueous solutions with Resin A at relatively low starch loading levels of 41 PHR and 45 PHR, respectively. However, formulations at higher loading levels of Starch E, 49 PHR and 55 PHR, respectively, were observed to form unstable liquid solutions, and for these two formulations, Resin A and Starch E phase separated into two layers. The phase separation behavior was observed to be similar to the solution phase separation image shown in Figure 1B.

[0301] The test results in this study clearly demonstrated that the combination of low molecular weight, amylose content, and type and degree of cationic modification of cationic starch A allows starch A to have good interactions with anionic resin A in aqueous solution, enabling the formation of a single-phase stable aqueous solution at starch loading levels of up to 80 PHR (or a starch:PVOH weight ratio of up to 4:1). Furthermore, no phase or bulk phase separation was observed in either the aqueous solutions containing resin A and starch A, or in the resulting water-soluble films, even at high starch loading levels of up to 80 PHR. However, for similar molecular weights and types and levels of cationic modification, starch B, with 0 wt. % amylose, phase separated from resin A at high starch loading levels of 49 PHR or higher. To investigate the effect of amylose content on the phase stability of liquid solutions obtained using the same formulations in Table 3, a 50:50 weight ratio blend of Starch A and Starch B (resulting in a starch blend with 12.5 wt.% amylose) was also investigated. The test results showed that the formulation with 49 PHR of the starch blend formed a stable single-phase aqueous solution, and no phase or bulk phase separation was observed in the resulting aqueous solution and water-soluble film. The test results clearly demonstrated that the higher amylose content of the cationic starch resulted in better interaction with the anionic PVOH, resulting in aqueous solutions with better phase stability at high starch loading levels.

[0302] When comparing the phase stability of formulations with unmodified starch D (25% amylose by weight) with formulations with unmodified starch E (0% amylose by weight), the test results demonstrated that unmodified starches with high amylose content tended to form highly viscous gels, while unmodified starches with lower amylose content tended to have phase separation from the PVOH at high starch loading levels, such as 49 PHR and above. Solutions made from formulations using nonionic group-modified starch C were also unstable and prone to phase separation at high starch loading levels, such as 49 PHR and above.

[0303] Phase stability of aqueous solutions of blends of two anionic polyvinyl alcohol resins (Resin A and Resin C) and 33 PHR starch. Aqueous solutions of blends of two anionic polyvinyl alcohol resins (33.73 wt. % Resin A and 15.64 wt. % Resin C) and formulations containing 33 PHR of different starches were prepared and further tested for phase stability. All 33 PHR starch formulations formed single-phase aqueous solutions with no phase or bulk phase separation between the starch and the polyvinyl alcohol resin by visual inspection and no formation of highly viscous gels. Furthermore, the aqueous solutions were phase stable, with no phase or bulk phase separation upon initial preparation and during and after storage in a 90°C oven for approximately 24 and 48 hours.

[0304] Mechanical properties of the obtained water-soluble films The resulting water-soluble films were tested for mechanical properties and solubility, and the test results are shown in Table 4 above.

[0305] As shown in Table 4, films formed with cationic starch A had excellent maximum stress at break and high strain at break, exceeding 20 MPa, at all starch loading levels tested in this study, with the best maximum stress at high starch loading levels of 49 and 55 PHR compared to films with other starches tested. At lower starch loading levels of 41 and 45 PHR, both cationic starch A and starch B, as well as nonionic group-modified starch C, showed comparable excellent maximum stress at break and strain at break.

[0306] In contrast, films made from unmodified starch D (25 wt% amylose) exhibited the worst maximum stress at break and strain at break compared to the other starches tested in this study. Films with unmodified starch E (0 wt% amylose) at low starch loading levels of 41 PHR and 45 PHR exhibited acceptable maximum stress at break and strain at break, respectively, but worse than those of modified starches A, B, and C.

[0307] Solubility of the obtained water-soluble film The water solubility of the different films obtained at 10°C was tested and the test results are shown in Table 4. The cold water solubility of the different films obtained at 5°C was tested and the test results are shown in Figure 2.

[0308] As shown in Table 4 and Figure 2, the amylose content and modification type and level of starch affect the cold water solubility of the corresponding films made from each starch. The water solubility of films made with cationic starch A at both 10°C and 5°C decreased (longer dissolution time) as the concentration of starch A in the film increased. Films made with cationic starch B at loading levels of 41 PHR and 45 PHR exhibited excellent cold water solubility at both 10°C and 5°C, as well as the best overall mechanical properties. Films made with nonionic starch C also demonstrated excellent cold water solubility at both 10°C and 5°C. Films made with unmodified starch D demonstrated slower cold water solubility at 10°C.

[0309] Effect of amylose on solubility: For the cationic starches Starch A (25 wt% amylose), Starch B (0 wt% amylose), and a blend of Starches A and B with similar type and degree of cationic modification (average 12.5 wt% amylose), lower amylose content of the starches resulted in better cold water solubility of the corresponding films (shorter dissolution times at both 10°C and 5°C). For the unmodified starches Starch D (25 wt% amylose) and Starch E (0 wt% amylose), lower amylose content of the starches also resulted in faster cold water solubility of the corresponding films at 10°C.

[0310] Effect of modification on solubility: For starches with the same amylose content (25 wt%), cationic starch A, nonionic starch C, and unmodified starch D, modification of the starches achieved faster cold water solubility of the corresponding films at 10° C. For starches without amylose, cationic starch B and unmodified starch E, modification of the starches also achieved faster cold water solubility of the corresponding films at 10° C.

[0311] Example 2 Water-soluble film containing anionic polyvinyl alcohol (resin B) In this study, various formulations with different weight ratios of polyvinyl alcohol to starch were developed, which are listed in Table 5 by their "PHR" starch. PHR starch is based on 100 parts of the total amount of PVOH and starch in the formulation, where PHR starch = 100 x starch. 重量% / (starch 重量% +PVOH 重量% The polyvinyl alcohol used in all formulations in Table 4 was Resin B (polyvinyl alcohol modified with methyl acrylate (MA)), an anionic group-modified polyvinyl alcohol. The starches in Table 2 were all investigated in the formulations in Table 5, respectively.

[0312] All percentages are by weight of the dry film. [Table 5]

[0313] Aqueous solutions for forming water-soluble films were prepared by dissolving the ingredients in the formulations in Table 5 in a manner similar to that previously disclosed herein in Example 1. The water-soluble films in this study were made by casting the corresponding aqueous solutions in a manner similar to that previously disclosed herein in Example 1.

[0314] The resulting films were further tested for their mechanical and solubility properties as shown in Table 6 below.

[0315] Phase stability of aqueous solutions with anionic polyvinyl alcohol (resin B) The phase stability of the aqueous solutions was investigated by visual inspection during storage for at least about 24 hours at 90° C. The test results are shown in Table 6 below. [Table 6]

[0316] As shown in Table 6, the liquid solution mixture of Sample 25 made with 49 PHR of nonionic starch C was unstable and the PVOH and starch phase separated in the liquid solution. All other aqueous solutions with Resin B were phase stable when initially prepared and during and after storage at 90°C for at least about 24 hours.

[0317] Mechanical properties of the obtained water-soluble films The resulting water-soluble films were tested for mechanical properties and the test results are shown in Table 6 above.

[0318] As shown in Table 6, films formed with cationic starch A had high maximum stress at break of over 20 MPa and high strain at break at both 43 and 49 PHR starch loading levels, which are favorable for packaging applications. At the 49 PHR starch loading level, films made with cationic starch A (25 wt% amylose), cationic starch B (0 wt% amylose), and unmodified starch E (0 wt% amylose) each demonstrated high maximum stress at break and strain at break, respectively, beneficial for packaging applications, while the film made with unmodified starch D exhibited the lowest mechanical properties. The test results demonstrated that unmodified starches with high amylose content resulted in water-soluble films with poorer mechanical properties.

[0319] The water solubility of the obtained water-soluble film The different films obtained were tested for water solubility at 10° C. and the test results are shown in Table 6 above.

[0320] As shown in Table 6, a film (Sample 27) made with unmodified Starch D (25 wt% amylose) was shown to be insoluble in water at 10° C. This again indicated that Starch D (unmodified, high amylose) is not suitable for water-soluble film applications. However, it may have potential applications outside of water-soluble films, for example, as an oxygen barrier film used in packaging applications.

[0321] Example 3 Optical microscope photographs of the stretched and unstretched films of Sample 31 In this study, Starch F (octenyl succinic acid (OSA) modified starch) was investigated using the formulation in Table 7, and the film sample prepared is labeled as Sample 31.

[0322] All percentages are by weight of the dry film. [Table 7]

[0323] Sample 31 had approximately 33 PHR of Starch F (octenyl succinic acid (OSA) modified starch) in its formulation, as shown in Table 5. This aqueous solution of this formulation and the resulting film were prepared according to a method similar to that disclosed in Example 1. The resulting film had many undesirable properties. Over time, the starch in the film oxidized, resulting in roll blocking and a color change from clear to brown. The film also exhibited substantial strain whitening upon stretching. Micrographs of the stretched and unstretched films are shown in Figure 3. Without intending to be bound by theory, it is believed that the stress whitening can be attributed to (solid) phase separation between the PVOH and starch on a 10-100 μm scale. This strain whitening behavior was not observed in the other PVOH / starch water-soluble films prepared in this study. The test results may suggest that highly non-polar and bulky OSA modification of starch is undesirable in water-soluble film applications.

[0324] Example 4 Capsule with pouch made from water-soluble film Capsules were prepared having pouches made from the water-soluble films prepared in Examples 1 and 2. A liquid composition was filled into each of the pouches. The liquid release times (LRT) of the pouches were tested according to the liquid release test described above, and the test results are shown in Table 8 below. As described above, the PHR levels of starch are based on the total content of starch and PVOH resin.

[0325] All capsules were formed to a stretch ratio of 2.5 (stretch ratio is calculated by the ratio of the final area of ​​the film perpendicular to the stretch direction to the original area), and samples were tested at room temperature and in deionized (DI) water. Capsules 1-4 were tested with a first liquid laundry detergent (LLD1). Only capsule 5 (sample 7 from Example 1) was tested with a second liquid laundry detergent (LLD2), which was different from the first liquid laundry detergent. The capsules were tested within one week of conversion from film to capsule. [Table 8]

[0326] As shown in Table 8, all capsules 1-5 made from starch / PVOH films had liquid release times longer than the 30-second threshold required by regulatory agencies for liquid laundry detergents. All capsules had liquid release times of at least 2 minutes, but less than 5 minutes. Capsule 5 made from the film of Sample 7 in Example 1 (having 51 PHR of Resin A and 49 PHR of Starch A) had a significantly longer liquid release time, which may be due to the use of a different LLD. There was no significant difference between capsule 3 (41 PHR of Starch A) and capsule 4 (41 PHR of Starch C), even though the Starch C formulation generally had faster water solubility.

[0327] Example 5 Capsule compression strength The compressive strength of capsules with pouches made from the films of Examples 1 and 2 was tested using the Capsule Compression Test described above. The test results are shown in Table 9. [Table 9]

[0328] In this study, premature seal failure was defined as failure of less than 25% of the maximum compressive strength for each sample set. The matte surface of the film refers to the surface that contacts the band and any release agent transferred to the film, which can also result in high seal failure.

[0329] The compression strength of the capsules depends on the mechanical properties of the film and the seal strength. All capsules in this study demonstrated an average compression strength ranging from approximately 600 to 1500 N, which far exceeds the typical industry requirement of 300 N. The formulations that gave the best matte-to-matt seals were capsules 1, 7, 8, and 9-10. Seal failures can usually be detected by applying light pressure to the capsules by hand.

[0330] Example 6 Residue Testing Residue testing was performed on the water-soluble films prepared in Examples 1 and 2 according to the Accelerated Quantitative Residue Evaluation Test Method described earlier in this specification. The test results are shown in Table 10 below. [Table 10]

[0331] All films were tested without exposure to liquid laundry detergent (LLD). LLD exposure can significantly alter residue results. All water used was tap water at 14°C. In Table 10 above, B refers to bench trial cast film samples, L refers to pilot trial cast film samples, and S refers to semi-work trial cast film samples.

[0332] As shown in Table 10, Film 6 (49 PHR Starch B) had 7% less residue than Film 3 (49 PHR Starch A). This is reinforced by the data presented in Example 1 that cationic starch A (25 wt. % amylose) was less water-soluble than cationic starch B (0 wt. % amylose). Film 4 had very similar residue compared to Film 3, despite having 3 PHR more starch A. Films 7 and 8 did not have significant differences in residue despite the different starches. Film 10 had substantially more residue than Film 7, which may be due to differences in processing conditions.

[0333] Example 7 Differential scanning calorimetry (DSC) thermal analysis of selected films Some of the bench trial cast film samples prepared in Examples 1 and 2 were further analyzed using differential scanning calorimetry (DSC) to measure the glass transition temperature (Tg), melting temperature (Tm), crystallization temperature (Tc), and melting and crystallization enthalpies. The thermal analysis test results are shown in Table 11 below. [Table 11]

[0334] Differential scanning calorimetry (DSC) measurements were performed on various starch / PVOH films. The enthalpies of melting and crystallization of the starch / PVOH hybrid films were lower than those of the control film (commercial polyvinyl alcohol (Resin A) film without starch). This suggests that the starch / PVOH films have lower crystallinity than existing commercial films without water-soluble starch. This may be due, in part, to differences in bench and production-scale process conditions (i.e., bench-scale films generally have lower crystallinity); however, starch is expected to have lower crystallinity than PVOH. Interestingly, some starches appear to reduce crystallinity more than other starches. For example, at two different loading levels, the Starch B / Resin A films (Films 9, 10, 12, and 13) had substantially higher crystallinity than the Starch D / Resin A films (Films 7, 8, 16, and 17). Films 14 and 15, which contained Starch A and Resin B, exhibited the highest crystallinity of the films tested in this study. This suggests that the type of starch used in the formulation can be used to tailor the crystallinity of the final film. Increasing crystallinity is beneficial because it improves mechanical properties, but it can also reduce dissolution time. Therefore, the ability to engineer crystallinity based on starch selection may allow for optimization of crystallinity to balance the effects of dissolution time and mechanical properties. Furthermore, all samples tested exhibited a single Tg.

[0335] Example 8 DVS analysis of selected formulations Dynamic vapor sorption (DVS) analysis was performed on some of the samples prepared in Examples 1 and 2, and the test results are shown in Table 12. [Table 12-1] [Table 12-2]

[0336] Dynamic vapor sorption (DVS) data indicates the water uptake and retention capacity at a specified humidity. In this experiment, the relative humidity (RH) was increased in 10 steps up to 80% RH and then returned to 0% in the next 10 steps. The RH value was held constant until all samples reached equilibrium moisture, and the percent moisture could be determined by mass gain. After equilibrating at 0% RH and 25°C for 16 hours, the percent moisture was calculated based on the minimum measured mass of the film.

[0337] Additionally, dynamic vapor sorption test results after equilibration at the indicated moisture contents for Film 5 (59 PHR Resin A and 41 PHR Starch A) and Film 6 (59 PHR Resin A and 41 PHR Starch C) at 23°C are also shown in Figure 4 and compared to a control film, Control M8630 (a commercially available film with Resin B without water-soluble starch). Dynamic vapor sorption test results over time for Films 1-3, 5, 22, and the Resin A-containing control film (containing Resin A without water-soluble starch) are shown in Figure 5. In Figure 5, the order of data plots from top to bottom around 80-90 hours is as follows: Film 1, Film 3, Film 2, Film 22 / Film 5 (substantially overlapping), and control.

[0338] The experimental results in Table 12 and Figures 4 and 5 show that there is not much variation in water uptake between the different PVOH / starch films in this study. The water uptake of the DVS of Films 5 and 6 was very similar to each other at all relative humidities measured and slightly lower than that of the control MonoSol M8630 film at relative humidities above 50%.

[0339] However, it is clear from Figure 5 that all of the PVOH / starch films behave very differently when compared to the Resin A-containing control film. For this control, at each new RH value, the weight percent water in the film rises sharply and then falls. Without intending to be bound by any particular theory, this is believed to be due to crystallization of the amorphous regions of the film, causing a decrease in the film's ability to uptake water. This effect was not observed for any of the PVOH / starch films, suggesting that additional crystallization does not occur at room temperature with increasing % RH.

[0340] Example 9 Water-soluble films containing PVOH, starch, and coagents were prepared according to the methods described herein in the amounts shown in Table 13. The total starch content of each composition was 0, 10, 20, 30, or 40 PHR, as shown in Table 13. The PVOH in all films was Resin A. The starch was one of Starches A-E, G, H, or J, or a 1:1 (wt:wt) blend of two cationic starches with the total amount of starch as listed in the table below. [Table 13]

[0341] The strain at break of films having the recipes listed in Table 13, including starch A, C, E, or G as the starch, was measured according to the method described herein. The results are shown in Table 14. [Table 14]

[0342] Films containing Starch C, a hydroxyethyl-modified starch, retained greater flexibility at increasing starch loadings up to 40 PHR than identical films containing Starch E (unmodified starch) or Starch A (cationic starch). Films containing Starch C also retained greater flexibility at increasing starch loadings up to 40 PHR than identical films containing Starch G, a hydroxyethyl-modified starch with a higher average molecular weight than Starch C.

[0343] The Young's modulus of films having the recipes listed in Table 13 and containing the starches or starch blends listed in Table 15 was measured according to the methods described herein. [Table 15]

[0344] Films containing unmodified starch showed an increase in Young's modulus with increasing starch loading (i.e., increasing the starch:PVOH ratio), resulting in stiffer films with increasing starch content. Films containing the hydroxyethylated starch, Starch G, also showed an increase in Young's modulus with increasing starch content, although increasing the content of hydroxyethylated starch with a lower average molecular weight than Starch G did not have the same effect. Notably, increasing the loading of the cationic modified starch, either as a single starch or as a blend of two cationic starches, generally did not increase the Young's modulus of the resulting film.

[0345] As used herein, the term "cook %" refers to the maximum water solubility after gelatinization of the starch, which is the maximum weight percentage of the starch that dissolves in water under cooking conditions, such as direct steam injection and mixing in water at about 95°C for about 30 minutes.

[0346] As used herein, and unless otherwise specified, the term "water-soluble film" refers to any film having a dissolution time of 300 seconds or less in water at a temperature of about 20°C (68°F) at a thickness of about 1.5 mils (about 0.038 mm) according to MonoSol Test Method MSTM-205 described herein. For example, the dissolution time can optionally be about 300 seconds or less, about 250 seconds or less, about 200 seconds or less, about 100 seconds or less, about 60 seconds or less, or about 30 seconds or less at temperatures of about 80°C, about 70°C, about 60°C, about 50°C, about 40°C, about 20°C, about 10°C, or about 5°C. The dissolution time can optionally be about 300 seconds or less at a temperature of about 40°C (104°F). In embodiments where a dissolution temperature is not specified, the water-soluble film has a dissolution time of 300 seconds or less at a temperature of about 80°C or less.

[0347] As used herein, and unless otherwise specified, the term "cold water soluble" refers to any film having a dissolution time of 300 seconds or less at 10° C. at a thickness of about 1.5 mils (about 0.038 mm), as determined according to MSTM-205. For example, the dissolution time can optionally be 200 seconds or less, 100 seconds or less, 60 seconds or less, or 30 seconds at a temperature of about 10° C.

[0348] As used herein, and unless otherwise specified, the term "5°C cold water soluble" refers to any film that is about 1.5 mils (about 0.038 mm) thick and has a dissolution time of 300 seconds or less at 5°C, as determined according to MSTM-205. For example, a 1.5 mil (about 38 μm) thick water-soluble film may have a dissolution time in water of 300 seconds or less, 200 seconds or less, 100 seconds or less, 60 seconds or less, 30 seconds or less, or 20 seconds or less at a temperature of about 5°C.

[0349] "Comprising," as used herein, refers to various ingredients, components, or steps that may be used in combination in practicing the present disclosure. Thus, the term "comprising" encompasses the more restrictive terms "consisting essentially of" and "consisting of." The compositions may comprise, consist essentially of, or consist of any of the required and optional elements disclosed herein. The inventions illustratively disclosed herein may be suitably practiced in the absence of any element or step not specifically disclosed herein.

[0350] All percentages, parts, and ratios referred to herein are based on the total dry weight, total solids, or article of the water-soluble film of the present disclosure, as the case may be, and all measurements are made at about 25°C unless otherwise specified.

[0351] All ranges set forth herein include all possible subset ranges and any combination of such subset ranges. By default, ranges include the recited endpoints unless otherwise stated. When a range of values ​​is provided, it is understood that each intervening value between the upper and lower limits of that range, and any other recited or intervening value within that recited range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limits in the recited range. When a recited range includes one or both of these limits, ranges excluding either or both of those included limits are also contemplated as part of the disclosure.

[0352] For any numerical value described herein, e.g., as part of a parameter of the described subject matter or a range associated with the described subject matter, alternatives forming part of the description are expressly contemplated as being functionally equivalent ranges surrounding the specific numerical value (e.g., for a dimension disclosed as "20 cP," an alternative embodiment considered is "about 40 cP"). Similarly, values ​​described by "about" expressly include the specific value itself as an alternative embodiment (e.g., for an endpoint described as "about 40," an alternative embodiment considered is "40").

[0353] As used herein, and unless otherwise stated, the terms "weight percent (wt.%)" and "weight percent (wt%)" are intended to refer to the composition of a particular element in "dry" (anhydrous) weight parts of the total water-soluble film, total solids, or article.

[0354] As used herein, and unless otherwise specified, the term "PHR" ("phr") is intended to refer to the parts of a composition of a particular element per 100 parts of total polymer in a water-soluble film or solution, or per 100 parts of PVOH and water-soluble starch combined.

[0355] The term "renewable carbon index ("RCI")" refers to the proportion (or percentage) of carbon atoms in the average structure of an anionic surfactant, hydrophilic syndetic, hydrophobic syndetic, or optionally a solvent that is derived from a feedstock other than, for example, petroleum or natural gas. Typically, when such components of a water-soluble film are produced from natural materials or sustainably, the RCI is greater than 0.75 or "75%" due to the use of materials found in nature or feedstocks derived from sustainable sources, such as plants, fungi, or algae, products of bacterial fermentation processes, or products of processing biomass derived from plants, fungi, or algae. A major challenge in formulating a water-soluble film with a desired high RCI is the selection of suitable materials that are economically viable while providing performance comparable to or better than conventional products.

[0356] Starch is a desirable high RCI material and is derived from raw material sources such as plants.

[0357] As used herein, the terms "substantially" or "essentially" refer to a specified majority, but not necessarily complete, of the specified substance, such as at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, or at least about 99.5% by weight of the specified substance, or in the range of about 80-100%, about 90-100%, about 95-100%, about 96-100%, about 97-100%, about 98-100%, or about 99-100% by weight of the specified substance.

[0358] As used herein, the term "bulk phase separation" refers to phase separation having phase domains less than about 2000 μm, or less than about 1000 μm, or less than about 900 μm, or less than about 800 μm, or less than about 700 μm, or less than about 600 μm, or less than about 500 μm, or less than about 400 μm, or less than about 300, or less than about 200 μm, or less than about 100 μm, or less than about 50 μm, or less than about 10 μm, or even less than about 1 μm.

[0359] As used herein, the term "consisting essentially of" limits the scope of a claim to the specified materials or steps and includes those that do not materially affect the basic and novel characteristics of the claimed invention.

[0360] As used herein, the term "consisting of" does not include any element, step, or ingredient not specified in a claim.

[0361] As used herein, the word "include" and variations thereof are intended to be open-ended, such that the recitation of items in a list does not exclude other similar items that may also be useful in the materials, compositions, devices, and methods of the present technology. Similarly, the terms "can" and "may" and variations thereof are intended to be open-ended, such that a recitation that an embodiment can comprise or may comprise particular elements or features does not exclude other embodiments of the present technology that do not contain those elements or features.

[0362] As used herein, the terms "comprising" or "comprises" are used in reference to compositions, methods, and their respective components that are essential to the invention, but are not limited to the inclusion of unspecified elements, whether essential or not. For example, the open-ended term "comprising," as synonymous with open-ended terms such as including, containing, or having, is used herein to describe and claim embodiments of the present technology; however, embodiments may alternatively be described using more restrictive terms such as "consisting of" or "consisting essentially of." Thus, for any given embodiment that lists materials, components, or process steps, the present technology also specifically includes embodiments that consist of or consist essentially of such materials, components, or processes, but do not include (consist essentially of) additional materials, components, or processes that affect the critical properties of the embodiment, even if such additional materials, components, or processes are not explicitly recited in this application.

[0363] As used herein, the term "consisting essentially of" refers to those elements required for a given embodiment. The term allows for the presence of additional elements that do not materially affect the basic and novel or functional characteristics of that embodiment of the invention.

[0364] The term "consisting of" refers to the compositions, methods, and their respective components described herein, which do not include any element not recited in that description of an embodiment.

[0365] Unless otherwise specified, all composition percentages as referenced herein are by weight of the total composition. The disclosure of ranges includes the endpoints, unless otherwise specified, and includes all different values ​​and subranges within the entire range. Thus, for example, a range of "A to B" or "about A to about B" includes A and B. The disclosure of a value and range of values ​​for a particular parameter (temperature, molecular weight, weight percentage, etc.) does not exclude other values ​​and ranges of values ​​useful herein. It is contemplated that two or more specific exemplified values ​​for a given parameter may define endpoints for a range of values ​​that may be claimed for the parameter. For example, if parameter X is exemplified herein as having a value A and also as having a value Z, it is contemplated that parameter X may have a range of values ​​from about A to about Z. Similarly, the disclosure of two or more ranges of values ​​for a parameter (whether such ranges are nested, overlapping, or distinct) is contemplated to encompass all possible combinations of value ranges that may be claimed using the endpoints of the disclosed ranges. For example, if a parameter X is exemplified herein as having a value in the range of 1 to 10, or 2 to 9, or 3 to 8, it is also contemplated that the parameter X can have other ranges of values, including 1 to 9, 1 to 8, 1 to 3, 1 to 2, 2 to 10, 2 to 8, 2 to 3, 3 to 10, and 3 to 9.

[0366] As used herein, "A" and "an" indicate the presence of "at least one" of an item, and where possible, multiple such items may be present.

[0367] When "about" is applied to a value, it indicates that calculation or measurement allows for some imprecision in the value (a certain approach to the accuracy of the value, roughly or reasonably close to the value, approximately). If, for any reason, the imprecision provided by "about" is not otherwise interpreted in the art in its ordinary sense, then "about" as used herein indicates at least the variation that can result from ordinary methods of measuring or using such parameters. As used herein, when used in connection with a value, the term "about" can refer to a ±10% variation from the value. Except in the operating examples, or where otherwise indicated, all numbers expressing quantities of components or reaction conditions used herein should be understood to be modified in all instances by the term "about."

[0368] As used herein, the terms "substantially no," "essentially free," or "substantially free," when used in reference to a particular ingredient, can mean that any of the ingredients present constitutes less than 10% by weight, e.g., less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.5%, or less than 0.1%.

[0369] As used herein, and unless otherwise specified, the term "partially" refers to a range of greater than 0% and less than 100%.

[0370] As used herein, the term "room temperature" may refer to a temperature in the range of 25°C ± 5°C, or 25°C ± 3°C.

[0371] As used herein, the term "substantially unchanged" by a process (e.g., reaction or heating) refers to a change in a property value of less than 20%. In embodiments, "substantially unchanged" refers to a change in a property value of less than 20%, less than 10%, less than 5%, less than 1%, less than 0.5%, or less than 0.1% compared to the property value before the process.

[0372] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0373] As used herein, and unless otherwise stated, the term "between" in the context of a range includes the two ends of the range.

[0374] The abbreviations "eg" or "ie" are used herein to indicate non-limiting examples. Thus, the abbreviations "eg" or "ie" are synonymous with the term "for example." As used herein, the terms "example" and "such as," particularly following a list of terms, are merely exemplary and illustrative and should not be construed as exclusive or comprehensive.

[0375] The foregoing description has been set forth for clarity of understanding only, and no unnecessary limitations should be understood therefrom, since modifications within the scope of the disclosure may be apparent to those skilled in the art.

[0376] All patents, publications, and references cited herein are incorporated by reference in their entirety. In the event of a conflict between the present disclosure and the incorporated patents, publications, and references, the present disclosure shall control.

Claims

1. A water-soluble film, Water-soluble polyvinyl alcohol (PVOH), and a water-soluble starch, the water-soluble starch has a cook percentage of at least about 5% by weight; the water-soluble starch is present in an amount ranging from about 5 to 65% by weight of the water-soluble film; A water-soluble film wherein the PVOH and the water-soluble starch are miscible or have phase domains in the water-soluble film that are less than 2000 μm.

2. 2. The water-soluble film according to claim 1, wherein the water-soluble polyvinyl alcohol (PVOH) is soluble in water within about 60 minutes at a temperature of about 60°C or less, or is soluble in water within about 60 minutes at a temperature of about 60°C, or is soluble in water within about 60 minutes at a temperature of about 40°C, or is soluble in water within about 60 minutes at a temperature of about 20°C, or is soluble in water within about 60 minutes at a temperature of about 10°C.

3. 2. The water-soluble film of claim 1, wherein the water-soluble polyvinyl alcohol (PVOH) is soluble in water within about 10 minutes at a temperature of about 40°C or less.

4. The water-soluble film of claim 1 , wherein the water-soluble film is a stand-alone film.

5. 10. The water-soluble film of claim 1, wherein the water-soluble film has a renewable carbon index (RCI) of greater than about 50%.

6. 10. The water-soluble film of claim 1, wherein the water-soluble starch comprises a substantially gelatinized starch.

7. 10. The water-soluble film of claim 1, wherein said water-soluble starch has a cook percentage of at least about 10% by weight.

8. 10. The water-soluble film of claim 1, wherein said water-soluble starch has a cook percentage of at least about 15% by weight.

9. The water-soluble starch is about 10 3 ~10 7 g / mol, or about 10 3 ~10 6 10. The water-soluble film of claim 1 having an average molecular weight in the range of g / mol.

10. The water-soluble starch is about 10 4 ~10 5 10. The water-soluble film of claim 9, wherein the average molecular weight is in the range of g / mole.

11. 10. The water-soluble film of claim 1, wherein the water-soluble starch comprises an amylose content ranging from 0 to 50% by weight of the water-soluble starch.

12. 2. The water-soluble film of claim 1, wherein the water-soluble starch has a Brookfield viscosity in a 5% by weight aqueous solution at about 20 rpm and about 87.8°C in the range of about 1 to 2000 cP.

13. 2. The water-soluble film of claim 1, wherein the water-soluble starch has a Brookfield viscosity in a 5% by weight aqueous solution at about 20 rpm and about 87.8°C in the range of about 2 to 100 cP.

14. 10. The water-soluble film of claim 1, wherein said water-soluble starch is present in an amount ranging from about 20 to 60% by weight of said water-soluble film.

15. 10. The water-soluble film of claim 1, wherein the water-soluble film dissolves in water at a temperature of about 15°C with less than 5.0% by weight residue by Wright of the water-soluble film at a specified temperature determined according to the Accelerated Quantitative Residue Evaluation Test Method.

16. The water-soluble film of claim 1 , wherein the water-soluble starch comprises a non-modified starch.

17. 10. The water-soluble film of claim 1, wherein the water-soluble starch comprises a nonionic group-modified starch having a modification level in the range of about 0.1 to 10 mole %.

18. 18. The water-soluble film of claim 17, wherein said water-soluble starch comprises said nonionic group-modified starch having said modification level in the range of about 1 to 5 mole %.

19. 2. The water-soluble film according to claim 1, wherein the water-soluble starch comprises a cationic group-modified starch having a degree of modification in the range of about 0.01 to 10 mole %.

20. 20. The water-soluble film according to claim 19, wherein the water-soluble starch comprises the cationic group-modified starch having the degree of modification in the range of about 0.1 to 1 mole %.

21. The cationic group-modified starch comprises a cationic quaternary ammonium group-modified starch having a structure of Formula A, wherein R 1 , R 2 , and R 3 are each independently H or C 1 ~C 10 Alkyl or C 1 ~C 10 is a hydroxyalkyl group, and R 4 optionally substituted with one or more heteroatom-containing groups, 1 ~C 10 Alkylene or C 1 ~C 10 is a hydroxyalkylene group, and X is R 4 21. The water-soluble film of claim 20, wherein the linkage is an ether or ester linkage connecting the linkage to the starch. 【Chemistry 1】

22. The R 1 , R 2 , and R 3 But the same C 1 ~C 4 is an alkyl group, and R 4 But C 1 ~C 6 22. The water-soluble film of claim 21, wherein the group is a hydroxyalkylene group.

23. R 4 But C 3 ~C 6 22. The water-soluble film of claim 21, wherein the group is a hydroxyalkylene group.

24. R 1 , R 2 , and R 3 are each a methyl group, and R 4 But C 3 ~C 6 22. The water-soluble film of claim 21, wherein the group is a hydroxyalkylene group.

25. 22. The water-soluble film of claim 21, wherein the cationic quaternary ammonium groups are quaternary 2-hydroxy-3-(trimethylammonium)propyl, 2-diethylaminoethyl, or 2,3-epoxypropyltrimethylammonium groups, or combinations thereof.

26. 22. The water-soluble film of claim 21, wherein the cationic group modified starch comprises a cationic trimethylammonium group modified starch.

27. 22. The water-soluble film of claim 21, wherein the cationic group-modified starch comprises starch modified with a 2-diethylaminoethyl salt, a 2,3-epoxypropyltrimethylammonium salt, or a 2-hydroxy-3-(trimethylammonium)propyl salt, or a combination thereof.

28. 28. The water-soluble film according to claim 27, wherein the 2-diethylaminoethyl salt comprises 2-diethylaminoethyl halide, the 2,3-epoxypropyltrimethylammonium salt comprises 2,3-epoxypropyltrimethylammonium halide, and the 2-hydroxy-3-(trimethylammonium)propyl salt comprises 2-hydroxy-3-(trimethylammonium)propyl halide.

29. 28. The water-soluble film according to claim 27, wherein the 2-diethylaminoethyl salt comprises 2-diethylaminoethyl chloride, the 2,3-epoxypropyltrimethylammonium salt comprises 2,3-epoxypropyltrimethylammonium chloride, and the 2-hydroxy-3-(trimethylammonium)propyl salt comprises 2-hydroxy-3-(trimethylammonium)propyl chloride.

30. 20. The water-soluble film according to claim 19, wherein the water-soluble starch further comprises unmodified starch and / or nonionic group-modified starch having a modification level ranging from about 0.1 to 10 mol %, or from about 1 to 5 mol %.

31. The water-soluble film according to claim 1 , wherein the water-soluble polyvinyl alcohol comprises unmodified polyvinyl alcohol, anionic group-modified polyvinyl alcohol, cationic group-modified polyvinyl alcohol, or a combination thereof.

32. 2. The water-soluble film according to claim 1, wherein the polyvinyl alcohol comprises an anionic group-modified polyvinyl alcohol having a degree of modification in the range of about 0.1 to 10 mol %.

33. 33. The water-soluble film according to claim 32, wherein the anionic group-modified polyvinyl alcohol has a degree of modification in the range of about 1.0 to 5.0 mol %.

34. 34. The water-soluble film of claim 33, wherein the anionic group-modified polyvinyl alcohol comprises polyvinyl alcohol modified with itaconic acid, monomethyl maleate (MMM), methyl acrylate (MA), aminopropyl sulfonate, maleic acid, maleic anhydride, n-vinylpyrrolidone, n-vinylcaprolactam, derivatives of any of the foregoing, or combinations thereof.

35. 35. The water-soluble film of claim 34, wherein the anionic group-modified polyvinyl alcohol comprises polyvinyl alcohol modified with monomethyl maleate, methyl acrylate, or a combination thereof.

36. 10. The water-soluble film of claim 1, further comprising a plasticizer present in the range of about 5.0 to 40.0 weight percent by weight of the water-soluble film.

37. 37. The water-soluble film of claim 36, wherein the plasticizer comprises sorbitol, glycerin, glycerol, diglycerol, propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols of MW up to 400, 2-methyl-1,3-propanediol, ethanolamine, trimethylolpropane (TMP), polyether polyols, isomalt, maltitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol, mannitol, sugar alcohols, or combinations thereof.

38. 37. The water-soluble film of claim 36, wherein the plasticizer comprises a bio-derived plasticizer.

39. 39. The water-soluble film of claim 38, wherein the bio-based plasticizer comprises glycerin and / or sorbitol.

40. The water-soluble film of claim 1 further comprising a surfactant.

41. 41. The water-soluble film of claim 40, wherein the surfactant comprises a linear aliphatic ethoxylated surfactant.

42. The linear fatty ethoxylated surfactant is selected from the group consisting of laureth-6 carboxylic acid, C 9 ~C 15 42. The water-soluble film of claim 41, comprising ethylene oxide, ethylene oxide, or a combination thereof.

43. 10. The water-soluble film of claim 1, further comprising one or more of an antifoaming agent, an antioxidant, a disinfectant, an antiblocking agent, a filler, sodium metabisulfite, sodium hydroxide, a matting agent, a slip agent, a dispersing agent, or a combination thereof.

44. 2. The water-soluble film according to claim 1, wherein the water-soluble film has a dissolution time in water in the range of 30 to 300 seconds at a temperature in the range of 5 to 95° C. according to MSTM-205.

45. 45. The water-soluble film of claim 44, wherein the dissolution time is in the range of 30 to 300 seconds at temperatures of about 10°C and about 5°C.

46. 10. The water-soluble film of claim 1, wherein the water-soluble film has a maximum stress of at least about 10 MPa.

47. 10. The water-soluble film of claim 1, wherein the water-soluble film has a strain at break of at least about 150%.

48. 2. The water-soluble film of claim 1, wherein the weight ratio of said polyvinyl alcohol to said water-soluble starch is in the range of about 10:1 to about 1:

8.

49. 49. The water-soluble film of claim 48, wherein the weight ratio of the polyvinyl alcohol to the water-soluble starch is in the range of about 9:1 to about 1:

7.

50. 50. The water-soluble film of claim 49, wherein the weight ratio of the polyvinyl alcohol to the water-soluble starch is in the range of about 5:1 to about 1:6, or about 4:1 to 1:2, or about 4:1 to about 1:

1.

51. 10. The water-soluble film of claim 1, wherein the polyvinyl alcohol has a degree of hydrolysis ranging from about 74 mole % to about 99 mole %.

52. 52. The water-soluble film of claim 51, wherein the polyvinyl alcohol has the degree of hydrolysis ranging from about 74 mole % to about 91 mole %.

53. A water-soluble film, a water-soluble anionic group-modified polyvinyl alcohol (PVOH) having a degree of modification in the range of about 1 to 5 mol %; a water-soluble cationic group-modified starch having a degree of modification in the range of about 0.05 to 5 mole % and a Brookfield viscosity at 20 rpm and 87.8°C in a 5 wt % aqueous solution in the range of about 1 to 200 cP; the cationic group-modified starch has a cook percentage of at least about 5% by weight; the cationic group-modified starch is present in an amount ranging from about 20 to 60 weight percent by weight of the water-soluble film; A water-soluble film, wherein the anionic group-modified PVOH and the cationic group-modified starch are miscible in the water-soluble film or have phase domains of less than 2000 μm.

54. 2. The aqueous solution for forming the water-soluble film according to claim 1, wherein the aqueous solution comprises: Water-soluble polyvinyl alcohol (PVOH), Water-soluble starch, water, the water-soluble starch has a cook percentage of at least about 5% by weight; the aqueous solution having a total solids content of at least 15% by weight, by weight of the aqueous solution; the water-soluble starch is present in an amount ranging from about 5 to 65% by weight of the total solids; 1. An aqueous solution wherein the water-soluble polyvinyl alcohol (PVOH) and the water-soluble starch are miscible or have no bulk phase separation in the aqueous solution by visual inspection at a temperature in the range of about 20 to 100° C. for at least 24 hours.

55. 55. The aqueous solution of claim 54, wherein the water-soluble polyvinyl alcohol (PVOH) is soluble in water within about 60 minutes at a temperature of about 60°C or less, or is soluble in water within about 60 minutes at a temperature of about 60°C, or is soluble in water within about 60 minutes at a temperature of about 40°C, or is soluble in water within about 60 minutes at a temperature of about 20°C, or is soluble in water within about 60 minutes at a temperature of about 10°C.

56. 56. The aqueous solution of claim 55, wherein the water-soluble polyvinyl alcohol (PVOH) is soluble in water within about 10 minutes at a temperature of about 40° C. or less.

57. 55. The aqueous solution of claim 54, wherein the total solids content has a renewable carbon index (RCI) of at least about 50%.

58. 55. The aqueous solution of claim 54, wherein the water-soluble starch comprises a substantially gelatinized starch.

59. 55. The aqueous solution of claim 54, wherein said water-soluble starch has a cook percentage of at least about 10% by weight.

60. 55. The aqueous solution of claim 54, wherein said water-soluble starch has a cook percentage of at least about 15% by weight.

61. The water-soluble starch is about 10 3 ~10 7 g / mol, or about 10 3 ~10 6 55. The aqueous solution of claim 54, having an average molecular weight in the range of g / mol.

62. The water-soluble starch is about 10 4 ~10 5 62. The aqueous solution of claim 61, wherein the average molecular weight is in the range of g / mol.

63. 55. The aqueous solution of claim 54, wherein the water-soluble starch comprises an amylose content in the range of 0 to 50% by weight of the water-soluble starch.

64. 64. The aqueous solution of claim 63, wherein the water-soluble starch comprises an amylose content in the range of 0 to 30% by weight of the water-soluble starch.

65. 55. The aqueous solution of claim 54, wherein the water-soluble starch has a Brookfield viscosity at about 20 rpm and about 87.8°C for a 5 wt % aqueous solution in the range of about 1 to 2000 cP.

66. 55. The aqueous solution of claim 54, wherein the water-soluble starch has a Brookfield viscosity at about 20 rpm and about 87.8°C for a 5 wt % aqueous solution in the range of about 2 to 100 cP.

67. 55. The aqueous solution of claim 54, wherein the aqueous solution has a total solids content of at least 25% by weight of the aqueous solution.

68. 55. The aqueous solution of claim 54, wherein said aqueous solution has a total solids content of at least 32% by weight by weight of said aqueous solution.

69. 55. The aqueous solution of claim 54, wherein the aqueous solution has the total solids content in the range of about 25 to 40% by weight of the aqueous solution.

70. 55. The aqueous solution of claim 54, wherein the water soluble starch is present in an amount ranging from about 15 to 65% by weight of the total solids.

71. 71. The aqueous solution of claim 70, wherein the water soluble starch is present in an amount ranging from about 25 to 60% by weight of the total solids.

72. 55. The aqueous solution of claim 54, wherein the water-soluble starch comprises unmodified starch, nonionic group modified starch, anionic group modified starch, cationic group modified starch, or a combination thereof.

73. 55. The aqueous solution of claim 54, wherein the water-soluble starch comprises a cationic group-modified starch having a degree of modification in the range of about 0.01 to 10 mole %.

74. 55. The aqueous solution of claim 54, wherein the water-soluble starch comprises a cationic group-modified starch having a degree of modification in the range of about 0.1 to 1 mole %.

75. The cationic group modified starch comprises a cationic quaternary ammonium group modified starch having the structure of Formula A, wherein R 1 , R 2 , and R 3 are each independently H or C 1 ~C 10 Alkyl or C 1 ~C 10 is a hydroxyalkyl group, and R 4 optionally substituted with one or more heteroatom-containing groups, 1 ~C 10 Alkylene or C 1 ~C 10 is a hydroxyalkylene group, and X is R 4 is an ether or ester bond connecting the hydroxyl group to the starch. 【Chemistry 2】

76. The R 1 , R 2 , and R 3 But the same C 1 ~C 4 is an alkyl group, and R 4 But C 1 ~C 6 76. The aqueous solution of claim 75, wherein the alkylene group is a hydroxyalkylene group.

77. R 4 But C 3 ~C 6 76. The aqueous solution of claim 75, wherein the alkylene group is a hydroxyalkylene group.

78. R 1 , R 2 , and R 3 are each a methyl group, and R 4 But C 3 ~C 6 76. The aqueous solution of claim 75, wherein the alkylene group is a hydroxyalkylene group.

79. 76. The aqueous solution of claim 75, wherein the cationic quaternary amine groups are quaternary 2-hydroxy-3-(trimethylammonium)propyl, 2-diethylaminoethyl, 2,3-epoxypropyltrimethylammonium groups, or combinations thereof.

80. 76. The aqueous solution of claim 75, wherein the cationic group modified starch comprises a cationic trimethylammonium group modified starch.

81. 76. The aqueous solution of claim 75, wherein the cationic group modified starch comprises starch modified with a 2-diethylaminoethyl salt, a 2,3-epoxypropyltrimethylammonium salt, or a 2-hydroxy-3-(trimethylammonium)propyl salt, or a combination thereof.

82. 82. The aqueous solution of claim 81, wherein the 2-diethylaminoethyl salt comprises a 2-diethylaminoethyl halide, the 2,3-epoxypropyltrimethylammonium salt comprises a 2,3-epoxypropyltrimethylammonium halide, and the 2-hydroxy-3-(trimethylammonium)propyl salt comprises a 2-hydroxy-3-(trimethylammonium)propyl halide.

83. 82. The aqueous solution of claim 81, wherein the 2-diethylaminoethyl salt comprises 2-diethylaminoethyl chloride, the 2,3-epoxypropyltrimethylammonium salt comprises 2,3-epoxypropyltrimethylammonium chloride, and the 2-hydroxy-3-(trimethylammonium)propyl salt comprises 2-hydroxy-3-(trimethylammonium)propyl chloride.

84. 74. The aqueous solution of claim 73, wherein the water-soluble starch comprises a combination of the cationic group-modified starch and an unmodified starch.

85. 55. The aqueous solution of claim 54, wherein the polyvinyl alcohol (PVOH) comprises unmodified polyvinyl alcohol, anionic group-modified polyvinyl alcohol, cationic group-modified polyvinyl alcohol, or a combination thereof.

86. 86. The aqueous solution of claim 85, wherein the polyvinyl alcohol comprises the anionic group-modified polyvinyl alcohol having a degree of modification in the range of about 0.1 to 10 mol %.

87. 86. The aqueous solution of claim 85, wherein the polyvinyl alcohol comprises the anionic group-modified polyvinyl alcohol having a degree of modification in the range of about 1 to 5 mol %.

88. 88. The aqueous solution of claim 87, wherein the anionic group-modified polyvinyl alcohol comprises polyvinyl alcohol modified with itaconic acid, monomethyl maleate (MMM), methyl acrylate (MA), aminopropyl sulfonate, maleic acid, maleic anhydride, n-vinylpyrrolidone, n-vinylcaprolactam, derivatives of any of the foregoing, or combinations thereof.

89. 88. The aqueous solution of claim 87, wherein the anionic group-modified polyvinyl alcohol comprises polyvinyl alcohol modified with monomethyl maleate, methyl acrylate, or a combination thereof.

90. 55. The aqueous solution of claim 54, further comprising a plasticizer present in the range of about 5 to 40 weight percent by weight of the total solids.

91. 91. The aqueous solution of claim 90, wherein the plasticizer comprises sorbitol, glycerin, glycerol, diglycerol, propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols up to MW 400, 2-methyl-1,3-propanediol, ethanolamine, trimethylolpropane (TMP), polyether polyols, isomalt, maltitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol, mannitol, sugar alcohols, or combinations thereof.

92. 91. The aqueous solution of claim 90, wherein the plasticizer comprises a bio-derived plasticizer.

93. 93. The aqueous solution of claim 92, wherein the bio-based plasticizer comprises glycerin and / or sorbitol.

94. 91. The aqueous solution of claim 90, wherein the plasticizer does not include trimethylolpropane (TMP).

95. 55. The aqueous solution of claim 54, further comprising a surfactant.

96. 96. The aqueous solution of claim 95, wherein the surfactant comprises a linear aliphatic ethoxylated surfactant.

97. The linear fatty ethoxylated surfactant is selected from the group consisting of laureth-6 carboxylic acid, C 9 ~C 15 97. The aqueous solution of claim 96, comprising ethylene oxide, or a combination thereof.

98. 55. The aqueous solution of claim 54, further comprising at least one of an antifoaming agent, an antioxidant, a disinfectant, an antiblocking agent, a filler, sodium metabisulfite, sodium hydroxide, a matting agent, a slip agent, a dispersing agent, or a combination thereof.

99. 55. The aqueous solution of claim 54, wherein the total solids content is in the range of about 28 to 35% by weight of the aqueous solution.

100. 55. The aqueous solution of claim 54, wherein the weight ratio of said polyvinyl alcohol to said water-soluble starch is in the range of about 10:1 to about 1:

8.

101. 101. The aqueous solution of claim 100, wherein the weight ratio of the polyvinyl alcohol to the water-soluble starch is in the range of about 6:1 to about 1:

6.

102. 10. A method for forming the water-soluble film of claim 1, comprising: Casting the aqueous solution of claim 54 onto a substrate at a specified thickness; and drying the water from the aqueous casting solution to form said water-soluble film.

103. An article, 10. An article comprising a pouch made from the water-soluble film of claim 1 defining an interior pouch volume.

104. 104. The article of claim 103, further comprising a chemical composition contained within said internal pouch volume.

105. 105. The article of claim 104, wherein the chemical composition is a household care composition.

106. 106. The article of claim 105, wherein the household care composition is a liquid laundry detergent or a dishwashing detergent.

107. 104. The article of claim 103, wherein the pouch has a compressive strength of at least about 300 N.

108. 108. The article of claim 107, wherein the pouch has a compressive strength of at least about 600 N.

109. 104. The article of claim 103, wherein the pouch has a matte-to-matte type seal.

110. 104. The article of claim 103, wherein the pouch has a release time of 300 seconds or less after mixing in water at a temperature of about 15°C according to MSTM-126.

111. 111. The article of claim 110, wherein the release time ranges from 30 to 150 seconds after mixing in water at about room temperature.

112. 18. The water-soluble film according to claim 17, wherein the nonionic group-modified starch is a hydroxyethyl-modified starch.

113. 113. The water-soluble film of claim 112, wherein the hydroxyethyl-modified starch is present in the film in an amount ranging from about 10 PHR to about 80 PHR, or from about 10 PHR to about 40 PHR.

114. 114. The water-soluble film of claim 113, characterized in that it has a strain at break of greater than 300% as measured according to the Strain at Break Test.

115. The water-soluble film of claim 1 , wherein the water-soluble polyvinyl alcohol comprises a bio-based polyvinyl alcohol.

116. 116. The water-soluble film of claim 115, wherein the ratio (by weight) of the amount of biobased polyvinyl alcohol to the amount of non-biologically based polyvinyl alcohol is in the range of about 99:1 to about 1:99, or about 95:5 to about 5:99, or about 80:20 to about 20:80, or about 70:30 to about 30:70, or about 60:40 to about 40:60.

Images