CN116471956A

CN116471956A - Multilayer film for airbags and footwear

Info

Publication number: CN116471956A
Application number: CN202280007412.0A
Authority: CN
Inventors: 迪雅·班迪奥帕迪亚雅; 纳拉亚南·阿什温·库马尔·巴拉德瓦吉; 张怡华; 克里斯多佛·J·狄米特里奥; 南希·D·艾森门格; 阿德里安·M·拉赫森; 沙伦·奥巴; 理查德·L·沃特金斯
Original assignee: Nike Innovate CV USA
Current assignee: Nike Innovate CV USA
Priority date: 2021-07-27
Filing date: 2022-07-27
Publication date: 2023-07-21
Also published as: WO2023010027A1; EP4199776B1; EP4199776A1; US20230042813A1

Abstract

Provided herein are cushions or bladders for articles of footwear that include a multilayer film. In one aspect, the cushion or bladder comprises a first sheet and a second sheet, wherein the first side of the first sheet faces the second side of the second sheet, wherein the first sheet and the second sheet are bonded together to form an interior cavity in a space between the first side of the first sheet and the second side of the second sheet, forming a bladder capable of holding a gas in the interior cavity at a pressure above, at or below atmospheric pressure; and wherein each of the first sheet and the second sheet comprises a multilayer film comprising: a core region comprising at least 20 gas barrier layers and more than one elastomeric layer, wherein the gas barrier layers alternate with the elastomeric layers.

Description

Multilayer film for airbags and footwear

Cross Reference to Related Applications

The present application claims the benefit of U.S. provisional application No. 63/203,596, filed 7/27 at 2021, which is incorporated herein by reference in its entirety.

Technical Field

The present disclosure relates to multilayer films. More particularly, the present disclosure relates to multilayer films having gas barrier properties, methods of making such multilayer films, articles incorporating multilayer films (e.g., airbags (airbag), fuel hose liners (fuel hose liner), and vehicle tires), and methods for making such articles. The present disclosure also relates to an article of footwear incorporating a bladder.

Background

This section provides background information related to the present disclosure, which is not necessarily prior art.

The design of athletic equipment and apparel, and footwear, involves a variety of factors ranging from aesthetic aspects to comfort and feel, to performance and durability. While designs and fashion may change rapidly, the need for enhanced performance is constant in the marketplace. To balance these needs, designers employ a variety of materials and a variety of components designed to construct athletic equipment and apparel, and footwear.

Articles of footwear conventionally include an upper and a sole structure. The upper may be formed from any suitable material to receive, secure, and support the foot on the sole structure. The upper may cooperate with laces, straps, or other fasteners to adjust the fit of the upper around the foot. A bottom portion of the upper proximate a bottom surface of the foot is attached to the sole structure.

The sole structure generally includes a layered arrangement (layered arrangement) that extends between the ground surface and the upper. One layer of the sole structure includes an outsole that provides both wear-resistance and traction with the ground surface. The outsole may be formed of rubber or other materials that impart durability and wear resistance, and enhance traction with the ground surface. The other layer of the sole structure includes a midsole disposed between the outsole and the upper. The midsole provides cushioning for the foot and may be formed, in part, from a polymer foam material that resiliently compresses under an applied load to cushion the foot by attenuating ground reaction forces. The sole structure may also include a comfort-enhancing insole or sockliner positioned within the void (void) proximate the bottom portion of the upper, and a strobel attached to the upper and disposed between the midsole and the insole or sockliner.

Brief Description of Drawings

Further aspects of the present disclosure will be readily appreciated after reviewing the detailed description set forth below in connection with the accompanying drawings.

FIG. 1 is a bottom front perspective view of an article of footwear incorporating a multilayer film of the present disclosure.

Fig. 2 is an exploded perspective view of the article of footwear shown in fig. 1.

Fig. 3 is a schematic top view of an article of footwear, with an upper of the footwear omitted for discussion purposes to illustrate a midsole layer (mid-sole) and a foot print (air cushion).

Fig. 4A is an enlarged side view of the heel area of the cushion in an uncompressed state.

Fig. 4B is an enlarged side view of the heel area of the cushion in a compressed state.

Fig. 5 is a cross-sectional view of a multilayer film of the present disclosure, such as for the article of footwear and cushion shown in fig. 1-4B.

Fig. 6 is an enlarged cross-sectional view of the core region of the multilayer film of the present disclosure shown in fig. 5.

Fig. 7A-7E are cross-sectional views of alternative multilayer films of the present disclosure.

Fig. 8 illustrates a spacer component according to an exemplary embodiment of the present disclosure.

Fig. 9A-9B illustrate an exemplary article of athletic equipment (i.e., soccer) incorporating the multilayer films of the present disclosure.

Fig. 10A-10B illustrate a tire incorporating the multilayer film of the present disclosure.

11A-11C show photomicrographs illustrating the extent of cracking of a bladder formed from layers of various constructions as disclosed herein after undergoing a KIM test as described herein.

Fig. 12A shows a comparison of gas transmission rates for a control bladder comprising 32 EVOH layers (bottom curve) versus a 50% thickness bladder having 24 EVOH layers and having a control (top curve) and a bladder having 32 EVOH layers and having a control 50% thickness (middle curve). Fig. 12B-12C are photomicrographs showing that 24 and 32 EVOH layer capsules, respectively, did not crack after undergoing KIM testing as described herein.

Fig. 13A shows a comparison of Gas Transmission Rate (GTR) for a control bladder comprising 32 EVOH layers (bottom curve) versus a 50% thickness bladder having 24 EVOH layers and having a control (top curve) and a 75% thickness bladder having 32 EVOH layers and having a control (middle curve). Fig. 13B is a micrograph showing that 32 EVOH layer capsules slightly cracked after undergoing a KIM test as described herein.

Fig. 14 shows a comparison of gas permeability for a control bladder comprising 32 EVOH layers (curve with square) versus a bladder having 64 EVOH layers and having 150% thickness compared to the control (curve with circular shape) and a bladder having 40 EVOH layers and having approximately the same thickness as the control (curve with triangular shape).

Corresponding reference characters indicate corresponding parts throughout the drawings.

Description of the invention

The present disclosure relates to multilayer films (e.g., microlayer films) having a thin gas barrier layer, which have been found to increase the flexibility of the film while also maintaining good film durability and gas barrier properties. Thus, the multilayer films of the present disclosure are suitable for use in a variety of articles requiring gas barrier properties and/or gas retention properties, such as airbags, fuel hose liners, vehicle tires, and the like. The multilayer film is particularly suitable for use in articles requiring gas barrier properties and/or gas retention properties while also experiencing repeated flexing conditions, such as bladders for footwear cushioning (referred to as "cushion" as defined below).

Fluid-filled bladders (fluid-filled bladders), including bladders configured to function as cushioning elements, may be formed from a multi-layer film that includes a gas barrier layer. Over time, the gas barrier layer may be sufficiently brittle to crack (and/or break). This may occur, for example, after a number of flexing and releasing cycles. Cracking (and/or breaking) may become visible to the naked eye. It may reduce the transparency of one or more regions of the cushioning element. It can increase the gas permeability of the cushioning element.

Bladders having bulbous protrusions and/or areas of relatively small radius of curvature may be more prone to cracking. These types of capsules are therefore particularly at risk of visible defects. They are also at risk of an unacceptable increase in gas permeability due to aligned cracks (catastrophic crazes) in many, and even all, layers. Therefore, it is generally not desirable in the art to commercially produce these types of bladders, particularly those used as cushioning elements, because they will be exposed to a very large number of flexing and release cycles during use.

Proposals to mitigate increased gas transmission due to cracking and reduce the visibility of cracks after crack formation include increasing the thickness of the individual gas barrier layers present in the film; and increasing the number of gas barrier layers present in the film. Any of these options may result in an increase in the total amount of gas barrier material present in the multilayer film.

In a multilayer film having a core region comprising a gas barrier material, the core region of the film presents the greatest barrier to rapid diffusion of gas molecules. When cracks are present in the gas barrier material forming the gas barrier layer of the core region, gas molecules can bypass the gas barrier material and diffuse faster through the more gas permeable material present in the membrane. When a crack aligns through many or all of the layers of the core region of the gas barrier film, the gas molecules may pass through a majority of the core region of the film or even through the entire core region of the film in a relatively short amount of time. Increasing the number of gas barrier layers reduces the likelihood that cracks will occur in an aligned manner in a large number or all of the layers of the core. When the cracks are not aligned, the gas molecules are forced to take a tortuous path in order to traverse the entire multilayer film. Similar effects have been proposed when increasing the thickness of the individual gas barrier layers. However, up to now, it is not well understood how to prevent or reduce the formation of cracks in the gas barrier layer in the first place.

Unexpectedly, it has now been found that reducing the thickness of each individual gas barrier layer can prevent or reduce the formation of cracks in the layer. Instead of using an average individual gas barrier layer thickness of a few microns, individual average gas barrier layer thicknesses of less than or equal to 0.75 microns (particularly less than or equal to 0.5 microns), including individual average gas barrier layer thicknesses in the range of about 0.01 microns to about 0.75 microns (particularly in the range of about 0.01 microns to about 0.5 microns), are proposed. It has been found that an average individual gas barrier layer thickness of less than about 0.75 microns, and particularly less than about 0.5 microns, reduces cracking and may reduce catastrophic cracking of the type mentioned above. It has also been found that the use of these thinner layers in a multilayer film can result in films and capsules that have a gas transmission that remains satisfactory compared to the gas transmission of the thicker layers (that is, without regard to any cracking, i.e., for films or capsules that are exposed to refraction and release). In particular, the membrane or bladder may have a gas transmission rate of less than or equal to 4 cubic centimeters per square meter per day or less than or equal to 3 cubic centimeters per square meter per day.

It has surprisingly been found that when using these thinner layers, no compensation is necessary in other ways. For example, when the individual thickness of the gas barrier layer is reduced, it is not necessary to increase the total amount of the gas barrier material by increasing the number of the gas barrier layers, or even to maintain the same total amount of the gas barrier material by increasing the number of the gas barrier layers. This is in contrast to the suggestion of increasing the number of gas barrier layers or increasing the thickness of each individual gas barrier layer; both increasing the number of gas barrier layers or increasing the thickness of each individual gas barrier layer tends to result in an increase in the total amount of gas barrier material.

It has been found that while more gas barrier layers, such as at least 30 gas barrier layers or at least 40 gas barrier layers, may be used in order to provide a particularly low gas transmission rate, a relatively smaller number of gas barrier layers, such as about 20 gas barrier layers (e.g., about 24 gas barrier layers, and thus fewer layers than the 32 gas barrier layers of the control bladder of the embodiments set forth below), may be used. The number of gas barrier layers may optionally not exceed 70. A particularly large amount of gas barrier material integrally present in the multilayer film may not be required.

The more crack and break resistant multilayer films disclosed herein can be used to make bladders (e.g., cushioning elements) having a greater variety of shapes and for a greater variety of uses than previously possible. It is possible to manufacture a cushioning element having spherical protrusions and/or regions of relatively small radius of curvature that maintain high definition and low gas diffusivity over long periods of use.

As used herein, the terms "balloon" and "bladder" are interchangeable and each refer to a fluid-filled and sealed component or a fluid-fillable and sealable component, wherein the latter may be filled with one or more fluids and sealed. As can be appreciated, the sealed and sealable terms may refer to a fixed seal (e.g., with welded seams) and/or a dynamic seal (e.g., with a valve) that may be switched between an open state and a closed state. Further, the balloons discussed herein may each have a single lumen that may be filled with a fluid, multiple lumens that are separate and may be filled independently with one or more fluids, and/or multiple lumens that are fluidly connected (at least some of them) and may be filled with one or more fluids, and combinations thereof. As further used herein, the term "cushion" refers to an air bladder that functions as a cushioning element in a footwear midsole component to provide cushioning and/or support to an article of footwear.

The bladder generally has a shape that includes an upper surface and a lower surface, with the sidewall positioned between the upper surface and the lower surface. While the bladder may be shaped such that the sidewall includes a convex curved region or a concave curved region, the sidewall generally includes a convex region that curves away from and extends beyond the upper surface of the bladder or the lower surface of the bladder or both. When the bladder is a midsole component of an article of footwear, an upper surface of the bladder may be positioned such that it faces an insole of the article of footwear or a void within an upper portion of the article of footwear that is configured to receive a foot of a wearer during use, while a lower surface of the bladder may be positioned such that it faces an outsole or ground of the article of footwear. The curved region of the sidewall is typically visible from, or even exposed and forms a portion of, the outer surface of the article of footwear. As used herein, the term "bulbous protrusion" or "bulbous portion" may refer to a portion or region of a bladder having one or more of the following features, such as at least two, at least three, or all four of the following features. The bulbous protrusion or bulbous portion may be a curved sidewall of the bladder, including a convexly curved sidewall of the bladder. In particular, the bulbous protrusion or bulbous portion may be a portion of a rearwardly and/or laterally extending bladder in the article of footwear that protrudes beyond an upper or lower surface of the bladder (alternatively beyond a rear portion of the article of footwear) and/or beyond one or more sides of the article of footwear by more than 1 millimeter, optionally more than 2 millimeters, optionally more than 3 millimeters, optionally more than 4 millimeters, optionally more than 5 millimeters. The bulbous protrusion or portion of the balloon may extend even further when flexed, such as extending beyond an additional 1 millimeter, or beyond an additional 2 millimeters, or beyond an additional 3 millimeters. Additionally or alternatively, the bulbous protrusion or bulbous portion may be a concave curved surface or a convex curved surface, particularly a convex curved surface, having a curvature that is at least about twice, at least about three times, or even at least about five times the minimum curvature found elsewhere in the bladder. Additionally or alternatively, the bulbous protrusion or bulbous portion may be a concave curved surface or a convex curved surface (such as a convex curved sidewall of a bladder in an article of footwear), wherein the height of the curved surface (such as its height when disposed in the article of footwear) is at least about 50% higher, at least about 100% higher, or at least about 150% higher than the minimum height found elsewhere in the bladder. Additionally or alternatively, the bulbous protrusion or bulbous portion may comprise a concave curved surface or convex curved surface, particularly a convex curved sidewall, having a radius of curvature that is less than half, less than one third, or even less than one fifth of the maximum radius of curvature found elsewhere in the bladder.

The multilayer film or sheets of multilayer film may be formed into a variety of wall geometries for the bladder (e.g., by thermoforming, blow molding, etc.) and the produced bladder may be inflated with one or more fluids (e.g., one or more gases) and sealed for a variety of applications, particularly as an air cushion for footwear.

Aspects of the invention

The following list of exemplary aspects supports and is supported by the disclosure provided herein.

According to aspect 1, the present disclosure relates to a multilayer film comprising:

one or more core regions, wherein each core region of the one or more core regions comprises more than one layer comprising gas barrier layers comprising at least one gas barrier material, the gas barrier layers alternating with elastomeric layers comprising at least one elastomeric material,

wherein each of the gas barrier layers has an average thickness in the range of from about 0.5 microns to about 2 microns, optionally from about 0.5 microns to about 1 micron; or each of the gas barrier layers has an average thickness in the range of about 0.01 microns to about 0.75 microns, particularly in the range of about 0.01 microns to about 0.5 microns;

Optionally wherein each of the elastomeric layers has an average thickness of from about 2 microns to about 8 microns thick, optionally from about 2 microns to about 4 microns thick.

According to aspect 2, the present disclosure relates to the multilayer film of aspect 1, wherein the number of gas barrier layers in each of the one or more core regions is in the range from about 20 to about 70; optionally wherein each of the one or more core regions comprises at least about 40 layers, optionally from about 50 to about 100 layers, from about 50 to about 90 layers, from about 50 to about 80 layers, from about 50 to about 70 layers, from about 60 to about 100 layers, from about 60 to about 90 layers, or from about 60 to about 80 layers.

According to aspect 3, the present disclosure relates to the multilayer film of aspect 1 or 2, wherein each of the one or more core regions has an average total thickness of less than 200 microns.

According to aspect 4, the present disclosure relates to the multilayer film of any one of the preceding aspects, wherein the gas barrier material comprises a nitrogen barrier material.

According to aspect 5, the present disclosure relates to the multilayer film of any one of the preceding aspects, wherein the gas barrier material comprises or consists essentially of one or more gas barrier polymers, and wherein the gas barrier material comprises a gas barrier polymer component consisting of all polymers present in the gas barrier material.

According to aspect 6, the present disclosure relates to the multilayer film of aspect 5, wherein the one or more gas barrier polymers comprise or consist essentially of: one or more thermoplastic vinylidene chloride polymers, one or more thermoplastic acrylonitrile polymers or copolymers, one or more thermoplastic polyamides, one or more thermoplastic epoxy resins, one or more thermoplastic amine polymers or copolymers, or one or more thermoplastic polyolefin homopolymers or copolymers.

According to aspect 7, the present disclosure relates to the multilayer film of aspect 6, wherein the one or more thermoplastic polyolefin homopolymers or copolymers comprise or consist essentially of one or more thermoplastic polyethylene copolymers.

According to aspect 8, the present disclosure relates to the multilayer film of aspect 6, wherein the one or more thermoplastic polyolefin homopolymers or copolymers comprise or consist essentially of one or more thermoplastic ethylene-vinyl alcohol copolymers.

According to aspect 9, the present disclosure is directed to the multilayer film of aspect 8, wherein the one or more thermoplastic ethylene-vinyl alcohol copolymers comprise from about 28 mole percent to about 44 mole percent ethylene content, optionally from about 32 mole percent to about 44 mole percent ethylene content.

According to aspect 10, the present disclosure relates to the multilayer film of any one of the preceding aspects, wherein the elastomeric material comprises or consists essentially of one or more thermoplastic elastomeric polymers, and wherein the elastomeric material comprises an elastomeric polymer component consisting of all of the polymers present in the elastomeric material.

According to aspect 11, the present disclosure relates to the multilayer film of aspect 10, wherein the one or more thermoplastic elastomeric polymers comprise or consist essentially of: one or more thermoplastic elastomer polyolefin homo-or copolymers, one or more thermoplastic elastomer polyamide homo-or copolymers, one or more thermoplastic elastomer polyester homo-or copolymers, one or more thermoplastic elastomer polyurethane homo-or copolymers, one or more thermoplastic elastomer styrene homo-or copolymers, or any combination thereof.

According to aspect 12, the present disclosure relates to the multilayer film of any one of the preceding aspects, wherein the elastomeric material comprises or consists essentially of one or more thermoplastic elastomeric polyurethane homo-or copolymers, optionally wherein the elastomeric material comprises or consists essentially of one or more thermoplastic elastomeric polyurethane homo-or copolymers based on polydiene polyols.

According to aspect 13, the present disclosure relates to the multilayer film of aspect 12, wherein the one or more thermoplastic elastomer polyurethane homo-or copolymers comprise more than one first segment derived from one or more polyols and more than one second segment derived from a diisocyanate.

According to aspect 14, the present disclosure relates to the multilayer film of aspect 12, wherein the one or more thermoplastic elastomer polyurethane homo-or copolymers are the polymerization product of a diisocyanate and one or more polyols.

According to aspect 15, the present disclosure relates to the multilayer film of aspect 12, wherein the thermoplastic elastomeric polyurethane homo-or copolymer comprises or consists essentially of one or more polydiene polyol-based thermoplastic elastomeric polyurethane homo-or copolymers, and wherein the polyol comprises or consists essentially of: polybutadiene polyol, polyisoprene polyol, partially or fully hydrogenated derivative of polybutadiene polyol, or partially or fully hydrogenated derivative of polyisoprene polyol, or any combination thereof.

According to aspect 16, the present disclosure relates to the multilayer film of aspects 13 or 14, wherein the one or more polyols comprise or consist essentially of: polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyethers, or any combination thereof.

According to aspect 17, the present disclosure relates to the multilayer film of aspects 13, 14 or 16, wherein the diisocyanate comprises or consists essentially of: aliphatic diisocyanates, aromatic diisocyanates, or any combination thereof.

According to aspect 18, the present disclosure relates to the multilayer film of aspect 17, wherein the aliphatic diisocyanate comprises or consists essentially of: hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene Diisocyanate (BDI), diisocyanato cyclohexyl methane (HMDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI), diisocyanato methylcyclohexane, diisocyanato methyltricyclodecane, norbornane Diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4' -dicyclohexylmethane diisocyanate (H12 MDI), diisocyanato dodecane, lysine diisocyanate, or any combination thereof.

According to aspect 19, the present disclosure relates to the multilayer film of aspect 17, wherein the aromatic diisocyanate comprises or consists essentially of: toluene Diisocyanate (TDI), TDI adducts with Trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), xylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hydrogenated Xylene Diisocyanate (HXDI), naphthalene-1, 5-diisocyanate (NDI), 1, 5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3' -dimethyldiphenyl-4, 4' -diisocyanate (DDDI), 4' -dibenzyl diisocyanate (DBDI), 4-chloro-1, 3-phenylene diisocyanate, or any combination thereof.

According to aspect 20, the present disclosure relates to the multilayer film of any one of the preceding aspects, wherein the gas barrier material has a melt flow index of from about 5 grams per 10 minutes to about 7 grams per 10 minutes at 190 degrees celsius when a weight of 2.16 kilograms is used.

According to aspect 21, the present disclosure is directed to the multilayer film of any one of the preceding aspects, wherein the elastomeric material has a melt flow index of from about 20 grams per 10 minutes to about 30 grams per 10 minutes at 190 degrees celsius when a weight of 2.16 kilograms is used.

According to aspect 22, the present disclosure relates to the multilayer film of aspect 20 or 21, wherein the melt flow index of the gas barrier material is from about 80% to about 120% of the melt flow index of the elastomeric material, optionally from about 90% to about 110% of the melt flow index of the elastomeric material, from about 95% to about 105% of the melt flow index of the elastomeric material, or wherein the melt flow index of the gas barrier material is substantially the same as the melt flow index of the elastomeric material, wherein when a weight of 2.16 kilograms is used, the melt flow index is measured in cubic centimeters per 10 minutes at 190 degrees celsius.

According to aspect 23, the present disclosure is directed to the multilayer film of any one of the preceding aspects, wherein the gas barrier material has a melting temperature of from about 165 degrees celsius to about 183 degrees celsius.

According to aspect 24, the present disclosure is directed to the multilayer film of any one of the preceding aspects, wherein the elastomeric material has a melting temperature from about 155 degrees celsius to about 165 degrees celsius.

According to aspect 25, the present disclosure relates to the multilayer film of aspects 23 or 24, wherein the melting temperature of the gas barrier material is within about 10 degrees celsius of the melting temperature of the elastomeric material, optionally within about 8 degrees celsius of the melting temperature of the elastomeric material, or within about 5 degrees celsius of the melting temperature of the elastomeric material.

According to aspect 26, the present disclosure relates to the multilayer film of any one of the preceding aspects, further comprising a blended material, wherein the blended material comprises or consists essentially of a blend of one or more additional thermoplastic elastomers and a second material, optionally wherein the second material comprises or consists essentially of one or more second polymers, optionally wherein the one or more second polymers comprises or consists essentially of one or more second thermoplastics.

According to aspect 27, the present disclosure is directed to the multilayer film of aspect 26, wherein the one or more second thermoplastics comprise one or more thermoplastic polyolefin homo-or copolymers, one or more thermoplastic polyamide homo-or copolymers, one or more thermoplastic polyester homo-or copolymers, one or more thermoplastic polyurethane homo-or copolymers, one or more thermoplastic styrene homo-or copolymers, or any combination thereof.

According to aspect 28, the present disclosure relates to the multilayer film of aspects 26 or 27, wherein the one or more second thermoplastics comprise or consist essentially of: thermoplastic polypropylene homo-or copolymer, thermoplastic polyethylene homo-or copolymer, thermoplastic polybutylene homo-or copolymer, or any combination thereof.

According to aspect 29, the present disclosure is directed to the multilayer film of any one of aspects 26-28, wherein the one or more second thermoplastics comprise or consist essentially of one or more thermoplastic polyethylene copolymers.

According to aspect 30, the present disclosure is directed to the multilayer film of any one of aspects 26-29, wherein the one or more second thermoplastics comprise or consist essentially of one or more thermoplastic ethylene-vinyl alcohol copolymers.

According to aspect 31, the present disclosure relates to the multilayer film of any one of aspects 26-30, wherein the polymer component of the blended material consists of one or more additional thermoplastic elastomeric polyurethane homopolymers or copolymers and one or more second thermoplastic ethylene-vinyl alcohol copolymers.

According to aspect 32, the present disclosure relates to the multilayer film of any one of aspects 26-31, wherein the polymer component of the thermoplastic elastomeric material consists of one or more additional thermoplastic elastomeric polyester-polyurethane copolymers and one or more second thermoplastic ethylene-vinyl alcohol copolymers.

According to aspect 33, the present disclosure is directed to the multilayer film of any one of aspects 26-32, wherein the blended material comprises one or more recycled additional thermoplastic elastomers, or one or more recycled secondary thermoplastics, or both.

According to aspect 34, the present disclosure relates to the multilayer film of any one of aspects 26-33, wherein the blended material is a phase separated blend of one or more additional thermoplastic elastomers and one or more second thermoplastics.

According to aspect 35, the present disclosure is directed to the multilayer film of aspect 34, wherein the phase separated blend comprises one or more phase separated regions comprising an interface between one or more additional thermoplastic elastomers and one or more second thermoplastics.

According to aspect 36, the present disclosure is directed to the multilayer film of any one of aspects 26-35, wherein the blend comprises about 95% by weight of one or more additional thermoplastic elastomers and about 5% by weight of one or more second thermoplastics, based on the total weight of the blend.

According to aspect 37, the present disclosure is directed to the multilayer film of any one of the preceding aspects, further comprising recycled material comprising one or more recycled polymers, optionally wherein the one or more recycled polymers comprise one or more recycled thermoplastics, optionally wherein the one or more recycled thermoplastics comprise one or more recycled thermoplastic elastomers; optionally wherein the recycled material comprises a recycled material polymer component consisting of one or more recycled thermoplastics, optionally wherein the recycled material polymer component comprises or consists essentially of one or more recycled thermoplastic elastomers.

According to aspect 38, the present disclosure relates to the multilayer film of aspect 37, wherein the recycled material comprises one or more recycled thermoplastic elastomers, optionally wherein the one or more recycled thermoplastic elastomers comprise one or more regrind thermoplastic elastomers, optionally wherein the one or more recycled thermoplastic elastomers or regrind thermoplastic elastomers comprise the thermoplastic elastomer material according to any one of aspects 10-19.

According to aspect 39, the present disclosure relates to the multilayer film of aspect 36 or 37, wherein the recycled material further comprises one or more recycled secondary thermoplastics, optionally wherein the one or more recycled secondary thermoplastics comprise one or more regrind secondary thermoplastics, optionally wherein the one or more recycled secondary thermoplastics or regrind secondary thermoplastics comprise the thermoplastic according to any of aspects 26-29.

According to aspect 40, the present disclosure is directed to the multilayer film of aspect 39, wherein the recycled material comprises one or more recycled thermoplastic polyurethane elastomers or regrind thermoplastic polyurethane elastomers, or one or more recycled thermoplastic ethylene-vinyl alcohol copolymers or regrind thermoplastic ethylene-vinyl alcohol copolymers, or both.

According to aspect 41, the present disclosure relates to the multilayer film of aspects 39 or 40, wherein the recycled material comprises one or more recycled thermoplastic elastomers or a blend of a recycled thermoplastic elastomer and one or more secondary thermoplastics, or wherein the recycled material comprises one or more thermoplastic elastomers and one or more recycled thermoplastics or a blend of one or more recycled secondary thermoplastics, optionally wherein the blend is a phase separated blend, and optionally wherein the phase separated blend comprises one or more interfaces between the one or more recycled thermoplastic elastomers and the one or more secondary thermoplastics.

According to aspect 42, the present disclosure relates to the multilayer film of any one of aspects 37-41, wherein the recycled material comprises from about 99% to about 90% by weight of the one or more recycled thermoplastic elastomers and from about 1% to about 10% by weight of the one or more second thermoplastic elastomers, based on the total weight of the recycled material, optionally wherein the recycled material comprises from about 99% to about 93% by weight of the one or more recycled thermoplastic elastomers and from about 1% to about 7% by weight of the one or more second thermoplastic elastomers, or from about 99% to about 95% by weight of the one or more recycled thermoplastic elastomers and from about 1% to about 5% by weight of the one or more second thermoplastic elastomers.

According to aspect 43, the present disclosure is directed to the multilayer film of any one of aspects 37-42, wherein the recycled material comprises from about 99% to about 50% recycled polymer or regrind polymer by weight, optionally from about 99% to about 75% recycled polymer or regrind polymer by weight, based on the total weight of the recycled material.

According to aspect 44, the present disclosure is directed to the multilayer film of any one of aspects 38-43, wherein the recycled material further comprises one or more virgin first thermoplastic elastomers, optionally wherein the one or more virgin first thermoplastic elastomers comprise one or more virgin thermoplastic polyurethane elastomers.

According to aspect 45, the present disclosure relates to the multilayer film of any one of the preceding aspects, further comprising one or more tie layers, each of the one or more tie layers comprising or consisting essentially of a tie material, wherein the one or more tie layers increase the bond strength between two adjacent layers.

According to aspect 46, the present disclosure is directed to the multilayer film of aspect 45, wherein the tie material of each of the one or more tie layers independently comprises or consists essentially of: polyurethane, polyacrylate, ethylene-acrylate copolymer, maleic anhydride grafted polyolefin, or any combination thereof, optionally wherein the linking material comprises or consists essentially of the blended material of any of aspects 26-36 or the recycled material of any of aspects 37-44.

According to aspect 47, the present disclosure relates to the multilayer film of aspects 45 or 46, wherein the tie material of the one or more tie layers independently comprises or consists essentially of one or more thermoplastic polyurethane elastomer homo-or copolymers, optionally wherein the one or more tie layers comprises or consists essentially of a polydiene polyol-based thermoplastic polyurethane.

According to aspect 48, the present disclosure relates to a multilayer film according to any one of the preceding aspects, further comprising one or more structural layers, each of the one or more structural layers independently comprising or consisting essentially of structural layer material, optionally wherein the structural layer material comprises or consists essentially of the blended material according to any one of aspects 26-36 or the recycled material according to any one of aspects 37-44.

According to aspect 49, the present disclosure is directed to the multilayer film of aspect 48, wherein the structural layer material of each of the one or more structural layers independently comprises or consists essentially of a polydiene polyol-based thermoplastic polyurethane.

According to aspect 50, the present disclosure relates to the multilayer film of any one of the preceding aspects, wherein the elastomeric material of the one or more core regions is a first elastomeric material, wherein the multilayer film further comprises a second elastomeric material, and wherein the formed multilayer film further comprises:

A first structural layer secured to a first side of one of the one or more core regions, optionally wherein the first structural layer comprises a second elastomeric material and optionally has an average thickness in a range from about 900 microns to about 1990 microns; and

a second structural layer secured to a second side of the core region opposite the first side of the core region, optionally wherein the second structural layer comprises a second elastomeric material and optionally has an average thickness in a range from about 900 microns to about 1990 microns.

According to aspect 51, the present disclosure relates to a multilayer film according to any one of the preceding aspects, further comprising one or more cap layers, wherein the one or more cap layers comprise or consist essentially of cap layer material, optionally wherein the cap layer material comprises or consists essentially of the blended material according to any one of aspects 26-36 or the recycled material according to any one of aspects 37-44.

According to aspect 52, the present disclosure relates to the multilayer film of aspect 51, wherein the cap layer material of the one or more cap layers comprises or consists essentially of: polyurethane, polyacrylate, ethylene-acrylate copolymer, maleic anhydride grafted polyolefin, or any combination thereof.

According to aspect 53, the present disclosure relates to the multilayer film of aspects 50 or 51, wherein the cap layer material of the one or more cap layers comprises, consists essentially of, or consists of a thermoplastic polyurethane, optionally a polydiene polyol-based thermoplastic polyurethane.

According to aspect 54, the present disclosure relates to the multilayer film of any one of aspects 51-53, wherein at least one of the one or more tie layers is positioned between one of the one or more structural layers and one of the one or more core regions.

According to aspect 55, the present disclosure is directed to the multilayer film of any one of aspects 51-54, wherein at least one of the one or more structural layers is positioned between one of the one or more tie layers and one of the one or more cap layers.

According to aspect 56, the present disclosure relates to the multilayer film of any one of the preceding aspects, wherein the multilayer film is a coextruded layered sheet or a laminated layered sheet.

According to aspect 57, the present disclosure is directed to the multilayer film of any one of the preceding aspects, wherein the multilayer film comprises a first cap layer, a first structural layer, a first tie layer, a core region, a second tie layer, a second structural layer, and a second cap layer, wherein the first cap layer inner surface contacts the first surface of the first structural layer, the second surface of the first structural layer contacts the first surface of the first tie layer, the second surface of the first tie layer contacts the first surface of the core region, the second surface of the core region contacts the first surface of the second tie layer, the second surface of the second tie layer contacts the first surface of the second structural layer, and the second surface of the second structural layer contacts the inner layer of the second cap layer.

According to aspect 58, the present disclosure relates to the multilayer film of any one of aspects 45-57, wherein the multilayer film has ase:Sub>A structure of ase:Sub>A-B-C-B-ase:Sub>A, wherein ase:Sub>A represents ase:Sub>A structural layer, B represents ase:Sub>A tie layer, and C represents ase:Sub>A core region.

According to aspect 59, the present disclosure relates to the multilayer film of any one of aspects 45-57, wherein the multilayer film has ase:Sub>A structure of D-ase:Sub>A-B-C-B-ase:Sub>A-D, wherein ase:Sub>A represents ase:Sub>A structural layer, B represents ase:Sub>A tie layer, C represents ase:Sub>A core region, and D represents ase:Sub>A cap layer.

According to aspect 60, the present disclosure is directed to the multilayer film of any one of the preceding aspects, wherein for a structure having a thickness of from about 72 micrometers to about 320 micrometers, one or more core regions have a gas permeability to nitrogen of from about 0.3 cubic centimeters per square meter per day to about 1.9 cubic centimeters per square meter per day measured at 23 degrees celsius and 0% relative humidity, optionally wherein each of the one or more core regions has a gas permeability to nitrogen of from about 0.3 cubic centimeters per square meter per day to about 1.9 cubic centimeters per square meter per day measured at 23 degrees celsius and 0% relative humidity.

According to aspect 61, the present disclosure is directed to the multilayer film of any one of the preceding aspects, wherein the multilayer film comprises or consists essentially of one or more protective layers, each of the one or more protective layers comprising or consisting of a protective material alone, wherein each of the one or more protective layers is adjacent to the core region and has a protective layer thickness, wherein the combination of the one or more protective layers and the adjacent core region has a minimum radius of curvature that is greater than a minimum radius of curvature that causes cracking of the core region or one or more individual layers within the core region.

According to aspect 62, the present disclosure relates to a method for manufacturing a multilayer film, wherein the multilayer film is the multilayer film according to any one of aspects 1 to 61, the method comprising:

the gas barrier material and the elastomeric material are co-extruded to form a multilayer film.

According to aspect 63, the present disclosure relates to the method of aspect 62, further comprising:

at least one tie layer is coextruded with a multilayer film including a core region to form a multilayer film including one or more core regions and tie layers.

According to aspect 64, the present disclosure relates to the method of aspect 62 or 63, further comprising:

at least one structural layer is applied to the multilayer film comprising the core region and the tie layer to form a multilayer film comprising one or more core regions, tie layer, and structural layer, wherein the structural layer comprises the structural layer material of aspect 48 or 49.

According to aspect 65, the present disclosure relates to the method of aspect 62 or 63, further comprising:

at least one structural layer is coextruded with a multilayer film comprising a core region and a tie layer to form a multilayer film comprising one or more core regions, tie layers, and structural layers.

According to aspect 66, the present disclosure relates to the method of any one of aspects 62-65, further comprising:

At least one cap layer is coextruded with a multilayer film comprising a core region, a tie layer, and a structural layer to form a multilayer film comprising a core region, a tie layer, a structural layer, and a cap layer.

According to aspect 67, the present disclosure is directed to a multilayer film produced by the method of any one of aspects 62-66.

According to aspect 68, the present disclosure is directed to an article comprising the multilayer film of any one of aspects 1-61 or 67, wherein the multilayer film of the article comprises a series of three or more layers comprising:

a first cap layer comprising or consisting essentially of a first cap layer material, the first cap layer comprising a first cap layer outer surface defining a first outer surface of the multilayer film, a first cap layer inner surface opposite the first cap layer outer surface, a first cap layer thickness extending from the first cap layer inner surface to the first cap layer outer surface, wherein the first cap layer outer surface defines a first outer surface of the article;

optionally a second cover layer comprising or consisting essentially of a second cover layer material, the second cover layer comprising a second cover layer outer surface defining a second outer surface of the multilayer film, a second cover layer inner surface opposite the second cover layer outer surface, a second cover layer thickness extending from the second cover layer inner surface to the second cover layer outer surface, optionally wherein the second cover layer outer surface defines a second outer surface of the article; and

One or more core regions, each core region of the one or more core regions comprising a core region first surface, a core region second surface, and a core region thickness extending from the core region first surface to the core region second surface, wherein each core region of the one or more core regions is positioned between the first cap layer inner surface and the second cap layer inner surface.

According to aspect 69, the present disclosure is directed to the article of aspect 68, wherein in the multilayer film, there is a second cap layer, and wherein the first cap layer material and the second cap layer material are substantially the same.

According to aspect 70, the present disclosure relates to the article of aspect 68, wherein in the multilayer film, there is a second cap layer, and wherein the first cap layer material and the second cap layer material are different.

According to aspect 71, the present disclosure is directed to the article of any one of aspects 68-70, wherein in the multilayer film, the first cap layer inner surface is in contact with the core region first surface, or the optional second cap layer inner surface is in contact with the core region second surface, or both.

According to aspect 72, the present disclosure is directed to the article of any one of aspects 68-71, wherein the multilayer film of the article is configured as a series of four or more layers comprising one or more structural layers, each of the one or more structural layers comprising a structural layer material and comprising a structural layer first surface, a structural layer second surface opposite the structural layer first surface, and a structural layer thickness extending from the structural layer first surface to the structural layer second surface;

Optionally wherein at least one of the one or more structural layers is positioned between the first cover layer and the core region, or between the second cover layer and the core region; or alternatively

Optionally wherein the one or more structural layers comprises two or more structural layers, and at least a first structural layer of the two or more structural layers is positioned between the inner surface of the first cap layer and the first surface of the core region, and at least a second structural layer of the two or more structural layers is positioned between the second surface of the core region and the inner surface of the second cap layer.

According to aspect 73, the present disclosure relates to the article of aspect 72, wherein in the multilayer film, a first surface of a first one of the structural layers is in contact with an inner surface of the first cap layer and a second surface of the first one of the structural layers is in contact with a first surface of one of the one or more core regions, or wherein a first surface of a second one of the one or more structural layers is in contact with a second surface of one of the one or more core regions and a second surface of the second one of the structural layers is in contact with an inner surface of the second cap layer, or both.

According to aspect 74, the present disclosure relates to an article of any one of aspects 68-73, wherein in the multilayer film, one or more structural layers comprise or consist essentially of the blended material of any one of aspects 26-36.

According to aspect 75, the present disclosure is directed to the article of any one of aspects 68-73, wherein in the multilayer film, one or more structural layers comprise or consist essentially of the recycled material of any one of aspects 37-44.

According to aspect 76, the present disclosure is directed to the article of any one of aspects 68-75, wherein the multilayer film of the article is configured as a series of five or more layers comprising one or more tie layers, each of the one or more tie layers comprising a tie layer first surface, a tie layer second surface opposite the tie layer first surface, and a tie layer thickness extending from the tie layer first surface to the tie layer second surface;

optionally wherein at least one of the one or more tie layers is positioned between one of the one or more structural layers and one of the one or more core regions, or between the first cap layer and one of the one or more structural layers, or between the second cap layer and one of the one or more structural layers, or any combination thereof; or alternatively

Optionally wherein the one or more tie layers comprise two or more tie layers and at least a first tie layer of the two or more tie layers is positioned between the second surface of the first structural layer and the first layer of the core region and at least a second tie layer of the two or more tie layers is positioned between the second surface of the core region and the first surface of the structural layer.

According to aspect 77, the present disclosure relates to the article of aspect 76, wherein in the multilayer film, a first surface of a first of the one or more tie layers is in contact with a second surface of a first of the one or more structural layers, and a second surface of the first of the one or more tie layers is in contact with a first surface of the core region; or wherein the first surface of the second one of the one or more connection layers is in contact with the second surface of one of the one or more core regions and the second surface of the second one of the one or more connection layers is in contact with the first surface of the second one of the one or more structural layers, or both.

According to aspect 78, the present disclosure is directed to the article of any one of aspects 76 or 77, wherein the multilayer film of the article comprises a first cap layer, a first structural layer, a first tie layer, a core region, a second tie layer, a second structural layer, and a second cap layer, wherein the first cap layer inner surface contacts the first surface of the first structural layer, the second surface of the first structural layer contacts the first surface of the first tie layer, the second surface of the first tie layer contacts the first surface of the core region, the second surface of the core region contacts the first surface of the second tie layer, the second surface of the second tie layer contacts the first surface of the second structural layer, and the second surface of the second structural layer contacts the inner layer of the second cap layer.

According to aspect 79, the present disclosure relates to the article of any one of aspects 68-78, wherein the article is a layered sheet, optionally wherein the layered sheet is a co-extruded layered sheet, or a laminated layered sheet.

According to aspect 80, the present disclosure is directed to an article of any one of aspects 68-79, wherein the article comprises a cushioning element.

According to aspect 81, the present disclosure is directed to the article of aspect 80, wherein the multilayer film forms an outwardly facing layer of the cushioning element.

According to aspect 82, the present disclosure is directed to the article of aspects 80 or 81, wherein the multilayer film is effective to retain the fluid in the cushioning element.

According to aspect 83, the present disclosure relates to an article of any one of aspects 80-82, wherein the cushioning element is a component of an article of footwear, an article of apparel, or an article of athletic equipment.

According to aspect 84, the present disclosure is directed to an article comprising the multilayer film of any one of aspects 1-61 or 67.

According to aspect 85, the present disclosure is directed to the article of aspect 84, wherein the article comprises an article of footwear, a component of an article of footwear, an article of apparel, a component of an article of apparel, an article of athletic equipment, a component of an article of athletic equipment, a personal protective article, a flexible flotation device, a rigid flotation device, a medical device, a prosthetic device, an orthopedic device, an accumulator, an article of furniture, or a component of an article of furniture.

According to aspect 86, the present disclosure is directed to the article of aspect 84, wherein the article comprises a tire or hose.

According to aspect 87, the present disclosure is directed to a method of manufacturing a consumer product, the method comprising attaching the article of any of aspects 84-86 to a second component.

According to aspect 88, the present disclosure relates to a consumer product produced by the method of aspect 87.

According to aspect 89, the present disclosure relates to a method for producing the multilayer film of any one of aspects 1-61, comprising:

the gas barrier material and the elastomeric material are co-extruded to form a multilayer film comprising one or more core regions.

According to aspect 90, the present disclosure relates to the method of aspect 89, further comprising:

at least one tie layer is applied to the multilayer film comprising one or more core regions to form a multilayer film comprising one or more core regions and a tie layer, wherein the tie layer comprises the tie material of aspect 45.

According to aspect 91, the present disclosure relates to the method of aspect 89, further comprising:

According to aspect 92, the present disclosure relates to the method of any one of aspects 89-91, further comprising:

at least one structural layer is applied to the multilayer film comprising the core region and the tie layer to form a multilayer film comprising one or more core regions, tie layer, and structural layer, wherein the structural layer comprises the structural layer material of aspect 47.

According to aspect 93, the present disclosure relates to the method of aspect 92, further comprising:

According to aspect 94, the present disclosure relates to the method of any one of aspects 89-93, further comprising:

at least one cap layer is applied to the multilayer film comprising the core region, the tie layer, and the structural layer to form a multilayer film comprising the core region, the tie layer, the structural layer, and the cap layer, wherein the cap layer comprises the cap layer material of any one of aspects 51-53.

According to aspect 95, the present disclosure relates to the method of any one of aspects 89-93, further comprising:

According to aspect 96, the present disclosure is directed to a bladder for an article of footwear, comprising:

a first sheet; and

a second sheet of material is provided which is formed from a first sheet of material,

wherein the first sheet, or the second sheet, or each of the first sheet and the second sheet comprises the multilayer film of any one of aspects 1-61 or 67,

wherein the first side of the first sheet faces the second side of the second sheet,

wherein the first sheet and the second sheet are joined together by a bond (bond) to form an interior cavity in a space between the first side of the first sheet and the second side of the second sheet,

wherein the bond extends around at least a portion of the perimeter of the lumen, optionally wherein the bond abuts around only one or more portions of the perimeter of the lumen, and comprises one or more holes capable of allowing gas to enter the lumen, forming an open lumen; or wherein the junction adjoins around the entire periphery of the inner cavity, forming a sealed bladder capable of retaining gas in the inner cavity at a pressure above, at or below atmospheric pressure, particularly at or above atmospheric pressure.

Wherein according to aspect 97, the present disclosure relates to the bladder of aspect 96, wherein the first sheet and the second sheet are adhesively bonded or thermally bonded, optionally wherein the bladder comprises a thermal bond formed by radio frequency welding between the first sheet and the second sheet.

According to aspect 98, the present disclosure relates to the bladder of aspects 96 or 97, wherein the junction is contiguous around the entire perimeter of the lumen, and the lumen comprises a gas, optionally wherein the gas is a pressurized gas.

According to aspect 99, the present disclosure relates to the bladder of aspect 98, the gas comprising nitrogen or air.

According to aspect 100, the present disclosure is directed to the bladder of any of aspects 96-99, wherein the inner lumen has an initial internal pressure of from about 20 pounds per square inch (137.9 kilopascals) to about 22 pounds per square inch (151.7 kilopascals).

According to aspect 101, the present disclosure relates to the bladder of aspect 100, wherein after 2 years of use, the inner lumen has a fill pressure of from at least about 70% to about 80% of the initial internal pressure.

According to aspect 102, the present disclosure is directed to the bladder of any of aspects 96-101, wherein each of the gas barrier layers has an average thickness in a range from about 0.5 microns to about 2 microns; or an average thickness in the range of from about 0.01 microns to about 0.75 microns, particularly in the range of from about 0.01 microns to about 0.5 microns.

According to aspect 103, the present disclosure is directed to the bladder of any of aspects 96-102, wherein each of the elastomeric layers has an average thickness in a range from about 2 microns to about 8 microns.

According to aspect 104, the present disclosure relates to the bladder of any of aspects 96-103, wherein the core region comprises at least 20, or at least 30, or at least 40, or at least 50 gas barrier layers; optionally up to 70 gas barrier layers.

According to aspect 105, the present disclosure is directed to the bladder of any of aspects 96-104, wherein the more than one elastomeric layer comprises at least 50 elastomeric layers.

According to aspect 106, the present disclosure is directed to the bladder of any of aspects 96-105, wherein the average total thickness of the core region is in the range from about 125 microns to about 200 microns, and wherein the multilayer film further comprises:

a first structural layer secured to the first side of the core region, optionally wherein the first structural layer has an average thickness in a range from about 900 microns to about 1990 microns; and

a second structural layer secured to a second side of the core region opposite the first side of the core region, optionally wherein the second structural layer has an average thickness in a range from about 900 microns to about 1990 microns.

According to aspect 107, the present disclosure is directed to the bladder of any of aspects 96-106, wherein the structural layer material of each of the one or more structural layers independently comprises or consists essentially of a polydiene polyol-based thermoplastic polyurethane.

According to aspect 108, the present disclosure relates to the bladder of any one of aspects 96-107, further comprising one or more cover layers, wherein the one or more cover layers comprise or consist essentially of cover layer material.

According to aspect 109, the present disclosure relates to the bladder of aspect 108, wherein the cap layer material of the one or more cap layers comprises or consists essentially of: polyurethane, polyacrylate, ethylene-acrylate copolymer, maleic anhydride grafted polyolefin, or any combination thereof.

According to aspect 110, the present disclosure relates to the bladder of aspects 108 or 109, wherein each cap layer has a thickness in a range from about 5 microns to about 25 microns.

According to aspect 111, the present disclosure is directed to the bladder of any of aspects 96-110, further comprising one or more tie layers, each of the one or more tie layers comprising or consisting essentially of a tie material, alone, wherein the one or more tie layers increase the bond strength between two adjacent layers.

According to aspect 112, the present disclosure is directed to the bladder of aspect 111, wherein the connective material of each of the one or more connective layers independently comprises or consists essentially of: polyurethane, polyacrylate, ethylene-acrylate copolymer, maleic anhydride grafted polyolefin, or any combination thereof.

According to aspect 113, the present disclosure relates to the bladder of aspects 111 or 112, wherein each of the one or more tie layers has an average thickness in a range from about 5 microns to about 20 microns.

According to aspect 114, the present disclosure relates to a bladder of any one of aspects 96-113, wherein the bladder is configured as an air cushion for an article of footwear, and wherein the bladder comprises one or more bulbous protrusions.

According to aspect 115, the present disclosure relates to the bladder of aspect 114, wherein the one or more bulbous protrusions are present in a heel portion of the cushion, a lateral portion of the cushion, a medial portion of the cushion, or any combination thereof.

According to aspect 116, the present disclosure relates to a bladder comprising:

a first sheet; and

wherein the first sheet and the second sheet are joined together by bonds at discrete locations.

According to aspect 117, the present disclosure is directed to the bladder of aspect 116, wherein the bond between the first sheet and the second sheet is formed

A first generally U-shaped chamber; and

a generally U-shaped second chamber spaced from the first chamber in a direction extending along the longitudinal axis of the bladder.

According to aspect 118, the present disclosure relates to the bladder of aspect 117, wherein the first chamber and the second chamber are in gaseous communication with each other.

According to aspect 119, the present disclosure relates to the balloon of aspects 117 or 118, wherein the first chamber is aligned with the second chamber in a direction extending along a longitudinal axis of the balloon.

According to aspect 120, the present disclosure is directed to the bladder of any of aspects 117-119, wherein the first chamber comprises a first leg and a second leg joined by a first arcuate segment, and the second chamber comprises a third leg and a fourth leg joined by a second arcuate segment.

According to aspect 121, the present disclosure relates to the bladder of aspect 120, wherein the first, second, third, and fourth legs extend in the same direction.

According to aspect 122, the present disclosure is directed to the bladder of any of aspects 120 or 121, wherein the first leg and the second leg are disposed between the first arcuate section and the second arcuate section.

According to aspect 123, the present disclosure is directed to the bladder of any of aspects 120-122, wherein at least one of the first, second, third, or fourth leg is elongate.

According to aspect 124, the present disclosure is directed to the bladder of any of aspects 120-123, further comprising a third chamber extending between the first leg and the second leg in a direction toward the first arcuate section.

According to aspect 125, the present disclosure is directed to the bladder of aspect 124, wherein the third chamber is spaced apart from the first leg and the second leg.

According to aspect 126, the present disclosure is directed to the bladder of any of aspects 120-125, further comprising a fourth chamber extending between the third leg and the fourth leg in a direction toward the second arcuate section.

According to aspect 127, the present disclosure relates to the bladder of aspect 126, wherein the fourth chamber is spaced apart from the third leg and the fourth leg.

According to aspect 128, the present disclosure relates to the bladder of aspects 126 or 127, wherein at least one of the third chamber or the fourth chamber is elongate.

According to aspect 129, the present disclosure is directed to the bladder of any of aspects 117-128, further comprising a web region (web area) defining the first chamber and the second chamber.

According to aspect 130, the present disclosure is directed to the bladder of aspect 129, wherein the web region comprises a first portion that is generally U-shaped and a second portion that is generally U-shaped.

According to aspect 131, the present disclosure is directed to the balloon of any one of aspects 96-130, wherein the balloon does not exhibit cleavage after at least 350,000 KIM cycles or at least 400,000 KIM cycles.

According to aspect 132, the present disclosure is directed to the bladder of any one of aspects 96-131, wherein the bladder has a gas permeability of no more than 120% of the original gas permeability after 320,000 KIM cycles.

According to aspect 133, the present disclosure is directed to the bladder of any one of aspects 96-132, wherein the bladder has a gas permeability to nitrogen of from about 0.5 cubic centimeters per square meter per day to about 2 cubic centimeters per square meter per day measured at 23 degrees celsius and 0 percent relative humidity after from about 0 KIM cycles to about 320,000 KIM cycles for a structure having a thickness of from about 72 micrometers to about 320 micrometers.

According to aspect 134, the present disclosure relates to the bladder of any one of aspects 96-133, wherein the bladder is a thermoformed bladder.

According to aspect 135, the present disclosure is directed to the multilayer film of any one of aspects 1-61 or 67 or the pouch of any one of aspects 96-134, the multilayer film or pouch further comprising a decorative element.

According to aspect 136, the present disclosure relates to a method for applying a decorative element to the multilayer film of any one of aspects 1-61 or 67 or the pouch of any one of aspects 96-134, wherein the method comprises printing, painting, brushing or spraying the decorative element onto the multilayer film or pouch; or immersing the multilayer film or capsule in a decorative element; or pressing the decorative element and the multilayer film or capsule together to apply the decorative element, wherein the decorative element is in the form of a solid, liquid, or gas when applied to the multilayer film or capsule, optionally wherein the decorative element comprises a pigment or dye or both a pigment and a dye.

According to aspect 137, the present disclosure relates to the method of aspect 135 or 136, wherein the decorative element comprises a pigment or dye or both, and the step of applying the decorative element to the multilayer film or bladder comprises curing the decorative element on the multilayer film or bladder, optionally wherein curing comprises drying the decorative element, or crosslinking the decorative element, or injecting at least a portion of the decorative element into the polymeric material of the outer surface of the multilayer film or bladder, or bonding the decorative element to the outer surface of the multilayer film or bladder, or any combination thereof.

According to aspect 138, the present disclosure relates to the method of aspect 137, wherein the method comprises the step of bonding the decorative element to the outer surface of the multilayer film or bladder, and the bonding comprises forming an adhesive bond by applying an adhesive to the first side of the decorative element or the outer surface of the multilayer film or bladder, or both, and then pressing the first side of the decorative element and the outer surface of the multilayer film or bladder together.

According to aspect 139, the present disclosure relates to the method of aspect 137, wherein the method comprises the step of bonding the decorative element to the outer surface of the multilayer film or bladder, and the bonding comprises forming a thermal bond between the thermoplastic material of the first side of the decorative element and the thermoplastic material defining the outer surface of the multilayer film or bladder by: softening or melting at least an outer portion of one or both of the thermoplastic materials, and pressing the first side of the decorative element and the outer surface of the multilayer film or bladder against each other while one or both of the thermoplastic materials is softened or melted, and then resolidifying the softened or melted outer portion.

According to aspect 140, the present disclosure relates to the method of aspect 137, wherein the decorative element is applied to the outer surface of the multilayer film or capsule, and the decorative element is injected into the material defining the outer surface of the multilayer film or capsule during application or during curing or both application and curing, optionally wherein the decorative element is applied as a solution of a dye.

According to aspect 141, the present disclosure relates to a multilayer film or pouch comprising a decorative element applied according to the method of any one of aspects 136-140.

According to aspect 142, the present disclosure is directed to the balloon of any one of aspects 96-134, wherein the lumen of the balloon further comprises a spacer member.

According to aspect 143, the present disclosure relates to the bladder of aspect 142, wherein the spacer component comprises a foamed component, an injection molded component, a 3D printed component, a textile component, or any combination thereof.

According to aspect 144, the present disclosure relates to the bladder of aspect 143, wherein the foamed member comprises more than one foam particle.

According to aspect 145, the present disclosure relates to the bladder of any of aspects 142-144, wherein the spacing member comprises:

a first layer;

A second layer; and

more than one connecting member extending between and joining the first and second layers.

According to aspect 146, the present disclosure relates to the balloon of any one of aspects 96-134, wherein the lumen of the balloon is hollow.

According to aspect 147, the present disclosure is directed to the bladder of any of aspects 96-134 or 142-146, wherein the bladder further comprises a textile.

According to aspect 148, the present disclosure relates to the bladder of aspect 147, wherein the textile forms a layer of the first sheet, a layer of the second sheet, or a layer of both the first sheet and the second sheet.

According to aspect 149, the present disclosure relates to the bladder of aspect 148, wherein the textile forms an outer layer of the first sheet and/or an outer layer of the second sheet, or wherein the textile forms an inner layer of the first sheet and/or an inner layer of the second sheet.

According to aspect 150, the present disclosure relates to the bladder of aspect 148 or 149, wherein the textile is a spacer textile (spacer textile) having a first textile face, a second textile face, and a textile thickness extending from the first textile face to the second textile face, wherein the textile thickness is from about 0.3 cm to about 3 cm or from about 0.5 cm to about 1 cm, optionally wherein the fiber density of the first textile face and the second textile face is at least 25% greater, or at least 50% greater, or at least 75% greater than the fiber density between the first textile face and the second textile face.

According to aspect 151, the present disclosure relates to the bladder of any of aspects 147-150, wherein the fibers or yarns of the textile comprise or consist essentially of synthetic fibers or yarns formed from one or more thermoplastic materials, optionally wherein the thermoplastic material of the synthetic fibers or yarns comprises or consists essentially of a thermoplastic elastomeric material.

According to aspect 152, the present disclosure relates to the bladder of aspect 151, wherein the melting temperature of the thermoplastic material of the synthetic fibers or yarns is within 20 degrees celsius of the melting temperature of the thermoplastic material forming the outer layer of the bladder.

According to aspect 153, the present disclosure relates to the bladder of aspects 151 or 152, wherein the first sheet, the second sheet, or both comprise layered sheets, and the polymeric component of the thermoplastic material of the synthetic fibers or yarns is substantially the same as the polymeric component of the thermoplastic material of the one or more layers of the first sheet and/or the one or more layers of the second sheet, optionally wherein the polymeric component of the thermoplastic material of the synthetic fibers or yarns is substantially the same as the polymeric component of the thermoplastic material of the cover layer or structural layer of the first sheet and/or the cover layer or structural layer of the second sheet.

According to aspect 154, the present disclosure relates to a cushioning element comprising a bladder according to any one of aspects 96-153.

According to aspect 155, the present disclosure relates to the cushioning element of aspect 154, wherein the cushioning element is a cushioning element for a consumer product, optionally wherein the cushioning element is a cushioning element for an article of apparel, an article of footwear, or an article of athletic equipment.

According to aspect 156, the present disclosure relates to the cushioning element of aspect 155, wherein the cushioning element is a cushioning element for an article of footwear and the cushioning element for the article of footwear is an air cushion.

According to aspect 157, the present disclosure relates to an article of footwear comprising:

the bladder of any of aspects 96-134 or 142-153.

According to aspect 158, the present disclosure relates to a sole structure for an article of footwear having an upper, the sole structure comprising:

a heel region disposed in the rear end;

a forefoot region disposed in the front end;

a midfoot region disposed intermediate between the heel region and the forefoot region; and

the bladder of any of aspects 96-134 or 142-153.

According to aspect 159, the present disclosure is directed to the sole structure of aspect 158, wherein the bladder is disposed in the heel area.

According to aspect 160, the present disclosure is directed to an article of footwear comprising a bladder according to any one of aspects 96-134 or 142-153.

According to aspect 161, the present disclosure relates to an article of footwear comprising a sole structure according to aspects 158 or 159.

According to aspect 162, the present disclosure relates to an article of footwear, the article of footwear comprising:

an upper for an article of footwear; and

the sole structure of the shoe is provided with a sole,

wherein the upper, the sole structure, or both the upper and the sole structure include a bladder that includes:

a first membrane secured to a second membrane to define a sealed lumen; and

a fluid disposed within the sealed interior cavity at a pressure of one atmosphere (101 kilopascals) or greater;

wherein the first film, the second film, or each of the first film and the second film is a multilayer film comprising a core region comprising at least 50 gas barrier layers and more than one elastomeric layer, wherein the gas barrier layers alternate with the elastomeric layers, wherein each of the gas barrier layers comprises at least one gas barrier material, and wherein each of the elastomeric layers comprises at least one elastomeric material, and wherein the core region has a total thickness of less than 200 microns.

According to aspect 163, the present disclosure is directed to an article of footwear according to aspect 162, wherein the article of footwear includes a sole structure that includes a bladder.

According to aspect 164, the present disclosure is directed to an article of footwear according to aspects 162 or 163, wherein the article of footwear further includes a bottom layer secured to the upper.

According to aspect 165, the present disclosure relates to an article of footwear according to any one of aspects 162-164, wherein the article of footwear further comprises an outsole, optionally wherein the outsole is secured to the bladder.

According to aspect 166, the present disclosure is directed to an article of footwear according to aspects 164 or 165, wherein the bladder is disposed between the bottom layer and the outsole.

According to aspect 167, the present disclosure is directed to an article of footwear having a forefoot region, a midfoot region, and a heel region along a longitudinal axis of the article of footwear, the article of footwear comprising:

a vamp; and

a sole structure, the sole structure comprising a bladder, wherein the bladder comprises a bulb, and wherein the bladder comprises at least a first multilayer film having more than one gas barrier layer and more than one elastomeric layer, wherein the gas barrier layers alternate with the elastomeric layers; optionally wherein the bulbous portion has a first height in the uncompressed state and a second height in the compressed state, the second height being less than 50% of the first height.

According to aspect 168, the present disclosure is directed to an article of footwear according to aspect 167, wherein the bulbous portion of the bladder is a bulbous heel portion and is in a heel region of the article of footwear.

According to aspect 169, the present disclosure relates to an article of footwear according to aspects 167 or 168, wherein the bladder comprises a second multilayer film, optionally wherein the structure of the second multilayer film differs from the structure of the first multilayer film in the number of gas barrier layers and elastomeric layers, or differs from the structure of the first multilayer film in the thickness of the gas barrier layers and elastomeric layers, or differs from the structure of the first multilayer film in both the number and thickness of the gas barrier layers and elastomeric layers.

According to aspect 170, the present disclosure is directed to an article of footwear according to any one of aspects 167-169, wherein the more than one gas barrier layer includes at least 20 (e.g., at least 30 or at least 40) gas barrier layers; and optionally up to 70 gas barrier layers.

According to aspect 171, the present disclosure is directed to an article of footwear according to any one of aspects 167-170, wherein the more than one gas barrier layer includes at least 50 gas barrier layers.

According to aspect 172, the present disclosure is directed to an article of footwear according to any one of aspects 167-171, wherein the average total thickness of the more than one gas barrier layers and the more than one elastomeric layers is less than 200 micrometers.

According to aspect 173, the present disclosure is directed to the article of footwear of aspect 172, wherein the average total thickness of the more than one gas barrier layers and the more than one elastomeric layers is less than 175 microns.

According to aspect 174, the present disclosure is directed to an article of footwear according to any one of aspects 167-173, wherein the first height is in a range from about 10 millimeters to about 24 millimeters.

According to aspect 175, the present disclosure is directed to an article of footwear of aspect 174, wherein the first height is in a range from about 15 millimeters to about 24 millimeters.

According to aspect 176, the present disclosure is directed to an article of footwear according to any one of aspects 167-175, wherein the second height is in a range from about 8.6 millimeters to about 13.6 millimeters.

According to aspect 177, the present disclosure is directed to the article of footwear of aspect 176, wherein the second height is in a range from about 8.6 millimeters to about 11 millimeters.

According to aspect 178, the present disclosure is directed to the article of footwear of any of aspects 167-177, wherein the more than one gas barrier layer comprises, in composition, one or more thermoplastic vinylidene chloride polymers, one or more thermoplastic acrylonitrile polymers or copolymers, one or more thermoplastic polyamides, one or more thermoplastic epoxy resins, one or more thermoplastic amine polymers or copolymers, one or more thermoplastic polyolefin homopolymers or copolymers, or any combination thereof.

According to aspect 179, the present disclosure is directed to an article of footwear according to any one of aspects 167-178, wherein the more than one gas barrier layer comprises ethylene vinyl alcohol in composition.

According to aspect 180, the present disclosure is directed to an article of footwear according to any one of aspects 167-179, wherein more than one elastomeric layer compositionally includes one or more thermoplastic elastomeric polymers.

According to aspect 181, the present disclosure is directed to an article of footwear according to any one of aspects 167-180, wherein the more than one elastomeric layer comprises a polyolefin copolymer, a polyester, a thermoplastic polyurethane, a styrene block copolymer, or any combination thereof in composition.

According to aspect 182, the present disclosure is directed to an article of footwear according to any one of aspects 167-181, wherein the more than one elastomeric layer comprises thermoplastic polyurethane in composition.

According to aspect 183, the present disclosure is directed to an article of footwear according to any of aspects 167-182, wherein the multilayer film further comprises at least one structural layer having an average thickness in a range from about 900 micrometers to about 1990 micrometers.

According to aspect 184, the present disclosure is directed to an article of footwear according to any one of aspects 167-183, wherein the ball heel portion extends beyond a first rearward distance of the outsole in the uncompressed state and extends beyond a second rearward distance of the outsole in the compressed state, and wherein a difference between the first rearward distance and the second rearward distance is in a range from about 1.1 millimeters to about 1.9 millimeters.

According to aspect 185, the present disclosure is directed to the article of footwear of aspect 184, wherein the difference between the first rearward distance and the second rearward distance is in a range from about 1.1 millimeters to about 1.5 millimeters.

According to aspect 186, the present disclosure is directed to an article of footwear according to any of aspects 167-185, further comprising a midsole layer disposed between the upper and the cushion.

According to aspect 187, the present disclosure relates to the article of footwear of aspect 186, wherein the geometry of the ball heel portion in the uncompressed state defines a first vector extending from a rearmost location (point) of the uncompressed ball heel portion to a rearmost location of the midsole floor, and a second vector extending from a rearmost location of the uncompressed ball heel portion to a rearmost location of the outsole, and wherein the first vector and the second vector extend from each other at an angle in a range from about 115 degrees to about 137.5 degrees.

According to aspect 188, the present disclosure is directed to the article of footwear of aspect 187, wherein the geometry of the ball heel portion in the compressed state defines a third vector extending from a rearmost location of the compressed ball heel portion to a rearmost location of the midsole floor and a fourth vector extending from the rearmost location of the compressed ball heel portion to a rearmost location of the outsole, and wherein the third vector and the fourth vector extend from each other at an angle in a range from about 38 degrees to about 107 degrees.

According to aspect 189, the present disclosure is directed to an article of footwear according to any one of aspects 167-188, further comprising a gas held within the cushion.

According to aspect 190, the present disclosure is directed to an article of footwear according to any of aspects 167-189, wherein the cushion has an initial inflation pressure of from about 20 pounds per square inch (137.9 kilopascals) to about 22 pounds per square inch (151.7 kilopascals).

According to aspect 191, the present disclosure is directed to the article of footwear of aspect 190, wherein the multilayer film is configured such that after 1 year of use, the cushion maintains a fill pressure of at least about 70% of the initial fill pressure, at least 80% of the initial fill pressure, or at least 90% of the initial fill pressure.

According to aspect 192, the present disclosure is directed to the article of footwear of aspect 191, wherein the multilayer film is configured such that after 2 years of use, the cushion maintains a fill pressure of at least about 70% of the initial fill pressure, at least 80% of the initial fill pressure, or at least 90% of the initial fill pressure.

The article of footwear of any of aspects 167-192, according to aspect 193, wherein the bulbous heel portion exhibits no visually observable cracking after at least 350,000 KIM cycles or at least 400,000 KIM cycles.

According to aspect 194, the present disclosure is directed to an article of footwear of any of aspects 167-193, wherein the cushion has a gas permeability of no more than 120% of the original gas permeability after 320,000 KIM cycles.

The article of footwear of any of aspects 167-194, according to aspect 195, wherein the air cushion has a gas permeability to nitrogen, measured at 23 degrees celsius and 0% relative humidity, ranging from about 0.5 cubic centimeters per square meter per day to about 2 cubic centimeters per square meter per day after from about 0 KIM cycles to about 320,000 KIM cycles for structures having a thickness ranging from about 72 micrometers to about 320 micrometers.

According to aspect 196, the present disclosure relates to a method of manufacturing a bladder according to any one of aspects 96-134 or 142-153, wherein the bladder comprises a first sheet and a second sheet, wherein a first side of the first sheet faces a second side of the second sheet, the method comprising:

bonding the first sheet and the second sheet together to form a cavity in a space between the first side of the first sheet and the second side of the second sheet, wherein the bond extends around at least a portion of the perimeter of the cavity, optionally wherein the bond abuts around only one or more portions of the perimeter of the cavity, and comprises one or more holes capable of allowing fluid to enter the cavity, forming an open cavity; or wherein the junction abuts around the entire perimeter of the lumen, forming a sealed bladder capable of retaining fluid in the lumen;

Wherein the first sheet, the second sheet, or both comprise the multilayer film according to any one of aspects 1-61 or 67.

According to aspect 197, the present disclosure relates to the method of aspect 196, wherein the balloon comprises one or more lumens, optionally wherein the one or more lumens comprise at least two lumens, and optionally wherein each of the one or more lumens is an open lumen, or each of the one or more lumens is a sealed balloon, or the one or more lumens comprise at least one open lumen and at least one sealed balloon.

According to aspect 198, the present disclosure relates to the method of aspect 197, wherein bonding comprises adhesively bonding or thermally bonding, optionally wherein the first sheet and the second sheet comprise a thermal bond formed by Radio Frequency (RF) welding.

According to aspect 199, the present disclosure is directed to the method of any one of aspects 196-198, wherein the method further comprises closing one or more holes in the perimeter of the inner lumen, thereby forming a sealed pouch.

According to aspect 200, the present disclosure relates to the method of aspect 199, wherein closing comprises forming an adhesive bond or a thermal bond between the first side of the first sheet and the second side of the second sheet at one or more apertures.

According to aspect 201, the present disclosure is directed to the method of any one of aspects 196-200, further comprising inflating the sealed bladder with a fluid.

According to aspect 202, the present disclosure relates to the method of any one of aspects 196-201, the method further comprising subjecting the balloon to a thermoforming step, optionally wherein the thermoforming step occurs prior to inflation of the balloon, or wherein the thermoforming step occurs simultaneously with inflation of the balloon, or wherein the thermoforming step occurs after inflation of the balloon, or any combination thereof.

According to aspect 203, the present disclosure relates to the method of aspect 202, wherein the bladder comprises an outer surface, and wherein thermoforming comprises placing the bladder in a mold, wherein the mold comprises an inner molding surface.

According to aspect 204, the present disclosure relates to the method of aspect 203, wherein the inner molding surface contacts an outer surface of the bladder.

According to aspect 205, the present disclosure relates to the method of aspect 203, wherein a protective sleeve having an outer surface is placed between at least a portion of the outer surface of the bladder and the inner molding surface, and wherein the outer surface of the protective sleeve contacts the inner molding surface.

According to aspect 206, the present disclosure relates to the method of aspect 205, wherein the protective sheath comprises an inner surface, wherein the inner surface of the protective sheath contacts the outer surface of the bladder; optionally wherein the inner surface of the protective sleeve comprises a raised pattern.

According to aspect 207, the present disclosure relates to the method of aspects 205 or 206, wherein the inner surface of the protective sleeve comprises a raised pattern, and wherein the raised pattern is embossed into the bladder during thermoforming.

According to aspect 208, the present disclosure is directed to the method of any one of aspects 202-207, wherein thermoforming includes increasing the temperature of the bladder to the softening temperature of the first sheet, the second sheet, or both, conforming the outer surface of the bladder to the shape of the inner molding surface.

According to aspect 209, the present disclosure is directed to the method of any one of aspects 202-208, wherein thermoforming further comprises applying a compressive force between the outer surface of the bladder and the inner molding surface, or optionally between the outer surface of the protective cover and the inner molding surface.

According to aspect 210, the present disclosure relates to the method of aspect 209, wherein the compressive force provides a pressure differential between the outer surface of the bladder and the inner molding surface, or optionally between the outer surface of the protective cover and the inner molding surface.

According to aspect 211, the present disclosure relates to the method of aspect 210, wherein the pressure differential is a positive pressure differential.

According to aspect 212, the present disclosure relates to the method of aspect 210, wherein the pressure differential is a negative pressure differential.

According to aspect 213, the present disclosure relates to a balloon made by the method of any one of aspects 196-212.

According to aspect 214, the present disclosure relates to a method for manufacturing an article of footwear, the method comprising:

the bladder of any of aspects 96-134 or 142-153 is secured to an upper for an article of footwear.

According to aspect 215, the present disclosure is directed to the method of aspect 214, further comprising securing the bladder of any of aspects 96-134, 142-153, or 213 to the outsole and midsole layers such that the bladder is disposed between the midsole layer and the outsole to create a sole structure; and

the midsole layer is secured to an upper for an article of footwear.

According to aspect 216, the present disclosure relates to an article of footwear manufactured by the method of aspects 214 or 215.

Bladder and balloon

In one aspect, the balloon may include a first sheet, a second sheet, or both, of a multilayer film that are bonded together (e.g., thermally bonded together) to form an interior cavity in a space between the first sheet and the second sheet, wherein the bond extends around at least a portion of a perimeter of the interior cavity. The lumen may be filled with one or more fluids (e.g., one or more gases) during or after the bonding step. In some aspects, the junction extends around the entire perimeter of the lumen, providing a sealed balloon. In other aspects, the junction extends around only a portion of the entire perimeter (e.g., around a majority of the entire perimeter) and defines a sealable aperture configured to receive a fluid/gas into the lumen. In each aspect, the resulting balloon is capable of retaining received fluid/gas in the inner cavity for long term use when inflated and sealed due to the gas barrier properties of the multilayer film. In some aspects, the bladder may include a second multilayer film, optionally wherein the structure of the second multilayer film differs from the structure of the first multilayer film in the number of gas barrier layers and elastomeric layers, or differs from the structure of the first multilayer film in the thickness of the gas barrier layers and elastomeric layers, or differs from the structure of the first multilayer film in both the number and thickness of the gas barrier layers and elastomeric layers.

As discussed in more detail below, the multilayer film includes one or more core regions, wherein each of the one or more core regions includes a plurality of layers alternating between a thin gas barrier layer (each having at least one gas barrier material) and an elastomeric layer (each having at least one elastomeric material). In aspects, the gas barrier material of the gas barrier layer and the elastomeric material of the elastomeric layer have similar processing characteristics in the core region and may be co-extruded with reduced interlayer shear. This allows alternating gas barrier layers and elastomeric layers to be coextensive while maintaining their structural integrity and desired layer thicknesses for the resulting multilayer film.

In aspects, to impart good gas barrier properties, the gas barrier material of the gas barrier layer is generally less flexible (e.g., more glass-like) than the elastomeric material of the elastomeric layer. In particular, the elastomeric material of the elastomeric layer may have a lower glass transition temperature than the gas barrier material of the gas barrier layer, for example 20 degrees celsius, in particular 50 degrees celsius lower. Thus, the gas barrier layer of the core region is more prone to micro-cracking when subjected to repeated excessive stress loads, such as potentially generated during flexing and release of the multilayer film.

However, in one aspect, it has been found that using at least about twenty, at least about thirty, or at least about forty gas barrier layers wherein each gas barrier layer has an average layer thickness of less than about 2 microns or from about 0.5 microns to about 2 microns, optionally less than about 0.5 microns, and a corresponding number of elastomeric layers such that each core region alternates between a gas barrier layer and an elastomeric layer, can increase the flexibility of the core region while maintaining the durability and gas barrier properties of the multilayer film. Thus, airbags incorporating multilayer films can be designed to withstand repeated flexing and release (e.g., by walking, running, and jumping) and have reduced or no visually observable cracking, breaking, or blurring (sizing) over prolonged use.

It has been found that using a multilayer film wherein each gas barrier layer has an average layer thickness of at least 20, or at least 30, or at least 40 gas barrier layers of less than about 2 microns, optionally less than about 0.75 microns, or optionally less than about 0.5 microns, or in the range from about 0.5 microns to about 2 microns, optionally in the range from about 0.01 microns to about 0.75 microns, or optionally in the range from about 0.01 microns to about 0.5 microns, and such that in each core region, the respective number of elastomer layers of alternating gas barrier layers and elastomer layers can increase the flexibility of the core region while maintaining the durability and gas barrier properties of the multilayer film. Thus, airbags incorporating multilayer films can be designed to withstand repeated flexing and release (e.g., by walking, running, and jumping) and have reduced or no visually observable cracking, or blurring over prolonged use.

In aspects, the multilayer films and airbags, bladders, and other enclosed articles and/or hollow articles comprised thereof are configured to withstand repeated flexing and release without cracking, breaking, or producing haze or other significant change in appearance. In an exemplary aspect, a bladder constructed from a sheet material that includes a multi-layer film may be incorporated into a sole structure of an article of footwear as a cushioning element. Further, in this aspect, actions such as walking, running, and jumping may cause the bag to flex and release; however, bladders and other articles that include multilayer films have a longer useful life than known cushioning elements. In one aspect, disclosed herein is an article comprising the disclosed multilayer film. In one aspect, the article is a cushioning element. In another aspect, the multilayer film forms an outwardly facing layer of the cushioning element and is effective to retain fluid in the cushioning element. In any of these aspects, the cushioning element is a component of a consumer product such as an article of footwear, an article of apparel, or an article of athletic equipment. In another aspect, the cushioning element is a cushioning element for an article of footwear, and the cushioning element for an article of footwear is an air cushion.

In another aspect, each of the elastomeric layers may have an average thickness of from about 2 microns to about 8 microns, or from about 2 microns to about 5 microns, from about 5 microns to about 8 microns, or from about 4 microns to about 6 microns.

In some aspects, the core region comprises at least 50 gas barrier layers, or from about 50 to about 100 gas barrier layers, from about 60 to about 80 gas barrier layers, or from about 60 to about 70 gas barrier layers. In one aspect, the core region comprises at least 50 elastomeric layers, or from about 50 to about 100 elastomeric layers, from about 60 to about 80 elastomeric layers, or from about 60 to about 70 elastomeric layers.

In one aspect, the average total thickness of the core region is in the range of from about 125 microns to about 200 microns, and the multilayer film further comprises a first structural layer secured to the first side of the core region, wherein the first structural layer has an average thickness of from about 900 microns to about 1990 microns, optionally from about 900 microns to about 1500 microns, from about 1500 microns to about 1990 microns, or from about 1000 microns to about 1400 microns; and a second structural layer secured to a second side of the core region opposite the first side of the core region, wherein the second structural layer has an average thickness of from about 900 microns to about 1990 microns, optionally from about 900 microns to about 1500 microns, from about 1500 microns to about 1990 microns, or from about 1000 microns to about 1400 microns.

In another aspect, the structural layer material of each of the one or more structural layers independently comprises or consists essentially of a polydiene polyol-based thermoplastic polyurethane.

In another aspect, the disclosed bladder further comprises one or more cover layers comprising or consisting essentially of cover layer material. In another aspect, the cap layer material of the one or more cap layers comprises or consists essentially of: polyurethane, polyacrylate, ethylene-acrylate copolymer, maleic anhydride grafted polyolefin, or any combination thereof. In yet another aspect, each cap layer has a thickness of from about 5 microns to about 25 microns, or from about 5 microns to about 10 microns, or from about 10 microns to about 20 microns.

In yet another aspect, the disclosed bladder further comprises one or more tie layers, each of the one or more tie layers comprising or consisting essentially of a tie material, wherein the one or more tie layers increase the bond strength between two adjacent layers. In another aspect, the joining material of each of the one or more joining layers independently comprises or consists essentially of: polyurethane, polyacrylate, ethylene-acrylate copolymer, maleic anhydride grafted polyolefin, or any combination thereof. In yet another aspect, each of the one or more tie layers has a thickness of from about 5 microns to about 20 microns, or from about 5 microns to about 10 microns, or from about 10 microns to about 20 microns.

The multilayer films, balloons, or bladders disclosed herein may include or consist of one or more gas barrier layers. As used herein, a gas barrier layer is understood to include or consist essentially of a gas barrier material, wherein the thickness of the gas barrier material in the gas barrier layer is at least 0.01 micrometer. Air flowThe body barrier material comprises or consists essentially of one or more gas barrier compounds including one or more polymeric gas barrier compounds (i.e., gas barrier polymers), or one or more non-polymeric gas barrier compounds, or a combination of one or more gas barrier polymers and one or more non-polymeric gas barrier compounds. Polymeric and non-polymeric gas barrier compounds have the ability to restrict the passage of gas through the material. Although no polymer provides an infinite gas barrier, gas barrier polymers generally exhibit a higher level of crystallinity and a higher level of intramolecular hydrogen bonding at room temperature than do polymers with poor gas barriers. Many examples of gas barrier polymers and non-polymeric gas barrier compounds are known in the art. The one or more gas barrier compounds may comprise one or more gas barrier polymers, in particular one or more thermoplastic gas barrier polymers. In a multilayer film, one or more gas barrier layers may be used alone or in combination with other layers formed from other materials including other polymeric materials such as elastomeric materials. Other layers formed from elastomeric materials are referred to as "elastomeric layers" and elastomeric materials include or consist essentially of one or more elastomers, particularly one or more thermoplastic elastomers. The "core region" is the interior region of the multilayer film in which one or more gas barrier layers are positioned. In many aspects, the core region includes more than one individual gas barrier layer, each individual gas barrier layer alternating with layers formed of other materials. In particular, the core region comprises more than one gas barrier layer, each gas barrier layer having an average thickness of less than or equal to about 0.75 microns, each of the gas barrier layers alternating with the elastomeric layer, optionally at least 20 individual gas barrier layers each alternating with the elastomeric layer. When used alone or in combination with other materials, particularly elastomeric materials, in a balloon or bladder, the core region springs The gas is maintained sexually. Depending on the configuration and use of the balloon or bladder, the core region may hold the gas at a pressure above atmospheric pressure, at atmospheric pressure, or below atmospheric pressure. Examples of gases include air, oxygen (O) ₂ ) And nitrogen (N) ₂ ) An inert gas. In one aspect, the gas barrier layer is a nitrogen barrier layer.

The gas permeability, such as oxygen permeability or nitrogen permeability, of the core region of the multilayer film or the entire multilayer film may be measured using ASTM D1434. Thus, as used herein, the term "gas barrier" material may refer to a material that forms one or more layers in a core region of a multilayer film having a total thickness of less than or equal to 500 microns, optionally less than or equal to 300 microns, or less than or equal to 200 microns, or less than or equal to 100 microns, wherein the core region or the multilayer film as a whole has an oxygen or nitrogen transmission rate of less than or equal to about 4 cubic centimeters per square meter per day, optionally less than or equal to about 3 cubic centimeters per square meter per day as measured using ASTM D1434.

In one aspect, the gas barrier layer comprises a multilayer film comprising more than one layer, the more than one layer comprising one or more gas barrier layers, the one or more gas barrier layers comprising or consisting essentially of one or more gas barrier compounds. The multilayer film comprises at least 5 layers or at least 10 layers. Optionally, the multilayer film comprises from about 5 to about 200 layers, from about 10 to about 100 layers, from about 20 to about 80 layers, from about 20 to about 50 layers, or from about 40 to about 90 layers. In particular, the multilayer film may include about 20 or more gas barrier layers, or about 30 or more gas barrier layers, or about 40 or more gas barrier layers, optionally less than 70 gas barrier layers.

In one aspect of the multilayer film, the more than one layer comprises a series of alternating layers, wherein the alternating layers comprise two or more gas barrier layers, each of the two or more gas barrier layers individually comprising a gas barrier material comprising or consisting essentially of one or more gas barrier compounds. In the series of alternating layers, adjacent layers are formed separately from each other by at least the individual components that are present in their chemical composition (e.g., the materials of the adjacent layers may differ based on whether a gas barrier compound is present or not, or based on the type or class of gas barrier compound that is present), the concentrations of the individual components that are present (e.g., the materials of the adjacent layers may differ based on the concentration of the particular type of gas barrier compound that is present), or the materials that are different based on both the components that are present and their concentrations.

The more than one layer of the multilayer film may include a first gas barrier layer comprising a first gas barrier material and a second gas barrier layer comprising a second gas barrier material, wherein the first gas barrier material and the second gas barrier material are different from each other based on the above. The first gas barrier material may be described as comprising a first gas barrier component consisting of all gas barrier compounds present in the first gas barrier material, and the second gas barrier material may be described as comprising a second gas barrier material component consisting of all gas barrier compounds present in the second gas barrier material. The first gas barrier component may consist of only one or more gas barrier polymers and the second gas barrier component may consist of only one or more inorganic gas barrier compounds. The first gas barrier component may be comprised of a first one or more gas barrier polymers and the second gas barrier component may be comprised of a second one or more gas barrier polymers, wherein the first one or more gas barrier polymers differ from the second one or more gas barrier polymers in polymer class, type or concentration. Both the first gas barrier component and the second gas barrier component may comprise the same type of gas barrier compound, but the concentration of the gas barrier compound may be different, optionally the concentrations may differ by at least 5 weight percent based on the weight of the gas barrier material. In these multilayer films, the first gas barrier layer and the second gas barrier layer may alternate with each other, or may alternate with additional gas barrier layers (e.g., a third gas barrier layer comprising a third gas barrier material, a fourth gas barrier layer comprising a fourth gas barrier material, etc., wherein each of the first gas barrier material, the second gas barrier material, the third gas barrier material, the fourth gas barrier material, etc., may be different from each other, as described above).

The gas barrier material comprises or consists essentially of one or more gas barrier compounds. The one or more gas barrier compounds may comprise one or more gas barrier polymers, or may comprise one or more non-polymeric gas barrier compounds comprising one or more inorganic gas barrier compounds, or may comprise a combination of at least one gas barrier polymer and at least one non-polymeric gas barrier compound. The combination of at least one gas barrier polymer and at least one non-polymeric gas barrier compound comprising at least one inorganic gas barrier compound may comprise a blend or mixture, or may comprise a composite wherein fibers, particles or flakes (platelets) of the non-polymeric gas barrier compound are surrounded by the gas barrier polymer.

The gas barrier material may comprise or consist essentially of one or more inorganic gas barrier compounds. The one or more inorganic gas barrier compounds may take the form of fibers, particles, flakes, or a combination thereof. The fibers, particles, flakes may comprise or consist essentially of nanoscale fibers, particles, flakes, or a combination thereof. Examples of inorganic gas barrier compounds include carbon fibers, glass flakes, silica, silicates, calcium carbonate, clays, mica, talc, carbon black, particulate graphite, metal flakes, and combinations thereof. The inorganic gas barrier component may comprise or consist essentially of one or more clays. Examples of suitable clays include bentonite, montmorillonite, kaolinite, and mixtures thereof. The inorganic gas barrier component may be composed of clay. Optionally, the gas barrier material may also include one or more additional ingredients, such as polymers, processing aids, colorants, or any combination thereof. In aspects in which the gas barrier material comprises or consists essentially of one or more inorganic barrier compounds, the gas barrier material may be described as comprising an inorganic gas barrier component consisting of all inorganic gas barrier compounds present in the gas barrier material. When one or more inorganic gas barrier compounds are included in the gas barrier material, the total concentration of inorganic gas barrier components present in the gas barrier material may be less than 60 weight percent, or less than 40 weight percent, or less than 20 weight percent of the total composition. Alternatively, the gas barrier material may consist essentially of one or more inorganic gas barrier materials.

The gas barrier compound may comprise or consist essentially of one or more gas barrier polymers. The one or more gas barrier polymers may include one or more thermoplastic polymers. The gas barrier material may comprise or consist essentially of one or more thermoplastic polymers, which means that the gas barrier material comprises or consists essentially of more than one thermoplastic polymer, including thermoplastic polymers that are not gas barrier polymers. In another example, the gas barrier material may comprise or consist essentially of one or more thermoplastic gas barrier polymers, meaning that all polymers present in the gas barrier material are thermoplastic gas barrier polymers. The gas barrier material may be described as comprising a polymer component consisting of all polymers present in the gas barrier material. For example, the polymer component of the gas barrier material may be composed of a single class of gas barrier polymers such as, for example, one or more polyolefins, or may be composed of a single type of gas barrier polymers such as, for example, one or more ethylene-vinyl alcohol copolymers. Optionally, the gas barrier material may also include one or more non-polymeric additives, such as one or more fillers, processing aids, colorants, or any combination thereof.

Many gas barrier polymers are known in the art. Examples of the gas barrier polymer include vinyl polymers such as vinylidene chloride polymers, acrylic polymers such as acrylonitrile polymers, polyamides, epoxy polymers, amine polymers, polyolefins such as polyethylene and polypropylene, copolymers thereof such as ethylene-vinyl alcohol copolymers, and mixtures thereof. Examples of thermoplastic gas barrier polymers include thermoplastic vinyl homopolymers and copolymers, thermoplastic acrylic homopolymers and copolymers, thermoplastic amine homopolymers and copolymers, thermoplastic polyolefin homopolymers and copolymers, and mixtures thereof. The one or more gas barrier polymers may include or consist essentially of one or more thermoplastic polyethylene copolymers such as, for example, one or more thermoplastic ethylene-vinyl alcohol copolymers. The one or more ethylene vinyl alcohol copolymers may include an ethylene content of from about 28 mole percent to about 44 mole percent or an ethylene content of from about 32 mole percent to about 44 mole percent. The one or more gas barrier polymers may comprise or consist essentially of: one or more polyethylenimine, polyacrylic acid, polyethylene oxide, polyacrylamide, polyamidoamine, or any combination thereof.

In another aspect, the multilayer film includes one or more second layers in addition to one or more gas barrier layers (e.g., including a first gas barrier layer, a second gas barrier layer, etc.), the one or more second layers including a second material. Optionally, the second material comprises one or more polymers. The one or more gas barrier layers may comprise more than one gas barrier layer alternating with more than one second layer. Each of the one or more barrier layers may be positioned between two second layers (e.g., one of the second layers is positioned on a first side of the barrier layer and the other second layer is positioned on a second side of the gas barrier layer, the second side being opposite the first side).

Depending on the type of gas barrier compound used and the intended use of the multilayer film, the second material may have a higher gas permeability than the gas barrier material, which means that the second material is a worse gas barrier than the gas barrier material. In some aspects, the one or more second layers serve as a substrate for the one or more gas barrier layers and may serve to increase the strength, elasticity, and/or durability of the multilayer film. Alternatively or additionally, one or more second layers may be used to reduce the amount of gas barrier material required, thereby reducing the overall material cost. The presence of one or more second layers, particularly when one or more second layers are positioned between one or more barrier layers, may help maintain the overall gas barrier properties of the film by increasing the distance between the cracks in the gas barrier layers, thereby increasing the distance that gas molecules must travel between the cracks in the barrier layers in order to pass through the multilayer film, even when the second material has a relatively high gas permeability. While small breaks or cracks in the gas barrier layer of the multilayer film may not significantly affect the overall barrier properties of the film, the use of thinner gas barrier layers or the use of a greater number of thinner gas barrier layers may avoid or reduce visible cracking, cracking or blurring of the multilayer film. The one or more second layers may include, but are not limited to, a tie layer positioned between and facilitating adhesion between two different layers of the multilayer film; a structural layer providing mechanical support to the multilayer film; a bonding layer comprising a bonding material such as a hot melt adhesive material to the outer surface of the multilayer film; a cap layer providing protection to the outer surface of the multilayer film; and any combination thereof.

The second material may be an elastomeric material comprising or consisting essentially of at least one elastomer. As used herein, the term elastomer may refer to a material having an elongation at break of greater than 400% as determined according to ASTM D-412-98 at 25 degrees celsius. Optionally, the term elastomer may refer to a material that when formed into a substrate has a breaking strength of from 10 to 35 kilograms force, such as from about 10 to about 25 kilograms force, from about 10 to about 20 kilograms force, from about 15 to about 35 kilograms force, or from about 20 to about 30 kilograms force. Optionally, the tensile break strength or ultimate strength of the elastomer, if adjusted for cross-sectional area, may be greater than 70 kilograms force per square centimeter or greater than 80 kilograms force per square centimeter. Optionally, the elastomer when formed into a substrate has a strain at break of from 450% to 800%, or from 500% to 750%, or from 600% to 750%, or from 450% to 700%. As another option, the elastomeric substrate may have a load at 100% strain of from 3 to 8 kilograms-force per millimeter, or from about 3 to about 7 kilograms-force per millimeter, from about 3.5 to about 6.5 kilograms-force per millimeter, or from about 4 to about 5 kilograms-force per millimeter. Optionally, the elastomeric substrate has a toughness of from 850 kg-mm to 2200 kg-mm, or from about 850 kg-mm to about 2000 kg-mm, or from about 900 kg-mm to about 1750 kg-mm, or from about 1000 kg-mm to about 1500 kg-mm, or from about 1500 kg-mm to about 2000 kg-mm. Optionally, the elastomeric substrate has a stiffness of from about 35 to about 155, or from about 50 to about 150, or from about 50 to about 100, or from about 50 to about 75, or from about 60 to about 155, or from about 80 to about 150. Optionally, the elastomeric substrate has a tear strength of from about 35 to about 80, or from about 35 to about 75, or from about 40 to about 60, or from about 45 to about 50. Many gas barrier compounds are brittle and/or relatively inflexible, and thus one or more gas barrier layers may be prone to cracking when subjected to repeated excessive stress loads, such as potentially generated during flexing and release of a multilayer film. Thus, the elastomeric material may have a glass transition temperature lower than the glass transition temperature of the gas barrier material (when it comprises one or more polymers), for example 20 degrees celsius lower, in particular 50 degrees celsius lower. A multilayer film comprising one or more gas barrier layers alternating with a second layer of elastomeric material results in a multilayer film that is better able to withstand repeated flexing and release while retaining its gas barrier properties than a film without an elastomeric second layer.

In one aspect, the second material comprises or consists essentially of one or more polymers. As used herein, one or more polymers present in the second material are referred to herein as one or more "second polymers" or "second polymers" because these polymers are present in the second material. References to "second polymer" are not intended to indicate that "first polymer" is present in the second material or in the multilayer film as a whole, although in many aspects there are multiple classes or types of polymers. In one aspect, the second material comprises or consists essentially of one or more thermoplastic polymers. In another aspect, the second material comprises or consists essentially of one or more elastomeric polymers. In yet another aspect, the second material comprises or consists essentially of one or more thermoplastic elastomers. The second material may be described as including a polymer component that is composed of all of the polymers present in the second material. In one example, the polymer component of the second material is comprised of one or more elastomers. Optionally, the second material may also include one or more non-polymeric additives, such as fillers, processing aids, and/or colorants.

Many polymers suitable for use in the second material are known in the art. Exemplary polymers that may be included in the second material (e.g., second polymer) include polyolefins, polyamides, polycarbonates, polyimides, polyesters, polyacrylates, polyesters, polyethers, polystyrenes, polyureas, and polyurethanes, including homopolymers and copolymers thereof (e.g., polyolefin homopolymers, polyolefin copolymers, and the like), and combinations thereof. In one example, the second material comprises or consists essentially of one or more polymers selected from the group consisting of polyolefins, polyamides, polyesters, polystyrene, and polyurethanes, including homopolymers and copolymers thereof, and combinations thereof. In another example, the polymer component of the second material consists of: one or more thermoplastic polymers, or one or more elastomers, or one or more thermoplastic elastomers, including thermoplastic vulcanizates. Alternatively, the one or more second polymers may include one or more thermoset or thermosettable elastomers such as, for example, natural rubber and synthetic rubber, including butadiene rubber, isoprene rubber, silicone rubber, and the like.

Polyolefins are a class of polymers comprising monomer units derived from simple olefins such as ethylene, propylene and butene. Examples of thermoplastic polyolefins include polyethylene homopolymers, polypropylene copolymers (including polyethylene-polypropylene copolymers), polybutenes, ethylene-octene copolymers, olefin block copolymers, propylene-butane copolymers, and combinations thereof, including blends of polyethylene homopolymers and polypropylene homopolymers. Examples of polyolefin elastomers include polyisobutylene elastomers, poly (alpha-olefin) elastomers, ethylene propylene diene monomer elastomers, and combinations thereof.

Polyamides are a class of polymers comprising monomer units linked by amide linkages. Naturally occurring polyamides include proteins such as wool and silk, while synthetic amides include polymers such as nylon and aromatic polyamides. The one or more second polymers may include thermoplastic polyamides such as nylon 6, nylon 6-6, and/or nylon-11, as well as thermoplastic polyamide copolymers.

Polyesters are a class of polymers comprising monomer units derived from ester functionality and are typically made by condensing a dibasic acid such as, for example, terephthalic acid with one or more polyols. In one example, the second material may include or consist essentially of one or more thermoplastic polyester elastomers. Examples of polyester polymers include homopolymers such as polyethylene terephthalate, polybutylene terephthalate, and poly (1, 4-cyclohexylene-dimethylene terephthalate), and copolymers such as polyester polyurethane.

Styrene polymers are a class of polymers comprising monomer units derived from styrene. The one or more second polymers may comprise or consist essentially of: styrene homopolymers, styrene random copolymers, styrene block copolymers, or combinations thereof. Examples of styrene polymers include styrene block copolymers such as acrylonitrile butadiene styrene block copolymers, styrene acrylonitrile block copolymers, styrene ethylene butadiene styrene block copolymers, styrene ethylene propylene styrene block copolymers, styrene butadiene styrene block copolymers, and combinations thereof.

Polyurethanes are a class of polymers that include monomer units linked by urethane linkages. Polyurethanes are most typically formed by reacting a polyisocyanate (e.g., a diisocyanate or triisocyanate) with a polyol (e.g., a diol or triol), optionally in the presence of a chain extender. The monomer units derived from the polyisocyanate are generally referred to as hard segments of the polyurethane, while the monomer units derived from the polyol are generally referred to as soft segments of the polyurethane. The hard segments may be derived from aliphatic polyisocyanates, or from organic isocyanates, or from a mixture of both. The soft segment may be derived from a saturated polyol, or from an unsaturated polyol such as a polydiene polyol, or from a mixture of both. When the multilayer film is to be bonded to natural rubber or synthetic rubber, the soft segments comprising the segments derived from one or more polydiene polyols can promote bonding between the rubber and the film when the rubber and the film are crosslinked in contact with each other, such as in a vulcanization process.

Examples of suitable polyisocyanates from which the hard segments of the polyurethane may be derived include Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene Diisocyanate (BDI), diisocyanatocyclohexylmethane (HMDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI), diisocyanatocyclohexane, diisocyanatocyclodecane, norbornane Diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4 '-dicyclohexylmethane diisocyanate (H12 MDI), diisocyanato dodecane, lysine diisocyanate, toluene Diisocyanate (TDI), TDI adducts with Trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), xylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hydrogenated Xylene Diisocyanate (HXDI), naphthalene-1, 5-diisocyanate (NDI), 1, 5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3' -dimethyl diphenyl-4, 4 '-diisocyanate (DDDI), 4' -dibenzylidene diisocyanate (DDDI), and any combination thereof. In one aspect, the polyurethane comprises or consists essentially of hard segments derived from Toluene Diisocyanate (TDI), or derived from methylene diphenyl diisocyanate (MDI), or derived from both.

The soft segment of the polyurethane may be derived from a wide variety of polyols including polyester polyols, polyether polyols, polyester-ether polyols, polycarbonate polyols, polycaprolactone polyethers, and combinations thereof. In one aspect, the polyurethane comprises or consists essentially of monomer units derived from: c (C) ₄ -C ₁₂ Polyols, or C ₆ -C ₁₀ Polyols, or C ₈ Or lower polyol, meaning a polyol having 4 to 12 carbon molecules, or having 6 to 10 carbon molecules, or having 8 or less carbon molecules in its chemical structure. In another aspect, the polyurethane comprises or consists essentially of monomer units derived from a polyester polyol, a polyester-ether polyol, a polyether polyol, or any combination thereof. In yet another aspect, the polyurethane includes or consists essentially of a soft segment derived from a polyol or diol having polyester functional units. The soft segments derived from the polyol or diol having polyester functional units may comprise from about 10 weight percent to about 50 weight percent, or from about 20 weight percent to about 40 weight percent, or about 30 weight percent of the soft segments present in the polyurethane.

Multilayer films may be produced in a variety of ways such as coextrusion, lamination, layer-by-layer deposition, or the like. When one or more barrier layers are co-extruded alone or with one or more second layers, selecting materials (e.g., first and second barrier materials, or a single barrier material and second material) having similar processing characteristics such as melt temperature and melt flow index may reduce interlayer shear during the extrusion process and may allow alternating barrier layers and second layers to be co-extruded while maintaining their structural integrity and desired layer thickness. In one example, one or more barrier materials and optionally a second material (when used) can be extruded into separate individual films, which can then be laminated together to form a multilayer film.

Multilayer films can be produced using a layer-by-layer deposition process. The substrate, which optionally may include a second material or barrier material, may be constructed into a multilayer film by depositing more than one layer onto the substrate. The layer may include one or more barrier layers (e.g., a first barrier layer, a second barrier layer, etc.). Optionally, the layer may comprise one or more second layers. The one or more barrier layers and/or the second layer may be deposited by any means known in the art, such as, for example, dipping, spraying, coating, or another method. The one or more barrier layers may be applied using a charged solution or suspension, such as a cationic solution or suspension or an anionic solution or suspension, including a charged polymer solution or suspension. The one or more barrier layers may be applied using a series of two or more solutions having opposite charges, for example, by applying a cationic solution, followed by an anionic solution, followed by a cationic solution, followed by an anionic solution, etc.

The barrier layer comprising the multilayer film has a total thickness of from about 40 microns to about 500 microns, or about 50 microns to about 400 microns, or about 60 microns to about 350 microns. In one aspect, each individual layer of the more than one layer of the multilayer film has a thickness from about 0.001 microns to about 10 microns. For example, the thickness of the individual barrier layers may range from about 0.001 microns to about 3 microns thick, or from about 0.5 microns to about 2 microns thick, or from about 0.5 microns to about 1 micron thick; optionally less than or equal to 0.75 microns thick, or less than or equal to 0.5 microns thick, or in the range from about 0.01 microns to about 0.75 microns thick, preferably in the range from about 0.01 microns to about 0.5 microns thick. The thickness of the individual second layers may range from about 2 microns to about 8 microns thick or from about 2 microns to about 4 microns thick.

In further aspects, the thickness of the films and/or their individual layers may be measured by any method known in the art such as, for example, ASTM E252, ASTM D6988, ASTM D8136, or using an optical microscope or an electron microscope.

In some aspects, the barrier layer comprising the multilayer film has a shore hardness of from about 35A to about 95A, optionally from about 55A to about 90A. In these aspects, hardness can be measured using ASTM D2240 using the shore a scale.

In one aspect, when a coextrusion process is used to form the barrier layer from more than one alternating barrier layer and second layer, the barrier material has a melt flow index of from about 5 grams per 10 minutes to about 7 grams per 10 minutes at 190 degrees celsius when a weight of 2.16 kilograms is used, and the second material has a melt flow index of from about 20 grams per 10 minutes to about 30 grams per 10 minutes at 190 degrees celsius when a weight of 2.16 kilograms is used. In a further aspect, the melt flow index of the barrier material is from about 80% to about 120% of the melt flow index of the barrier material per 10 minutes when measured at 190 degrees celsius when using a weight of 2.16 kilograms. In any of these aspects, the melt flow index can be measured using ASTM D1238. Alternatively or additionally, the barrier material or the second material or both have a melting temperature of from about 165 degrees celsius to about 183 degrees celsius or from about 155 degrees celsius to about 165 degrees celsius. In one such example, the barrier material has a melting temperature from about 165 degrees celsius to about 183 degrees celsius, and the second material has a melting temperature from about 155 degrees celsius to about 165 degrees celsius. Further, in these aspects, the melting temperature may be measured using ASTM D3418.

In aspects, the multilayer film exhibits low gas permeability such that a balloon incorporating the multilayer film can be inflated and sealed for long term use. Such bladders may provide good cushioning and support when incorporated into consumer products (e.g., as an air cushion for footwear). In further aspects, due to the low gas permeability of the multilayer film, once the airbag is inflated with gas, the level of cushioning or support does not significantly decrease over an extended period of time, which substantially reduces escape of inflation gas.

In one aspect, the balloon lumen is inflated to a positive pressure, i.e., having an inflation internal pressure of greater than about 15 pounds per square inch (about 100 kilopascals). In a further aspect, the balloon lumen has an inflation internal pressure in the range of from about 17 pounds per square inch (about 117 kilopascals) to about 30 pounds per square inch (about 207 kilopascals). In a further aspect, the balloon lumen has an inflation internal pressure in the range of from about 20 pounds per square inch (about 138 kilopascals) to about 22 pounds per square inch (about 152 kilopascals). In one aspect, after 2 years of use, the balloon lumen still has an internal pressure that fills at least about 60% of the internal pressure. In a further aspect, the balloon lumen still has an internal pressure of at least about 70% of the inflation internal pressure after 2 years of use.

In some aspects, the balloon has a gas permeability of no more than 120% of the original gas permeability after 320,000 KIM cycles, wherein the KIM cycles are performed using the KIM test protocol defined in the property analysis and characterization procedure section included herein. In one aspect, the bladder has a gas permeability to nitrogen ranging from about 0.5 cubic centimeters per square meter per day to about 2 cubic centimeters per square meter per day measured at 23 degrees celsius and 0% relative humidity after from 0 to 320,000 KIM cycles for a film having a thickness ranging from 72 to 320 microns. In one aspect, the balloon does not exhibit rupture or cracking after at least 350,000 KIM cycles or after at least 400,000 KIM cycles.

In some embodiments, the multilayer film may further include additional layers on one or both opposite sides of the core region. For example, the multilayer film may include one or more thicker structural layers to increase the structural integrity and durability of the multilayer film during use in an article, such as an air cushion for footwear. Additionally or alternatively, the multilayer film may also include one or more cover layers to improve abrasion resistance, aid in balloon formation (e.g., during thermoforming or blow molding), improve bonding with other article components, improve surface properties for printed graphics and indicia, improve visual aesthetics and/or tactile properties, water resistance, and other properties.

As shown in fig. 1 and 2, footwear 1010 is an exemplary article of footwear incorporating the multilayer films of the present disclosure. As shown in fig. 1, article of footwear 1010 may be divided longitudinally along longitudinal axis a1010 into one or more regions, such as into forefoot region 1012, midfoot region 1014, and heel region 1016. Forefoot region 1012 may also be described as including a toe portion corresponding with a portion of footwear 1010 that surrounds the phalanges of a wearer's foot when worn; and a ball portion corresponding with a portion of footwear 1010 that, when worn, surrounds a plantar-toe (MTP) joint of a wearer's foot. Midfoot region 1014 corresponds with a portion of the arch region surrounding the foot of the wearer when worn, and heel region 1016 corresponds with a portion of footwear 1010 surrounding a rear portion of the foot of the wearer including the calcaneus bone when worn.

Footwear 1010 may also include a forward end 1018 associated with a forward-most position of forefoot region 1012, and a rearward end 1020 corresponding with a rearward-most position of heel region 1016. As further shown in fig. 1, a longitudinal axis a1010 of footwear 1010 extends along a length of footwear 1010 from a front end 1018 to a rear end 1020 and generally divides footwear 1010 into a medial side 1022 and a lateral side 1024. Accordingly, medial side 1022 and lateral side 1024 correspond with opposite sides of footwear 1010, respectively, and extend through regions 1012, 1014, and 1016.

Footwear 1010 also includes an upper 1026 and a sole structure 1028, wherein upper 1026 forms a structure configured to cover a portion or all of a wearer's foot and to enable the wearer's foot to be fitted to sole structure 1028. Upper 1026 includes an interior surface (not shown) that defines an interior void configured to receive and secure a foot of a wearer for support on sole structure 1028. The interior void may be accessed at ankle opening 1026a and may be shaped and sized to match and conform to the foot of the wearer. For example, upper 1026 may extend over the instep and toe areas of the wearer's foot (at forefoot area 1012), along the medial and lateral sides of the wearer's foot (at midfoot area 1014), and around the heel area of the wearer's foot (at heel area 1016).

Upper 1026 may be formed from one or more components that may be stitched, adhesively bonded, thermally bonded, or otherwise joined together to form an interior void, such as a mesh, textile, foam, leather, and synthetic leather. These materials may be selected and positioned to impart durability, breathability, abrasion resistance, flexibility, comfort, and the like. More specific examples of suitable materials for upper 1026 are discussed below.

Upper 1026 may also have any suitable design, shape, size, and/or color design for footwear applications. For example, in certain aspects, for example, if footwear 1010 is a basketball shoe, upper 1026 may be a high-top profile shaped to provide high support to the wearer's ankle. Alternatively, in certain aspects, for example, if footwear 1010 is a running shoe, upper 1026 may have a low-upper profile.

In the example shown in fig. 1 and 2, sole structure 1028 includes a midsole 1030 configured to provide cushioning, support, and aesthetic properties, and an outsole 1032 configured to provide a ground-engaging surface of footwear 1010. In the illustrated embodiment, midsole 1030 of sole structure 1028 is also divided into a plurality of sub-components that may provide different forms of cushioning, support, and aesthetics, such as bottom layer 1034 and cushion 1036.

The bottom layer 1034 may be attached to the upper 1026 to provide an interface between the upper 1026 and the cushion 1036. In the embodiment illustrated in fig. 1 and 2, the bottom layer 1034 is a single component bottom layer formed from one or more elastic materials, such as foam and/or rubber, to impart cushioning, responsiveness, and energy distribution properties to the wearer's foot.

In the illustrated embodiment, bottom layer 1034 is depicted as having a single full length component extending from forefoot region 1012 to heel region 1016. Alternatively, bottom layer 1034 may include multiple components, such as a first component extending from forefoot region 1012 to midfoot region 1014 and a second component extending from midfoot region 1014 to heel region 1016. In yet further alternative aspects, bottom layer 1034 may include multiple components of a zonal region (zone) that provides cushioning and/or rigid support at forefoot region 1012, midfoot region 1014, and/or heel region 1016. The components of the bottom layer 1034 may be preformed from any suitable resilient material (e.g., foam and rubber) and/or rigid material (e.g., plate and molded parts). In embodiments incorporating an elastic material, the components of the bottom layer 1034 may include molded foam parts, loose foam beads held in a carrier shell, fused foam bead parts (e.g., by compression molding or vapor chamber molding (steam chest molding)), foam beads embedded in an elastic polymer resin matrix, and the like to impart cushioning, responsiveness, support, and energy distribution properties to the wearer's foot.

Examples of suitable elastic materials for the foam include thermoplastic elastomers such as, for example, thermoplastic elastomer polyolefin homo-or copolymers, thermoplastic elastomer polyamide homo-or copolymers, thermoplastic elastomer polyester homo-or copolymers, thermoplastic elastomer polyurethane homo-or copolymers, thermoplastic elastomer styrene homo-or copolymers, or any combination thereof. These materials may also include one or more additives such as foaming agents, cross-linking agents, colorants, fillers, and the like. Suitable chemical blowing agents include azo compounds such as azodicarbonamide, sodium bicarbonate, isocyanates, and combinations thereof. Alternatively, the foam of bottom layer 1034 may be produced using one or more physical blowing agents that may phase change to a gas based on changes in temperature and/or pressure. Suitable crosslinking agents (for crosslinked foams) include peroxide-based crosslinking agents such as dicumyl peroxide. Suitable fillers include modified or natural clays, modified or unmodified synthetic clays, talc, glass fibers, glass frit, modified or natural silica, calcium carbonate, mica, paper, wood chips, and combinations thereof.

In some embodiments, the bottom layer 1034 may include one or more semi-rigid plate components, such as carbon fiber board, polymeric (e.g., polyamide-based) plates, and the like. In further alternative embodiments, the bottom layer 1034 may be omitted and the cushion 1036 may be secured directly to the upper 1026.

As shown in fig. 1 and 2, outsole 1032 may have a geometry that matches the geometry of air cushion 1036 and is configured to provide a ground-engaging surface of footwear 1010. For example, outsole 1032 may be provided as a polymer component that is overmolded onto cushion 1036, adhered to cushion 1036, or otherwise secured to cushion 1036 to provide cushion 1036 with increased durability, puncture resistance, and/or wear resistance in a ground-facing direction. Examples of suitable materials for outsole 1032 include materials that are capable of being bonded directly to cushion 1036 and/or bonded to cushion 1036 with an adhesive, and that preferably exhibit wear and/or puncture resistance, such as polyurethane, thermoplastic polyurethane, polyether block amine, vulcanized rubber, and combinations thereof.

Cushion 1036 is an exemplary bladder for use with footwear 1010 and incorporating the multilayer films of the present disclosure. As briefly described above, the multilayer film exhibits an increased balance between durability and flexibility while also maintaining good gas barrier properties. Thus, the cushion incorporating the multilayer film may have a wider range of unique and advanced three-dimensional geometries than are achievable with current barrier films.

For example, cushion 1036 may include one or more protrusions and/or bulbous portions, such as heel portion 1038 at heel region 1016, medial portions 1040a, 1040b, and 1040c at medial side 1022, and/or lateral portions 1042a, 1042b, and 1042c at lateral side 1024. These protruding portions, particularly heel portion 1038, due to their extreme geometry, may potentially experience high stress loads due to flexing and release during each foot strike, potentially resulting in significant flexing deformation of the multilayer film and barrier layer therein. This is best illustrated in fig. 3, which shows a portion 1038 of the air cushion 1036; portions 1040a, 1040b, and 1040c; and portions 1042a, 1042b, and 1042c that extend beyond the top-down cross-sectional footprint of the bottom layer 1034 of midsole 1030. As can be appreciated, during each foot strike, downward pressure applied to the cushion 1036 by the weight of the wearer and transferred through the upper 1026 and bottom 1034 may create high stress loads on the protrusions 1038, the protrusions 1040a, 1040b, and 1040c, and the protrusions 1042a, 1042b, and 1042c. These high stress loads resulting from the flexing and release of the multi-layer film may be particularly high at heel portion 1038 due to heel strike during walking and running. In addition, these high stress loads are compounded over time by repeated flexing and release of the multi-layer film of the cushion 1036, which may occur with each foot strike.

The effect of the refraction and release of the multilayer film is illustrated in fig. 4A and 4B. Fig. 4A is an enlarged view of heel portion 1038 at heel region 1016 in an uncompressed state, such as when footwear 1010 is raised during a walking or running stride or when footwear 1010 is seated on a lower surface (e.g., surface 1044) without any applied weight.

Referring still to fig. 4A and 4B, heel portion 1038 is a bulbous protrusion having a height 1046 in an uncompressed state, wherein height 1046 is a distance from a top of air cushion 1036 at bottom layer 1034 to a bottom of air cushion 1036 at outsole 1032 as taken along axis 1048, which axis 1048 is a vertical axis that is perpendicular to surface 1044 when footwear 1010 is resting upright on surface 1044. In exemplary aspects, a suitable height 1046 can range from about 10 millimeters to about 24 millimeters, from about 10 millimeters to 20 millimeters, or from about 15 millimeters to about 24 millimeters. Heel portion 1038 further protrudes rearward from bottom layer 1034 a distance 1050 in a direction along axis a1010 or parallel to axis a 1010.

In one aspect, location 1052 may be defined as the most rearward location on heel portion 1038 along axis a 1010. As shown in fig. 4A, the extension (extension) of the bulbous protrusion geometry of heel portion 1038 may be defined by two vectors. These two vectors include a first vector 1054, the first vector 1054 beginning at location 1052 and extending through the rearmost contact location 1056 between the bottom layer 1034 and the air pad 1036; and a second vector 1058, the second vector 1058 beginning at location 1052 and extending through a rearmost contact location 1060 between the outsole 1032 and the cushion 1036. In some aspects, the angle 1062 between the first vector 1054 passing through the locus 1056 and the second vector 1058 passing through the locus 1060 is in a range from about 115 degrees to about 137.5 degrees, or from about 115 degrees to about 125 degrees, or from about 120 degrees to about 137.5 degrees.

As can be appreciated, the bulbous protrusion geometry of heel portion 1038, as can be characterized by height 1046, rearward distance 1050, and angle 1062 independently, is not vertically supported by outsole 1032 or bottom layer 1034. As can also be appreciated, a greater rearward distance 1050 will cause the multi-layer film of air cushion 1036 at the location of location 1052 to experience a greater potential stress load during each foot strike. Thus, examples of suitable distances 1050 may range from about 4.5 millimeters to about 7.1 millimeters, or from about 4.5 millimeters to about 6.0 millimeters, or from about 6.0 millimeters to about 7.1 millimeters.

Fig. 4B is an enlarged view of heel portion 1038 in a compressed state, such as when footwear 1010 is receiving a load applied by a foot strike surface 1044 of a wearer. In one aspect, in a compressed state, heel portion 1038 has a reduced height 1064, where height 1064 is the distance from the top of cushion 1036 at bottom layer 1034 to the bottom of cushion 1036 at outsole 1032 as taken along axis 1048. Examples of suitable heights 1064 are in the range from about 8.6 millimeters to about 13.6 millimeters, or from about 8.6 millimeters to about 11 millimeters, or from about 10 millimeters to about 13.6 millimeters. Further, in this aspect, heel portion 1038 protrudes rearward a distance 1066 taken along axis a1010 or in a direction parallel to axis a 1010. Examples of suitable distances 1066 are in the range of from about 6.4 millimeters to about 8.2 millimeters, or from about 6.4 millimeters to about 7.0 millimeters, or from about 7.0 millimeters to about 8.2 millimeters.

In one aspect, a 200 pound weight is placed on the disclosed bladder and/or article of footwear including the bladder in a compressed state. In an alternative aspect, in the compressed state, the bladder and/or article of footwear experiences an applied force equivalent to that applied by a person wearing a pair of footwear including the bladder in its sole structure.

As shown in fig. 4A and 4B, the height 1046 in the uncompressed state is greater than the height 1064 in the compressed state. Examples of suitable differences in height 1046 and height 1064 range from about 1.4 millimeters to about 10.4 millimeters as measured by the load compression test protocol described in the property analysis and characterization procedure section herein. In another aspect, the height 1064 in the compressed state is in a range from about 56.7% to about 86.0% of the height 1046 in the uncompressed state, as measured by the load compression test protocol. In further aspects, the difference between the uncompressed height 1046 and the compressed height 1064 is applicable at the time of manufacture and within 3 months of use, within 6 months of use, within 1 year of use, or within 2 years of use. Without wishing to be bound by theory, the inflated cushion, which does not exhibit cracking or cracking after at least 320,000 KIM cycles or more, maintains a low gas permeability and a high proportion of its inflation internal pressure, thus limiting the amount of compression possible and thus the compressed height 1064 as a proportion of the uncompressed height 1046 after a period of regular use.

As can also be appreciated, the distance 1050 in the uncompressed state is less than the distance 1066 in the compressed state. Examples of suitable differences in distance 1050 and distance 1066 are in the range from about 1.1 millimeters to about 1.9 millimeters, as measured by the load compression test protocol. In further aspects, suitable differences in distance are applicable at the time of manufacture, within 3 months of use, within 6 months of use, within 1 year of use, or within 2 years of use. In another aspect, the distance 1050 in the uncompressed state is in the range of from about 70.3% to about 86.6% of the distance 1066 in the compressed state, as measured by the load compression test protocol.

As shown, location 1068 is a location on heel portion 1038 that is furthest rearward along axis a1010 when the cushion is in a compressed state, and location 1052 is a location on heel portion 1038 that is furthest rearward along axis a1010 when the cushion is in an uncompressed state. In some aspects, sites 1068 and 1052 are positioned on the same physical location of heel portion 1038, while in other aspects, such as when air cushion 1036 has an asymmetric shape and/or a curved position, sites 1068 and 1052 may be positioned on different physical points (physical spots) of heel portion 1038.

The degree of compression of the bulbous protrusion geometry of heel portion 1038 may be defined by two vectors. These two vectors include a first vector 1070 that begins at location 1068 and extends through the rearmost contact location 1056 between the bottom layer 1034 and the air pad 1036; and a second vector 1072 begins at location 1068 and extends through the rearmost contact location 1060 between the outsole 1032 and the cushion 1036. Still further, in this aspect, the angle 1074 between the first vector 1070 and the second vector 1072 is in the range from about 38 degrees to about 107 degrees, or from about 38 degrees to about 80 degrees, or from about 80 degrees to about 107 degrees. As can be appreciated, the bulbous protrusion geometry of heel portion 1038, as can be characterized by height 1064, rearward distance 1066, and angle 1074 independently, is not vertically supported by outsole 1032 or bottom layer 1034. As can also be appreciated, a greater rearward distance 1066 will cause the multi-layer film of the cushion 1036 at the location of the location 1068 to experience a greater potential stress load during each foot strike. Thus, examples of suitable distances 1066 may range from about 6.4 millimeters to about 8.2 millimeters, or from about 6.4 millimeters to about 7.0 millimeters, or from about 7.0 millimeters to about 8.2 millimeters.

In any of these aspects, the angle 1074 in the compressed state is less than the angle 1062 in the uncompressed state. Examples of suitable differences for angles 1062 and 1074 are in the range from about 37.5 degrees to about 77 degrees, as measured by the load compression test protocol. Furthermore, suitable differences in angle are applicable at the time of manufacture, within 3 months of use, within 6 months of use, within 1 year of use, or within 2 years of use. In another aspect, angle 1074 is in the range of from about 33.0% to about 77.8% of angle 1062, as measured by the load compression test protocol.

Although the air cushion 1036 depicted in fig. 4A and 4B is depicted symmetrically, in some aspects the contour or shape of the air cushion 1036 may be different than that depicted. In one aspect, the air cushion 1036 may be made from two multi-layer films as disclosed herein, wherein the multi-layer films are sheets joined together around the perimeter. In aspects, one sheet may be thermoformed, and in some aspects may form a bottom of the cushion 1036 that is in partial contact with the outsole 1032. Further, in this aspect, a second sheet may form the top of the cushion 1036, wherein the second sheet may or may not be thermoformed, and wherein the second sheet may be partially in contact with the bottom layer 1034. In any of these aspects, the stress load caused by the flexing and release of the multi-layer film at heel portion 1038 may not be symmetrically distributed around the example asymmetric air cushion 1036, depending on its particular geometry. For purposes of determining distance 1050, vector 1070, and vector 1072, and angle 1074, longitudinal axis a1010 is parallel to surface 1044 because footwear 1010 is oriented vertically on surface 1044 (e.g., axis a1010 is oriented horizontally in the illustrations of fig. 4A and 4B).

In any of the above aspects, the flexing and stress-relieving loads applied to the multi-layer film of air cushion 1036 may exceed the performance tolerances of currently known barrier films in repeated foot strikes in footwear applications, which may create a visible cracking or hazing effect in the barrier film. While these burst and hazy effects do not significantly affect the performance of the barrier film (e.g., gas hold), they can detract from the aesthetics of the gas cushion, which can be an undesirable effect for many consumers. However, the multilayer films of the present disclosure can withstand higher repeated stress loads than current barrier films used in footwear applications while exhibiting reduced or no visually observable cracking, or blurriness, and further maintaining good gas barrier properties. The gas barrier layer of the core region in the disclosed multilayer film may particularly have an average layer thickness of less than about 2 microns, optionally less than or equal to 0.75 microns or less than about 0.5 microns, such as an average layer thickness in the range from about 0.01 microns to about 0.75 microns, particularly in the range from about 0.01 microns to about 0.5 microns; and has increased flexibility properties and/or elastic properties as compared to currently known barrier films, allowing the multilayer films of the present disclosure to undergo repeated flex-release cycles without substantially losing gas barrier properties and without cracking, blurring, or similar appearance. Further, in this aspect, these superior properties allow the disclosed gas cushion 1036 to have a longer useful life without significant changes in gas permeability.

Furthermore, while particularly beneficial for use with airbags having more extreme geometries (e.g., cushion 1036 having uncompressed height 1046), the multilayer films of the present disclosure may be used as suitable alternatives in any current gas barrier application that incorporates multilayer films (e.g., microlayer films). For example, in footwear applications, the multilayer film may be incorporated into an air cushion having any suitable geometry, such as the air cushions disclosed in U.S. patent nos. 10,149,513, 11,019,880, and 11,019,881, and U.S. patent application publication nos. 2019/021027, 2020/0205514, 2021/0145119, and 2021/0195996. This allows the same multilayer film to be interchangeably used as a feedstock for a variety of different cushion geometries, thereby improving manufacturing efficiency, reducing raw material waste and reducing manufacturing carbon impact.

As shown in fig. 5, the multilayer film 1076 is an exemplary multilayer film of the present disclosure, such as for air cushion 1036. In some aspects, articles disclosed herein may include multiple layers, as illustrated, for example, in fig. 5. In this exemplary embodiment, the article is a sheet comprising a gas barrier layer and comprises two structural layers, 2200a having thickness 2180a and 2200b having thickness 2180b and a core region or film 2160 having thickness 2140. In one aspect, the article may be double-sided. Further, in this aspect, the two-sided article may include a symmetrical arrangement of layers on both sides of the core region 2160. Suitable examples of thicknesses 2180a and 2180b are in the range from about 900 microns to about 1990 microns, or from about 900 microns to about 1400 microns, or from about 1400 microns to about 1990 microns. Suitable examples of the thickness 2140 are in the range from about 125 microns to about 200 microns, or from about 125 microns to about 175 microns, or from about 150 microns to about 200 microns.

In one such aspect of the example according to fig. 5, the structural layers 2200a and 2200b may comprise or consist essentially of structural layer material. In such aspects, core region 2160 may comprise or consist essentially of a multilayer film that includes a gas barrier layer as disclosed herein.

In any of these aspects, the structural layer 2200a can have a first surface 2200a 'and a second surface 2200a ", and the structural layer 2200b can have a first surface 2200b' and a second surface 2200 b". In another aspect, the core region 2160 may have a first surface 2160a and a second surface 2160b. In some aspects, the second surface 2200a "of the structural layer 2200a and the first surface 2160a of the core region 2160 may be adjacent to each other or otherwise in contact with each other. In one aspect, the second surface 2160b of the core region 2160 and the second surface 2200b "of the structural layer 2200b may be adjacent to each other or otherwise in contact with each other. In some aspects, the first surface 2200a 'of the structural layer 2200a and/or the first surface 2200b' of the structural layer 2200b can independently optionally be an outer surface of an article incorporating the multilayer films disclosed herein. In any of these aspects, the structural layer 2200a and the structural layer 2200b may be made of the same material or different materials, and may have the same or different thicknesses.

In one aspect, provided herein is an article comprising a multilayer film disclosed herein, the article comprising:

a first cap layer comprising or consisting essentially of a first cap layer material, the first cap layer comprising a first cap layer outer surface defining a first outer surface of the multilayer film, a first cap layer inner surface opposite the first cap layer outer surface, extending from the first cap layer inner surface to

A first cover layer thickness of the first cover layer outer surface, wherein the first cover layer outer surface defines a first outer surface of the article;

a second cap layer comprising or consisting essentially of a second cap layer material, the second cap layer comprising a second cap layer outer surface defining a second outer surface of the multilayer film, a second cap layer inner surface opposite the second cap layer outer surface, a second cap layer thickness extending from the second cap layer inner surface to the second cap layer outer surface, optionally wherein the second cap layer outer surface defines a second outer surface of the article; and

one or more core regions, wherein each of the one or more core regions comprises or consists essentially of a multilayer film, each of the one or more core regions comprising a core region first surface, a core region second surface, and a core region thickness extending from the core region first surface to the core region second surface, wherein each of the one or more core regions is positioned between the first cap layer inner surface and the second cap layer inner surface.

In another aspect, the first and second cap layer materials are substantially the same. In an alternative aspect, the first and second cap layer materials are different. In some aspects, the first cap layer inner surface is in contact with the core region first surface, or the second cap layer inner surface is in contact with the core region second surface, or both.

In one aspect, the gas barrier material comprises or consists essentially of a nitrogen barrier material. In a further aspect, the gas barrier material comprises or consists essentially of one or more gas barrier polymers. Further, in this aspect, the gas barrier material may include a gas barrier polymer component composed of all polymers present in the gas barrier material. In another aspect, the one or more gas barrier polymers comprise or consist essentially of: one or more thermoplastic vinylidene chloride polymers, one or more thermoplastic acrylonitrile polymers or copolymers, one or more thermoplastic polyamides, one or more thermoplastic epoxy resins, one or more thermoplastic amine polymers or copolymers, or one or more thermoplastic polyolefin homopolymers or copolymers. In one aspect, the one or more thermoplastic polyolefin homopolymers or copolymers comprise or consist essentially of one or more thermoplastic polyethylene copolymers, or comprise or consist essentially of one or more thermoplastic ethylene-vinyl alcohol copolymers. In one aspect, the one or more ethylene vinyl alcohol copolymers comprise from about 28 mole percent to about 44 mole percent ethylene content or from about 32 mole percent to about 44 mole percent ethylene content.

In another aspect, the elastomeric material comprises or consists essentially of one or more thermoplastic elastomeric polymers, and further comprises an elastomeric polymer component consisting of all of the polymers present in the elastomeric material. In another aspect, the one or more thermoplastic elastomeric polymers comprise or consist essentially of: one or more thermoplastic elastomer polyolefin homo-or copolymers, one or more thermoplastic elastomer polyamide homo-or copolymers, one or more thermoplastic elastomer polyester homo-or copolymers, one or more thermoplastic elastomer polyurethane homo-or copolymers, one or more thermoplastic elastomer styrene homo-or copolymers, or any combination thereof.

In further aspects, the one or more styrene homopolymers or copolymers may include one or more styrene block copolymers, such as acrylonitrile butadiene styrene block copolymers, styrene acrylonitrile block copolymers, styrene ethylene butylene styrene block copolymers, styrene ethylene butadiene styrene block copolymers, styrene ethylene propylene styrene block copolymers, styrene butadiene styrene block copolymers, and combinations thereof.

In aspects, the elastomeric material comprises or consists essentially of one or more thermoplastic elastomeric polyurethane homo-or copolymers, optionally wherein the elastomeric material comprises or consists essentially of one or more thermoplastic elastomeric polyurethane homo-or copolymers based on polydiene polyols.

In some aspects, the one or more thermoplastic elastomer polyurethane homopolymers or copolymers include more than one first segment derived from one or more polyols and more than one segment derived from a diisocyanate. In another aspect, the one or more thermoplastic elastomer polyurethane homo-or copolymers are the polymerization product of a diisocyanate and one or more polyols.

In another aspect, the thermoplastic elastomeric polyurethane homo-or copolymer comprises or consists essentially of one or more thermoplastic elastomeric polyurethane homo-or copolymers based on polydiene polyols, wherein the polyol comprises or consists essentially of: polybutadiene polyol, polyisoprene polyol, partially or fully hydrogenated derivative of polybutadiene polyol, or partially or fully hydrogenated derivative of polyisoprene polyol, or any combination thereof.

In another aspect, the one or more polyols comprise or consist essentially of: polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyethers, or any combination thereof.

In yet another aspect, the diisocyanate comprises or consists essentially of: aliphatic diisocyanates, aromatic diisocyanates, or any combination thereof. In one aspect, the aliphatic diisocyanate comprises or consists essentially of: hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene Diisocyanate (BDI), diisocyanato cyclohexyl methane (HMDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI), diisocyanato methylcyclohexane, diisocyanato methyltricyclodecane, norbornane Diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4' -dicyclohexylmethane diisocyanate (H12 MDI), diisocyanato dodecane, lysine diisocyanate, or any combination thereof. In another aspect, the aromatic diisocyanate comprises or consists essentially of: toluene Diisocyanate (TDI), TDI adducts with Trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), xylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hydrogenated Xylene Diisocyanate (HXDI), naphthalene-1, 5-diisocyanate (NDI), 1, 5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3' -dimethyldiphenyl-4, 4' -diisocyanate (DDDI), 4' -dibenzyl diisocyanate (DBDI), 4-chloro-1, 3-phenylene diisocyanate, or any combination thereof.

In aspects, in the multilayer film, the gas barrier material may have a melt flow index of from about 5 grams per 10 minutes to about 7 grams per 10 minutes at 190 degrees celsius when a weight of 2.16 kilograms is used. In another aspect, when a weight of 2.16 kilograms is used, the elastomeric material can have a melt flow index of from about 20 grams per 10 minutes to about 30 grams per 10 minutes at 190 degrees celsius. In any of these aspects, in the multilayer film, the melt flow index of the gas barrier material may be from about 80% to about 120% of the melt flow index of the elastomeric material, or from about 90% to about 110% of the melt flow index of the elastomeric material, from about 95% to about 105% of the melt flow index of the elastomeric material, or may be substantially the same as the melt flow index of the elastomeric material, wherein the melt flow index is measured in cubic centimeters per 10 minutes at 190 degrees celsius when a weight of 2.16 kilograms is used.

In one aspect, the gas barrier material may have a melting temperature from about 165 degrees celsius to about 183 degrees celsius, while in another aspect, the elastomeric material may have a melting temperature from about 155 degrees celsius to about 165 degrees celsius. In any of these aspects, the melting temperature of the gas barrier material is within about 10 degrees celsius of the melting temperature of the elastomeric material, optionally within about 8 degrees celsius of the melting temperature of the elastomeric material, or within about 5 degrees celsius of the melting temperature of the elastomeric material.

In any of these aspects, without wishing to be bound by theory, the thin gas barrier layers alternating with the elastomeric layers as disclosed herein may improve the flexibility tolerance of the core region or the multilayer film without compromising durability or gas barrier properties. Further, in this aspect, the disclosed multilayer films allow for the production of articles incorporating multilayer films, wherein the articles may incorporate extreme geometries without exhibiting cracking, blurring, or loss of gas barrier properties over time.

In some aspects, the multilayer films disclosed herein further comprise a blended material, wherein the blended material comprises or consists essentially of a blend of one or more additional thermoplastic elastomers and a second material, optionally wherein the second material comprises or consists essentially of one or more second polymers, optionally wherein the one or more second polymers comprise or consist essentially of one or more second thermoplastics.

In aspects, the one or more second thermoplastics may include one or more thermoplastic polyolefin homopolymers, one or more thermoplastic polyamide homopolymers or copolymers, one or more thermoplastic polyester homopolymers or copolymers, one or more thermoplastic polyurethane homopolymers or copolymers, one or more thermoplastic styrene homopolymers or copolymers, or any combination thereof.

In another aspect, the one or more second thermoplastics may comprise or consist essentially of: thermoplastic polypropylene homo-or copolymer, thermoplastic polyethylene homo-or copolymer, thermoplastic polybutylene homo-or copolymer, or any combination thereof.

In some aspects, the one or more second thermoplastics comprise or consist essentially of one or more thermoplastic polyethylene copolymers. In another aspect, the one or more second thermoplastics comprise or consist essentially of one or more thermoplastic ethylene-vinyl alcohol copolymers. In one aspect, the polymeric component of the blended material is comprised of one or more additional thermoplastic elastomeric polyurethane homo-or copolymers and one or more second thermoplastic ethylene vinyl alcohol copolymers. In an alternative aspect, the polymer component of the thermoplastic elastomer material consists of one or more additional thermoplastic elastomer polyester-polyurethane copolymers and one or more second thermoplastic ethylene-vinyl alcohol copolymers. In some aspects, the blended material includes one or more recycled additional thermoplastic elastomers, or one or more recycled secondary thermoplastics, or both.

In some aspects, the blended material is a phase separated blend of one or more additional thermoplastic elastomers and one or more second thermoplastics. In some aspects, the phase separated blend includes one or more phase separated regions that include an interface between one or more additional thermoplastic elastomers and one or more second thermoplastics. In some aspects, the blend includes about 95% by weight of the one or more second thermoplastics and about 5% by weight of the one or more second thermoplastics based on the total weight of the blend.

As used herein, the term recycled material may refer to polymeric materials that have been previously extruded into films and may have been previously thermoformed into capsules before being chopped or ground and re-extruded into films. Thus, optionally, the thermal history of the material may provide evidence that it is recycled material rather than virgin material. Optionally, the recycled material, in particular the recycled polymeric material, may comprise up to 10% by weight of the gas barrier polymeric material, as it may be recycled by grinding or shredding the multilayer film comprising the gas barrier material. In aspects, the disclosed multilayer films further comprise recycled material comprising one or more recycled polymers, optionally wherein the one or more recycled polymers comprise one or more recycled thermoplastics, optionally wherein the one or more recycled thermoplastics comprise one or more recycled thermoplastic elastomers; optionally wherein the recycled material comprises a recycled material polymer component consisting of one or more recycled thermoplastics, optionally wherein the recycled material polymer component comprises or consists essentially of one or more recycled thermoplastic elastomers.

In another aspect, the recycled material may include one or more recycled thermoplastic elastomers, and optionally the one or more recycled thermoplastic elastomers include one or more regrind thermoplastic elastomers, optionally wherein the one or more recycled thermoplastic elastomers or regrind thermoplastic elastomers include a thermoplastic elastomer material as disclosed herein.

In some aspects, the recycled material further comprises one or more recycled secondary thermoplastics, and the one or more recycled secondary thermoplastics optionally comprise one or more regrind secondary thermoplastics, optionally wherein the one or more recycled secondary thermoplastics or regrind secondary thermoplastics comprise a thermoplastic as disclosed herein.

In one aspect, the recycled material comprises one or more recycled thermoplastic polyurethane elastomers or regrind thermoplastic polyurethane elastomers, or one or more recycled thermoplastic ethylene-vinyl alcohol copolymers or regrind thermoplastic ethylene-vinyl alcohol copolymers, or both. In aspects, the recycled material comprises a blend of one or more recycled thermoplastic elastomers or a regrind thermoplastic elastomer and one or more secondary thermoplastics, or comprises a blend of one or more thermoplastic elastomers and one or more recycled thermoplastics or one or more recycled thermoplastics, optionally wherein the blend is a phase separated blend, and optionally wherein the phase separated blend comprises one or more interfaces between the one or more recycled thermoplastic elastomers and the one or more secondary thermoplastics.

In another aspect, in the multilayer film, the recycled material comprises from about 99% to about 90% by weight of one or more recycled thermoplastic elastomers and from about 1% to about 10% by weight of one or more second thermoplastic elastomers, based on the total weight of the recycled material, optionally wherein the recycled material comprises from about 99% to about 93% by weight of one or more recycled thermoplastic elastomers and from about 1% to about 7% by weight of one or more second thermoplastic elastomers, or from about 99% to about 95% by weight of one or more recycled thermoplastic elastomers and from about 1% to about 5% by weight of one or more second thermoplastic elastomers.

In aspects, the recycled material comprises from about 99% to about 50% recycled polymer or regrind polymer by weight, or from about 99% to about 75% recycled polymer or regrind polymer by weight, based on the total weight of the recycled material.

In some aspects, the recycled material further comprises one or more virgin first thermoplastic elastomers, optionally wherein the one or more virgin thermoplastic elastomers comprise one or more virgin thermoplastic polyurethane elastomers.

In one aspect, the multilayer film further comprises one or more tie layers, each of the one or more tie layers comprising or consisting essentially of a tie material, wherein the one or more tie layers increase the bond strength between two adjacent layers. In some aspects, the connection material of each of the one or more connection layers independently comprises or consists essentially of: polyurethane, polyacrylate, ethylene-acrylate copolymer, maleic anhydride grafted polyolefin, or any combination thereof, and optionally the linking material comprises or consists essentially of a blended material or recycled material as disclosed herein. In another aspect, the tie layer material of the one or more tie layers independently comprises or consists essentially of one or more thermoplastic polyurethane elastomer homo-or copolymers, optionally wherein the one or more tie layers comprises or consists essentially of a polydiene polyol-based thermoplastic polyurethane.

In one aspect, in the multilayer film, the elastomeric material may be a first elastomeric material and the multilayer film further comprises a second elastomeric material and the formed multilayer film further comprises a first structural layer secured to the first side of one of the one or more core regions, wherein the first structural layer comprises a second elastomeric material and has an average thickness in a range from about 900 microns to about 1990 microns, optionally from about 900 microns to about 1500 microns, from about 1500 microns to about 1990 microns, from about 1200 microns to about 1800 microns, or from about 1000 microns to about 1400 microns.

In another aspect, the multilayer film further comprises or consists essentially of one or more structural layers, each of the one or more structural layers independently comprising or consisting essentially of a structural layer material, optionally wherein the structural layer material comprises or consists essentially of a blended or recycled material as described herein. In some aspects, the structural layer material of the one or more structural layers independently comprises or consists essentially of a polydiene polyol-based thermoplastic polyurethane.

In yet another aspect, the multilayer film may comprise or consist essentially of one or more cap layers, wherein the one or more cap layers comprise or consist essentially of cap layer material, optionally wherein the cap layer material comprises or consist essentially of blended or recycled material as disclosed herein. In some aspects, the cap layer material of the one or more cap layers comprises or consists essentially of: polyurethane, polyacrylate, ethylene-acrylate copolymer, maleic anhydride grafted polyolefin, or any combination thereof. In another aspect, the cap layer material of the one or more cap layers comprises, consists essentially of, or consists of a thermoplastic polyurethane, optionally a polydiene polyol-based thermoplastic polyurethane.

In some aspects, at least one of the one or more connection layers is positioned between one of the one or more structural layers and one of the one or more core regions. In another aspect, at least one of the one or more structural layers is positioned between one of the one or more connection layers and one of the one or more cap layers. In another aspect, the multilayer film may be a coextruded layered sheet or a laminated layered sheet.

In one aspect, disclosed herein is a multilayer film comprising a first cap layer, a first structural layer, a first tie layer, a core region, a second tie layer, a second structural layer, and a second cap layer, wherein the first cap layer inner surface contacts the first surface of the first structural layer, the second surface of the first structural layer contacts the first surface of the first tie layer, the second surface of the first tie layer contacts the first surface of the core region, the second surface of the core region contacts the first surface of the second tie layer, the second surface of the second tie layer contacts the first surface of the second structural layer, and the second surface of the second structural layer contacts the inner layer of the second cap layer.

In an alternative aspect, the disclosed multilayer films have ase:Sub>A structure of ase:Sub>A-B-C-B-ase:Sub>A, wherein ase:Sub>A represents ase:Sub>A structural layer, B represents ase:Sub>A tie layer, and C represents ase:Sub>A core region. In another aspect, the disclosed multilayer film has ase:Sub>A structure of D-ase:Sub>A-B-C-B-ase:Sub>A-D, wherein ase:Sub>A represents ase:Sub>A structural layer, B represents ase:Sub>A tie layer, C represents ase:Sub>A core region, and D represents ase:Sub>A cap layer.

In aspects, in any of the disclosed multilayer films, each of the one or more core regions may have a gas transmission rate for nitrogen measured at 23 degrees celsius and 0% relative humidity of from about 0.3 cubic centimeters per square meter per day to about 1.9 cubic centimeters per square meter per day, optionally for structures having a thickness of from about 72 micrometers to about 320 micrometers, optionally wherein each of the one or more core regions may have a gas transmission rate for nitrogen measured at 23 degrees celsius and 0% relative humidity of from about 0.3 cubic centimeters per square meter per day to about 1.9 cubic centimeters per square meter per day.

In any of these aspects, the multilayer film further comprises one or more protective layers, each of the one or more protective layers comprising or consisting essentially of a protective material alone, wherein each of the one or more protective layers is adjacent to the core region and has a protective layer thickness, wherein the combination of the one or more protective layers and the adjacent core region has a minimum radius of curvature that is greater than a minimum radius of curvature that causes cracking of the core region or one or more individual layers within the core region.

Turning to fig. 6, in one aspect, disclosed herein is a multilayer film comprising one or more core regions 2160, wherein each of the one or more core regions comprises more than one layer comprising a gas barrier layer 3020 comprising at least one gas barrier material, the gas barrier layer 3020 alternating with an elastomeric layer 3010 comprising at least one elastomeric material; wherein each of the gas barrier layers has a thickness from about 0.5 microns to about 2 microns or from about 0.5 microns to about 1 micron; or optionally less than or equal to 0.75 microns thick, or less than or equal to 0.5 microns thick, or in the range from about 0.01 microns to about 0.75 microns thick, particularly in the range from about 0.01 microns to about 0.5 microns thick 3021; and wherein each of the elastomeric layers has a thickness 3011 of from about 2 microns to about 8 microns thick or from about 2 microns to about 4 microns thick. In some aspects, the core region 2160 is adjacent to another layer 3030, such as, for example, a tie layer, structural layer, or cover layer.

In another aspect, each of the one or more core regions comprises at least 50 layers, or from about 50 to about 100 layers, from about 50 to about 90 layers, from about 50 to about 80 layers, from about 50 to about 70 layers, from about 60 to about 100 layers, from about 60 to about 90 layers, or from about 60 to about 80 layers. In one aspect, each of the one or more core regions has an average total thickness of less than 200 microns, optionally from about 125 microns to about 200 microns, or from about 125 microns to about 175 microns, or from about 150 microns to about 200 microns.

Referring now to fig. 7A, in an alternative aspect, a sheet or multilayer film may incorporate a single structural layer 2200a comprising structural material and a core region 2160 comprising a gas barrier layer.

In some aspects, articles disclosed herein may include multiple layers, as illustrated, for example, in fig. 7B. In this exemplary embodiment, the article is a sheet comprising a gas barrier layer and comprises two cover layers, 2120a having a thickness 2100a and 2120b having a thickness 2100 b; two structural layers, 2200a with thickness 2180a and 2200b with thickness 2180 b; and a core region 2160 having a thickness 2140. Suitable examples of thicknesses 2180a and 2180b are in the range from about 900 microns to about 1990 microns, or from about 900 microns to about 1400 microns, or from about 1400 microns to about 1990 microns. Suitable examples of the thickness 2140 are in the range from about 125 microns to about 200 microns, or from about 125 microns to about 175 microns, or from about 150 microns to about 200 microns. Suitable examples of thicknesses 2100a and 2100b are in the range from about 5 microns to about 25 microns. In one aspect, the article may be double-sided. Further, in this aspect, the two-sided article may include a symmetrical arrangement of layers on both sides of the core region 2160.

In one such aspect according to the example of fig. 7B, cap layer 2120a and cap layer 2120B may comprise or consist essentially of cap layer material. In such aspects, structural layers 2200a and 2200b can further comprise or consist essentially of structural layer material, or can comprise or consist essentially of barrier material. In such aspects, core region 2160 may comprise or consist essentially of a multilayer film as disclosed herein.

In any of these aspects, cap layer 2120a can have a first surface 2120a 'and a second surface 2120a ", and cap layer 2120b can have a first surface 2120b' and a second surface 2120 b". In another aspect, the structural layer 2200a can have a first surface 2200a 'and a second surface 2200a ", and the core region 2200b can have a first surface 2200b' and a second surface 2200 b". In yet another aspect, the core region 2160 may have a first surface 2160a and a second surface 2160b. In some aspects, the second surface 2120a "of the cap layer 2120a and the first surface 2200a' of the structural layer 2200a may be adjacent to or otherwise in contact with each other. In further aspects, the second surface 2200a "of the structural layer 2200a and the first surface 2160a of the core region may be adjacent to or otherwise in contact with each other. In one aspect, the second surface 2160b of the core region 2160 and the second surface 2200b "of the structural layer 2200b may be adjacent to each other or otherwise in contact with each other. In yet another aspect, the first surface 2200b' of the structural layer 2200b and the second surface 2120b″ of the cap layer 2120b may be adjacent to each other or otherwise in contact with each other. In some aspects, the first surface 2120a 'of the cap layer 2120a and/or the first surface 2120b' of the cap layer 2120b can independently optionally be an outer surface of an article incorporating the multilayer film disclosed herein. In any of these aspects, the structural layer 2200a and the structural layer 2200b may be made of the same material or different materials, and may have the same or different thicknesses. In another aspect, cap layer 2120a and cap layer 2120b may be made of the same material or different materials, and may have the same or different thicknesses.

In another aspect, an article may be configured as a series of four or more layers including one or more structural layers, each of the one or more structural layers including a structural layer material and including a structural layer first surface, a structural layer second surface opposite the structural layer first surface, and a structural layer thickness extending from the structural layer first surface to the structural layer second surface;

In another aspect, a first surface of a first one of the structural layers is in contact with an inner surface of the first cap layer and a second surface of the first one of the structural layers is in contact with a first surface of one of the one or more core regions, or a second surface of the second one of the one or more structural layers is in contact with a second surface of one of the one or more core regions, or both.

In one aspect, one or more structural layers comprise or consist essentially of a blended material or recycled material as disclosed herein.

Referring now to fig. 7C, in an alternative aspect, a sheet or multilayer film may incorporate a single structural layer 2200a comprising structural material, a single cap layer 2120a comprising cap layer material, and a core region 2160 comprising gas barrier layers.

In some aspects, articles disclosed herein may include multiple layers, as illustrated, for example, in fig. 7D. In this exemplary embodiment, the article is a sheet comprising a gas barrier layer, and comprises two cap layers, specifically cap layer 2120a (having thickness 2100 a), cap layer 2120b (having thickness 2100 b); two structural layers, specifically structural layer 2200a (having thickness 2180 a), structural layer 2200b (having thickness 2180 b); two connection layers, specifically connection layer 2240a (having thickness 2220 a) and connection layer 2240b (having thickness 2220 b); and a core region or layer 2160 (having a thickness 2140). Suitable examples of thicknesses 2180a and 2180b are in the range from about 900 microns to about 1990 microns, or from about 900 microns to about 1400 microns, or from about 1400 microns to about 1990 microns. Suitable examples of the thickness 2140 are in the range from about 125 microns to about 200 microns, or from about 125 microns to about 175 microns, or from about 150 microns to about 200 microns. Suitable examples of thicknesses 2100a and 2100b are in the range from about 5 microns to about 25 microns. Suitable examples of thicknesses 2220a and 2220b are in the range from about 5 microns to about 20 microns. In one aspect, the article may be double-sided. Further, in this aspect, the two-sided article may include a symmetrical arrangement of layers on both sides of the core region 2160.

In one such aspect of the example according to fig. 7D, cap layer 2120a and cap layer 2120b may comprise or consist essentially of cap layer material. In such aspects, structural layers 2200a and 2200b can further comprise or consist essentially of structural layer material, or can comprise or consist essentially of barrier material. In such aspects, the connection layer 2240a and the connection layer 2240b may comprise or consist essentially of a connection material, or may comprise or consist essentially of a barrier material. In such aspects, core region 2160 may comprise or consist essentially of a multilayer film as disclosed herein.

In any of these aspects, cap layer 2120a can have a first surface 2120a 'and a second surface 2120a ", and cap layer 2120b can have a first surface 2120b' and a second surface 2120 b". In another aspect, the structural layer 2200a can have a first surface 2200a 'and a second surface 2200a ", and the core region 2200b can have a first surface 2200b' and a second surface 2200 b". In yet another aspect, the connection layer 2240a may have a first surface 2240a 'and a second surface 2240a ", while the connection layer 2240b may have a first surface 2240b' and a second surface 2240 b". In yet another aspect, the core region 2160 may have a first surface 2160a and a second surface 2160b. In some aspects, the second surface 2120a "of the cap layer 2120a and the first surface 2200a' of the structural layer 2200a may be adjacent to or otherwise in contact with each other. In further aspects, the second surface 2200a "of the structural layer 2200a and the first surface 2240a' of the connection layer 2240a may be adjacent to each other or otherwise in contact with each other. In still further aspects, the first surface 2160a of the core area and the second surface 2240a "of the connection layer 2240a may be adjacent to or otherwise in contact with each other. In one aspect, the second surface 2160b of the core area 2160 and the second surface 2240b″ of the connection layer 2240b may be adjacent to each other or otherwise in contact with each other. In another aspect, the first surface 2240b' of the connection layer 2240b and the second surface 2200b "of the structural layer 2200b may be adjacent to each other or otherwise in contact with each other. In yet another aspect, the first surface 2200b' of the structural layer 2200b and the second surface 2120b″ of the cap layer 2120b may be adjacent to each other or otherwise in contact with each other. In some aspects, the first surface 2120a 'of the cap layer 2120a and/or the first surface 2120b' of the cap layer 2120b can independently optionally be an outer surface of an article incorporating the multilayer film disclosed herein. In any of these aspects, the structural layer 2200a and the structural layer 2200b may be made of the same material or different materials, and may have the same or different thicknesses. In further aspects, cap layer 2120a and cap layer 2120b may be made of the same material or different materials, and may have the same or different thicknesses. In still further aspects, the connection layer 2240a and the connection layer 2240b may be made of the same material or different materials, and may have the same or different thicknesses.

Referring now to fig. 7E, in an alternative aspect, a sheet or multilayer film may incorporate a single structural layer 2200a comprising structural material, a single cap layer 2120a comprising cap layer material, a single tie layer 2240a comprising tie layer material, and a core region 2160 comprising gas barrier layers.

In aspects, the article may be configured as a series of five or more layers including one or more tie layers, each of the one or more tie layers including a tie layer first surface, a tie layer second surface opposite the tie layer first surface, and a tie layer thickness extending from the tie layer first surface to the tie layer second surface;

In one aspect, a first surface of a first of the one or more connection layers is in contact with a second surface of the first of the one or more structural layers and a second surface of the first of the one or more connection layers is in contact with a first surface of the core region, or wherein a first surface of a second of the one or more connection layers is in contact with a second surface of one of the one or more core regions and a second surface of the second of the one or more connection layers is in contact with a first surface of the second of the one or more structural layers, or both.

In aspects, an article includes a first cap layer, a first structural layer, a first tie layer, a core region, a second tie layer, a second structural layer, and a second cap layer, wherein the first cap layer inner surface contacts the first surface of the first structural layer, the second surface of the first structural layer contacts the first surface of the first tie layer, the second surface of the first tie layer contacts the first surface of the core region, the second surface of the core region contacts the first surface of the second tie layer, the second surface of the second tie layer contacts the first surface of the second structural layer, and the second surface of the second structural layer contacts the inner layer of the second cap layer, and optionally the core region includes one or more core regions or includes more than one microlayers.

One or both of the sheets comprising the gas barrier layer as shown in fig. 5 and 7A-7E may independently be transparent, translucent and/or opaque. As used herein, the term "transparent" as used with respect to the barrier layer and/or the bladder means that the light passes through the barrier layer in a substantially straight line and is visible to a viewer through the barrier layer. In contrast, for an opaque barrier layer, light does not pass through the barrier layer and one cannot see clearly through the barrier layer at all. A translucent barrier layer is interposed between a transparent barrier layer and an opaque barrier layer because light passes through the translucent layer, but some of the light is scattered so that it is not clearly visible to an observer through the layer.

The gas cushion 1036 may be produced from a sheet material including a gas barrier layer as shown in fig. 5 and 7A-7E using any suitable technique, such as thermoforming (e.g., vacuum thermoforming), blow molding, extrusion, injection molding, vacuum molding, rotational molding, transfer molding, pressure forming, heat sealing, casting, low pressure casting, rotational casting, reactive injection molding, radio Frequency (RF) welding, and the like. In aspects, sheets including a gas barrier layer as shown in fig. 5 and 7A-7E may be produced by coextrusion followed by vacuum thermoforming to form the contours of the gas cushion 1036, the gas cushion 1036 may optionally include one or more valves (e.g., one-way valves) that allow the gas cushion 1036 to be filled with a fluid (e.g., gas).

In any of these aspects, the multilayer film and articles produced therefrom are suitable for use in mass market products including, but not limited to, articles of footwear, articles of athletic equipment, articles of athletic apparel, personal protective equipment, and the like.

In aspects, the multilayer film and articles formed therefrom may include one or more textiles, or in the case of a bladder or balloon, one or more spacer materials, where the spacer materials may be textiles, foamed components, 3D printed components, or other materials as described herein.

The multilayer film and/or articles formed therefrom may be subjected to additional processes including, but not limited to, application of decorative elements and thermoforming to impart a useful structure, shape or texture. Consumer products incorporating the multilayer films and articles comprising the multilayer films and methods of making consumer products are also disclosed.

In one exemplary embodiment, provided herein is a method for producing a multilayer film disclosed herein, the method comprising co-extruding a gas barrier material and an elastomeric material to form a multilayer structure comprising one or more core regions.

In one aspect, the method further comprises applying at least one tie layer to the multilayer film to form a multilayer film comprising one or more core regions and the tie layer, wherein the tie layer comprises a tie material as described herein. In some aspects, the method includes coextruding at least one tie layer with the multilayer film to form a multilayer film including one or more core regions and the tie layer.

In another aspect, the method includes applying at least one structural layer to a multilayer film including a core region and a tie layer to form a multilayer film including one or more core regions, tie layers, and structural layers, wherein the structural layers include a structural layer material. Further, in this aspect, the method can include coextruding at least one structural layer with a multilayer film including a core region and a tie layer to form a multilayer film including one or more core regions, tie layers, and structural layers.

In yet another aspect, the method further comprises applying at least one cap layer to the multilayer film comprising the core region, the tie layer, and the structural layer to form a multilayer film comprising the core region, the tie layer, the structural layer, and the cap layer, wherein the cap layer comprises a cap layer material as described herein. In some aspects, the method further comprises coextruding at least one cap layer with the multilayer film comprising the core region, the tie layer, and the structural layer to form a multilayer film comprising the core region, the tie layer, the structural layer, and the cap layer.

In some aspects, the article is a layered sheet, optionally a coextruded layered sheet or a laminated layered sheet.

In another aspect, disclosed herein are articles comprising the multilayer films disclosed herein. In another aspect, the article may include an article of footwear, a component of an article of footwear, an article of apparel, a component of an article of apparel, an article of athletic equipment, a component of an article of athletic equipment, an article of personal protection, a flexible flotation device, a rigid flotation device, a medical device, a prosthetic device, an orthopedic device, an accumulator, an article of furniture, or a component of an article of furniture. In some aspects, the article may be a tire or hose. Also disclosed herein are methods of manufacturing consumer products, the methods comprising attaching the disclosed articles to a second component. Further, disclosed herein are consumer products produced by the disclosed methods.

In aspects, disclosed herein is a polymeric material comprising: one or more core regions, wherein each core region of the one or more core regions comprises more than one layer comprising gas barrier layers comprising at least one gas barrier material alternating with elastomeric layers comprising at least one elastomeric material, wherein each of the gas barrier layers is from about 0.5 microns to about 2 microns thick or from about 0.5 microns to about 1 micron thick; optionally less than or equal to 0.75 microns thick, or less than or equal to 0.5 microns thick, or in the range from about 0.01 microns to about 0.75 microns thick, particularly in the range from about 0.01 microns to about 0.5 microns thick; and wherein each of the elastomeric layers is from about 2 microns to about 8 microns thick or from about 2 microns to about 4 microns thick.

In another aspect, each of the one or more core regions comprises at least 50 layers, or from about 50 to about 100 layers, from about 50 to about 90 layers, from about 50 to about 80 layers, from about 50 to about 70 layers, from about 60 to about 100 layers, from about 60 to about 90 layers, or from about 60 to about 80 layers.

In another aspect, the gas barrier material comprises or consists essentially of one or more gas barrier polymers, wherein the gas barrier material comprises a gas barrier polymer component consisting of all of the polymers present in the gas barrier material. In some aspects, the gas barrier material comprises a nitrogen barrier material.

In aspects, the one or more gas barrier polymers comprise or consist essentially of: one or more thermoplastic vinylidene chloride polymers, one or more thermoplastic acrylonitrile polymers or copolymers, one or more thermoplastic polyamides, one or more thermoplastic epoxy resins, one or more thermoplastic amine polymers or copolymers, or one or more thermoplastic polyolefin homopolymers or copolymers. In some aspects, the one or more thermoplastic polyolefin homopolymers or copolymers comprise or consist essentially of one or more thermoplastic ethylene-vinyl alcohol copolymers. In another aspect, the one or more thermoplastic ethylene vinyl alcohol copolymers comprise from about 28 mole percent to about 44 mole percent ethylene content or from about 32 mole percent to about 44 mole percent ethylene content.

In another aspect, the elastomeric material comprises or consists essentially of one or more thermoplastic elastomeric polymers and includes an elastomeric polymer component that consists of all of the polymers present in the elastomeric material. In one aspect, the one or more thermoplastic elastomeric polymers comprise or consist essentially of: one or more thermoplastic elastomer polyolefin homo-or copolymers, one or more thermoplastic elastomer polyamide homo-or copolymers, one or more thermoplastic elastomer polyester homo-or copolymers, one or more thermoplastic elastomer polyurethane homo-or copolymers, one or more thermoplastic elastomer styrene homo-or copolymers, or any combination thereof.

In some aspects, the elastomeric material comprises or consists essentially of one or more thermoplastic elastomeric polyurethane homo-or copolymers, and optionally comprises or consists essentially of one or more thermoplastic elastomeric homo-or copolymers based on polydiene polyols.

In one aspect, the one or more thermoplastic elastomer polyurethane homopolymers or copolymers include more than one first segment derived from one or more polyols and more than one second segment derived from a diisocyanate. In another aspect, the one or more thermoplastic elastomeric polyurethane homo-or copolymers are the polymerization product of a diisocyanate and a polyol.

In one aspect, the thermoplastic elastomeric polyurethane homo-or copolymer comprises or consists essentially of one or more thermoplastic elastomeric polyurethane homo-or copolymers based on polydiene polyols, and the polyol comprises or consists essentially of: polybutadiene polyol, polyisoprene polyol, partially or fully hydrogenated derivative of polybutadiene polyol, or partially or fully hydrogenated derivative of polyisoprene polyol, or any combination thereof. In one aspect, the polyol comprises or consists essentially of: polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyethers, or any combination thereof.

In one aspect, the diisocyanate may comprise or consist essentially of: aliphatic diisocyanates, aromatic diisocyanates, or any combination thereof. In one aspect, the aliphatic diisocyanate comprises or consists essentially of: hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene Diisocyanate (BDI), diisocyanato cyclohexyl methane (HMDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI), diisocyanato methylcyclohexane, diisocyanato methyltricyclodecane, norbornane Diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4' -dicyclohexylmethane diisocyanate (H12 MDI), diisocyanato dodecane, lysine diisocyanate, or any combination thereof. In another aspect, the aromatic diisocyanate comprises or consists essentially of: toluene Diisocyanate (TDI), TDI adducts with Trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), xylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hydrogenated Xylene Diisocyanate (HXDI), naphthalene-1, 5-diisocyanate (NDI), 1, 5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3' -dimethyldiphenyl-4, 4' -diisocyanate (DDDI), 4' -dibenzyl diisocyanate (DBDI), 4-chloro-1, 3-phenylene diisocyanate, or any combination thereof.

In one aspect, the multilayer films disclosed herein and/or balloons incorporating the multilayer films may include a spacer component in the lumen. For example, as shown in fig. 8, the spacer material may include or consist essentially of: a textile, a foamed part, an injection molded part, a part produced by 3D printing or additive manufacturing, or any combination thereof. In another aspect, the foamed part may comprise or consist essentially of more than one foam particle. In one aspect, the spacer component additionally comprises a surrounding thermoplastic material as described herein.

In one aspect, the spacer component or textile may have a decorative function, such as adding a color or pattern to the multilayer film that is visible when the article incorporating the multilayer film is worn. In another aspect, the spacer component or textile may help to maintain the layers or sheets forming the structure, such as the bladder, properly aligned with one another and may resist forces that would otherwise move the different components of the bladder, thus stabilizing the bladder, air bladder, and other articles incorporating the multilayer films disclosed herein. In another aspect, the lumen of the balloon may be hollow.

In aspects, the spacer component may include a first layer, a second layer, and more than one connecting member extending between and joining the first layer and the second layer.

In one aspect, provided herein is a bladder or bladder for an article of footwear, the bladder or bladder comprising a first sheet and a second sheet, wherein the first sheet, the second sheet, or both the first sheet and the second sheet comprise a multilayer film as disclosed herein, wherein the first side of the first sheet faces the second side of the second sheet, wherein the first sheet and the second sheet are joined together by a bond to form an interior cavity in a space between the first side of the first sheet and the second side of the second sheet, wherein the bond extends around at least a portion of a perimeter of the interior cavity, optionally wherein the bond abuts only around one or more portions of the perimeter of the interior cavity. In some aspects, the bladder further comprises a textile. In one aspect, the textile forms a layer of the first sheet, a layer of the second sheet, or a layer of both the first sheet and the second sheet. In one aspect, the textile forms an outer layer of the first sheet and/or an outer layer of the second sheet, or wherein the textile forms an inner layer of the first sheet and/or an inner layer of the second sheet.

In another aspect, the textile may be a spacer textile having a first textile face, a second textile face, and a textile thickness extending from the first textile face to the second textile face, wherein the textile thickness is from about 0.3 cm to about 3 cm or from about 0.5 cm to about 1 cm, optionally wherein the fiber density of the first textile face and the second textile face is at least 25% greater, or at least 50% greater, or at least 75% greater than the fiber density between the first textile face and the second textile face.

In aspects, the fibers or yarns of the textile comprise or consist essentially of synthetic fibers or yarns formed from one or more thermoplastic materials, optionally wherein the thermoplastic material of the synthetic fibers or yarns comprises or consists essentially of a thermoplastic elastomeric material. In another aspect, the melting temperature of the thermoplastic material of the synthetic fibers or yarns is within 20 degrees celsius of the melting temperature of the thermoplastic material forming the outer layer of the bladder.

In one aspect, the first sheet, the second sheet, or both comprise layered sheets, and the polymeric component of the thermoplastic material of the synthetic fibers or yarns is substantially the same as the polymeric component of the thermoplastic material of the one or more layers of the first sheet and/or the one or more layers of the second sheet, optionally wherein the polymeric component of the thermoplastic material of the synthetic fibers or yarns is substantially the same as the polymeric component of the thermoplastic material of the cover layers or structural layers of the first sheet and/or the second sheet.

In one aspect, the core 3150 includes a first wall 3130a, the first wall 3130a being generally spaced apart from a second wall 3130b by a predetermined distance, as seen in fig. 8. More than one connecting member 3140 extends between the first wall 3130a and the second wall 3130 b. When the fluid pressurizes bladder 3100, the fluid exerts an outward force on air mattress layer 3110a and air mattress layer 3110 b. The outward force expands connecting member 3140, placing connecting member 3140 in tension and restricting further outward movement of air cushion layer 3110a and air cushion layer 3110 b.

In further aspects, the connecting member 3140 can include doffing, each including a plurality of drawn filaments anchored to the first wall 3130a and the second wall 3130 b. One method of making the core 3150 is double needle bed raschel knitting (double needle bar Raschel knitting). In some aspects, a portion of the first wall 3130a and the second wall 3130b may be formed from air textured yarns or otherwise textured yarns, such as false twist textured yarns having a combination of nylon 6,6 and nylon 6. The connecting member 3140 may be formed of a similar material. In some aspects, first wall 3130a and second wall 3130b also include a fuse (fusing filent). Although the thickness of the core 3150 measured when the connecting member 3140 is in a stretched state between the first wall 3130a and the second wall 3130b may vary significantly within the scope of the present disclosure, a thickness suitable for footwear applications may range from 8 millimeters to 15 millimeters. In some aspects, the peripheral bond 3120 may be formed by compressing and heat sealing the air cushion layer 3110a and the air cushion layer 3110b together around substantially the entire periphery of the core 3150.

In some aspects, the double-walled fabric core is typically secured within the outer barrier (outer barrier) of the bladder by: layers of heat activated flux are attached to the first and second walls of the core and then the outer barrier, core and flux are heated to cause the flux to fuse the walls of the core to the outer barrier. The heat activated flux is typically a sheet of thermoplastic material that is heated and pressed into contact with the first and second walls prior to placing the core between the layers of the outer barrier. Although this process may be used to effectively secure the core 3150 and the gas cushion layer 3110a and the gas cushion layer 3110b to each other, it adds manufacturing steps and adds additional expense to the manufacturing process.

In alternative aspects, more than one fuse 3160 may be used, wherein the fuse 3160 is integrated into the first wall 3130a and the second wall 3130b, for example, by braiding. Fuse 3160 is formed from a material that will fuse, bond, or otherwise become secured to cushion layer 3110a and cushion layer 3110b when the various components of bladder 3100 are heated and compressed together.

During or after the double needle bed raschel knitting process, the fusing filaments 3160 may be knitted or otherwise mechanically manipulated into the walls 3130a and 3130 b. Thus, the fuse 3160 may be integrated into the walls 3130a and 3130b during the manufacturing process of the core 3150, or the fuse 3160 may be subsequently added to the walls 3130a and 3130 b. The configuration of the fuse 3160 and the manner in which the fuse 3160 is integrated into the walls 3130a and 3130b may vary greatly within the scope of the present disclosure.

In some aspects, in the disclosed spacer elements having more than one connecting member, the spacer elements comprise a textile, and the more than one member comprises yarns or fibers, which in some aspects comprise a spacer thermoplastic material. Further, in these aspects, the spacing element comprises a surrounding thermoplastic material surrounding more than one yarn or fiber of the textile and consolidating at least a portion of the textile, wherein the surrounding thermoplastic material has a melting temperature that is lower than the melting temperature of the fibrous thermoplastic material.

In other cases, in the disclosed spacer textile having more than one connecting yarn or fiber, the more than one connecting yarn or fiber comprises a spacer thermoplastic material and a surrounding thermoplastic material surrounding the more than one connecting yarn or fiber of the textile and consolidating at least a portion of the textile, wherein the surrounding thermoplastic material has a melting temperature that is lower than the melting temperature of the spacer thermoplastic material.

In any of these aspects, the disclosed bladder may be a thermoformed bladder.

Method for manufacturing a balloon and a balloon

In one aspect, disclosed herein is a method for manufacturing a bladder, wherein the bladder comprises a first sheet and a second sheet, wherein a first side of the first sheet faces a second side of the second sheet, the method comprising:

wherein the first sheet, the second sheet, or both comprise a multilayer film as disclosed herein.

In another aspect, in the disclosed method, the balloon comprises one or more lumens, optionally wherein the one or more lumens comprise at least two lumens, and optionally wherein each of the one or more lumens is an open lumen, or each of the one or more lumens is a sealed balloon, or the one or more lumens comprise at least one open lumen and at least one sealed balloon. In yet another aspect, bonding comprises adhesively bonding or thermal bonding, optionally wherein the first sheet and the second sheet comprise thermal bonds formed by Radio Frequency (RF) welding.

In yet another aspect, the disclosed method further comprises closing one or more holes in the perimeter of the lumen, thereby forming a sealed bladder. In yet another aspect, closing includes forming an adhesive bond or a thermal bond between the first side of the first sheet and the second side of the second sheet at one or more apertures.

In any of these aspects, the method further comprises inflating the sealed bladder with a fluid.

Method for producing a multilayer film

In aspects, the sheet comprising the gas barrier layer may be produced by coextrusion followed by vacuum thermoforming to form the contours of the gas cushion, which may optionally comprise one or more valves (e.g., check valves) that allow the gas cushion to be filled with a fluid (e.g., gas).

In one embodiment, provided herein is a method for making a multilayer film disclosed herein, the method comprising at least the step of co-extruding a gas barrier material and an elastomeric material to form a multilayer film comprising one or more core regions, wherein each of the one or more core regions comprises more than one layer comprising gas barrier layers comprising a gas barrier material alternating with elastomeric layers comprising an elastomeric material.

In one aspect, the disclosed method further comprises applying at least one tie layer to the multilayer film comprising one or more core regions to form a multilayer film comprising one or more core regions and a tie layer, wherein the tie layer comprises a tie material as disclosed herein. In a further aspect, the disclosed method further comprises coextruding at least one tie layer with the multilayer film comprising the core region to form a multilayer film comprising one or more core regions and tie layers.

In one aspect, the disclosed method further comprises applying at least one structural layer to the multilayer film comprising the core region and the tie layer to form a multilayer film comprising one or more core regions, tie layer, and structural layer, wherein the structural layer comprises a structural layer material as disclosed herein. In an alternative aspect, the disclosed method further comprises coextruding at least one structural layer with the multilayer film comprising the core region and the tie layer to form a multilayer film comprising one or more of the core region, the tie layer, and the structural layer.

In one aspect, the disclosed method further comprises applying at least one cap layer to the multilayer film comprising the core region, the tie layer, and the structural layer to form a multilayer film comprising the core region, the tie layer, the structural layer, and the cap layer, wherein the cap layer comprises a cap layer material as disclosed herein. In an alternative aspect, the disclosed method further comprises coextruding at least one cap layer with the multilayer film comprising the core region, the tie layer, and the structural layer to form a multilayer film comprising the core region, the tie layer, the structural layer, and the cap layer.

Article and method for manufacturing the same

In one aspect, provided herein is an article comprising a multilayer film disclosed herein, the article comprising a multilayer film comprising:

one or more core regions, wherein each of the one or more core regions comprises one or more gas barrier layers, optionally one or more gas barrier layers each having an average thickness of less than or equal to about 0.75 microns, particularly at least about 20 individual gas barrier layers, or consists essentially of one or more gas barrier layers, optionally one or more gas barrier layers each having an average thickness of less than or equal to about 0.75 microns, particularly at least about 20 individual gas barrier layers, each gas barrier layer alternating with an elastomeric layer, each of the one or more core regions comprising a core region first surface, a core region second surface, and a core region thickness extending from the core region first surface to the core region second surface, wherein each of the one or more core regions is positioned between the first cap layer inner surface and the second cap layer inner surface.

In one aspect, a first surface of a first of the one or more connection layers is in contact with a second surface of a first of the one or more structural layers, and a second surface of the first of the one or more connection layers is in contact with the first surface of the core region; or wherein the first surface of the second one of the one or more connection layers is in contact with the second surface of one of the one or more core regions and the second surface of the second one of the one or more connection layers is in contact with the first surface of the second one of the one or more structural layers, or both.

In another aspect, disclosed herein are articles comprising the multilayer films disclosed herein. In another aspect, the article may include an article of footwear, a component of an article of footwear, an article of apparel, a component of an article of apparel, an article of athletic equipment, a component of an article of athletic equipment, an article of personal protection, a flexible flotation device, a rigid flotation device, a medical device, a prosthetic device, an orthopedic device, an accumulator, an article of furniture, or a component of an article of furniture. In some aspects, the article may be a tire or hose. Also disclosed herein are methods of manufacturing consumer products, the methods comprising attaching the disclosed articles to a second component. In a further aspect, disclosed herein are consumer products produced by the disclosed methods.

Methods for manufacturing articles of footwear.In another aspect, disclosed herein is a method for manufacturing an article of footwear, the method comprising securing the disclosed bladder to an upper for the article of footwear. In another aspect, the method further includes securing the bladder to the outsole and midsole layer such that the bladder is disposed between the midsole layer and the outsole to create a sole structure; and securing the midsole layer to an upper for the article of footwear. Also disclosed herein are articles of footwear manufactured using the disclosed methods.

Thermoforming

In any of the foregoing aspects, the bladder may undergo a thermoforming step, optionally wherein thermoforming occurs prior to inflation of the bladder, or wherein the thermoforming step occurs simultaneously with inflation of the bladder, or wherein the thermoforming step occurs after inflation of the bladder. In one aspect, thermoforming the bladder may impart one or more structural or other properties to the bladder, such as imparting a three-dimensional shape or structure, rigidity, abrasion resistance, water resistance, or the like to one or more portions of the bladder. In some aspects, the thermoforming process may be useful in imparting a texture, wherein the texture may be decorative, functional, or both decorative and functional.

In aspects, a portion of the bladder may be selectively thermoformed, for example, by masking portions of the bladder that are not desired to be exposed to the thermoforming process, or by using a tool that contacts or covers only a portion of the bladder.

In one aspect, the bladder includes an outer surface and thermoforming includes placing the bladder in a mold, wherein the mold includes an inner molding surface. Further, in this aspect, the inner molding surface contacts the outer surface of the bladder.

In some aspects, a protective sleeve having an outer surface is placed between at least a portion of the outer surface of the bladder and the inner molding surface, and the outer surface of the protective sleeve contacts the inner molding surface. In a further aspect, the protective sleeve includes an inner surface, and the inner surface of the protective sleeve contacts the outer surface of the bladder. In an optional aspect, the inner surface of the protective sleeve comprises a raised pattern. In some aspects, the raised pattern of the inner surface of the protective sleeve is embossed into the bladder during thermoforming. In one aspect, the use of a protective sleeve may effectively reduce the number of bubbles that form and become trapped in any layer of the bladder during the thermoforming process.

In some aspects, thermoforming includes increasing the temperature of the bladder to the softening temperature of the first sheet, the second sheet, or both, conforming the outer surface of the bladder to the shape of the inner molding surface.

In aspects, thermoforming further comprises applying a compressive force between the outer surface of the bladder and the inner molding surface, or optionally between the outer surface of the protective cover and the inner molding surface. In some aspects, the compressive force provides a pressure differential between the outer surface of the bladder and the inner molding surface, or optionally between the outer surface of the protective cover and the inner molding surface. In one aspect, the pressure differential may be a positive pressure differential. In another aspect, the pressure differential may be a negative pressure differential.

In any of these aspects, the bladder may be cooled after thermoforming. During and after cooling, in aspects, the bladder retains shape and/or other properties imparted during or as a result of the disclosed thermoforming process.

Decoration device

In one aspect, disclosed herein is a multilayer film or pouch, wherein the multilayer film or pouch further comprises a decorative element.

Also disclosed herein are methods for applying a decorative element to a multilayer film or pouch. In one aspect, the method includes applying the decorative element by printing, painting, brushing, or spraying the decorative element onto the multilayer film or pouch. In another aspect, the method includes immersing the multilayer film or bladder into the decorative element, or pressing the decorative element into the multilayer film or bladder. In aspects, the decorative element is in the form of a solid, liquid, or gas when applied to the multilayer film or pouch. In an optional aspect, the decorative element comprises a pigment or a dye or both a pigment and a dye.

In one aspect, the decorative element comprises a pigment or dye or both, and the step of applying the decorative element to the multilayer film or bladder comprises curing the decorative element on the multilayer film or bladder, optionally wherein curing comprises drying the decorative element, crosslinking the decorative element, or injecting at least a portion of the decorative element into a polymeric material of an outer surface of the multilayer film or bladder, or bonding the decorative element to an outer surface of the multilayer film or bladder, or any combination thereof.

In another aspect, the method includes the step of bonding the decorative element to the outer surface of the multilayer film or bladder, and the bonding includes forming an adhesive bond by applying an adhesive to the first side of the decorative element or to the outer surface of the multilayer film or bladder, or both, and then pressing the first side of the decorative element and the outer surface of the multilayer film or bladder together.

In an alternative aspect, the method includes the step of bonding the decorative element to the outer surface of the multilayer film or bladder, and the bonding includes forming a thermal bond between the thermoplastic material of the first side of the decorative element and the thermoplastic material defining the outer surface of the multilayer film or bladder by: softening or melting at least an outer portion of one or both of the thermoplastic materials, and pressing the first side of the decorative element and the outer surface of the multilayer film or bladder against each other while one or both of the thermoplastic materials is softened or melted, and then resolidifying the softened or melted outer portion.

In aspects, the decorative element is applied to the outer surface of the multilayer film or bladder, and the decorative element is injected into the material defining the outer surface of the multilayer film or bladder during application or during curing or both application and curing, optionally wherein the decorative element is applied as a solution of the dye.

Also disclosed herein are multilayer films and/or bladders comprising decorative elements applied according to any of the disclosed methods.

Article incorporating a multilayer film

A sole structure.In aspects, disclosed herein is a sole structure for an article of footwear having an upper, the sole structure comprising: a heel region disposed in the rear end; a forefoot region disposed in the front end; a midfoot region disposed intermediate between the heel region and the forefoot region; and a bladder as disclosed herein. In one aspect, the bladder is disposed in the heel area.

Also disclosed are articles of footwear including the disclosed bladders and articles of footwear including the disclosed sole structures.

In one aspect, disclosed herein is an article of footwear comprising an upper and a sole structure, wherein the upper, the sole structure, or both the upper and the sole structure comprise a bladder comprising:

a first membrane secured to a second membrane to define a sealed lumen; and

a fluid disposed within the sealed interior cavity at a pressure of about one atmosphere (101 kilopascals) or greater;

In one aspect, the sole structure includes a bladder. In another aspect, the article of footwear further includes a bottom layer secured to the upper. In yet another aspect, the article of footwear further includes an outsole, and optionally the outsole is secured to the bladder. In some aspects, in an article of footwear, a bladder may be disposed between the sole layer and the outsole.

Sports equipment.In another aspect, an article of athletic equipment including a multilayer film is disclosed herein. Also in this aspect, the sports apparatusThe articles of manufacture include any article for which flexible and gas barrier properties are useful, such as, for example, inflatable balls, rafts, boats, cushions, balance trains, flotation devices, and the like.

Referring now to fig. 9A, in one non-limiting aspect, a multilayer film may be incorporated into a soccer ball. Further, in this aspect, the soccer ball may have an outer cover 4000, one or more intermediate layers (shown herein as 4010a, 4010b, and 4010c, although other embodiments having more or fewer intermediate layers should also be considered disclosed), and an innermost gas barrier layer 4020 comprising the disclosed multilayer film, wherein the gas barrier layer 4020 allows the soccer ball to remain inflated during play by reducing the rate of gas (e.g., inflation air) transfer through the multilayer film. Fig. 9B shows a cross section of the soccer ball of fig. 9A, where the positioning between the innermost intermediate layer 4010c and the multilayer film 4020 includes alternating gas barrier layers 4040 and elastomer layers 4050. The interior 4030 is hollow and filled with air or another gas upon filling of the ball. The interior 4030 is surrounded by a multilayer film 4020, the multilayer film 4020 providing a low gas transmission rate (e.g., a gas transmission rate of less than about 0.5 cubic centimeters per square meter per day to about 2 cubic centimeters per square meter per day for nitrogen measured at 23 degrees celsius and 0 percent relative humidity for films having thicknesses in the range of from 72 micrometers to 320 micrometers).

And (5) transporting equipment.In yet another aspect, disclosed herein are articles useful for transportation comprising a multilayer film. In one aspect, the article may be a tire for a bicycle, automobile, tractor, motor scooter, motorcycle, or any other vehicle that uses pneumatic tires.

An exemplary tire is shown in fig. 10A and 10B. In one aspect, the outer surface 5000 of the tire may display a pattern of tread for improved traction and/or other aspects of operation on a road or track. Further, in this aspect, the tire may include rubber or another material 5010, the rubber or another material 5010 being vulcanized in some aspects to enhance the strength, flexibility, and durability of the tire. In any of these aspects, the inner layer of the tire 5020 comprises the multilayer film disclosed herein that in some aspects provides a surface area that reduces gas permeation in order to maintain inflation of the tire during use.

In one aspect, the multilayer film may cover the entire inner surface of the tire including the (shown) sidewall. In alternative aspects, the multilayer film may cover a portion of the tire. The disclosed tire may be incorporated into an inner tire (tube) or may be a tubeless tire, and may include any other layers in addition to the disclosed multilayer film typically associated with a particular application (e.g., belts, noise reducers, and the like for automotive tires).

Property analysis and characterization procedure

Specific gravity/density test protocol.The specific gravity (s.g.) or density of samples obtained using the component sampling procedure as described herein was measured using a digital balance or Denscom tester (qualite, plant, florida, USA). Each sample was weighed and then immersed in a distilled water bath (at 22 degrees celsius plus or minus 2 degrees celsius). To avoid mistakes, bubbles are removed from the surface of the sample, for example, by wiping isopropyl alcohol over the sample before immersing the sample in water or using a brush to remove bubbles from the surface of the sample after the sample is immersed. The weight of the sample in distilled water was recorded. The specific gravity was calculated using the following formula:

melting temperature, glass transition temperature, and enthalpy of fusion test protocol.Melting temperatures and glass transition temperatures were determined using a commercially available differential scanning calorimeter ("DSC") using samples prepared using a material sampling procedure according to ASTM D3418-97. Briefly, 10-15 g samples were placed into an aluminum DSC pan and then capped with a tablet press. DSC is configured to scan from-100 degrees Celsius to 225 degrees Celsius at a heating rate of 20 degrees Celsius per minute, hold at 225 degrees Celsius for 2 minutes, and then at-10 degrees Celsius per minute Is cooled to 25 degrees celsius. The DSC curve resulting from this scan is then analyzed using standard techniques to determine the glass transition temperature and melting temperature. The melting enthalpy is calculated by integrating the area of the melting endotherm and normalizing the sample mass.

Alternatively, the glass transition temperature may be determined using Dynamic Mechanical Analysis (DMA). In this technique, a multi-layer film sheet of about 1 mm thick, about 5 mm to about 10 mm wide and about 20 mm long is mounted on a film tension fixture of a DMA device. The sample is heated at a fixed rate, for example, about 1 degree celsius to about 5 degrees celsius per minute, over a predetermined temperature range. During heating, the sample is tested at a fixed frequency (e.g., about 1 hertz) and a small oscillation amplitude (e.g., about 0.05% strain). The storage modulus (or complex shear) is recorded.

G' is the storage modulus and represents the elastic portion of the viscoelastic material. G' is the loss modulus and represents the viscous fraction. G' measures the stored energy and G "measures the energy lost/dissipated as heat. tan delta is the ratio of G "/G', and the peak area indicates the glass transition temperature of the sample.

Melt flow index test protocol. The melt flow index is determined according to ASTM D1238-13 using procedure A described in detail in the Standard test method for determining the melt flow of thermoplastics with an extrusion plastometer (ASTM D1238-13 Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer). Briefly, melt flow index measures the rate at which a thermoplastic is extruded through an orifice at a specified temperature and load. In the test method, about 7 grams of material was loaded into a barrel of a melt flow apparatus that had been heated to a temperature specified for the material. A specified weight for the material is applied to the plunger and the molten material is forced through the die. The timed extrudate was collected and weighed. Melt flow values were calculated in grams/10 minutes.

Creep relaxation temperature test protocol.Creep relaxation temperatures are determined according to exemplary techniques described in U.S. Pat. No. 5,866,058. Creep relaxationThe relaxation temperature is calculated as the temperature at which the stress relaxation modulus of the tested material is 10% relative to the stress relaxation modulus of the tested material at the curing temperature of the material, wherein the stress relaxation modulus is measured according to ASTM E328-02. The cure temperature is defined as the temperature at which there is little or no change in stress relaxation modulus or little or no creep after about 300 seconds after stress is applied to the test material, which can be observed by plotting the stress relaxation modulus (in pascals) as a function of temperature (in degrees celsius).

KIM test protocol.For each KIM test, the multi-layered article as described herein was extruded and formed into a cushioning device component having an average wall thickness between 400 microns and 1000 microns. When the cushioning device is inflated with nitrogen to 15.0 to 25.0 pounds force per square inch (about 103 to about 172 kilopascals), the cushioning device is intermittently compressed by a reciprocating piston having a platen with a diameter of 4.0, 5.0, or 6.0 inches, or by a platen with a geometry similar to a shoe last, to evenly distribute the force across the entire air cushion. The stroke of each piston is calibrated as follows. The multi-layered article was first subjected to a force control test in which the multi-layered article reached a peak load of 2250 newtons, resulting in a compression of from about 25% to about 70% based on the fill pressure. The displacement at this peak load is recorded using a gauge block (gage block) and used to set the peak displacement in the KIM test. Typical KIM tests run to a predetermined cycle count, such as 320,000 or 400,000 cycles, to simulate the mileage count of an average athlete (e.g., 175 lbs and 6 ft high).

Load compression test protocol.For load compression testing, an air cushion or other cushioning device is subjected to compression in a suitable apparatus. In one aspect, the KIM testing device as described above may be used to perform load compression testing on a footwear component such as an air cushion, wherein the piston simulates the force of a foot of an average wearer when the component is in use (e.g., when the air cushion is deformed by the wearer taking steps, jumping, standing, or the like). The piston or other device being held in position The length of time sufficient to measure the distances as shown in fig. 4A-4B, including height 1046 and height 1064, length 1050 and length 1066, and angle 1062 and angle 1074. In one aspect, these heights, distances, and angles may be measured by any technique known in the art (e.g., scale, caliper, laser measurement, angle finder, indexer, smart phone or tablet application, or the like, depending on the amount being measured).

Sampling procedure

Using the test protocols described above, various properties of the materials disclosed herein and articles formed therefrom can be characterized using samples prepared using the following sampling procedure.

And (5) a material sampling procedure.The material sampling procedure may be used to obtain a pure sample of the polymeric material or polymer, or in some cases, a sample of the material used to form the polymeric material or polymer. The material is provided in a medium form such as flakes, granules, powder, pellets or the like. If the polymeric material or source of the polymer is not available in pure form, the sample may be cut from a component or element (such as a composite element or sole structure) containing the polymeric material or polymer, thereby isolating the sample of material.

Component sampling procedure.The program may be used to obtain a sample of material from a component of an article of footwear, a component of an article of apparel, a component of an article of athletic equipment, or an article of athletic equipment. A sample containing material in a non-wet state (e.g., at 25 degrees celsius and 20% relative humidity) is cut from an article or part using a blade. If a material is bonded to one or more additional materials, the procedure may include separating the additional materials from the material to be tested.

The sample is taken at a location along the article or component that provides a substantially constant material thickness (within plus or minus 10% of the average material thickness) for the material as present on the article or component. For many of the test protocols described above, a sample having a surface area of 4 square centimeters was used. The sample is cut to size and shape (e.g., dog bone sample) to fit into the test equipment. In the event that material is not present on an article or component having any section of 4 square centimeters surface area and/or the thickness of the material is not substantially constant for a section of 4 square centimeters surface area, a sample size having a smaller cross-sectional surface area may be obtained and the measurement of the particular area adjusted accordingly.

Definition of the definition

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

All publications, patents and patent applications cited in this specification are cited to disclose and describe the methods and/or materials in connection with which the publications are cited. All such publications, patents, and patent applications are herein incorporated by reference as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. Such incorporation by reference is expressly limited to the methods and/or materials described in the referenced publications, patents and patent applications and does not extend to any dictionary definitions from the referenced publications, patents and patent applications. Any dictionary definitions in the cited publications, patents and patent applications that have not been explicitly repeated in this specification should not be considered as such dictionary definitions and should not be construed to define any terms appearing in the appended claims.

The disclosure is not limited to the particular aspects, implementations, or examples described, and thus may, of course, vary. The terminology used herein is for the purpose of describing particular aspects, embodiments and examples only, and is not intended to be limiting, as the scope of the present disclosure will be limited only by the appended claims.

Where a range of values is provided, each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated 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 present disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.

It will be apparent to those of skill in the art after reading this disclosure that each of the various aspects, embodiments, and examples described and illustrated herein have discrete components and features that can be readily separated from or combined with the features of any of the other several aspects, embodiments, and examples without departing from the scope or spirit of the present disclosure. Any recited method may be implemented in the order of recited events or any other order that is logically possible.

Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. For the sake of brevity and/or clarity, well-known functions or constructions may not be described in detail. Unless otherwise indicated, aspects of the present disclosure will employ nanotechnology, organic chemistry, materials science and engineering, and similar techniques within the skill of the art. Such techniques are well explained in the literature.

It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. Where the stated range includes one or both of the extrema, ranges excluding either or both of those included extrema are also included in the present disclosure, e.g., the phrase "x to y" includes ranges from 'x' to 'y' as well as ranges greater than 'x' and less than 'y'. Ranges can also be expressed as upper limits, such as 'about x, y, z, or less', and should be construed to include the specific ranges of 'about x', 'about y', and 'about z', as well as ranges of 'less than x', 'less than y', and 'less than z'. Likewise, the phrase 'about x, y, z, or greater' should be construed to include the specific ranges of 'about x', 'about y', and 'about z', as well as ranges of 'greater than x', 'greater than y', and 'greater than z'. Further, the phrase "about 'x' to 'y'" wherein 'x' and 'y' are numerical values includes "about 'x' to about 'y'". It is to be understood that such range format is used for convenience and brevity and thus should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For purposes of illustration, a numerical range of "about 0.1% to 5%" should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.5%, 1.1%, 2.4%, 3.2%, and 4.4%) within the indicated range.

As used herein, the term "polymer" refers to a compound formed from more than one repeating structural unit referred to as a monomer. Polymers are typically formed by polymerization reactions in which more than one structural unit becomes covalently bound together. When the monomer units forming the polymer all have the same chemical structure, the polymer is a homopolymer. When the polymer comprises two or more monomer units having different chemical structures, the polymer is a copolymer. One example of a type of copolymer is a terpolymer that includes three different types of monomer units. The copolymer may include two or more different monomers randomly distributed in the polymer (e.g., random copolymer). Alternatively, one or more blocks comprising more than one monomer of a first type may be combined to one or more blocks comprising more than one monomer of a second type to form a block copolymer. A single monomer unit may include one or more different chemical functional groups.

Polymers having repeating units comprising two or more types of chemical functional groups may be referred to as having two or more segments. For example, polymers having repeating units of the same chemical structure may be referred to as having repeating segments. Based on the chemical structure of the segments, the segments are generally described as relatively hard or soft, and the polymer generally comprises relatively hard segments and relatively soft segments that are combined with each other in a single monomer unit or in different monomer units. When the polymer includes repeating segments, physical interactions or chemical bonds may exist within the segments or between the segments, or both within the segments and between the segments. Examples of segments commonly referred to as "hard segments" include segments containing urethane linkages, which may be formed by reacting an isocyanate with a polyol to form a polyurethane. Examples of segments commonly referred to as "soft segments" include segments containing alkoxy functionality, such as segments containing ether or ester functionality, and polyester segments. The segments may be referred to based on the names of the functional groups present in the segments (e.g., polyether segments, polyester segments), and based on the names of the chemical structures that react to form the segments (e.g., polyol-derived segments, isocyanate-derived segments). When referring to a segment of a particular functional group or a segment of a particular chemical structure from which the segment is derived, it is understood that the polymer may contain up to 10 mole percent of segments of other functional groups or segments derived from other chemical structures. For example, as used herein, polyether segments should be understood to include up to 10 mole percent of non-polyether segments.

The terms "material sampling procedure" and "component sampling procedure" as used herein refer to the respective sampling procedures and testing methods described in the property analysis and characterization procedure section. These sampling procedures and testing methods characterize the materials, films, articles, and components recited, as well as other properties, and need not be performed as an effective step in the claims.

The term "about" as used herein may include conventional rounding according to significant figures of the numerical value. In some aspects, the term "about" is used herein to mean a deviation from the specified value of 10%, 5%, 2.5%, 1%, 0.5%, 0.1%, 0.01% or less.

The articles "a" and "an" as used herein, when applied to any feature in aspects of the present disclosure described in the specification and claims, mean one or more. The use of "a" and "an" does not limit the meaning to a single feature unless such a limit is specifically stated. The article "the" preceding singular or plural nouns or noun phrases denotes a particular specified feature or particular specified features and may have singular or plural connotation depending upon the context in which it is used.

As used herein, the terms "about", "at" or "about" and "substantially" mean that the amount or value in question may be the exact value or a value that provides an equivalent result or effect to that recited in the claims or taught herein. That is, it is to be understood that the amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximated and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and other factors known to those of skill in the art such that an equivalent result or effect is achieved. In some cases, the value that provides an equivalent result or effect cannot be reasonably determined. In such cases, it is generally understood that "about" and "at or about" as used herein means a variation of ±10% of the indicated nominal value unless otherwise indicated or inferred. Generally, an amount, size, formulation, parameter, or other quantity or property is "about," "about," or "in or about," whether or not explicitly stated as such. It is to be understood that, unless specifically stated otherwise, where "about", or "in or about" is used prior to a quantitative value, the parameter also includes the particular quantitative value itself.

As used herein, the phrase "consisting essentially of (consists essentially of)" or "consisting essentially of (consisting essentially of)" refers to those features disclosed as having predominantly the listed features without other active components (relative to the listed features) and/or without substantially affecting one or more of the listed features. For example, the gas barrier material may consist essentially of the gas barrier material, which means that the gas barrier material may comprise a filler, a colorant, etc. that does not substantially interact with or with the change in the function or chemical properties of the gas barrier material. In another example, the gas barrier material may consist essentially of a thermoplastic ethylene vinyl alcohol copolymer, meaning that the gas barrier material does not include a sufficient amount of another type of thermoplastic polymer or copolymer to alter the properties (e.g., melt temperature, melt flow index, creep relaxation temperature, or the like) of the gas barrier material. Further, in this aspect, when the gas barrier material consists essentially of one polymer type (e.g., thermoplastic ethylene vinyl alcohol copolymer), it may contain less than 1 weight percent of another type of polymer.

As used herein, "polyurethane" refers to copolymers (including oligomers) comprising urethane groups (-N (c=o) O-). In addition to urethane groups, these polyurethanes may contain additional groups such as esters, ethers, ureas, allophanates, biurets, carbodiimides, oxazolidines, isocyanurates, uretdiones (uretdiones), carbonates and the like. In aspects, one or more of the polyurethanes can be produced by polymerizing one or more isocyanates with one or more polyols to produce copolymer chains having (-N (c=o) O-) linkages.

As used herein, the terms "at least one" element and "one or more" elements are used interchangeably and have the same meaning as including a single element and more than one element, and may also be represented by the suffix "(s)" at the end of the element. For example, "at least one polyurethane", "one or more polyurethanes", and "polyurethane (polyurethane (s))" may be used interchangeably and have the same meaning.

As used herein, "sheet" or "film" refers to a flexible strip comprising one or more polymeric materials, the sheet or film having a thickness that is substantially less than its length and/or width. As used herein, a "core" may refer to an inner layer of a material in a multilayer sheet or film. Similarly, as used herein, a "core region" may refer to one or more layers that are or collectively form an interior region of a material in a multiwall sheet or film. As used herein, "cap layer" may refer to an outward-facing layer of a material in a multiwall sheet or film. Also as used herein, "structural layer" may refer to a layer of material in a multi-layer sheet or film that is disposed between a cap layer and a core layer. As used herein, "tie layer" may also refer to an inner layer in a multilayer sheet or film; wherein typically the tie layer comprises a material that increases the bond strength of adjacent layers.

When an element or layer is referred to as being "on," "engaged to," "connected to," "attached to" or "coupled to" another element or layer, it can be directly on, engaged, connected, attached or coupled to the other element or layer or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly on," "directly engaged to," "directly connected to," "directly attached to," or "directly coupled to" another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a similar manner (e.g., "between" versus "directly between", "adjacent" versus "directly adjacent", etc.). As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections. These elements, components, regions, layers, and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as "first," "second," and other numerical terms do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, first component, first region, first layer, or first section discussed below could be termed a second element, second component, second region, second layer, or second section without departing from the teachings of the example configurations.

As used herein, the terms "crack", "split", "crack", "break" and "break" may be used interchangeably to describe a break in a gas barrier material that forms one or more gas barrier layers in a core region of a multilayer film. As described below, the degree or level of cracking may be classified as "severe cracking," "mild cracking," or "little or no cracking" based on the degree of cracking within the core region and the effect that the cracking has on the properties of the multilayer film, including gas permeability and clarity.

"little or no cracking" may describe a level of cracking in which there is no cracking in the gas barrier core, or in which a single crack in the gas barrier material of the gas barrier layer of the core may extend within or across only a single gas barrier layer, or within or across only a few gas barrier layers (and the elastomer layers immediately adjacent to them). For example, the degree of individual breakage can be determined by observing an enlarged cross section of the thickness of the core region of the film. When viewed in this manner, no cracking is typically observed in the gas barrier layer, or a fracture affecting less than 20% of the cross-sectional thickness of the core region is observed. Typically, any broken edges that are present do not pull apart from each other and create gaps in the core region. Fig. 11C shows a photomicrograph of two cross-sectional thicknesses of the core region of the multilayer film, both of which exhibit little or no cracking. Multilayer films exhibiting little or no cracking typically do not have any cracking or cracking visible to the naked eye and have acceptably low gas transmission rates.

A "light crack" may describe a level of cracking in which a single crack in a gas barrier layer may extend across several gas barrier layers or across several gas barrier layers (and the elastomeric layer immediately adjacent to them), but which does not extend across a majority of the gas barrier layer and elastomeric layer present in the core region, or which does not extend across a majority of the total thickness of the core region. For example, the degree of individual breakage can be determined by observing an enlarged cross section of the thickness of the core region of the film. When viewed in this manner, a fracture affecting 3-10 gas barrier layers, or a fracture affecting less than 50% of the cross-sectional thickness of the core region is typically observed. Although some broken edges may pull away from each other and create small gaps in the core area, this does not occur in most breaks. Fig. 11B shows a photomicrograph of two cross-sectional thicknesses of the core region of the multilayer film, both of which exhibit slight cracking. Multilayer films exhibiting light cracking may exhibit a small decrease in transparency because the presence of light cracking may make the film appear somewhat hazy. In some examples, some minor cracks may be visible to the naked eye.

"severe cracking" may describe a level of cracking in which a single break in the gas barrier layer of the core may extend across a majority of the gas barrier layer and elastomeric layer present in the core region, or across a majority of the thickness of the core region. For example, the degree of individual breakage may be determined by observing an enlarged cross section of the thickness of the core region of the multilayer film. When viewed in this manner, the break may extend across at least 50% of the cross-sectional thickness of the core region, or more than 75% of the cross-sectional thickness of the core region, or the entire cross-sectional thickness of the core region. Typically, the broken edges pull away from each other and create a gap in the core region. Fig. 11A shows a photomicrograph of two cross-sectional thicknesses of the core region of the multilayer film, both of which exhibit severe cracking. Multilayer films exhibiting severe cracking will typically exhibit unacceptably high gas diffusion rates, have reduced transparency levels compared to their initial transparency levels, and include macroscopic cracks and fissures.

Examples

The present disclosure is more particularly described in the following embodiments, which are intended as illustrations only, since numerous modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art.

Example 1.A multi-layer control film and test film were prepared and formed into control and test pouches. These bladders undergo repeated flexing and release cycles to simulate conditions to which the bladder is exposed during wear when used as a cushioning element in the midsole of an article of footwear.

The control film and the test film are both extruded films and both include a gas barrier core region formed by extruding a gas barrier material and an elastomeric material into alternating layers. The same gas barrier material (including ethylene vinyl alcohol) and the same elastomeric material (including thermoplastic polyurethane) were used in the control and test films. Each film also includes structural layers (2 total structural layers) positioned on either side of the core region, and cap layers (2 total cap layers) on each film surface. The structural layers of the control film and the test film are formed of the same material as each other (including thermoplastic polyurethane). The cover layers of the control film and the test film are also formed of the same material as each other, including thermoplastic polyurethane.

The capsules were prepared by the following steps: two membranes of the same type (i.e., 2 control membranes for control bladder, 2 test membranes for test bladder) were thermoformed, the two membranes were bonded to each other to form the perimeter of the bladder, and the bladder was filled with nitrogen gas to form a sealed bladder containing nitrogen gas at a pressure of about 138 kilopascals.

The sealed control and test pouches were then each subjected to multiple KIM test cycles. After about 350,000 (350 k) to about 400,000 (400 k) KIM test cycles, the appearance of the membrane of the pouch was assessed by the naked eye and the level of cracking (severe cracking, mild cracking, or little or no cracking) was specified. Samples of the core region of the film exhibiting macroscopic cracking were taken and examined with a microscope. When little or no cracking is visible to the naked eye, the area of the test cell selected for microscopy corresponds to the same area where extensive cracking is observed in the control cell.

The control films each included a gas barrier core region comprising 32 gas barrier layers and 32 elastomeric layers, wherein each gas barrier layer was immediately adjacent to an elastomeric layer in an alternating pattern. In the control film, the thickness of the individual gas barrier layers ranged from about 1.0 microns to about 1.2 microns. Each of the two control films individually had a total thickness of about 25.4 microns to 30.8 microns. After about 350,000 KIM cycles, the control membrane of the control capsule exhibited severe cracking. FIG. 11A shows a micrograph of a cross-section of the core region of the control film exhibiting macroscopic cracking taken from the control balloon after about 350k KIM cycles.

The first test films each included a gas barrier core region comprising 32 gas barrier layers and 32 elastomeric layers, wherein each gas barrier layer was immediately adjacent to an elastomeric layer in an alternating pattern. In the first test film, the thickness of the individual gas barrier layer was about 75% as thick as the individual gas barrier layer in the control film, and thus was in the range from about 0.8 microns to about 0.9 microns. After about 400k KIM cycles, the first test membrane of the first test pouch exhibited slight cracking based on visual inspection by the naked eye and microscopy. FIG. 11B shows a photomicrograph of a cross-section of the core region of the first test membrane exhibiting macroscopic light cracking taken from the first test bladder after about 400k KIM cycles.

The second test films each included a gas barrier core region comprising 32 gas barrier layers and 32 elastomeric layers in the same alternating pattern as described above. In the second test film, the thickness of the individual gas barrier layer was about 50% of the thickness of the individual gas barrier layer in the control film, and thus was in the range from about 0.5 microns to about 0.6 microns. After about 400k KIM cycles, the second test film of the second test pouch exhibited little or no cracking based on visual inspection using the naked eye as well as microscopy. FIG. 11C shows a photomicrograph of a cross-section of the core region of the first test membrane exhibiting macroscopic light cracking taken from the second test pouch after about 400k KIM cycles.

Example 2.As described in example 1, a multi-layer control film and test film were prepared and formed into control and test sachets. These bladders undergo repeated flexing and release cycles to simulate conditions to which the bladder is exposed during wear when used as a cushioning element in the midsole of an article of footwear. The sealed control and test sachets each underwent a total of 400,000 (400 k) KIM test cycles. The gas permeability of each cell was measured before the KIM test and after 60,000 (60 k), 120,000 (120 k) and/or 320,000 (320 k) KIM test cycles (see fig. 12A, 13A and 14 for the exact number of cycles after which the gas permeability of the control cell and test cell was measured). Gas Transmission Rate (GTR) is measured in cubic centimeters per square meter per day. The measured gas permeability was used to develop a gas permeability fatigue model using the following equation:

G＝G _m -(G _m -G ₀ )(1-e ^(-kx) )

wherein G is gas permeability, G ₀ Is the gas permeability before any KIM cycle, G _m Is the gas transmission rate after 320,000 KIM cycles, and k is a growth parameter that depends on the gas barrier layer thickness and the type and number of gas barrier layers in the membrane of the capsule. After 400,000 (400 k) KIM test cycles, the appearance of the membrane of the capsule was evaluated as described in example 1.

Example 2A.The control membrane and control pouch and the second test membrane and second test pouch used in example 2A were the same as in example 1. The third test films each included a gas barrier core region including and 24 cartridgesThe sex layers alternate 24 gas barrier layers, which are 33% less than in the control film and the second test film. In the third test film, the thickness of the individual gas barrier layer was about 50% of the individual gas barrier layer in the control film, and thus was in the range from about 0.5 microns to about 0.6 microns.

Figure 12A shows the GTR measured for the control bladder (bottom curve) and the second (middle curve) and third (top curve) test bladders after the indicated number of KIM cycles. FIG. 12A also shows the calculated GTR (GTR) using the above equation for 240,000 KIM cycles _240k ). Unexpectedly, both the measured GTR and calculated GTR for the second and third test bags were only slightly higher than the control bag and still well below the expected maximum of 3 cubic centimeters per square meter per day. This is unexpected because the gas barrier layers of both the second and third test films are 50% thinner than the gas barrier layers of the control film, and the third test film contains 33% less of these thinner gas barrier layers than the second and control test films.

As in example 1, after 400k KIM cycles, the area of the control membrane of the control pouch exhibited severe cracking, while the area of the second test membrane of the second test pouch exhibited little or no cracking. The third test membrane of the third test pouch also exhibited little or no cracking. Fig. 12B shows a micrograph of a cross section of the core region of the second test film. Fig. 12C shows a photomicrograph of a cross-section of the core region of the third test film exhibiting little or no cracking.

Example 2B.The control membrane and control pouch and the first test membrane and first test pouch used in example 2B were the same as in example 1. The third test membrane and third test pouch were the same as in example 2A.

Figure 13A shows the GTR measured for the control bladder (bottom curve) and the first (middle curve) and third (top curve) test bladders after the indicated number of KIM cycles. Fig. 13A also shows the GTR as calculated in example 2A. Unexpectedly, as in example 2A, the testing of both the first test pouch and the third test pouchBoth the amount of GTR and calculated GTR were only slightly higher than the control capsule and still marginally lower than the expected maximum of 3 cubic centimeters per square meter per day. Calculated GTR of first test capsule (2.10 cc/m ² Day) is only slightly lower than the calculated GTR (2.15 cc/m for the second test capsule ² Day). This is unexpected because the gas barrier layer of the second test film is about one third thinner than the first test film (the thickness of the gas barrier layer in the second test film is about 50% of the thickness of the gas barrier layer in the control film, and the thickness of the gas barrier layer in the first test film is about 75% of the thickness of the gas barrier layer in the control film).

As in example 1 and example 2A, after 400k KIM cycles, the area of the control film of the control pouch exhibited severe cracking, while the area of the first test film of the first test pouch exhibited mild cracking, and the third test film of the third test pouch exhibited little or no cracking. Fig. 13B shows a micrograph of a cross section of the core region of the first test film.

Example 2C.The control membrane and control pouch used in example 2C were the same as in example 1. The fourth test films each included a gas barrier core region comprising 40 gas barrier layers alternating with 40 elastomer layers, as described above. The fourth test membrane included 25% more gas barrier layer than the control membrane. In the fourth test film, the thickness of the individual gas barrier layer was the same as in the control film, and thus was in the range from about 1.0 microns to about 1.2 microns. The fifth test films each included a gas barrier core region comprising 60 gas barrier layers alternating with 60 elastomeric layers, as above. The fifth test film included more than 87% of the gas barrier layer than the control film. In the fifth test film, the individual gas barrier layers were 150% of their thickness in the control film, and thus ranged from about 1.5 microns to about 1.8 microns.

Figure 14 shows the GTR measured for the fourth test pouch (top curve) and the fifth test pouch (bottom curve) after a specified number of KIM cycles. Fig. 13A also shows the GTR as calculated in example 2A and example 2B. The measured and calculated GTR for the fifth test cell were lower than for the control cell and other test cells, as would be expected based on the increased thickness and number of gas barrier layers. The fourth test pod measured GTR and calculated GTR (2.24 cubic centimeters per square meter per day) were higher than the fifth test pod, but surprisingly were also higher than the first and second test pods (calculated GTR was 2.10 cubic centimeters per square meter per day and 2.15 cubic centimeters per square meter per day, respectively). This is unexpected because the first and second test films each have a thinner gas barrier layer and fewer gas barrier layers than the fourth test film.

As in example 1, example 2A, and example 2B, after 400k KIM cycles, the area of the control membrane of the control bladder exhibited severe cracking, while both the area of the fourth test membrane of the fourth test bladder and the area of the fifth test membrane of the fifth test bladder exhibited mild cracking.

The results of examples 1 to 2C are summarized in table 1.

As those skilled in the art will readily appreciate, the above description is meant as an illustration of an embodiment of the principles of the present invention. This description is not intended to limit the scope or application of this invention in that the invention is susceptible to modification, variation and change, without departing from the spirit of this invention, as defined in the appended claims.

Claims

1. An article of footwear having a forefoot region, a midfoot region, and a heel region along a longitudinal axis of the article of footwear, the article of footwear comprising:

a vamp; and

a sole structure, the sole structure comprising a bladder, wherein the bladder comprises a bulbous portion, optionally wherein the bulbous portion has a first height in an uncompressed state and a second height in a compressed state, the second height being less than 86% of the first height, and wherein the bladder comprises at least a first multilayer film having more than one gas barrier layer and more than one elastomeric layer, wherein the gas barrier layers alternate with the elastomeric layers.

2. The article of footwear according to claim 1, wherein the bulbous portion of the bladder is a bulbous heel portion and is in a heel region of the article of footwear.

3. The article of footwear of claim 1 or 2, wherein the bladder comprises a second multilayer film, optionally wherein the structure of the second multilayer film differs from the structure of the first multilayer film in the number of gas barrier layers and elastomeric layers, or differs from the structure of the first multilayer film in the thickness of the gas barrier layers and elastomeric layers, or differs from the structure of the first multilayer film in both the number and thickness of the gas barrier layers and elastomeric layers.

4. The article of footwear of any of the preceding claims, wherein the more than one gas barrier layer of the first multilayer film includes at least 20 gas barrier layers, optionally at least 30 gas barrier layers.

5. The article of footwear of any of the preceding claims, wherein in the first multilayer film, the average total thickness of the more than one gas barrier layers and the more than one elastomeric layers is less than 200 microns, optionally less than 175 microns.

6. The article of footwear of any of the preceding claims, wherein the first height of the bulbous portion of the bladder is in a range from about 10 millimeters to about 24 millimeters, optionally from about 15 millimeters to about 24 millimeters.

7. The article of footwear of any of the preceding claims, wherein the second height of the bulbous portion of the bladder is in a range from about 8.6 millimeters to about 13.6 millimeters, optionally from about 8.6 millimeters to about 11.0 millimeters.

8. The article of footwear of any of the preceding claims, wherein the more than one gas barrier layer of the first multilayer film compositionally comprises one or more thermoplastic vinylidene chloride polymers, one or more thermoplastic acrylonitrile polymers or copolymers, one or more thermoplastic polyamides, one or more thermoplastic epoxy resins, one or more thermoplastic amine polymers or copolymers, one or more thermoplastic polyolefin homopolymers or copolymers, or any combination thereof; in particular one or more thermoplastic polyethylene copolymers, such as one or more thermoplastic ethylene-vinyl alcohol copolymers.

9. The article of footwear of any of the preceding claims, wherein the more than one gas barrier layer of the first multilayer film comprises ethylene vinyl alcohol in composition.

10. The article of footwear of any of the preceding claims, wherein the more than one elastomeric layer of the first multilayer film compositionally includes one or more thermoplastic elastomeric polymers.

11. The article of footwear of any of the preceding claims, wherein the more than one elastomeric layer of the first multilayer film compositionally includes a polyolefin copolymer, a polyester, a thermoplastic polyurethane, a styrene block copolymer, or any combination thereof.

12. The article of footwear of any of the preceding claims, wherein the bulbous portion extends a first distance beyond a bite line of the article of footwear in the uncompressed state and a second distance beyond the bite line in the compressed state, and wherein a difference between the first distance and the second distance is in a range from about 1.0 millimeters to about 3.0 millimeters.

13. The article of footwear of claim 12, wherein a difference between the first distance and the second distance is in a range from about 1.1 millimeters to about 1.9 millimeters or in a range from about 1.1 millimeters to about 1.5 millimeters.

14. The article of footwear of any of the preceding claims, further comprising a midsole layer disposed between the upper and the bladder.

15. The article of footwear of any of the preceding claims, further comprising an outsole disposed on an outer surface of the bladder.

16. The article of footwear according to claim 15, wherein the bulbous portion is a bulbous heel portion, a geometry of the bulbous heel portion in the uncompressed state defining a first vector extending from a rearmost location of the uncompressed bulbous heel portion to a rearmost location of the midsole layer, and a second vector extending from the rearmost location of the uncompressed bulbous heel portion to a rearmost location of the outsole layer, and wherein the first vector and the second vector extend from each other at an angle in a range from about 115.0 degrees to about 137.5 degrees.

17. The article of footwear according to claim 16, wherein a geometry of the ball heel portion in the compressed state defines a third vector extending from a rearmost location of the compressed ball heel portion to the rearmost location of the midsole layer, and a fourth vector extending from the rearmost location of the compressed ball heel portion to the rearmost location of the outsole, and wherein the third vector and the fourth vector extend from each other at an angle in a range from about 38 degrees to about 107 degrees.

18. The article of footwear of any of the preceding claims, further comprising a fluid retained within the bladder.

19. The article of footwear of any of the preceding claims, wherein the bladder has an initial inflation pressure in a range from about 20 pounds per square inch (137.9 kilopascals) to about 22 pounds per square inch (151.7 kilopascals).

20. The article of footwear of any of the preceding claims, wherein the bulbous portion of the bladder does not exhibit visually observable cracking after at least 350,000 KIM cycles or at least 400,000 KIM cycles.