阅读说明：本技术 包括水溶性层和气相沉积无机涂层的膜 (Film comprising a water-soluble layer and a vapor-deposited inorganic coating ) 是由 艾米莉·夏洛特·博斯韦尔 斯里尼瓦斯·克里希那斯瓦米·米尔 维塞林·尼科洛夫·沙诺夫 拉希特· 于 2018-06-22 设计创作，主要内容包括：本发明公开了一种包括水溶性层和气相沉积无机涂层的膜。该膜表现出增强的阻隔性能。无机涂层包含金属氧化物,并且包含在无机涂层中的多个微裂缝。(A film comprising a water-soluble layer and a vapor-deposited inorganic coating is disclosed. The film exhibits enhanced barrier properties. The inorganic coating includes a metal oxide and includes a plurality of microcracks in the inorganic coating.)

1. A membrane, comprising:

a layer of water-soluble polymer material; and

a vapor deposited inorganic coating disposed on a surface of the layer, wherein the inorganic coating comprises a metal oxide; and

wherein the inorganic coating comprises a plurality of microcracks in the inorganic coating.

2. The film of claim 1, wherein the water-soluble polymer material comprises polyvinyl alcohol.

3. The film of any one of claims 1 or 2, wherein the inorganic coating consists of a metal oxide.

4. The membrane of any one of claims 1 to 3, wherein the metal oxide comprises one or more of alumina, silica, magnesia, and titania.

5. The film according to any one of claims 1 to 4, wherein the inorganic coating is directly attached to the surface of the layer.

6. The film of any one of claims 1 to 5, wherein a surface of the layer is at least partially ablated.

7. The film of claim 6, wherein the surface of the layer is ablated by a helium-oxygen plasma.

8. The film of claim 6, wherein the surface of the layer is ablated by an argon-oxygen plasma.

9. The film of any one of claims 1 to 8, wherein each of the microcracks has a total length of from 5 to 50 microns.

10. The film of any one of claims 1-9, wherein each of the microcracks has an overall width of 1 micron or less.

11. The film of any one of claims 1-10, wherein each of the microcracks extends entirely through the inorganic coating.

12. The film of any one of claims 1 to 10, wherein each of the microcracks extends only partially through the inorganic coating.

13. The film of any one of claims 1 to 12, wherein the inorganic coating comprises a plurality of discrete regions, each of the discrete regions being defined by some or all of the microcracks.

14. The film of claim 13, wherein each of the discrete regions has a maximum linear dimension of 100 microns or less.

15. The film of claim 13, wherein each of the discrete regions has a maximum linear dimension of 35 microns or less.

16. An article comprising the film of claim 1, wherein the film forms at least a portion of a package for the article.

17. The article of claim 16, wherein the article is a soluble unit dose article.

Technical Field

The present disclosure generally relates to films comprising a water-soluble layer and a vapor-deposited inorganic coating.

Background

Polymeric films including water-soluble components are useful in the construction of various articles and packages. For example, such polymer films may be used to: health and hygiene products, including disposable diapers and training pants, incontinence articles, and feminine care products (e.g., pads and liners); medical products such as bags for bodily fluids and/or waste (e.g. ostomy pouches); and other household items such as trash bags, laundry bags, dirty-basket liners, and the like. Such polymer films may also be used to form packaging for various compounds. For example, the polymeric film may be advantageously formed into packaging for detergents, agrochemicals, water treatment chemicals, natural cleaning products containing bacteria/microorganisms, dyes, food, laundry, embroidery, beauty, personal care products, shaving products, healthcare products, and pharmaceuticals. Packaging can simplify the dispensing, pouring, dissolving, and/or dosing of the contents contained in the package by eliminating the need to measure the contents, directly handle the contents, or dispense the contents. An example of a particular type of package that is advantageously formed from a water-soluble polymer film is a soluble unit dose article. The soluble unit dose articles are useful for facilitating the delivery of a predetermined amount of one or more compositions, such as a cleaning detergent, contained in the article. Soluble packaging is also useful to address some of the problems associated with the entry of waste into waterways and oceans. For example, most packages made from soluble films do not leave any waste in waterways or oceans because the package eventually dissolves and the remaining polymer biodegrades. However, known polymeric films that include water-soluble components suffer from a number of impairments, including migration of compounds and elements through the film. In addition, splashing water onto the package prior to intentional contact, such as with wet hands during handling, can damage or weaken the package, resulting in accidental leakage. Such damage can limit the contents and usability of articles and packages formed from polymeric films.

Disclosure of Invention

According to one embodiment, a film includes a layer of water-soluble polymeric material and a first vapor-deposited inorganic coating bonded to at least one surface of the layer of water-soluble polymeric material. The first vapor-deposited inorganic coating comprises a metal oxide. The first vapor-deposited inorganic coating defines a plurality of microcracks extending along a surface of the inorganic coating.

According to another embodiment, the film comprises a water-soluble polyvinyl alcohol layer and a vapor deposited inorganic coating bonded to at least one surface of the polyvinyl alcohol layer. The vapor deposited inorganic coating comprises a metal oxide and has a thickness of about 2 nanometers to about 1000 nanometers. The vapor deposited inorganic coating defines a plurality of microcracks extending along a surface of the inorganic coating. Each of the plurality of microcracks has a length of about 5 to about 50 microns. The film has a thickness of about 76 microns and exhibits a thickness of about 2,000 g/(m) when measured according to the water vapor transmission rate test method²Day) to about 5,500 g/(m)²Day) water vapor transmission rate.

According to another embodiment, a film includes a water-soluble polyvinyl alcohol layer and a vapor deposition inorganic bonded to at least one surface of the polyvinyl alcohol layerAnd (4) coating. The vapor deposited inorganic coating comprises a metal oxide and has a thickness of about 2 nanometers to about 1000 nanometers. The vapor deposited inorganic coating defines a plurality of microcracks extending along a surface of the inorganic coating. Each of the plurality of microcracks has a length of about 5 to about 50 microns. The film has a thickness of about 76 microns and exhibits a thickness of about 7.75 cc/(m) when measured according to the oxygen transmission rate test method²Day) [0.5cc/(100 in)²Sky)]To about 38.75 cc/(m)²Day) [2.5cc/(100 in)²Sky)]The oxygen transmission rate of (2).

According to another embodiment, a method of forming a film comprises: providing a layer of water-soluble polymer material; vapor depositing an inorganic coating onto at least one surface of the layer of water-soluble polymeric material; and forming a plurality of microcracks extending along the surface of the inorganic coating. The inorganic coating comprises a metal oxide.

Drawings

Fig. 1 depicts a cross-sectional view of a membrane according to an embodiment.

Fig. 2 is a photomicrograph showing a vapor deposited inorganic coating having a plurality of microcracks.

Fig. 3 is a photomicrograph at a greater magnification of the vapor deposited inorganic coating shown in fig. 2.

Fig. 4 is a photomicrograph of the vapor deposited inorganic coating depicted in fig. 2 and 3 after being stretched 150%.

Fig. 5 is a photomicrograph at greater magnification of the vapor deposited inorganic coating shown in fig. 4.

Fig. 6 is a photomicrograph at greater magnification of the vapor deposited inorganic coating shown in fig. 5.

Fig. 7A shows a top view of a unit dose article with a flat top, a circular bottom and a compartment according to one example.

Fig. 7B shows a side view of the unit dose article of fig. 7A.

FIG. 7C shows an end view of the unit dose article of FIG. 7A.

FIG. 7D shows a cross-sectional end view of the unit dose article of FIG. 7A.

Fig. 8A shows a top view of a unit dose article with a rounded top, a rounded bottom and a compartment according to one example.

Fig. 8B shows a side view of the unit dose article of fig. 8A.

FIG. 8C shows an end view of the unit dose article of FIG. 8A.

FIG. 8D shows a cross-sectional end view of the unit dose article of FIG. 8A.

Figure 9A shows a top view of an exemplary soluble unit dose article with a rounded top, a rounded bottom and two overlapping compartments, according to one embodiment.

Fig. 9B shows a side view of the unit dose article of fig. 9A.

FIG. 9C shows an end view of the unit dose article of FIG. 9A.

FIG. 9D shows a cross-sectional end view of the unit dose article of FIG. 9A.

Fig. 10A shows an exemplary soluble unit dose article with a rounded top, a flat bottom and two side-by-side compartments according to one embodiment.

Fig. 10B shows a side view of the unit dose article of fig. 10A.

FIG. 10C shows an end view of the unit dose article of FIG. 10A.

FIG. 10D shows a cross-sectional end view of the unit dose article of FIG. 10A.

Fig. 11A shows a soluble unit dose article having a rounded top, a rounded bottom and two smaller side-by-side compartments, each compartment overlapping a larger bottom compartment, according to one example.

FIG. 11B shows a side view of the unit dose article of FIG. 11A.

FIG. 11C shows an end view of the unit dose article of FIG. 11A.

FIG. 11D shows a cross-sectional end view of the unit dose article of FIG. 11A.

Detailed Description

Definition of

As used herein, the term "about," when modifying a particular value, refers to a range equal to the particular value plus or minus twenty percent (+/-20%). For any of the embodiments disclosed herein, any disclosure of a particular value can also be understood to be approximately equal to the disclosed range of that particular value (i.e., +/-20%) in various alternative embodiments.

As used herein, the term "about" when modifying a particular value refers to a range equal to the particular value plus or minus fifteen percent (+/-15%). For any of the embodiments disclosed herein, any disclosure of a particular value can also be understood to be approximately equal to the disclosed range for that particular value (i.e., +/-15%) in various alternative embodiments.

As used herein, the term "substantially" when modifying a particular value refers to a range equal to the particular value plus or minus five percent (+/-5%). For any of the embodiments disclosed herein, any disclosure of a particular value can also be understood to be approximately equal to the disclosed range for that particular value (i.e., +/-5%) in various alternative embodiments.

As used herein, the term "substantially" when used in reference to a particular value refers to a range equal to the particular value plus or minus ten percent (+/-10%). For any of the embodiments disclosed herein, any disclosure of a particular value can also be understood to be approximately equal to the disclosed range for that particular value (i.e., +/-10%) in various alternative embodiments.

As used herein, the term "copolymer" refers to a polymer formed from two or more types of monomeric repeat units. As used herein, the term "copolymer" also encompasses terpolymers, such as terpolymers having a distribution of vinyl alcohol monomer units, vinyl acetate monomer units, and butylene glycol monomer units. If the copolymer is substantially completely hydrolyzed, vinyl acetate monomer units may be substantially absent.

Film comprising a water-soluble layer and a vapor-deposited inorganic coating

As will be described herein, films are disclosed that include a water-soluble layer and a vapor-deposited inorganic coating. For example, a cross-sectional view of an exemplary membrane is depicted in fig. 1. As shown in fig. 1, the film 100 may include a water-soluble layer 105 formed of a water-soluble polymer material and a vapor-deposited inorganic coating 115 bonded to one surface of the water-soluble layer 105.

It is understood that the membranes described herein can have many variations. For example, as depicted in fig. 1, the film may include a vapor deposited inorganic coating on only one surface of the water-soluble layer, or in certain embodiments (not shown), the film may have a vapor deposited inorganic coating on both surfaces of the water-soluble layer. Additional layers, such as a marker layer, may also be included in certain embodiments.

In certain embodiments, multiple coatings may be vapor deposited. For example, in certain embodiments, the film may include a water-soluble layer and a plurality of vapor deposited inorganic coatings.

In certain embodiments, the film may comprise more than one water-soluble layer. For example, in various embodiments, the films described herein can include two water-soluble layers, three water-soluble layers, five water-soluble layers, or more water-soluble layers.

Vapor deposition of inorganic coatings

It has been found that the application of a vapor deposited inorganic coating can improve the film properties and performance in a variety of ways. For example, films including vapor deposited inorganic coatings can exhibit desirable chemical and physical properties, including improved barrier properties, controlled dissolution times, and reduced stickiness, as compared to uncoated films. These improved properties may make such films useful in forming products (including water-soluble articles and water-soluble packaging materials) that are typically formed from uncoated water-soluble films. However, it will be appreciated that the films described herein may also be used in other articles and applications due to the superior mechanical and chemical properties exhibited by the films.

In certain embodiments, suitable vapor deposition inorganic coatings can be formed from metal oxides and related compounds. As used herein, metal oxides include aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, metalloid oxides such as silicon oxide, silicon oxycarbide, and silicon nitride. It is understood that various processes may be used to vapor deposit the metal oxide. For example, in various embodiments, the metal oxide coating may be vapor deposited using a chemical vapor deposition process or a physical vapor deposition process. In general, most chemical vapor deposition processes may be suitable due to the stability of the metal oxide and metal oxide precursors. In these oxide chemistries, a variety of stoichiometries are possible, and when referring to oxides, any possible stoichiometry is meant.

In certain embodiments, the vapor deposited inorganic coating may be formed using a plasma assisted chemical vapor deposition process. Plasma-assisted chemical vapor deposition is a modified chemical vapor deposition process in which the thermal activation energy is provided by a high-energy plasma, rather than direct heating. A plasma-assisted chemical vapor deposition process useful for the films described herein includes the steps of: vaporizing the metal oxide precursor; introducing a plasma to thermally modify the precursor and form an intermediate compound; and cooling the intermediate compound to form a coating on at least one surface of the water-soluble layer. Plasma-assisted chemical vapor deposition processes can be particularly advantageous because such processes can provide the thermal energy required for the vapor deposition process without melting or otherwise damaging the water-soluble layer.

To form the metal oxide coating, various precursor compounds can be vaporized. For example, tetramethylsilane ("TMS") and trimethylaluminum ("TMA") can be vaporized to form silica ("SiO"), respectively₂") and alumina (" Al₂O₃") coating. Hexamethyldisilazane ("HMDS"), hexamethyldisiloxane ("HMDSO"), and tetraethylorthosilicate ("TEOS") can be similarly vaporized to form silicon oxide ("SiO_x") coating.

In certain embodiments, an atomic layer chemical vapor deposition process may alternatively be used. Atomic layer deposition is a chemical vapor deposition process based on sequential self-saturating surface reactions. In such a process, a metal oxide precursor is pulsed into a chemical vapor deposition chamber and deposited layer by layer.

In certain embodiments, a physical vapor deposition process may alternatively be utilized. Physical vapor deposition processes differ from chemical vapor deposition processes in that they instead use physical processes such as heating or sputtering to generate vapor from a solid precursor. The vaporized compound is adsorbed onto the substrate to directly form a thin layer. In certain embodiments, suitable physical vapor deposition processes for forming the inorganic layer can include sputtering, such as magnetron sputtering, thermal evaporation, and electron beam ("e-beam") evaporation.

It will be appreciated that the physical vapour deposition process does not require the use of precursor compounds, but rather directly vaporises the material of the final coating. For example, the alumina coating may be formed on the surface of the water-soluble layer by sputtering or electron beam evaporation of solid alumina granules or granules.

In certain embodiments, one example of an apparatus that can be used to form an Al2O3 coating by physical vapor deposition is a Temescal FC 1800E-beam electron evaporator. In this apparatus, the distance between the target and the substrate was about 45cm, the energy of the electron beam was 450W (950 KV at 50 uA), and the chamber was evacuated to about 1X 10 before starting deposition^-5The vacuum of the tray.

It has been unexpectedly found that in certain embodiments, it can be advantageous for the vapor deposited inorganic coating to have a plurality of microcracks extending along at least the surface of the inorganic coating. Without being bound by theory, it is theorized that the microcracks can maintain excellent water solubility of the films described herein by allowing water to penetrate the inorganic coating in a controlled manner and ultimately dissolve the underlying water-soluble layer. Unexpectedly, the microcracks do not interfere with certain benefits, such as improved barrier properties and reduced tack imparted by vapor deposited inorganic coatings.

Generally, one or more of a variety of processes or controlled parameters can be used to form a plurality of microcracks in a vapor deposited inorganic coating. For example, certain processing conditions may be used to form microcracks in vapor deposited inorganic coatings. In certain embodiments, the processing conditions may be mechanical processing, such as stretching, bending, or out-of-plane deformation. It is understood that the film may be mechanically treated during web processing of the film or during the process used to manufacture the article. For example, if the unit dose article is formed from a film as described herein, the stretching resulting from the formation of the soluble unit dose article may be used as a mechanical treatment.

Additionally or alternatively, certain parameters of the vapor deposited inorganic coating, such as the thickness of the coating, may be selected to favor the formation of microcracks. It has been unexpectedly found that relatively thicker inorganic coatings can have a greater tendency to form microcracks. For example, a coating having a thickness of about 300 nanometers or greater may have a greater tendency to crack or develop microcracks after application of a mechanical treatment.

In certain embodiments, the microcracks can have a length of about 2.5 microns to about 100 microns, or any integer value between about 2.5 microns to about 100 microns, or any range formed by any of the foregoing values, e.g., about 5 microns to about 50 microns, about 10 microns to about 25 microns, etc. In certain embodiments, the microcracks can have a width of about 5 microns to about 0.001 microns, or any integer value between about 5 microns to about 0.001 microns, or any range formed by any of the foregoing values, such as about 5 microns to about 0.5 microns, about 2.5 microns to about 1 micron, and the like. It is understood that a combination of multiple microcracks, and the like, can provide a portion of the microcracks with a length and width outside of the ranges described herein.

In certain embodiments, the boundaries of the microcracks can define a plurality of discrete regions on the vapor-deposited inorganic coating. In certain embodiments, the discrete regions may be approximately uniform in size and shape. For example, in certain embodiments, the discrete regions may be generally rectangular or square in shape. In certain embodiments, the length and width of each discrete region can independently be from about 150 microns to about 10 microns, or any integer value between about 150 microns to about 10 microns, or any range formed by any of the foregoing values, such as from about 100 microns to about 50 microns, from about 15 microns to about 50 microns, and the like. For example, in certain embodiments, the vapor deposited inorganic coating can have a plurality of discrete regions having a length of about 35 microns and a width of about 35 microns.

Fig. 2-6 depict alumina (Al) having a thickness of 1000 nanometers₂O₃) Scanning electron microscopy ("SEM") of a 76 micron film of vapor deposited coatingAnd (4) an image. The photomicrograph of figure 2 has a magnification of 150 and is in an unstretched state. As shown in a 1000-fold enlarged view of fig. 3, the unstretched film of fig. 2 includes a small amount of microcracks.

Fig. 4-6 depict the films of fig. 2 and 3 after bilateral stretching to 150% of their original size. Figure 4 shows a low magnification (180x) image of the membrane. Fig. 5 and 6 show high magnification (1000x, 1800x) images of the film. As shown in fig. 5 and 6, the vapor deposited inorganic coating has a plurality of discrete regions bounded by microcracks.

It will be appreciated that each of the microcracks present in the vapor-deposited inorganic coating may extend through the entire thickness of the coating, or may extend only partially through the thickness of the coating. For example, certain microcracks may only exist along the outer surface of the vapor deposited inorganic coating. In certain embodiments, each of the microcracks can extend through the entire thickness of the vapor-deposited inorganic coating. In certain embodiments, only certain microcracks may extend through the entire thickness of the vapor-deposited inorganic coating. In certain embodiments, none of the microcracks extend through the entire thickness of the vapor-deposited inorganic coating.

In any of the various embodiments described herein, the vapor deposited inorganic coating can have a thickness of from about 2 nanometers to about 1,000 nanometers, or any integer value between about 2 nanometers and about 1,000 nanometers, or any range formed by any of the foregoing values, such as from about 100 nanometers to about 500 nanometers, from about 100 nanometers to about 300 nanometers, and the like.

In certain embodiments, the vapor deposited inorganic coating may be applied to less than substantially all of the water soluble layer. For example, the vapor deposited inorganic coating may be applied to about 50% to about 100% of the water soluble layer, or any integer percentage of the water soluble layer between about 50% to about 100%, or any range formed by any of the foregoing values, such as about 60% or more, or about 95% of the water soluble layer. In certain embodiments, a mask may be used to apply the vapor deposited inorganic coating to less than substantially all of the water soluble layer. It will be appreciated that other methods of reducing the area of the coating may be used. For example, the water-soluble layer may be selectively modified to reduce adhesion of the vapor deposited inorganic coating to selected areas. In certain embodiments, a vapor deposited inorganic coating may be applied to substantially all of the water-soluble layer.

According to certain embodiments, the vapor deposited inorganic coating may be directly or indirectly joined to a layer of the water soluble layer. For example, in certain embodiments, the inorganic vapor deposition coating may be applied directly to the untreated water-soluble layer using a chemical vapor deposition process as previously described. As used herein, an untreated water-soluble layer refers to a layer that has not undergone any treatment steps (e.g., ablation) after being cast from a water-soluble polymeric material. It can be appreciated that certain vapor deposition processes can eliminate the need to use a processing step. For example, the plasma-assisted chemical vapor deposition process may inherently clean the water-soluble layer and may minimize any need to prepare the water-soluble layer prior to applying the inorganic coating.

Alternatively, in certain embodiments, the vapor deposited inorganic coating may be applied to the water-soluble layer after the water-soluble layer is prepared by, for example, cleaning. It will be appreciated that cleaning of the water-soluble layer may promote improved adhesion of the vapour-deposited inorganic coating and may minimise any defects in the inorganic coating.

In general, the water-soluble layer can be cleaned in any suitable manner. For example, in certain embodiments, the water-soluble layer may be cleaned by solvent treatment or physical abrasion treatment.

In certain embodiments, the water soluble layer may be cleaned by an ablation process. In such embodiments, one or more surfaces of the water-soluble layer may be at least partially ablated to remove any undesired material prior to applying the vapor deposited inorganic coating. In addition, certain ablation processes, such as plasma ablation processes, can also functionalize the surface and provide functional groups to adhere the vapor deposited inorganic coating.

In general, any suitable ablation process may be used, including, for example, plasma treatment, solvent treatment, flame treatment, photon ablation treatment, electron beam radiation treatment, ion bombardment treatment, ultraviolet treatment, vacuum annealing treatment, or physical abrasion treatment. For example, in certain embodiments, prior to vapor depositing the inorganic coating, a helium oxygen plasma or an argon oxygen plasma may be used to ablate the surface of the water-soluble layer at a flow rate of 30.0L/min at a power of 100W to about 150W. Other gases may also be used for plasma ablation, including nitrogen and ammonia. It is to be understood that in various embodiments, the surface of the water-soluble layer may be partially ablated, substantially completely ablated, or completely ablated.

In certain embodiments, a vapor deposition inorganic coating may be applied over the intermediate layer. For example, in certain embodiments, a vapor deposition inorganic coating may be applied to the marking layer.

In certain embodiments, two or more vapor deposited inorganic coatings may be applied to the water soluble layer. In general, each additional vapor deposited inorganic coating layer may be applied similar to the vapor deposited inorganic coating layers previously described.

Water-soluble layer

It will be appreciated that the water-soluble layer of the film may be formed from any of a variety of water-soluble polymeric materials. As used herein, a water-soluble polymeric material is a material that, when formed as part of a film, dissolves in about 5 minutes (300 seconds) or less when immersed in water at a temperature of about 20 ℃. Advantageously, in certain embodiments, a suitable water-soluble layer of the film may dissolve at a temperature of about 24 ℃ or less, or about 10 ℃ or less. In certain embodiments, suitable water-soluble polymeric materials may also dissolve in a shorter period of time. For example, in certain embodiments, the water-soluble polymeric material may dissolve in about 90 seconds or less when immersed in water at a temperature of about 20 ℃.

Examples of suitable water-soluble polymeric materials for forming the film layer may include polyvinyl alcohol ("PVOH"), polyvinyl alcohol copolymers, polyvinyl pyrrolidone, polyalkylene oxides such as polyethylene oxide, copolymers of butylene glycol and vinyl acetate ("BVOH"), acrylamide, acrylic acid, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and salts, polyethylene glycol, polyamino acids or peptides, polyamides, polyacrylamides, copolymers of maleic acid/acrylic acid, polysaccharides including starch and gelatin, natural gums such as xanthan gum and carrageenan, polyacrylate and water-soluble acrylate copolymers, methyl cellulose, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, maltodextrin, polymethacrylates, homopolymers thereof, polyvinyl acetate, polyvinyl alcohol, copolymers thereof, and combinations thereof. In certain embodiments, the water-soluble polymeric material may be one or more of polyvinyl alcohol, polyvinyl alcohol copolymer, and hydroxypropylmethylcellulose ("HPMC"). In certain embodiments, the water-soluble polymeric material may be free of carboxylate groups. However, it is to be understood that the present disclosure is not particularly limited and may be used with any other known water-soluble polymer material.

The water-soluble polymeric material can have any suitable weight average molecular weight. For example, in certain embodiments, the water-soluble polymeric material can have a weight average molecular weight of about 1,000 to about 1,000,000, or any integer value between about 1,000 to about 1,000,000, or any range formed from any of the foregoing values, such as about 10,000 to about 300,000, about 20,000 to about 150,000, and the like.

In certain embodiments, mixtures of water-soluble polymeric materials may also be used. Mixtures of one or more water-soluble polymeric materials can be used to control the mechanical and/or dissolution properties of articles formed from the water-soluble polymeric materials. In such embodiments, the water-soluble polymeric material may be selected based on considerations such as the degree of water solubility, mechanical strength, and chemical miscibility of the material.

In certain embodiments, suitable mixtures of water-soluble polymeric materials may have different weight average molecular weights. For example, a suitable mixture can include a first PVOH polymer or copolymer thereof having a weight average molecular weight of about 10,000 to about 40,000 (e.g., about 20,000) and a second PVOH or copolymer thereof having a weight average molecular weight of about 100,000 to about 300,000 (e.g., about 150,000). However, it will be appreciated that it may also be advantageous in certain embodiments to select water-soluble polymeric materials having similar molecular weights.

In certain embodiments, suitable water-soluble polymeric materials may be formed from blends of different polymers or copolymers. For example, a suitable blend may include a polylactic acid polymer and a polyvinyl alcohol polymer. In certain embodiments, about 1% to about 35% by weight of the blend may be polylactic acid polymer, and about 65% to 99% by weight of the blend may be polyvinyl alcohol.

Suitable water-soluble polymeric materials can have any suitable degree of hydrolysis. For example, suitable PVOH polymer materials can have a degree of hydrolysis of about 60% to about 100% (e.g., about 99.95%), or any integer percentage between about 60% to about 100%, or any range formed by any of the foregoing values, such as about 60% to about 95%, about 80% to about 90%, and so forth. It will be appreciated that the degree of hydrolysis may vary depending on the polymer, the desired water solubility and the molecular weight. For example, in certain embodiments, the BVOH copolymer may be substantially completely hydrolyzed while maintaining water solubility.

In certain embodiments, the water-soluble layer of the film may contain a relatively small amount of moisture. Moisture can prevent the water-soluble layer of the film from cracking. Generally, suitable levels of moisture can include from about 2% water to about 15% water by weight of the water-soluble layer. In certain embodiments, a suitable level of moisture may alternatively comprise from about 3.5% water to about 10% water, by weight of the water-soluble layer. It is further understood that the moisture content may vary depending on environmental conditions and may range from about 2% water to outside about 15% water. For example, under very dry conditions, the water-soluble layer may reach a moisture content of about 1% water or less. In very humid environments, the water-soluble layer may reach a moisture content of greater than about 15% water.

Certain films described herein may include only a single water-soluble layer formed from any of the water-soluble polymeric materials described herein. In such embodiments, the water-soluble layer may generally be formed at any suitable thickness that exhibits suitable properties such as barrier strength and solubility. For example, the water-soluble layer may have a thickness of about 5 microns to about 300 microns, any integer value between about 5 microns to about 300 microns, or any range formed by any of the foregoing values, such as 35 microns to about 150 microns, and about 50 microns to about 100 microns.

Alternatively, the films described herein may comprise an additional water-soluble layer, wherein a vapor deposition inorganic coating is applied onto the surface of the outermost layer. In general, the multilayer film may be formed in any suitable manner. For example, the multilayer film may be coextruded as known in the art. Alternatively, the multilayer film may be formed by a lamination or solvent welding process. It will be appreciated that many variations are possible. For example, each layer may be formed from the same polymeric material. The use of a single polymeric material can be used to minimize compatibility issues between polymers having different characteristics (e.g., different molecular weights). Alternatively, at least one of the layers may be formed from a second polymeric material. It will be appreciated that the second polymeric material may generally be any polymer or copolymer capable of satisfactorily forming a film with the polymeric material of the other layers. In certain embodiments, the second polymeric material can be a water-soluble material, such as another PVOH polymer, or can be a water-insoluble polymeric material, such as polyethylene or ethylene vinyl acetate. The use of a second water-soluble polymer material may allow for easier formation of water-soluble layers and films having particular properties than by blending multiple polymers together in a single water-soluble layer.

In any embodiment describing multiple water-soluble layers, the number of layers may vary. For example, in various embodiments, the film may include 3 water-soluble layers, 5 water-soluble layers, 7 water-soluble layers, 9 water-soluble layers, or more than 9 water-soluble layers.

The total thickness of the film comprising the plurality of water-soluble layers can generally vary depending on the desired dissolution time and barrier properties. In certain embodiments, the total thickness of such films may be from about 5 microns to about 300 microns. In certain embodiments, a film having a plurality of water-soluble layers may have a thickness of about 25 microns to about 200 microns. In certain embodiments, a film having a plurality of water-soluble layers may have a thickness of about 50 microns to about 100 microns.

Additional ingredients contained in the water-soluble layer

It is to be understood that any of the water-soluble layers described herein can also include a number of optional components. For example, the water-soluble layer may additionally comprise one or more plasticizers and gas barrier additives. When included, these components can be blended with the water-soluble polymeric material prior to forming the water-soluble layer.

For example, any of the water-soluble polymeric materials described herein can further comprise one or more plasticizers to improve the rheology of the water-soluble layer. In such embodiments, the plasticizer may improve the flexibility and plasticity of the final film. It will be appreciated that when a plasticizer is included in the water-soluble layer as described herein, the size and mobility of the plasticizer will affect the barrier properties of the film. For example, a less mobile plasticizer such as sorbitol may facilitate the formation of a water-soluble layer with greater barrier properties than a water-soluble layer that includes a more mobile plasticizer such as glycerol. Suitable plasticizers may include, but are not limited to, glycerin, ethylene glycol, diethylene glycol, hexylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, alkyl citrates, sorbitol, isosorbide, pentaerythritol, glucosamine, N-methylglucamine, sodium cumene sulfonate, water, and mixtures thereof. In certain examples, the plasticizer may be glycerol. It will be appreciated that other plasticizers may also be suitable, including vegetable oils, polysorbates, polyethylene oxides, polydimethylsiloxanes, mineral oils, paraffins, C₁-C₃Alcohols, dimethyl sulfoxide, N-dimethylacetamide, sucrose, corn syrup, fructose, dioctyl sodium sulfosuccinate, triethyl citrate, tributyl citrate, 1, 2-propanediol, monoacetates, diacetates, or triacetates of glycerol, natural gums, citrates, and mixtures thereof.

In any of the various embodiments that include a plasticizer, the plasticizer may be included at a level of from about 8% to about 30%, or any integer percentage between about 8% to about 30%, or any range formed from any of the foregoing values, such as from about 8% to about 25%, from about 8% to about 20%, from about 10% to about 15%, etc., by weight of the water-soluble layer. It will be appreciated that mixtures of plasticizers may also be included in any embodiment containing a plasticizer, for example to tailor the rheological and barrier properties of the water-soluble layer.

In certain embodiments, the plasticizer may be glycerin, and may be included at a level of about 1% to about 15% by weight of the water-soluble layer. In other embodiments, the plasticizer may be polyethylene glycol. In certain such embodiments, the polyethylene glycol may be included at a level of from about 1% to about 7.5% by weight of the water-soluble layer.

The amount of plasticizer can be verified using techniques known in the art. For example, the amount of glycerol can be determined by using gas chromatography with a flame ionization detector ("GC-FID"). In such processes, ethanol may be used to extract glycerol from a small portion of the water-soluble layer or resin. The amount of glycerol can be determined by comparison with known commercial glycerol materials. It is understood that other processes may be used to determine the amount of other types of plasticizers, including, for example, time-of-flight mass spectrometry ("MALDI-TOF MS") and raman spectroscopy.

Certain water-soluble layers described herein may optionally include gas barrier additives to further improve the barrier properties of the film. In general, suitable gas barrier additives can include any compound or polymer that is compatible with the water-soluble polymeric material, which can improve the barrier properties of the film. For example, suitable gas barrier additives may include nanoclays, cellulose nanofibrils, cellulose nanocrystals, talc, graphene, and polymers such as chitin, cellulose, starch, soy, whey, and gluten. An example of a suitable nanoclay is methyl-bis (hydroxyethyl) octadecyl ammonium surface compatible montmorillonite.

In any embodiment that includes a gas barrier additive, the gas barrier additive may be added in any suitable manner. For example, the gas barrier additive may be incorporated into the water-soluble polymeric material feedstock and then dispersed sufficiently to exfoliate the additive. When included, the gas barrier additive may be added in any suitable amount that does not cause obstruction to the film. For example, the gas barrier additive may be included in an amount in certain embodiments from about 0.1% to about 5%, in certain embodiments from about 0.5% to about 4%, in certain embodiments from about 1% to about 3%, in certain embodiments about 2%, by weight of the water-soluble layer.

It will be appreciated that the water-soluble layer may still optionally contain adjuvants and processing agents such as plasticizer compatibilizers, lubricants, mold release agents, surfactants, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, antifoams, blowing agents, bleaching agents (e.g. sodium metabisulfite or sodium bisulfite), aversive agents such as bittering agents (e.g. denatonium benzoate, denatonium saccharin, denatonium chloride, sucrose octaacetate, quinine, flavonoids such as quercetin and nafil, and quassinoids such as quassin and strychnine), and pungent agents (e.g. capsaicin, piperine, allyl isothiocyanate and resiniferatoxin), as is known in the art. Suitable examples of fillers, extenders, detackifiers, humectants, and/or tackifiers may include starch, modified starch, crosslinked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose, silicon dioxide, metal oxides, calcium carbonate, talc, and mica.

Suitable lubricants and mold release agents may include fatty acids and salts thereof, fatty alcohols, fatty esters, fatty amines of acetic acid, fatty amides, and silicones.

Suitable surfactants for use in the water-soluble layer of the films described herein can include nonionic, cationic, anionic, and zwitterionic surfactants. Specific examples of suitable surfactants may include, but are not limited to, polyoxyethylated polypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides (nonionic), polyoxyethylated amines, quaternary ammonium salts and polyoxyethylated quaternary amines (cationic), as well as amine oxides, N-alkyl betaines and sulfobetaines (zwitterionic). Other suitable surfactants may include dioctyl sodium sulfosuccinate, acylated fatty acid esters of glycerol 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 glycerol and propylene glycol, and combinations thereof.

In embodiments of the water-soluble layer comprising an aversive agent such as denatonium benzoate, the aversive agent may be included in a suitable amount to ensure that the aversive effect provides a sufficient response without interfering with the performance of the film. For example, denatonium benzoate may be included in an amount of about 100 parts per million ("ppm") to about 500 ppm.

It will be appreciated that any of the various water-soluble layers for the film described herein can be tailored by including a selection of these optional components. In embodiments where the water-soluble layer includes multiple layers, any optional components may be included in only certain layers or may be included in each layer. For example, in certain embodiments, the aversive agent may be included only in layers that may be in contact with a human. It is also useful to include gas barrier additives only in the inner water-soluble layer. The inclusion of a gas barrier additive in the inner water-soluble layer can minimize any damage caused by the gas barrier additive, such as the sealing properties of the film. It will be appreciated that certain gas barrier additives may have no effect on the sealing properties and may be included in any layer.

Method for producing water-soluble layer

Any of the water-soluble layers described herein can be formed by any suitable method, including extrusion, solution casting, mixing, co-casting, and welding of the water-soluble polymeric material with any optional components, such as plasticizers. However, it will be appreciated that in certain embodiments, it may be advantageous to form the water-soluble layer using a cast extrusion process or a blow extrusion process.

Extrusion processes may provide a number of advantages over alternative processes such as solution casting. For example, the extrusion process may facilitate the inclusion of additional components such as additional resins and gas barrier additives, and may facilitate the formation of a multilayer film. Extrusion processes can also be used to extrude compositions that cause phase separation. Furthermore, the extrusion process may provide improvements in ease and cost of manufacture compared to other processing methods. For example, certain water-soluble polymeric materials may exhibit a large temperature difference between the melting temperature and the decomposition temperature. This difference may facilitate the use of the extrusion process by minimizing product loss due to thermal decomposition. In general, the water-soluble layers for films described herein can be formed using known extrusion processes, including cast extrusion processes and blow extrusion processes.

The films described herein may be further modified by single-sided or double-sided film orientation. In general, any film can be oriented by known techniques, such as using a special machine using high temperature biaxial orientation. Biaxially oriented films may exhibit a variety of improved properties, including improved barrier properties.

Film characteristics

The films described herein can exhibit a number of beneficial properties, including excellent barrier properties and low adhesion values.

Barrier properties

The films described herein exhibit improved barrier properties as evidenced by the favorable water vapor transmission rates and oxygen transmission rates measured by the water vapor transmission rate test and the oxygen transmission rate test.

As used herein, the water vapor transmission rate test is a test conducted on a Mocon permantan 100K permeability instrument at a controlled temperature of 37.8 ℃ using a test gas having a relative humidity of 60%. The carrier gas was nitrogen with a relative humidity of 0% and passed through the filter/dryer. The samples were allowed to equilibrate for about 30 minutes prior to testing.

As used herein, the oxygen transmission rate test indicates that the test was performed at a controlled temperature of 40 ℃ using a 100% oxygen test gas having a relative humidity of 80%. The carrier gas was 100% nitrogen. The samples were measured on a Mocon Oxtran oxygen permeameter according to ASTM D3985.

Any of the membranes described herein, including any of the membranes described in alternative embodiments, can have a water vapor transmission rate of about 1,500 g/(m) as measured according to the Water vapor Transmission Rate test²Day) to about 6,000 g/(m)²Day), or about 1,500 g/(m)²Day) to about 6,000 g/(m)²Days), or any range formed by any of the foregoing values, e.g., about 2,000 g/(m)²Day) to 5,500 g/(m)²Day), and 2,5000 g/(m)²Day) to about 4,000 g/(m)²Day), etc.

Any of the films described herein, including any alternative embodiments, can have a value of about 4.65 cc/(m) measured according to the oxygen transmission rate test²Day) [0.3cc/(100 in)²Sky)]To about 46.5 cc/(m)²Day) [3cc/(100 in)²Sky)]Or about 4.65 cc/(m)²Day) [0.3cc/(100 in)²Sky)]To about 46.5 cc/(m)²Day) [3.2cc/(100 in)²Sky)]Any integer value in between, or any range formed by any of the preceding values, e.g., about 7.75 cc/(m)²Day) [0.5cc/(100 in)²Sky)]To 38.75 cc/(m)²Day) [2.5cc/(100 in)²Sky)]About 15.5 cc/(m)²Day) [1cc/(100 in)²Sky)]To about 23.25 cc/(m)²Day) [1.5cc/(100 in)²Sky)]And the like. It will be appreciated that such oxygen and water vapour transmission rates may be substantially lower than known PVOH films.

It will also be appreciated that the films described herein may also exhibit reduced transmission and migration rates for other compounds, such as compounds contained within a package formed from the film or compounds contained in the film. For example, the film may exhibit improved resistance to migration of optical dyes, surfactants, and fragrances contained in the unit dose article. Additionally, compounds contained in the film, such as bitterants, may resist migration out of the film.

It will be appreciated that improving the barrier properties of the film may result in articles formed from the film exhibiting a number of beneficial improvements. For example, reduced oxygen migration may improve the stability of the composition contained in the article.

Other benefits are also possible. For example, improved barrier properties may prevent migration of chemicals into or out of a package formed from the films described herein. Such characteristics may improve the useful life of the package or prevent a "wet-out" or sticky feel of the chemical upon removal from the package.

Viscosity of

The films described herein may also exhibit reduced tackiness compared to uncoated water-soluble films. For example, the films described herein can exhibit a tack force of about 5,000N or less when measured according to the tack force method. The uncoated polyvinyl alcohol film may have a tack force in excess of 30,000N.

In the adhesion method, two film samples were cut and mounted on a Texture Analyzer (Texture Analyzer XT Plus, Texture Technologies, Hamilton, MA) using 5cm × 5cm double-sided adhesive tape. The top sample was 5cm x 6cm in size. The bottom sample was 7cm x 10cm in size. The samples were evaluated at a temperature of 22 ℃ and a relative humidity of 35% using a 50kg weighing cell with a contact time of 2 seconds. Before measuring the viscous force, the sample was sprayed with water from a distance of 110mm at a pressure of 0.2bar and allowed to relax for 10 seconds.

Method for measuring microcracks

The surface of the uncoated film and the micro cracks in the inorganic coating layer were observed using a Scanning Electron Microscope (SEM). 1000nm Al shot using Hitachi TM3000 bench SEM₂O₃SEM images before and after stretching. For cases where higher magnification is required, for Al₂O₃As the coating, FEI XL-30ESEM can be used. Where the samples were stretched, they were stretched using an Instron machine. To stretch the film, an Instron 5948MicroTester was used. If a sample is stretched from 1cm to 2.5cm, the sample is said to be stretched to 150% of its original length.

Method for measuring thickness of coating layer in coating process

To monitor the thickness of the inorganic coating, an InFICON XTC/3 thin film deposition controller was used in-situ (in a vacuum chamber) during deposition.

Method for measuring coating thickness and chemical analysis of coating film

To measure the thickness of the coating on the film (or even determine if a coating is present on the film), a high resolution Scanning Electron Microscope (SEM) may be used. To prepare a sample for thickness measurement using a high resolution SEM, the sample is cut in half using a microtome, preferably a cryomicrotome, to obtain a cross section in order to obtain an optimal cut without dirtying the surface to be inspected. This assumes that the film has been separated from the other elements of the product. However, if the film is part of a commercial consumer product, such as a fabric care unit dose pod product, for example, then a small portion of the film is cut from the product and then cleaned. Cleaning can be achieved by carefully wiping any liquid product from inside the membrane in direct contact with the product. Air guns may be used to remove dust and dirt from particles from other surfaces. The sample was then placed on the vertical stub using double-sided carbon tape to secure the sample in place. The sample may be sputter coated with Au-Pd prior to SEM analysis to ensure a good image is obtained. The cross-sectional area of the sample was examined to determine if there was a coating on either film surface. The thickness of the coating, if present, is determined by the scale on the SEM.

To determine the chemical composition of the coating, EDAX (usually in conjunction with SEM) can be used to determine the chemical composition of the inorganic coating. Furthermore, XPS can also be used to identify the chemical properties of inorganic coatings.

Samples for chemical identification were prepared by cutting out a small piece from the finished product and cleaning as described previously. If EDAX is used, the sample is placed on a stub with a double-sided carbon tape (the sample is not coated with Au — Pd for EDAX analysis). For XPS analysis, the sample was placed on a silicon wafer and held in place with a carbon tape (or any other vacuum compatible tape) at the corners.

Dissolution test method

Solubility test method for water-soluble films the total time (in seconds) for a particular film sample to completely dissolve was measured when tested according to the slide solubility test of MONOSOL test method 205(MSTM205), as described in paragraph 116-131 of U.S. published patent application No. US201500935210a1 entitled "water-soluble films with improved solubility and stress properties and packages made therefrom," the entire disclosure of which is incorporated herein by reference; the solubility test method used herein is the same as set forth in US201500935210a1, except that in the solubility test method of the present disclosure, instead of maintaining distilled water at 10 ℃, distilled water is maintained at 15 ℃. While the standard version of the solubility test method uses distilled water maintained at 15 ℃, the solubility test method may be performed in a modified form in which the distilled water is maintained at another specified temperature in order to provide additional comparative data at different temperatures. The solubility test method is not applicable to any material other than a water-soluble film having a total thickness of 3mm or less.

Other test requirements

In testing and/or measuring materials, if the relevant test method does not specify a particular temperature, the test and/or measurement is performed on the specimen at a temperature of 22 ℃ (+/-3 ℃) (where the specimen is pre-conditioned to that temperature). In testing and/or measuring materials, if a particular humidity is not specified by the relevant test method, the test and/or measurement is performed on a sample at a relative humidity of 35% (+/-5%) to which such sample is pre-conditioned. All tools and/or instruments used for testing and/or measuring must be properly calibrated prior to testing and/or measuring. All tests and/or measurements should be performed by a skilled, skilled and experienced technician. All tests and/or measurements should be performed according to good laboratory specifications in order to obtain accurate results.

Article of manufacture

In certain embodiments, some or all of the films described herein can be used to form unit dose articles, such as soluble unit dose articles. The soluble unit dose article is a package containing a predetermined amount of one or more compositions such as detergents. The composition may be contained in a compartment formed by sealing one or more films together. It will be appreciated that soluble unit dose articles provide convenient dispensing of compositions for applications such as laundry and dishwashing.

It is understood that other articles may alternatively be formed from the films described herein. For example, packages for water softening compositions, medical compositions, health care compositions, nutritional compositions, shaving compositions, personal cleansing compositions, hard surface cleansing compositions, natural cleansing products containing bacteria/microorganisms, pharmaceutical compositions, dental care compositions, beauty care compositions, disinfectant compositions, antimicrobial compositions, antiseptic compositions, food products, herbs, flavoring agents, and adjuvants or supplements thereof may be formed in various embodiments. Additional details of various possible articles are disclosed in U.S. patent application 2002/0150708 and U.S. patent application 2009/0250370. In addition, the film can be used to form soluble laundry bags, including those described in U.S. patent application 2002/0150708.

In certain embodiments, dry or low moisture content articles, such as durable or semi-durable articles, e.g., shavers, toothbrushes, may be packaged in these films in addition to disposable articles such as tampons, diapers, and other sanitary protection articles. It will be appreciated that the outer surface of such an article will delay dissolution before the package begins to dissolve. In other embodiments, the films may be used to package single-use or multi-use powder-based products, such as those used for laundry or personal cleansing.

Method for manufacturing an article

Generally, a method of manufacturing an article, such as a unit dose article, may comprise the steps of: forming an open bag, filling the open bag with the composition, and closing the open bag filled with the composition. The open pocket may be formed by placing the film into a mold. The pouch can be closed with a second film. It is understood that the one or more films used to form the article may be the films described herein. Other articles may be made in a manner known in the art.

It is further understood that vapor deposited inorganic coatings as described herein may alternatively be formed on finished articles. In such embodiments, the finished article, such as a unit dose article, can undergo a process similar to that used to form the vapor deposited inorganic coating on the film described herein. For example, a plasma-assisted chemical vapor deposition process can be used to form a vapor deposited inorganic coating on the exterior surface of a unit dose article formed from an uncoated PVOH polymer film.

In any of the embodiments described herein, the article may be formed in a web process that forms multiple articles at once. After the web is sealed, the web may be cut to form individual articles.

The articles described herein can be manufactured by thermoforming, vacuum forming, or a combination thereof. The article may be sealed using any sealing method known in the art. Suitable sealing methods may include heat sealing, solvent sealing, pressure sealing, ultrasonic sealing, pressure sealing, laser sealing, impulse sealing, infrared ("IR") sealing, or combinations thereof. For example, water or another suitable aqueous solvent may be applied to the rim to partially dissolve the film, thereby forming a seal.

In certain examples, the article may also be dusted with a dedusting agent (e.g., talc, silica, zeolite, carbonate, or mixtures thereof) to prevent sticking of the film. However, it will be appreciated that the necessity of such dedusting agents can be eliminated by the non-stick nature of the vapor deposited inorganic coating.

In some instances, the package may be formed by a simple forming, filling, sealing process, as is used today to form package sachets and pouches. Examples of such processes are provided in the packaging abstracts, such as those described in http:// www.packagingdigest.com/form-file-seal or https:// vikingmask.com/packaging-machine-resources/packaging-machine-block/a-guide-to-vertical-form-file-seal-machines.

Fig. 7A-11D illustrate various embodiments of exemplary soluble unit dose articles. In these figures, the flexible materials are shown with exaggerated thicknesses to more clearly show their location and relationship.

Fig. 7A-7D show various views of an exemplary soluble unit dose article 300 having a flat top 301, a rounded bottom 302 and one compartment 331. Fig. 7A is a top view, fig. 7B is a side view, fig. 7C is an end view, and fig. 7D is a sectional end view. In top view, the overall shape of the article 300 is rectangular with rounded corners. Article 300 is formed from a first flexible material 311, which first flexible material 311 is sealed to a second flexible material 312 over a sealing region 321. The sealing region 321 forms a continuous connection between the flexible materials 311 and 312 around the entire periphery of the article 300. The flexible materials 311 and 312 are independent of each other except for the sealing area 321. The first flexible material 311 is disposed above the second flexible material 312 and is oriented approximately horizontally. On the bottom 302, in the middle of the article 300, the second flexible material 312 is bent downward from the sealed region 321 and away from the first flexible material 311, such that the space between the flexible materials 311 and 312 forms a compartment 331, the side profile of which is generally like an inverted bell. The compartment 331 surrounds and encloses the composition 341.

Fig. 8A-8D show various views of an exemplary soluble unit dose article 400 having a rounded top 401, a rounded bottom 402, and one compartment 431. Fig. 8A is a top view, fig. 8B is a side view, fig. 8C is an end view, and fig. 8D is a sectional end view. In top view, the overall shape of the article 400 is rectangular with rounded corners. The article 400 is formed from a first flexible material 412, which first flexible material 412 is sealed to a second flexible material 413 over a sealing area 421. The sealing region 421 forms a continuous connection between the flexible materials 412 and 413 around the entire periphery of the article 400. The flexible materials 411 and 412 are independent of each other except for the sealing area 421. On the bottom 402, in the middle of the article 400, the first flexible material 412 is bent downwards from the sealing area 421, and on the top 401, in the middle of the article 400, the second flexible material 413 is bent upwards from the sealing area 421, so that the second flexible material 413 is deflected away from the first flexible material 412, and the space between the flexible materials 412 and 413 forms a compartment 431, which compartment 431 has an overall shape like the side profile of a pillow. The compartment 431 surrounds and encloses the composition 441.

Fig. 9A-9D show various views of an exemplary soluble unit dose article 500 having a rounded top 501, a rounded bottom 502, and two overlapping compartments 531 and 532. Fig. 9A is a top view, fig. 9B is a side view, fig. 9C is an end view, and fig. 9D is a sectional end view. In a top view, the overall shape of the article 500 is rectangular with rounded corners. Article 500 is formed from first flexible material 511, second flexible material 512, and third flexible material 513, all sealed together over a sealing area 521. Sealing region 521 forms a continuous connection between flexible materials 511, 512, and 513 around the entire periphery of article 500. Flexible materials 511, 512, and 513 are independent of each other except for sealing region 521. First flexible material 511 is disposed between second flexible material 512 and third flexible material 513 and is oriented approximately horizontally. On the bottom 502, in the middle of the article 500, the second flexible material 512 is bent downward from the sealing region 521 such that the second flexible material 512 is offset from the first flexible material 511, and the space between the flexible materials 511 and 512 forms a first compartment 531, the first compartment 531 having a side profile with an overall shape like an inverted bell. The first compartment 531 surrounds and encloses a first composition 541. On the top 501, in the middle of the article 500, the third flexible material 513 is bent upward from the sealing region 521 such that the third flexible material 513 is offset from the first flexible material 511 and the space between the flexible materials 512 and 513 forms a second compartment 532, the second compartment 532 having a side profile with an overall shape like a bell. The second compartment 532 surrounds and encloses the second composition 542. The article 500 has an overall shape like the side profile of a pillow.

Fig. 10A-10D show various views of an exemplary soluble unit dose article 600 having a rounded top 601, a flat bottom 602, and two side-by- side compartments 633 and 634. Fig. 10A is a top view, fig. 10B is a side view, fig. 10C is an end view, and fig. 10D is a sectional end view. In a top view, the overall shape of the article 600 is rectangular with rounded corners. The article 600 is formed from a first flexible material 611, which first flexible material 611 is sealed to a second flexible material 613 over a sealing area 621. The sealing region 621 forms a continuous connection between the flexible materials 611 and 613 around the entire periphery of the article 600 and through a portion of the middle of the article 600. The flexible materials 611 and 613 are independent of each other except for the sealing area 621. The first flexible material 611 is disposed below the second flexible material 613 and is oriented approximately horizontally. On top 601, in a first portion of the middle of article 600, a first portion of second flexible material 613 is bent upward from sealing area 621 such that the first portion of second flexible material 613 is offset from first flexible material 611 and the space between flexible materials 611 and 613 forms a first compartment 633, the first compartment 633 having a side profile that is overall shaped like a circular tube. The first compartment 633 surrounds and encloses the first composition 643. On the top 601, in a second portion of the middle of the article 600, a second portion of the second flexible material 613 is bent upward from the sealing region 621 such that the second portion of the second flexible material 613 is offset from the first flexible material 611 and the space between the flexible materials 611 and 613 forms a second compartment 634, the second compartment 634 having a side profile that is overall shaped like a circular tube. The second compartment 634 surrounds and encloses a second composition 644 that is different from the first composition 643.

Fig. 11A to 11D show various views of an exemplary soluble unit dose article 700 having a rounded top 701, a rounded bottom 702 and two smaller side-by- side compartments 733 and 734, each compartment overlapping a larger bottom compartment 731. Fig. 11A is a top view, fig. 11B is a side view, fig. 11C is an end view, and fig. 11D is a sectional end view. In top view, the overall shape of the article 700 is rectangular with rounded corners. The article 700 is formed from a first compliant material 711, a second compliant material 712, and a third compliant material 713 that are sealed together over a first sealing region 721 and a second sealing region 722, as described below. The first sealing region 721 forms a continuous connection between the flexible materials 711, 712, and 713 around the entire periphery of the article 700. The second sealing region 722 forms a continuous connection between the first compliant material 711 and the third compliant material 713 through an intermediate portion of the article 700 between the compartments 733 and 734 (as shown, bounded by the reference line). The compliant materials 711, 712, and 713 are independent of each other except for the sealing regions 721 and 722. First compliant material 711 is disposed between second compliant material 712 and third compliant material 713 and is oriented approximately horizontally. On the bottom 702, in the middle of the article 700, the second flexible material 712 bends downward from the sealing area 721 such that the second flexible material 712 is offset from the first flexible material 711 and the space between the flexible materials 711 and 712 forms a larger compartment 731, the larger compartment 731 having a side profile with an overall shape like an inverted bell. Compartment 731 surrounds and encloses first composition 741. On the top 701, in the middle first portion of the article 700, a first portion of the third flexible material 713 is bent upwards from the sealing areas 721 and 722, such that the first portion of the second flexible material 713 is offset from the first flexible material 711, and the space between the flexible materials 711 and 713 forms a first smaller compartment 733, the first smaller compartment 733 having an overall shape like the side profile of a circular tube. The compartment 733 surrounds and encloses a second composition 743 that is different from the first composition 741. On top 701, in a second portion of the middle of article 700, a second portion of second compliant material 713 is bent upward from sealing regions 721 and 722 such that the second portion of second compliant material 713 is offset from first compliant material 711 and the space between compliant materials 711 and 713 forms a second smaller compartment 734, the second smaller compartment 734 having a side profile that is overall shaped like a circular tube. The compartment 734 surrounds and encloses a third composition 744, which third composition 744 is different from the first composition 741 and the second composition 743.

A portion, portions, or all of any of the soluble unit dose article embodiments of fig. 7A-11D can be made, used, and/or modified in any manner known in the art. For example, any of these articles may be configured to have any convenient size and shape and any number of compartments, as described herein and/or as known in the art. By way of example, the soluble Unit Dose Article may be configured in accordance with any of the embodiments disclosed in U.S. patent 9,725,685 entitled "Unit Dose Article," which is incorporated herein by reference, or any commercially available embodiment of a soluble Unit Dose Article (e.g., TIDE PODS and CASCADE ACTION PACS manufactured by Procter & gamble, Cincinnati, Ohio). Any compartment for these articles can be configured to have any convenient size, shape, configuration, and relationship, as described herein and/or as known in the art. Any compartment of these articles may be filled with one or more of any of the compositions described herein and/or known in the art of soluble unit dose articles. By way of example, such compositions may include any one or more of the following: fabric care compositions (detergents, surfactants, bleaches, fabric softeners, dyes, brighteners, perfumes, and the like), dish care compositions, agrochemicals, water treatment chemicals, dyes, and the like. Any of the compositions disclosed herein may take any convenient form disclosed herein or known in the art, such as: liquids, pastes, solids, fibers, granules, powders, and the like. Any flexible material used to form these articles can be the same material or different versions of the same material or different materials as described herein and/or known in the art; for example, any of the water-soluble films disclosed herein may be used (alone and/or as part of a laminate/composite) for a portion, portions, or all of any of these flexible materials. Also, any of the water-soluble films disclosed herein can be used (alone and/or as part of a laminate/composite) to form a portion, portions, or all of a soluble unit dose article known in the art, and can include any additive and/or coating (e.g., bitterant, gas barrier additive, etc.) known in the art of soluble unit dose articles. Some, or all of any of these aspects may be combined together in any feasible manner to form additional alternative embodiments. In addition, any of the water-soluble films disclosed herein may be used (alone and/or as part of a laminate/composite) to form part, parts, or all of components in health and hygiene products (e.g., disposable diapers and training pants), incontinence articles and feminine care products (e.g., pantiliners and pads), medical products (e.g., bags for bodily fluids and/or waste (e.g., ostomy bags)), and other household products (e.g., trash bags, laundry bags, dirty-basket liners, etc.). The water-soluble film may also be used to form embroidery products, cosmetic products (e.g., face masks containing water-soluble components), personal care products, shaving products, health care products, pharmaceuticals, and the like. Additionally, any of the water-soluble films disclosed herein can be used (alone and/or as part of a laminate/composite) to form a portion, portions, or all of a flexible package (e.g., a pouch) to provide improved disposability of the package; such packages may be of any convenient size, and may include any number of doses (e.g., single dose, multiple doses, etc.). Any of the films described herein may be used as part, or all of a primary package and/or a secondary package and/or any other type of package or packaging material known in the art.