Cushioning element for a footwear item

Abstract

Provided are components including foam for footwear articles and sports equipment articles. The foam portions of the components and articles include a composition comprising a thermoplastic copolyester, the composition having a foam structure. A polymer layer is provided on at least one surface of the foam portion. The polymer layer can control or reduce water absorption of the foam portion. Methods of making the composition, the foam, and the components, and a method of making a footwear article including one of the foam components are provided. In some aspects, the foam and foam components can be made by injection molding or injection molding followed by compression molding.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority and the benefit of the co - pending U.S. Provisional Applications Ser. Nos. 62 / 899,688 and 62 / 899,696, both filed on Sep. 12, 2019, entitled “FOAM COMPOSITIONS AND USES THEREOF”, the content of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure generally relates to foams formed from thermoplastic copolyesters, and particularly to foams formed from thermoplastic copolyesters suitable for footwear and related industries and their uses.

[0004] Background

[0005] The design of sports equipment, clothing, and footwear involves multiple factors, from aesthetics, to comfort and feel, to performance and durability. While designs and fashions may change rapidly, the market demand for enhanced performance remains constant. To balance these needs, designers employ a variety of materials and designs for the various components that make up sports equipment, clothing, and footwear. Summary of the Invention

[0006] The present disclosure provides the following items:

[0007] 1. A cushioning element for an article of footwear, the cushioning element comprising:

[0008] A first foam, wherein the first foam is a thermoplastic porous foam having an open - cell foam microstructure, an average pore size from about 50 microns to about 500 microns, and a specific gravity from about 0.15 to about 0.25;

[0009] wherein the first foam compositionally comprises a first thermoplastic composition, the first thermoplastic composition comprising one or more copolyesters;

[0010] wherein the first foam is a physically foamed product of a single - phase solution of a supercritical fluid and the first thermoplastic composition in a molten state; and

[0011] wherein the first thermoplastic composition of the first foam contains no or substantially no nucleating agent, or no or substantially no filler, or no or substantially no nucleating agent and filler both.

[0012] 2. The cushioning element according to item 1, wherein the cushioning element is produced by a method comprising:

[0013] Form a single-phase solution of the first thermoplastic composition comprising the one or more thermoplastic copolyesters and the supercritical fluid, wherein the first thermoplastic composition is melted in the single-phase solution;

[0014] Inject the single-phase solution into a mold cavity, the single-phase solution having an injection temperature during the injection;

[0015] Reduce the pressure in the mold cavity and cause the melted first thermoplastic composition to foam, the single-phase solution having a foaming temperature during the foaming, thereby forming a first foam, wherein the first foam is a thermoplastic porous foam having an open-cell foam microstructure;

[0016] Solidify the first foam; and

[0017] Remove the solidified first foam from the mold cavity to form the buffer element.

[0018] 3. The buffer element according to item 1 or 2, wherein the supercritical fluid comprises supercritical carbon dioxide or supercritical nitrogen.

[0019] 4. The buffer element according to any one of items 1 - 3, wherein the supercritical fluid is present in the single-phase solution in an amount of about 1 percent to about 3 percent by weight based on the total weight of the single-phase solution.

[0020] 5. The buffer element according to any one of items 1 - 4, wherein the foaming temperature is from about the melting temperature of the thermoplastic copolyester determined by dynamic scanning calorimetry to about 50 degrees Celsius higher than the peak tail temperature of the thermoplastic copolyester determined by dynamic scanning calorimetry.

[0021] 6. The buffer element according to any one of items 1 - 5, wherein the first foam has a split tear of greater than or equal to about 2.0 kg / cm, or an energy efficiency of greater than or equal to about 60 percent, or both.

[0022] 7. The buffer element according to any one of items 1 - 6, wherein the first thermoplastic composition of the first foam comprises less than 5 weight percent of a dye or pigment.

[0023] 8. The buffer element according to any one of items 1 - 7, wherein the first thermoplastic composition of the first foam further comprises a non-polymer component, the non-polymer component comprising all non-polymer ingredients present in the first thermoplastic composition, and the non-polymer component constitutes less than one weight percent of the first thermoplastic composition based on the total weight of the first thermoplastic composition.

[0024] 9. The buffer element according to any one of Items 1 - 8, wherein the first thermoplastic composition of the first foam comprises a polymer component, the polymer component comprising all the polymers present in the first thermoplastic composition, and the polymer component constitutes at least 95 weight percent of the first thermoplastic composition based on the total weight of the first thermoplastic composition.

[0025] 10. The buffer element according to any one of Items 1 - 9, wherein the first thermoplastic composition of the first foam comprises a polymer component, the polymer component comprising all the polymers present in the first thermoplastic composition, and in addition to the one or more copolyesters, the polymer component further comprises a polyester, a polyolefin, or both.

[0026] 11. The buffer element according to any one of Items 1 - 10, wherein the first thermoplastic composition of the first foam comprises a polymer component, the polymer component comprising all the polymers present in the first thermoplastic composition, and the polymer component consists essentially of the one or more copolyesters.

[0027] 12. The buffer element according to any one of Items 1 - 11, wherein the thermoplastic copolyester comprises:

[0028] (a) More than one first segment, each first segment being derived from a dihydroxy - terminated polyglycol;

[0029] (b) More than one second segment, each second segment being derived from a diol; and

[0030] (c) More than one third segment, each third segment being derived from an aromatic dicarboxylic acid.

[0031] 13. The buffer element according to any one of Items 1 - 12, wherein the open - cell foam microstructure of the first foam comprises less than 10 percent of the pores having a closed - cell foam microstructure.

[0032] 14. The buffer element according to any one of Items 1 - 13, wherein the open - cell foam microstructure of the first foam comprises less than 5 percent of the pores having a closed - cell foam microstructure.

[0033] 15. The buffer element according to any one of Items 1 - 14, wherein the open - cell foam microstructure of the first foam comprises less than 1 percent of the pores having a closed - cell foam microstructure.

[0034] 16. The buffer element according to any one of Items 1 - 15, wherein up to 80% of the open - cells in the first foam have an average diameter ranging from about 50 microns to about 200 microns.

[0035] 17. The buffer element according to any one of items 1-16, wherein the thermoplastic copolyester comprises:

[0036] (a) More than one first copolyester unit, each of the more than one first copolyester units comprising a first segment derived from a dihydroxy-terminated polyglycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0037]

[0038] wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(alkylene oxide) glycol of the first segment, wherein the poly(alkylene oxide) glycol of the first segment is a poly(alkylene oxide) glycol having a number average molecular weight of from about 400 to about 6000; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment; and

[0039] (b) More than one second copolyester unit, each of the more than one second copolyester units comprising a second segment derived from a diol and the third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0040]

[0041] wherein R3 is the group remaining after removing the hydroxyl group from the diol of the second segment derived from a diol, wherein the diol is a diol having a molecular weight of less than about 250; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment.

[0042] 18. The buffer element according to any one of items 1-17, wherein the one or more thermoplastic copolyesters comprise at least one thermoplastic copolyester elastomer.

[0043] 19. The buffer element according to any one of items 1-18, wherein the buffer element is a midsole or a heel buffer.

[0044] 20. A footwear item comprising the buffer element according to any one of items 1-19. Brief Description of the Drawings

[0046] Additional aspects of the present disclosure will be readily understood when the detailed description set forth below is read in conjunction with the accompanying drawings.

[0047] Figure 1 is a front view of a footwear item having a sole component according to one aspect of the present invention.

[0048] Figure 2 yes Figure 1 An exploded view of a sole component of an article of footwear.

[0049] Figure 3 yes Figure 1 A plan view of a bottom portion of a sole component of an article of footwear.

[0050] Figure 4 is a bottom view of an insert for a sole component of an article of footwear.

[0051] Figure 5 is inserted into the first part to form the sole component Figure 4 Top view of the insert.

[0052] Figure 6 Representative compression data are shown for a representative foam plaque comprising the disclosed compositions and prepared using the disclosed methods.

[0053] Figure 7 Representative schematic diagrams illustrating disclosed foam parts or articles having a second thermoplastic composition are shown.

[0054] Figure 8 A representative schematic diagram illustrating the disclosed method for determining peak and tail temperatures is shown.

[0055] Figures 9A - 9D Representative images of cross-sectional views of foam substrates prepared at different temperatures using the disclosed thermoplastic copolyester elastomers are shown. Each image shows a scalar bar (500 microns). The foam substrates were prepared at the following temperatures: 175 degrees Celsius ( Figure 9A ); 190 degrees Celsius ( Figure 9B ); 205 degrees Celsius ( Figure 9C ); and 245 degrees Celsius ( Figure 9D ).

[0056] Figure 10 Shown is a representative image of a cross-sectional view of a foam substrate prepared using the disclosed thermoplastic copolyester elastomer at 160 degrees C. The image shows a scale bar (500 microns).

[0057] Figure 11 Representative coefficient of friction data for various polymer materials on wood surfaces are shown.

[0058] Figure 12 Representative coefficient of friction data for various polymer materials on concrete surfaces are shown.

[0059] Figure 13 Shows representative coefficient of friction data for various polymer materials used in a blown shoe outsole on a concrete surface.

[0060] Figure 14 Shows representative specific gravity data for various polymer materials in unfoamed samples and various foamed samples.

[0061] Detailed description

[0062] The present disclosure relates to a foam article that includes a first component, namely a thermoplastic foam component, which compositionally comprises a foamed first thermoplastic composition. In other words, the foamed first thermoplastic composition retains its thermoplastic properties and can be recycled by melting the foamed first thermoplastic composition and reforming the first thermoplastic composition into a new foamed article or a new solid (i.e., unfoamed) article. The first component is a foam component that includes the foamed first thermoplastic composition having a porous foam structure. In some aspects, the porous foam structure is an open-cell foam structure. In other aspects, the porous foam structure is a closed-cell foam structure. In some aspects, the foamed first thermoplastic composition comprises one or more copolyesters, such as, for example, one or more copolyester elastomers. In some aspects, the first thermoplastic composition further comprises one or more non-polymeric components, such as fillers or nucleating agents or pigments. One or more non-polymeric components may be 5 weight percent or less of the first thermoplastic composition based on the total weight of the first thermoplastic composition. It has been found that for thermoplastic foams, particularly thermoplastic foams that compositionally comprise at least one thermoplastic copolyester elastomer, including low levels (e.g., 5 weight percent or less) of non-polymeric components such as fillers, nucleating agents, and pigments can improve the consistency of the pore size in the porous thermoplastic foam. In addition to improving the pore structure, due to the high polymer content of these thermoplastic compositions, including low levels of non-polymeric components in the first thermoplastic composition can also increase the recyclability of the first thermoplastic composition. The first thermoplastic composition may be free or substantially free of fillers. The first thermoplastic composition may be free or substantially free of nucleating agents. The first thermoplastic composition may be free or substantially free of pigments. The first thermoplastic composition may be free or substantially free of fillers and nucleating agents, or may be free or substantially free of fillers, nucleating agents, and pigments. The first thermoplastic composition may be free or substantially free of non-polymeric components. The foam article is particularly useful as a cushioning element.

[0063] In some aspects, the disclosed foam article further includes a second component comprising a second thermoplastic composition. In such aspects, the second component can be disposed on at least a portion of the first component or within at least a portion of the first component. The second component can include a polymer layer disposed on at least a portion of the outer surface of the foamed first thermoplastic composition of the first component. The second component comprises a second thermoplastic composition that retains its thermoplastic properties and can be recycled by melting the second thermoplastic composition and reforming the second thermoplastic composition into a new foamed article or a new solid (i.e., unfoamed) article. Since both the first component and the second component are formed of a thermoplastic composition, the first component and the second component need not be separated prior to recycling. For example, the foam article can be recycled by grinding or shredding the entire article and forming a molten polymer composition that is a mixture of both the first thermoplastic composition and the second thermoplastic composition. The second thermoplastic composition can include a thermoplastic elastomer or a thermoplastic vulcanizate material. The second thermoplastic composition can include one or more thermoplastic styrene copolymer elastomers, including styrene-ethylene-butene-styrene (SEBS) copolymer elastomers. The second thermoplastic composition can include a single one or more thermoplastic polyurethane elastomers or one or more thermoplastic polyurethane elastomers blended with other polymers such as, for example, ethylene-vinyl alcohol copolymers or styrene copolymer elastomers. It has been found that a second thermoplastic composition comprising a thermoplastic copolyester elastomer, or a thermoplastic polyurethane elastomer, or a thermoplastic styrene copolymer elastomer, or a thermoplastic vulcanizate material forms a strong thermal bond with the foamed first thermoplastic composition comprising one or more thermoplastic copolyester elastomers. The foam articles disclosed herein are particularly useful as cushioning elements. The foam article including the first component and the second component is particularly useful as a cushioning element for footwear articles, clothing articles, or sports equipment articles. For example, the first component of the foam article can be a midsole or a midsole component. The second component of the foam article can be a ground-engaging component such as an outsole on a footwear article or a protective element such as a rand that provides a greater level of abrasion resistance or provides better attachment friction or provides both a greater level of abrasion resistance and better attachment friction compared to the first foam component alone. The second component of the foam article can be a protective layer or a reinforcing layer or a containment layer on the first foam component, such as when the first foam component is a cushioning element or in other applications. In some aspects, when the first component has an open-cell foam structure, the second component can be a waterproof barrier to reduce or prevent water absorption by the open-cell structure of the foam.

[0064] Conventionally, vulcanized and peroxide-cured natural and synthetic rubbers such as isoprene rubber and polybutadiene rubber have been used to form durable, abrasion-resistant outer protective layers for various articles, including shoe outsoles for footwear articles. Rubber formulations for shoe outsoles typically also provide traction. One disadvantage of using conventional rubber materials is that these materials are highly crosslinked during the curing process, making the cured rubber a thermoset material and difficult to recycle or reuse the cured rubber. Additionally, it may be difficult to incorporate other materials into the cured rubber. Both rubber materials and foam materials commonly used in various consumer goods are highly crosslinked materials that are separately formed and cured and then adhered to each other using an adhesive system. These adhesive systems require several labor-intensive processing steps, such as cleaning the surfaces, priming the surfaces, applying the adhesive to the surfaces, and pressing the surfaces together to bond them.

[0065] It has been found that thermoplastic compositions (e.g., thermoplastic compositions comprising one or more thermoplastic copolyester elastomers) can be used to form porous foams having advantageous properties for consumer articles such as cushioning elements. When foamed as described herein, these foams retain thermoplastic properties such that the thermoplastic composition can be easily recycled and reused. Additionally, it has been found that these foams can be directly molded and foamed onto other polymeric materials (i.e., foamed onto a second thermoplastic composition as described herein), which thermally bonds the foam firmly to the second thermoplastic composition without the need for additional adhesives or manual processing steps for applying an adhesive system. The second thermoplastic composition bonded to the thermoplastic foam can be a thermoplastic elastomeric material, such as a second thermoplastic composition as described herein. Examples of two second thermoplastic compositions are described herein, and it has been found that both of them bond well to thermoplastic copolyester-based foams during the molding and foaming processes when used in solid form or in a slightly foamed form (e.g., having a specific gravity of 0.85 or greater), and also provide a high level of abrasion resistance and traction in both wet and dry conditions. The fact that the foam comprises a first thermoplastic copolyester and the polymeric layer comprises a second thermoplastic copolyester composition when the second thermoplastic composition comprises a second thermoplastic copolyester provides the advantage that the entire article can be easily melted and the combined materials can be recycled. In this case, the second copolyester compositions can each separately comprise one or more of the same individual copolyesters present in the first thermoplastic copolyester composition (in the same proportion or in a different proportion). Alternatively, the first copolyester composition and the second copolyester composition can each separately comprise different copolyesters.

[0066] The foam component disclosed herein is formed by foaming a thermoplastic composition comprising one or more thermoplastic elastomers into a porous foam having an open-cell foam structure or a closed-cell foam structure. In some instances, the one or more thermoplastic elastomers can comprise a thermoplastic copolyester elastomer or consist essentially of a thermoplastic copolyester elastomer. Examples of thermoplastic copolyester elastomers include polymers having one or more carboxylic acid moieties present in the polymer backbone, present on one or more side chains, or both present in the polymer backbone and present on one or more side chains. The one or more carboxylic acid moieties of the thermoplastic copolyester can include free carboxylic acids, salts of carboxylic acids, or acid anhydrides of carboxylic acids. In certain instances, the carboxylic acid moiety can be an acrylic moiety or a methacrylic moiety. The foam articles of the present disclosure, including porous open-cell or closed-cell thermoplastic foams and polymer layers, are suitable for use in a variety of articles, including for sports equipment and apparel, particularly footwear (e.g., athletic footwear midsole / outsole). As discussed below, the porous open-cell or closed-cell thermoplastic foams exhibit a unique balance of properties, such as high energy efficiency or energy return, and low specific gravity. In some instances, the porous foam also exhibits high split tear and low compression set. The presence of the polymer layer on at least a portion of the outer surface of the foam can reduce or prevent liquid absorption of the porous foam, particularly porous open-cell foam, and increase its performance when used under conditions where the foam is in contact with a liquid. Additionally, the thermoplastic foam can also be reprocessed (e.g., for recycling) with minimal loss of physical properties, providing a solution for the sustainability of the material.

[0067] The second thermoplastic composition of the polymer layer can be selected to allow the entire foam article to be recycled in a single step without removing or separating the polymer layer from the foam. For example, the second thermoplastic composition can comprise one or more thermoplastic copolyesters.

[0068] A foam article or foam component comprising a thermoplastic foam can be formed by injection molding and foaming a thermoplastic composition as described herein, or by injection molding and foaming a thermoplastic composition as described herein into a foam preform and subsequently compression molding the foam preform into a finished foam. A second thermoplastic composition can be disposed on an outer surface of the foam component during the injection molding and foaming process, wherein the first thermoplastic composition is injected into a mold comprising the second thermoplastic composition, and the second thermoplastic composition is incorporated into the foam during the molding process. Alternatively or additionally, the second thermoplastic composition can be disposed on an outer surface of the foam component during the compression molding step, wherein the foam component is compression molded in a mold comprising the second thermoplastic composition, and the second thermoplastic composition is incorporated into the foam during the molding process. Alternatively or additionally, the second thermoplastic composition can be disposed on the foam component after the foam component has been formed, such as, for example, by vacuum forming a film comprising the second thermoplastic composition onto the foam component.

[0069] An article made using the disclosed foam.

[0070] Footwear 10 is an exemplary athletic footwear article that includes a thermoplastic foam of the present disclosure. Although illustrated as a running shoe, the footwear 10 can alternatively be configured for any suitable athletic performance, such as a baseball shoe, a basketball shoe, a soccer / futbol shoe, a football shoe, a running shoe, a cross-training shoe, a cheerleading shoe, a golf shoe, and the like. Although athletic shoes are Figure 1 illustrated, it will be readily understood that some of the terms employed will also be applicable to other footwear articles or to other styles of shoes. The footwear 10 includes an upper 12 and a sole component 14 that is secured to the upper 12. The sole component 14 can be secured to the upper 12 by an adhesive or any other suitable means. As used herein, the sole component 14 can be a monolithic component formed entirely of a thermoplastic foam material as described herein, or a multi-component assembly formed of more than one monolithic component, wherein at least one of the monolithic components is formed entirely of a thermoplastic foam material as described herein.

[0071] The footwear 10 has an inner side or medial side 16 and an outer side or lateral side 18. For ease of discussion, the footwear 10 can be divided into three portions: a forefoot portion 20, a midfoot portion 22, and a heel portion 24. The portions 20, 22, and 24 are not intended to precisely demarcate regions of the footwear 10. Instead, the portions 20, 22, and 24 are intended to denote respective regions of the footwear 10 that provide a reference framework during the following discussion. Unless otherwise indicated, directional terms used herein, such as rearward, forward, top, bottom, inward, downward, upward, etc., refer to directions relative to the footwear 10 itself. The footwear 10 is Figure 1is shown in a generally horizontal orientation as it would be positioned on a horizontal surface when worn by a wearer. However, it should be understood that the footwear 10 need not be limited to such an orientation. Thus, in Figure 1 , backward is toward the heel portion 24 (as Figure 1 seen in Figure 1 , to the right), forward is toward the toe portion 20 (as Figure 1 seen in Figure 1 , to the left), and downward is toward the bottom of the page as Figure 1 seen. Top refers to an element toward the top of the view in Figure 1 , while bottom refers to an element toward the bottom of the view in Figure 1 Figure 1 . Inward is toward the center of the footwear 10, and outward is toward the outer peripheral edge of the footwear 10.

[0072] The component can be a sole component, such as the sole component 14 depicted in Figures 1 - 5 , which includes a thermoplastic foam as described herein, including a thermoplastic copolyester foam. The component can be an insert, such as the insert 36 or insert 60 depicted in Figures 1 - 5 Figures 4 - 5 , which includes a thermoplastic foam as described herein. The sole component and the insert for the sole component can be made in part or in whole from the thermoplastic foam described herein. Any part of the sole component or the insert for the sole component can be made from the thermoplastic foam described herein. For example, the first part 26 of the sole component (optionally including the ground-engaging lower surface 44, such as more than one protrusion 46 and / or a groove 48 surrounding the protrusion), the entire insert 36, the part 62 or 64 of the insert 60, a separate outsole component, or any combination thereof, can include a thermoplastic foam as described herein. The sole component and the insert can be made by foaming a thermoplastic composition as described herein, such as by injection molding as described herein or by injection molding, optionally followed by compression molding. In some aspects, the thermoplastic foam can be formed by physical foaming of the thermoplastic composition. The thermoplastic foam and the component can exhibit improved physical properties, including enhanced energy efficiency or energy return, enhanced delamination tear, reduced specific gravity, or a combination of one or more thereof.

[0073] The sole member 14, which is typically disposed between the wearer's foot and the ground, provides attenuation of the ground reaction force (i.e., imparts cushioning), attachment friction, and can control the movement of the foot, such as pronation. As with conventional footwear items, the sole member 14 can include an insole (not shown) located within the upper 12. In some aspects, the sole member is an insole or sockliner, or a multi-component assembly including an insole or sockliner, and can also include an insole or sockliner located within the upper, where the insole or sockliner is formed entirely or partially of the thermoplastic foam described herein. The footwear item described herein can include an insole or sockliner formed entirely or partially of the thermoplastic foam described herein.

[0074] As Figure 2 can be seen, the sole member 14 is composed of a first portion 26, which has an upper surface 27 with a recess 28 formed therein. The upper surface 27 is fixed to the upper 12 with an adhesive or other suitable fastening means. More than one generally horizontal rib 30 is formed on the exterior of the first portion 26. In certain aspects, the rib 30 extends from the central portion of the front part 20 of the shoe on the inner side surface 16 along the first portion 26 rearward, around the heel part 24 and forward on the outer side surface 18 of the first portion 26 to the central portion of the front part 20 of the shoe.

[0075] The first portion 26 provides the exterior attachment friction surface of the sole member 14. In certain aspects, it should be understood that a separate outsole member can be fixed to the lower surface of the first portion 26. When a separate outsole member is fixed to the lower surface of the first portion 26, the first portion 26 is a midsole member. In some aspects, the article is a midsole member for a footwear item. In other aspects, the article is a combined midsole-outsole member for a footwear item.

[0076] The article can be an insert. The insert 36 can be received within the recess 28. As Figure 2 illustrated, the insert 36 can provide cushioning or resiliency within the sole member. The first portion 26 can provide structure and support for the insert 36. In such aspects, the first portion 26 can be formed of a material having a higher specific gravity and / or hardness compared to the insert 36, such materials including, for example, non-foam materials such as rubber and thermoplastic polyurethane, as well as foam materials. In certain aspects, the insert 36 can be formed of the thermoplastic foam as disclosed herein.

[0077] The insert 36 has a curved rear surface 38 for mating with the curved rear surface 32 of the recess 28, and a transverse front surface 40 for mating with the transverse front surface 34 of the recess 28. The upper surface 42 of the insert 36 contacts the upper 12 and is secured thereto with an adhesive or other suitable fastening means. For example, when the insert 36 is present, the recess 28 can extend from the heel portion 24 to the toe portion 20 of the shoe. In some aspects, the rear surface 32 of the recess 28 is curved to generally follow the contour of the rear of the heel portion 24, and the front surface 34 of the recess 28 extends transversely across the first portion 26.

[0078] As Figure 3 best seen in, the ground-engaging lower surface 44 of the first portion 26 includes more than one protrusion 46. Each protrusion 46 is surrounded by a groove 48. More than one transverse slot 50 is formed in the lower surface 44 and extends between adjacent protrusions 46. A longitudinal slot 52 extends along the lower surface 44 from the heel portion 24 to the toe portion 20.

[0079] Figure 4 and Figure 5 show a bottom view and a top view of an insert 60 that can be used in a sole member as described herein. The insert 60 is similar to the insert 36, but as Figure 4 and Figure 5 illustrated, the insert 60 is formed of two types of materials 62 and 64, at least one of the materials being a thermoplastic foam as disclosed herein. Figure 4 shows a bottom view of the insert 60, while Figure 5 shows a top view of the insert 60, which is formed of two types of materials 62 and 64, where the insert is placed inside a first portion 66 to form the sole member 14. Inserts having more than two types of materials can also be used, at least one of the more than two types of materials being a thermoplastic foam as disclosed herein. In the Figure 4 and Figure 5 illustrated example, a portion of the first material 62 can be used for the heel region of the insert, and a portion of the second material 64 can be used for the toe region of the insert. A higher specific gravity material can be used to support the heel region, while a lower specific gravity material can be used to support the toe region. For example, the specific gravity of the first material can be at least 0.02 units greater than the specific gravity of the second material. The portions of the two materials 62 and 64 of the insert can be any suitable shape. For example, the heel region can be wedge-shaped. Inserts formed of two types of materials can be useful in running shoes as well as in basketball shoes.

[0080] The article includes a foam article or component that comprises a thermoplastic foam, such as a thermoplastic copolyester foam having an open-cell structure, and a layer of a second thermoplastic composition disposed on at least a portion of the outer surface of the foam as described herein. Reference Figure 7 , in an aspect, the foam component 70 may have a foam portion 72 that comprises a polymeric material that includes a thermoplastic copolyester porous foam having an open-cell foam structure or a closed-cell foam structure. The foam portion 72 has one or more sides that are oriented towards the outer-facing side or surface of the article (e.g., Figure 1 the outer peripheral edge) of the footwear article 10 when the foam component 70 is disposed in an article such as a footwear article. A polymeric layer 74 is disposed on at least a portion of the outer-facing side or surface of the foam portion 72. The polymeric layer 74 comprises a second thermoplastic composition that may be the same as or different from the first thermoplastic composition of the foam portion 72. According to the aspect, the polymeric layer 74 is not a foamed material. The polymeric layer 74 may be used as an outsole, for example, which may provide improved abrasion resistance on one or more surfaces of the foam portion 72.

[0081] In some aspects, the article may be other components in addition to the sole component. For example, the article may be an upper or an upper component. An upper component refers to a piece that is stitched or otherwise connected to one or more other pieces to form the upper portion of a footwear article. The material of the upper typically contributes to properties such as breathability, compliance, weight, and flexibility or softness. A lower component refers to a piece that is connected to one or more other pieces to form the lower portion of a footwear article. The lower portion may include, for example, an outsole and a midsole. The choice of outsole material and design will contribute to, for example, durability, traction friction, and pressure distribution during use. Midsole material and design contribute to factors such as cushioning and support. Grindery components include all additional components that may be attached to the upper, the lower, or both. Grindery components may include, for example, eyelets, toe puffs, shanks, nails, shoelaces, velcro, buckles, backers, linings, pads, heel backings, heel foxings, toe caps, etc.

[0082] The upper can be a lasted upper. As used herein, a "lasted upper" refers to an upper that is formed into a shoe shape before being attached to a sole by one or more mechanical means. The lasted upper can include a heel counter formed to shape the heel of the upper. The lasted upper can include a strobel or strobel board that is typically attached to the upper via a strobel stitch.

[0083] Although the thermoplastic foams described herein, including the thermoplastic copolyester foams described herein, can be used to manufacture any of a variety of components (including a variety of components for footwear articles), in certain aspects, the components include a midsole, an outsole, an insole, or an insert. Additional articles can include a tongue pad, a collar pad, and combinations thereof. As described above and more fully detailed below, articles including the thermoplastic foams described herein can exhibit a unique and beneficial balance of physical properties, such as high energy efficiency or energy return and low specific gravity. In addition, the thermoplastic foams can also be reprocessed (e.g., for recycling) with minimal loss of physical properties, providing a solution for the sustainability of the material.

[0084] In some cases, the disclosed articles can include a first component and a second component, the first component comprising a foamed thermoplastic composition such as a foamed thermoplastic copolyester composition, and the second component comprising a second thermoplastic composition. Articles including the first component and the second thermoplastic composition can be characterized by a good bond strength between the second thermoplastic composition and the foam component. When determined using the Ply Adhesion Test method described herein, the interlayer adhesion strength between the second thermoplastic composition and the foam component is greater than 2.5 kg force / cm or greater than 3.0 kg force / cm.

[0085] First component

[0086] The first component is a foam component comprising a thermoplastic composition, which thermoplastic composition comprises one or more thermoplastic elastomers. In one aspect, the thermoplastic composition is a thermoplastic copolyester composition comprising one or more thermoplastic copolyester elastomers. The first component can be a component such as, but not limited to, a midsole or a component of a midsole component. It should be understood that the first component comprises a foamed thermoplastic composition. For example, the thermoplastic composition comprises at least 90 weight percent, or at least 95 weight percent, or at least 99 weight percent of a thermoplastic polymer, such as, for example, the thermoplastic copolyesters disclosed herein, based on the total weight of the thermoplastic composition. In some cases, the polymer component of the thermoplastic composition (which comprises all polymers present in the thermoplastic composition) comprises one or more thermoplastic elastomers, such as one or more of the disclosed thermoplastic copolyester elastomers, or consists essentially of said one or more thermoplastic elastomers. In other words, the only polymer present in the thermoplastic composition can be a thermoplastic elastomer, or the only polymer present in the thermoplastic composition can be a thermoplastic copolyester elastomer.

[0087] The second component

[0088] The second component comprising a second thermoplastic composition can be a component such as, but not limited to, an outsole or a component of an outsole component. It should be understood that the second component can be foamed, partially foamed, or substantially unfoamed. In some cases, the second component is a foamed component, i.e., a second foam component. In other cases, the second component is an unfoamed component, i.e., a solid component. In some cases, the second thermoplastic composition is the disclosed thermoplastic composition, such as a thermoplastic copolyester composition. For example, the second thermoplastic composition can comprise at least 90 weight percent, or at least 95 weight percent, or at least 99 weight percent of a thermoplastic elastomer as disclosed herein, based on the total weight of the second thermoplastic composition. In some cases, the second thermoplastic composition comprises a polymer component consisting essentially of one or more of the disclosed thermoplastic elastomers, and one or more of the disclosed thermoplastic elastomers include one or more of the disclosed copolyester elastomers. In other cases, the second thermoplastic composition can comprise a polymer component substantially free of thermoplastic copolyesters, for example, the polymer component can consist essentially of a thermoplastic polyurethane elastomer or a thermoplastic vulcanizate material as disclosed herein. In still other cases, the second thermoplastic composition can comprise a mixture of the disclosed thermoplastic copolyesters and a polymer material that is not a disclosed thermoplastic copolyester, such as a thermoplastic elastomer or a thermoplastic vulcanizate material.

[0089] Properties of the thermoplastic copolyester foam component.

[0090] As discussed above, the first component can be a foam component comprising the disclosed first thermoplastic composition, i.e., the first foam component. In some cases, the second component can be a foam component comprising the disclosed second thermoplastic composition, i.e., the second foam component. That is, each of the first foam component or the second foam component can independently comprise the disclosed thermoplastic foam component. It should be understood throughout this document that reference to "thermoplastic foam" includes the first foam component, the second component, or both the first foam component and the second foam component, and each of the first foam component and the second foam component can independently comprise one or more of the disclosed thermoplastic compositions as disclosed below. The disclosed thermoplastic foam can exhibit a variety of beneficial properties.

[0091] For example, the thermoplastic foam can exhibit beneficial delamination tear, such as high delamination tear for a sole component in a footwear article. In some aspects, when determined using the delamination tear test method described herein, the thermoplastic foam can have a delamination tear value greater than about 1.5 kilograms per centimeter (kg / cm), or greater than about 2.0 kg / cm, or greater than about 25 kg / cm. In some aspects, when determined using the delamination tear test method described herein, the thermoplastic foam can have a delamination tear value of about 1.0 kg / cm to 4.5 kg / cm, about 1.5 kg / cm to 4.0 kg / cm, about 2.0 kg / cm to 4.0 kg / cm, about 2.0 kg / cm to 3.5 kg / cm, or about 2.5 kg / cm to 3.5 kg / cm. In some aspects, the thermoplastic foam is injection molded, or injection molded and then compression molded in a separate compression mold having a different size than the mold used in the injection molding step. The thermoplastic foam can have a delamination tear of about 0.08 kg / cm to 4.0 kg / cm, about 0.9 kg / cm to 3.0 kg / cm, about 1.0 kg / cm to 2.0 kg / cm, about 1.0 kg / cm to 1.5 kg / cm, or about 2 kg / cm. In some aspects, the thermoplastic foam is injection molded and has a delamination tear of about 0.07 kg / cm to 2.0 kg / cm, or about 0.8 kg / cm to 1.5 kg / cm, or about 0.9 kg / cm to 1.2 kg / cm, about 1.5 kg / cm to 2.2 kg / cm.

[0092] When using foams in footwear or sports equipment items, the specific gravity of the disclosed thermoplastic foams is also an important physical property to consider. As discussed above, the thermoplastic foams of the present disclosure exhibit a low specific gravity, which beneficially reduces the weight of the midsole or other components containing the thermoplastic foam. When determined using the specific gravity testing method described herein, the thermoplastic foams of the present disclosure can have a specific gravity ranging from 0.02 to 0.22, or from 0.03 to 0.12, or from 0.04 to 0.10, or from 0.11 to 0.12, or from 0.10 to 0.12, from 0.15 to 0.2, 0.15 to 0.30. Optionally or additionally, when determined using the specific gravity testing method described herein, the thermoplastic foam can have a specific gravity ranging from 0.01 to 0.10, or from 0.02 to 0.08, or from 0.03 to 0.06, 0.08 to 0.15, or from 0.10 to 0.12. For example, the specific gravity of the thermoplastic foam can be from 0.15 to 0.20, or can be from 0.10 to 0.12. The thermoplastic foam can be injection molded, or can be injection molded and subsequently compression molded. In some aspects, when determined using the specific gravity testing method described herein, the thermoplastic foam has a specific gravity of about 0.7 or less, or 0.5 or less, or 0.4 or less, or 0.3 or less. In some aspects, when determined using the specific gravity testing method described herein, the thermoplastic foam, including the thermoplastic foam present in the midsole and midsole components, can have a specific gravity of about 0.05 to 0.25, about 0.05 to 0.2, about 0.05 to 0.15, about 0.08 to 0.15, about 0.08 to 0.20, about 0.08 to 0.25 or about 0.1 to 0.15. In some aspects, when determined using the specific gravity testing method described herein, the thermoplastic foam has a specific gravity of about 0.15 to 0.3, about 0.2 to 0.35 or about 0.15 to 0.25.

[0093] In a specific example, the first component is a cushioning element for a footwear item, and when determined using the specific gravity testing method described herein, the thermoplastic foam of the first component has a specific gravity ranging from 0.05 to 0.25, or from 0.17 to 0.22, or from 0.18 to 0.20. The thermoplastic foam can be a physically foamed thermoplastic foam, such as a physically foamed thermoplastic foam formed using a single-phase solution of a supercritical fluid and a thermoplastic composition described herein. The thermoplastic composition can be a thermoplastic copolyester composition comprising one or more thermoplastic copolyester elastomers.

[0094] When determined using a cyclic compression test with a 45 millimeter diameter cylindrical sample, the thermoplastic foam portion of an article or a component of an article can have a stiffness of from about 200 kPa to about 1000 kPa, or from about 300 kPa to about 900 kPa, or from about 400 kPa to about 800 kPa, or from about 500 kPa to about 700 kPa. When determined using a cyclic compression test with a footform sample, the thermoplastic foam portion of an article or a component of an article can have a stiffness of from about 200 kPa to about 1000 kPa, or from about 300 kPa to about 900 kPa, or from about 400 kPa to about 800 kPa, or from about 500 kPa to about 700 kPa. The thermoplastic foam article or article component can be formed by injection molding, or by injection molding and subsequent compression molding.

[0095] When determined using the Durometer Hardness Test described herein, the thermoplastic foam portion of an article or a component of an article can have an Asker C durometer hardness of from about 30 to about 50, or from about 35 to about 45, or from about 30 to about 45, or from about 30 to about 40.

[0096] The energy input of the foam is the integral of the force-displacement curve during the loading of the foam during the cyclic compression test. The energy return of the foam is the integral of the force-displacement curve during the unloading of the foam during the cyclic compression test. When determined using a cyclic compression test with a 45 millimeter diameter cylindrical sample, the thermoplastic foam portion of an article or a component of an article can have an energy return of from about 200 millijoules (mJ) to about 1200 mJ, or from about 400 mJ to about 1000 mJ, or from about 600 mJ to about 800 mJ.

[0097] The energy efficiency, which is a measure of the percentage of energy returned by the thermoplastic foam portion of an article or component when released after being compressed under load, can provide improved performance for a sports shoe, such as for reducing energy loss or dissipation during running. This is especially true for running shoes and other sports shoes. In some aspects, when determined using a cyclic compression test with a 45 millimeter diameter cylindrical sample, the thermoplastic foam portion of the articles and components provided herein has an energy efficiency of from about 50 percent to 97 percent, from about 60 percent to 95 percent, from about 60 percent to 90 percent, from about 60 percent to 85 percent, from about 65 percent to 85 percent, or from about 70 percent to 85 percent.

[0098] By varying the conditions and components used to make the foam, one or more properties of the foam can be altered. In one aspect, when the foam is a physically foamed product of a single-phase solution of a supercritical fluid and a first thermoplastic composition in a molten state, the resulting foam can have a reduced specific gravity and high energy efficiency or energy return. In one aspect, additives such as nucleating agents and fillers are not used or are used at low levels because it has been found that the use of non-polymeric components can reduce the consistency of the pore sizes in the porous foam, especially when foaming a thermoplastic copolyester composition. Additionally, including higher levels of non-polymeric additives such as fillers, nucleating agents, and pigments can make recycling the foam more challenging.

[0099] In other aspects, the temperature at which the molten first thermoplastic composition is foamed can alter the properties of the foam. In one aspect, the foaming temperature of the thermoplastic composition, i.e., the temperature at which the thermoplastic composition begins to foam, is from about the melting temperature of the thermoplastic composition to about 50 degrees Celsius, or about 40 degrees Celsius, or about 30 degrees Celsius, or about 20 degrees Celsius above the peak tail temperature of the thermoplastic composition. Alternatively, the foaming temperature can be from the crystallization temperature of the thermoplastic composition to about 50 degrees Celsius, or about 40 degrees Celsius, or about 30 degrees Celsius, or about 20 degrees Celsius above the crystallization temperature of the thermoplastic composition. The melting temperature, peak tail temperature, and crystallization temperature of the thermoplastic composition can be determined using differential scanning calorimetry (DSC). In this aspect, properties such as reduced specific gravity, consistent foam pore size, and / or high energy efficiency or energy return can be achieved, especially when foaming a thermoplastic copolyester composition.

[0100] The resulting foam can have a porous closed-cell or open-cell foam structure. Pores are hollow structures formed during the foaming process, where gas bubbles are formed in the polymeric material by a blowing agent. The pore walls are typically defined by the polymeric material. The pores can be completely encapsulated by the polymeric material, or they can be at least partially open, e.g., interconnected with one or more adjacent pores. A "closed-cell" structure refers to a structure in which at least 60 percent or more of the pores are closed cells, or at least 80 percent of the pores are closed cells, or at least 90 percent of the pores are closed cells, or at least 95 percent of the pores are closed cells. As described herein, an "open-cell" structure refers to a foam structure in which less than about 15 percent, or less than about 10 percent or 5 percent, or less than 4 percent, or less than 3 percent or less than 1 percent of the pores are closed cells.

[0101] The disclosed thermoplastic foam may have an average pore diameter ranging from about 50 microns to about 1000 microns, or from about 80 microns to about 800 microns, or from about 100 microns to about 500 microns. The disclosed thermoplastic foam may have an average pore diameter ranging from about 50 microns to about 500 microns, or from about 70 microns to about 300 microns, or from about 80 microns to about 200 microns, or from about 50 microns to about 200 microns.

[0102] The proportion of pores in the foam having an average pore diameter of about 50 microns to about 300 microns is preferably not less than 40 percent, or not less than 50 percent or not less than 60 percent relative to all pores. If the proportion of pores is less than 40 percent, the pore structure will tend to be non-uniform and / or have a coarse pore structure. As used herein, "coarse pore structure" refers to a foam structure in which the average pore diameter is greater than 1 mm, and / or for greater than 20 percent of the pores, a 1 mm line drawn across the maximum dimension of the pore will not cross the pore wall or strut (i.e., the open cell wall or a portion thereof).

[0103] The number of open and / or closed pores and the pore diameter of the pores in the foam can be determined visually, for example, by capturing an image of the cut surface with a camera or digital microscope, determining the number of pores, the number of open pores and / or the number of closed pores, and determining the average pore diameter of the cross-section of a sample of the foam. For the pores of a closed cell foam, the diameter is determined from wall to wall of the pore. For the pores of an open cell foam, the diameter is determined between the planes formed by the intersections of the supporting struts (i.e., the open cell wall or a portion thereof) between the pores. In one aspect, a portion of the foam can be cut, and the pores in the cross-sectional area can be visually inspected under a microscope or by software to determine the percentage of open or closed pores within the area and to determine the average size of the pores. In one aspect, samples from about 75 percent to about 100 percent of the area of the foam article representative of the maximum thickness of the foam article can be used to determine the nature and size of the pores.

[0104] Methods for manufacturing the disclosed foams.

[0105] In some instances, the disclosed foams can be prepared by a variety of methods as disclosed herein and as known in the art. That is, the disclosed articles or components of articles such as midsole, midsole components, inserts, and insert components can be prepared by injection molding a melt composition comprising a first thermoplastic composition as described herein using a physical blowing agent and / or a chemical blowing agent. The disclosed foam components, such as the disclosed first foam component or the disclosed second foam component, can be prepared by the methods disclosed below.

[0106] Disclosed herein are methods for manufacturing foam articles or components, the methods comprising: forming a mixture of a molten first thermoplastic composition and a foaming agent, wherein the first thermoplastic composition comprises the disclosed thermoplastic elastomer; injecting the mixture into a mold cavity; causing the molten first thermoplastic composition to foam, thereby forming a foamed molten first thermoplastic composition; causing the foamed molten first thermoplastic composition to solidify, thereby forming a foam article having a porous foam structure; and removing the foam article from the mold cavity. In one aspect, the first thermoplastic composition is a first thermoplastic copolyester composition comprising the disclosed thermoplastic copolyester elastomer, and the porous foam structure is an open-cell porous foam structure.

[0107] Also disclosed are methods for manufacturing foam articles or components, the methods comprising: forming a mixture of a molten first thermoplastic composition and a foaming agent, wherein the first thermoplastic composition comprises the disclosed thermoplastic elastomer; injecting the mixture into a mold cavity; causing the molten first thermoplastic composition to foam, thereby forming a foamed molten first thermoplastic composition; causing the foamed molten first thermoplastic composition to solidify, thereby forming a foam article having a porous foam structure; and removing the foam article from the mold cavity; wherein during injection, the mixture has an injection temperature; and wherein the injection temperature is from about the melting temperature of the thermoplastic elastomer to about 50 degrees Celsius above the peak tail temperature of the thermoplastic composition. In one aspect, the first thermoplastic composition is a first thermoplastic copolyester composition comprising the disclosed thermoplastic copolyester elastomer, and the porous foam structure is an open-cell porous foam structure.

[0108] Also disclosed are methods for manufacturing foam articles or components, the methods comprising: forming a mixture of a molten first thermoplastic composition and a foaming agent, wherein the first thermoplastic composition comprises the disclosed thermoplastic elastomer; injecting the mixture into a mold cavity; causing the molten first thermoplastic composition to foam, thereby forming a foamed molten first thermoplastic composition; causing the foamed molten first thermoplastic composition to solidify, thereby forming a foam article having a porous foam structure; and removing the foam article from the mold cavity; wherein the foaming occurs at a foaming temperature; and wherein the foaming temperature is from about the melting temperature of the thermoplastic elastomer to about 50 degrees Celsius above the peak tail temperature of the thermoplastic elastomer. In one aspect, the first thermoplastic composition is a first thermoplastic copolyester composition comprising the disclosed thermoplastic copolyester elastomer, and the porous foam structure is an open-cell porous foam structure.

[0109] Dynamic scanning calorimetry (DSC) is used to determine the melting temperature, peak tail temperature, and crystallization temperature of a thermoplastic elastomer, and an exemplary method is described below. Briefly, a 10 mg - 30 mg piece of undried resin pellets is cycled from -90 °C to 225 °C at 20 °C / min and cooled to -90 °C at 10 °C / min. In some cases, the experiment uses a heat - cold - heat curve run at a ramp rate of 10 °C / min, a minimum temperature of 0 °C, and a maximum temperature of 250 °C. The analysis should be done in duplicate and averaged. The melting temperature value and the crystallization temperature value are recorded. The melting "peak" and the crystallization "peak" are determined as the local maxima of melting or crystallization. If there is more than one peak in the DSC curve, the peak that occurs at the hotter temperature is chosen as the temperature reference. The peak tail is determined as the intersection of the tangent of the line on the higher temperature side of the peak with the extrapolated baseline. The schematic diagram showing the method for determining the melting peak temperature and the peak tail temperature is shown in Figure 8 is shown in.

[0110] For example, the disclosed first thermoplastic composition for foaming can be prepared using a suitable extruder. The extruder (e.g., single - screw or twin - screw) can be used to provide the composition. The extruder can have a motor to rotate the screw inside the extruder. The extruder can be a single - screw or twin - screw made of various elements of different sizes and pitches suitable for mixing or kneading the particular materials used. In some instances, the extruder is a twin - screw.

[0111] The various components that make up the first thermoplastic composition for forming the thermoplastic foams described herein are added to the extruder through one or more ports. The various components can be added as a melt or as solid particles of appropriate size, such as chips or pellets, which are melted in segments as they are mixed in the barrel of the extruder. The contents of the extruder can be heated to melt the composition. A supercritical fluid can be added to the melt as a physical blowing agent. In certain instances, the thermoplastic foam is prepared by using a physical blowing agent that causes the thermoplastic composition to foam after the pressure drops to a level at which the supercritical fluid phase transitions to a gas, such as after the thermoplastic composition exits the extruder, and thus the thermoplastic foam is substantially free of chemical blowing agents or their decomposition products.

[0112] The composition can be added as a melt at a temperature close to the melting temperature of the first thermoplastic composition.

[0113] If a chemical blowing agent is used, the processing temperature within the extruder used can be sufficiently below the temperature that will trigger the blowing agent. To foam the first thermoplastic composition, the temperature near the outlet of the extruder or within the barrel of the syringe can be raised in order to heat the thermoplastic composition to a temperature that is near or at the trigger temperature of the chemical blowing agent, such that as the composition exits the extruder (e.g., as the composition is injected into an injection molding die), a chemically foamed thermoplastic foam is produced.

[0114] Optionally or additionally, a physical blowing agent can be used to foam the composition to form a physically foamed thermoplastic foam, or a physically and chemically foamed thermoplastic foam. For example, a supercritical fluid such as supercritical carbon dioxide or supercritical nitrogen can be mixed with the molten first thermoplastic composition in the barrel of the extruder to form a single-phase solution. As used herein, "single-phase" refers to a composition in which two or more components are present and there is no discernible phase separation between the components. For example, when a supercritical fluid is mixed with the molten first thermoplastic composition, the resulting composition is a homogeneous solution in which droplets of the supercritical fluid are not detected. As the single-phase solution exits the extruder or syringe, the pressure drop between the higher pressure within the extruder or syringe and the lower pressure outside the extruder or syringe causes the supercritical fluid to transition to the gas phase and foam the first thermoplastic composition.

[0115] Numerous examples include methods of manufacturing an article of footwear or a component for an article of footwear. In some examples, a method of manufacturing an article of footwear includes injection molding a first thermoplastic composition to form a thermoplastic foam as described herein to produce a foamed article or a component of an article such as an article of footwear. The article or component of the article can be a midsole or a component of a midsole, and the method can include providing an upper and an outsole for the article of footwear; and combining the midsole or midsole component, the upper, and the outsole to manufacture the article of footwear. In some examples, a method of manufacturing an article of footwear includes combining an article that includes a thermoplastic foam and an upper to manufacture the article of footwear.

[0116] Articles or components of articles such as midsole, midsole components, inserts, and insert components can be prepared by injection molding the molten first thermoplastic composition described herein using a physical blowing agent. The injection molding can be performed using a screw-type syringe, which allows maintaining and controlling the pressure in the syringe barrel. The injection molding machine can allow metering a supercritical fluid such as supercritical carbon dioxide or nitrogen before injection and delivering it into the composition. The supercritical fluid can be mixed into the first thermoplastic composition within the syringe barrel to form a single-phase solution, and then the single-phase solution can be injected into the mold cavity. The pressure drop within the mold cavity can cause the supercritical fluid to expand to generate cell nuclei and cause the cells to expand to form a foam within the mold cavity. The injection molding system for forming the thermoplastic foam can include a physical foaming process such as, for example, the "MUCELL" process (Trexel, Wilmington, DE, USA).

[0117] The thermoplastic foams described herein can be manufactured using a process that involves impregnating a first thermoplastic composition (e.g., at or above the softening temperature of the composition) with a physical blowing agent at a first concentration or a first pressure. As used herein, the term "impregnating" generally means dissolving or suspending the physical blowing agent in the first thermoplastic composition. Then, the impregnated first thermoplastic composition can be foamed or can be cooled (when applicable) and re-softened (when applicable) for foaming at a later time. In a particular instance, the impregnated first thermoplastic composition is a single-phase solution comprising supercritical carbon dioxide or nitrogen and a molten thermoplastic composition.

[0118] The impregnated first thermoplastic composition is foamed by reducing the solubility of the physical blowing agent in the single-phase solution via a pressure change or a temperature change. The reduction in the solubility of the physical blowing agent can release an additional amount (e.g., to produce a secondary expansion of the initially formed foam) of the impregnated physical blowing agent from the first thermoplastic composition to further foam the first thermoplastic composition to form a thermoplastic foam having a porous foam structure.

[0119] In addition to injection molding, the thermoplastic foams of the present disclosure can be foamed and molded using a variety of processes known in the art. For example, the thermoplastic foam can be formed into slab foam, filament or strand foams, particulate (e.g., bead) foams of various shapes and sizes, etc. These various forms of the foam can then be used in different ways. For example, like injection-molded foams, slab foam and filament or strand foams can be used directly as the finished foam article, or can be shaped (e.g., cut, polished or trimmed) to form the finished foam article, or can be compression molded to form the finished foam article. Optionally, the thermoplastic foam can undergo an annealing process as part of forming the finished foam article. The pellets of the composition can be used to form individual particulate thermoplastic foams, or can be foamed and molded to form an integrally molded foam article that includes separate portions of foam attached to one another.

[0120] The thermoplastic foams of the various examples described herein can be further shaped or molded by any known method for forming articles from thermoplastic materials. Optionally, the thermoplastic foams of the present disclosure that have been foamed using any suitable foaming process (e.g., foaming using a physical blowing agent and / or a chemical blowing agent), including injection molding using only a physical blowing agent, can then be compression molded to form a compression molded foam.

[0121] The thermoplastic foams of the present disclosure can be prepared by a process comprising: (i) softening a first thermoplastic composition (e.g., by heating at a first temperature that is at or above the softening temperature of the composition); (ii) simultaneously or sequentially (when applicable) with the softening, contacting the first thermoplastic composition with a physical blowing agent at a first concentration or first pressure sufficient to drive a quantity of the physical blowing agent into the first thermoplastic composition or to combine the physical blowing agent with the first thermoplastic composition; (iii) changing the concentration or pressure of the physical blowing agent (e.g., reducing the pressure or concentration) to a second concentration or second pressure effective to foam the first thermoplastic composition, thereby forming a thermoplastic foam (e.g., a thermoplastic foam having a porous structure); and (iv) after the change, cooling (when applicable) the thermoplastic foam (e.g., cooling to a temperature below the softening temperature of the composition) to form a solidified thermoplastic foam.

[0122] The thermoplastic foam of the present disclosure can be prepared by: (i) in some instances, contacting a first thermoplastic composition with a first concentration of a chemical blowing agent (e.g., dissolving or suspending) at or above the softening temperature of the first thermoplastic composition; (ii) triggering the chemical blowing agent to foam the first thermoplastic composition, thereby forming a thermoplastic foam (e.g., a thermoplastic foam having a porous structure); and (iii) after triggering, in some instances, cooling the thermoplastic foam to a temperature, e.g., below its softening temperature, to form a cured thermoplastic foam. In some instances, the "triggering" of the chemical blowing agent is carried out by any suitable method, including heating a composition containing a certain concentration of the chemical blowing agent to a temperature sufficient to "trigger" the chemical blowing agent, wherein the concentration of the chemical blowing agent effectively foams the first thermoplastic composition, thereby forming a thermoplastic foam (e.g., a thermoplastic foam having a porous structure). In some instances, the contacting includes contacting at a pressure from about 10 MPa to about 100 MPa (e.g., from about 30 MPa to about 100 MPa, about 20 MPa to about 80 MPa, about 30 MPa to about 60 MPa, or about 40 MPa to about 70 MPa).

[0123] The chemical blowing agent can be endothermic or exothermic, which refers to the type of decomposition they undergo to produce the gas for foaming. The decomposition can be the result of inputting thermal energy into the system. Endothermic blowing agents absorb energy and typically release a gas, such as carbon dioxide, upon decomposition. Exothermic blowing agents release energy and produce a gas, such as nitrogen, upon decomposition. Regardless of the chemical blowing agent used, the thermal variables of the first thermoplastic composition being molded and the thermal variables of the blowing agent to be decomposed are linked together such that the process parameters are selected so that the first thermoplastic composition can be molded and the blowing agent can decompose at an appropriate stage of the molding operation.

[0124] The disclosed foamed first thermoplastic composition and article can be prepared by using a conventional injection molding system, such as all or some of the elements of the injection molding system disclosed in U.S. Patent Application No. 62 / 734,912, which is incorporated herein by reference. Briefly, the system provides reduced overall system pressure loss and controls (e.g., intentionally increases or decreases) the elongation, apparent shear, and / or zero shear viscosity of the molten first thermoplastic composition flowing into the mold. The method can include flowing the molten first thermoplastic composition from an upstream device into a shot tuning chamber and adjusting the temperature, pressure, or both within the shot tuning chamber to produce a tuned molten first thermoplastic composition. The method additionally includes flowing the tuned molten first thermoplastic composition from the shot tuning chamber into a mold cavity. It will be understood that fine-tuning the temperature of the molten first thermoplastic composition and / or the pressure applied to the molten first thermoplastic composition enables the system to have a desired effect on the physical and mechanical properties of the molded article. In particular, the temperature of the molten first thermoplastic composition can be controlled to achieve a desired range of shear / tensile viscosities, which reduces (e.g., substantially eliminates) uncontrolled bubble growth and / or nucleation. In one example, the method can further include adjusting (e.g., increasing and / or decreasing) the pressure within the mold cavity via a gas counterpressure (GCP) assembly before or simultaneously with the molten first thermoplastic composition flowing from the shot tuning chamber or directly from a syringe into the mold cavity. In such an example, the molten first thermoplastic composition can flow into the mold cavity at a pressure far above ambient pressure. Additionally, GCP can be introduced into the mold cavity to control nucleation and bubble growth during polymer foaming and to increase the surface quality of the molded article. Nucleation and bubble growth control can enhance the cell density uniformity, cell diameter consistency, and mechanical properties of the thermoplastic foam. In some examples, the improvement in cell density uniformity or cell diameter consistency can be particularly beneficial in thermoplastic foams having a low specific gravity such as less than or equal to 0.3 and / or in foam components having large dimensions such as articles having a thickness of ≥1.0 cm.

[0125] The system can include a shot tuning chamber configured to receive the molten first thermoplastic composition from an upstream device. The shot tuning chamber is further configured to adjust one or more of the temperature of the molten first thermoplastic composition and the pressure applied to the molten first thermoplastic composition to produce a conditioned molten first thermoplastic composition and to dispense the conditioned molten first thermoplastic composition. In this way, the system can selectively adjust the temperature and / or pressure of the tuning chamber to achieve the desired properties, as previously mentioned. In one example, the system can further include an adjustable mold runner configured to regulate the fluid communication between the shot tuning chamber and the mold cavity in the mold.

[0126] In another example, the system can include a GCP assembly coupled to the mold cavity and configured to regulate the amount of backpressure gas flowing into and out of the mold cavity. Providing GCP regulation allows tuning of the first thermoplastic composition as the first thermoplastic composition enters the mold and cools within the mold.

[0127] Optionally, the disclosed foams and articles can be prepared using the methods and systems described in International Patent Application No. PCT / US2018 / 035128. Briefly, the method can include a method for molding a single-phase solution comprising a thermoplastic composition and a supercritical fluid. The single-phase solution is maintained under pressure during the molding operation to prevent the supercritical fluid in the single-phase composition from coming out of the solution to form a porous structure. The single-phase solution is introduced into a mold cavity for molding purposes and the mold cavity is pressurized to a mold pressure sufficient to keep the single-phase solution as a single-phase solution when the mold cavity is filled. After filling the mold cavity with the single-phase solution under pressure, the single-phase solution can be cured, entrapping the supercritical fluid. Optionally, prior to curing, the single-phase solution can be exposed to a pressure reduction, causing the entrapped supercritical fluid to phase transition to a gas and the softened thermoplastic composition to expand to form a porous structure, after which the thermoplastic composition cures into a solidified porous foam.

[0128] The method can include forming a single-phase solution, such as by introducing a supercritical fluid and a first thermoplastic composition into a barrel (e.g., a screw) of an injection molding device, the first thermoplastic composition being melted at a temperature, for example, from about the melting temperature of the thermoplastic elastomer of the thermoplastic composition up to about 50 degrees Celsius above the melting peak tail temperature of the thermoplastic elastomer as described herein, the barrel of the injection molding device effectively mixing the supercritical fluid and the melted thermoplastic composition under pressure to form a single-phase solution. The method continues by pressurizing the mold cavity of the mold above atmospheric pressure to a mold pressure. Atmospheric pressure is the pressure of the environment to which the mold cavity is exposed (e.g., ambient pressure in general). The mold pressure is at least the pressure to keep the single-phase solution as a single-phase. The method also includes injecting the single-phase solution into the pressurized mold cavity. The method also includes maintaining at least the mold pressure in the mold cavity during injection of the single-phase solution. As a result, the pressure in the mold cavity prevents the supercritical fluid from phase transitioning to a gas and coming out of the solution to form a two-phase mixture (e.g., foaming) after leaving the injection molding device. When the pressure is maintained, premature foaming during injection of the thermoplastic composition from the injection molding device is avoided, allowing decoupling of process parameters associated with the blowing agent and the thermoplastic composition.

[0129] A molding system can be used to prepare the disclosed foams. The molding system includes means configured to receive a first thermoplastic composition and heat the first thermoplastic composition to form a molten first thermoplastic composition or a single-phase solution. Optionally, the molding system can include a feed tuning chamber configured to receive the molten first thermoplastic composition or single-phase solution from the means and adjust the temperature of the molten first thermoplastic composition or single-phase solution or the pressure applied to the molten first thermoplastic composition or single-phase solution. Optionally, the molding system can further include an adjustable die runner configured to regulate the flow of the molten first thermoplastic composition or single-phase solution between the feed tuning chamber and the die cavity. In one example, the means can be an injection device or an extrusion device. The molding system allows the properties of the first thermoplastic composition or single-phase solution to be adapted to achieve desired end-use goals, such as, for example, achieving a desired injection temperature or a desired foaming temperature or both.

[0130] In some aspects, the present disclosure relates to compression-molded thermoplastic foams and to methods of forming compression-molded thermoplastic foams for use in footwear articles or sports equipment articles and other applications. In some examples, the method can be a process that includes providing (e.g., preparing) a thermoplastic foam preform and then compression molding the thermoplastic foam preform to form a compression-molded thermoplastic foam. For example, the thermoplastic foam can be compression molded by placing the thermoplastic foam preform in a compression mold having a height less than the initial height of the thermoplastic foam preform and closing the mold, thereby compressing the thermoplastic foam preform to the height of the mold. Simultaneously with or sequential to the compression, the thermoplastic foam preform can be heated in the closed compression mold. During the compression molding, the temperature of at least a portion of the thermoplastic foam preform in the closed mold can be raised to a temperature within ±30 degrees Celsius of the softening temperature of the composition. The temperature can be raised by heating the closed mold. After raising the temperature, while the thermoplastic foam preform remains enclosed in the compression mold, the temperature of at least a portion of the thermoplastic foam preform can be lowered. The temperature can be lowered by cooling the closed mold. The lowering can reduce the temperature of at least a portion of the thermoplastic foam preform to a temperature at least 35 degrees Celsius below the softening temperature of the composition, thereby forming a compression-molded thermoplastic foam. After cooling, the compression mold can be opened, and the compression-molded thermoplastic foam can be removed from the compression mold.

[0131] Examples contemplated herein relate to methods of manufacturing footwear articles, apparel articles, or sports equipment articles. For example, the method can include providing components of a footwear article, such as a midsole and an insert, according to the present disclosure and combining the components with a footwear upper and an outsole to form a footwear article.

[0132] Thermoplastic foams can be manufactured using a process that involves impregnating a first thermoplastic composition (e.g., at or above the softening temperature of the composition) with a physical blowing agent at a first concentration or a first pressure. The impregnated first thermoplastic composition can then be foamed, or can be cooled (when applicable) and re-softened (when applicable) for blowing at a later time. In some cases, the impregnated first thermoplastic composition is foamed by reducing the temperature or pressure, which affects the solubility of the physical blowing agent. The reduction in the solubility of the physical blowing agent can release an additional amount of the impregnated physical blowing agent from the first thermoplastic composition to further blow the composition and form a thermoplastic foam (e.g., a thermoplastic foam having a porous structure).

[0133] Thermoplastic foams can have a closed skin. The closed skin can be formed by foaming and molding a thermoplastic copolyester foam in a closed mold. The closed skin can also be formed by compression molding a thermoplastic foam preform in a compression mold. However, during compression molding, care should be taken not to subject the thermoplastic foam preform to conditions that cause the pore structure of the foam to collapse by more than a desired amount. One way to avoid collapsing the pore structure by more than a desired amount is to control the temperature of the thermoplastic foam during the compression molding process, e.g., by controlling the temperature of the mold. For example, during the compression molding step, heating of the thermoplastic foam preform in the compression mold can be carried out for a time ranging from 100 seconds to 1,000 seconds or from 150 seconds to 700 seconds.

[0134] After the thermoplastic foam has been heated in the compression mold at an appropriate temperature for a desired length of time to soften the thermoplastic foam to a desired level, the softened preform is cooled to a temperature, e.g., at least 35 degrees Celsius below its softening temperature, or at least 50 degrees Celsius below its softening temperature, or at least 80 degrees Celsius below its softening temperature, to re-solidify the softened foam, thereby forming a compression-molded foam. After cooling, the compression-molded thermoplastic foam is removed from the compression mold. After heating, cooling of the foam preform in the compression mold can be carried out for a time ranging from 50 seconds to 1,000 seconds, or for a time ranging from 100 seconds to 400 seconds.

[0135] Thermoplastic foams can be foamed using any of the methods described above. Thermoplastic foams can be included in components of a footwear article as described above, e.g., in the first portion 26 depicted as Figure 1 in.

[0136] A method of manufacturing the disclosed article.

[0137] Multiple examples include methods of making an article that includes a first component and a second component. As discussed above, the first component can be a foam component, such as a first foam component, and the second component can be a foam component, such as a second foam component. The first component can be, but is not limited to, a midsole or a component of a midsole. The second component can be, but is not limited to, an outsole or an upper. It should be understood that the second component can be foamed, partially foamed, or substantially unfoamed. In some cases, the second thermoplastic composition includes one or more of the disclosed thermoplastic elastomers. For example, the second thermoplastic composition includes at least 90 weight percent, or at least 95 weight percent, or at least 99 weight percent of the thermoplastic elastomers disclosed herein, based on the total weight of the second thermoplastic composition. In some cases, the second thermoplastic composition includes a greater concentration of filler, pigment, or dye as compared to the first thermoplastic composition of the first foam component. The disclosed methods of making an article that includes a first component and a second component can also include steps or adjustments known to one of ordinary skill in the art.

[0138] In some aspects, a method of making a footwear article includes injection molding a first thermoplastic composition to form a thermoplastic foam as described herein to produce a foam article or a component of an article, such as a cushioning element for a footwear article. The method can also include making an article or a component of an article, including providing a midsole or a component of a midsole, and then providing an upper and / or an outsole or an outsole component for the footwear article; and subsequently combining the midsole or the midsole component with the upper and / or the outsole or the outsole component to make a footwear article. In some cases, a method of making a footwear article includes combining an article that includes a thermoplastic foam, an upper, and an outsole to make a footwear article. In various aspects, the upper and / or the outsole can include the same or different thermoplastic compositions, second thermoplastic compositions, or combinations thereof. In some cases, the outsole used in the method can be foamed, partially foamed, or generally unfoamed. It should be understood that the midsole, the midsole component, the outsole, or the outsole component can be foamed or partially foamed using the methods disclosed herein for preparing foam articles.

[0139] A variety of the disclosed methods can include coupling a first component to a second component. In some aspects, the disclosed methods include forming a first component and a second component together. For example, a first thermoplastic composition for the first component (i.e., the disclosed thermoplastic composition) and a second thermoplastic composition can be sequentially added to a mold during an injection molding process to provide an integral component having a first component (i.e., a foam portion comprising the first thermoplastic composition) and a second component (e.g., a polymer layer comprising the second thermoplastic composition). In this aspect, a mold having a first mold portion with a mold surface can be provided. The second thermoplastic composition can be added to the mold to form a polymer layer on at least a portion of the mold surface. The second thermoplastic composition can be added to the mold as a film or coating applied to the mold surface. The process of adding the second thermoplastic composition can include injecting the second thermoplastic composition into the mold cavity before injecting the first thermoplastic composition into the mold cavity. Optionally, after injecting the second thermoplastic composition into the mold cavity but before injecting the first thermoplastic composition into the mold cavity, the pressure within the mold cavity or the temperature of the mold cavity or both can be changed. For example, after injecting the second thermoplastic composition into the mold, the pressure within the mold can be increased to better cover the surface of the mold cavity with the second thermoplastic composition and form a polymer layer on the surface of the mold cavity. The first thermoplastic composition for the first component, i.e., the disclosed thermoplastic composition, can be injected into a mold comprising the second component, i.e., a polymer layer comprising the second thermoplastic composition, and foamed when in contact with the polymer layer. The resulting injection molded component is an integral component having a second component (i.e., the polymer layer) thermally bonded to the first component (i.e., the foam component).

[0140] In one example, when injecting a second thermoplastic composition and a first thermoplastic composition to form an integral part as described above, the second thermoplastic composition can be free or substantially free of a foaming agent so as to form an integrally foamed article that includes an unfoamed polymer layer comprising the second thermoplastic composition, the unfoamed polymer layer covering a thermoplastic foam having a porous foam structure that compositionally comprises the first thermoplastic composition. For example, the step of injecting the second thermoplastic composition can include injecting a molten second thermoplastic composition that is free or substantially free of a physical or chemical foaming agent, and the step of injecting the first thermoplastic composition can include injecting a single-phase solution of the first thermoplastic composition and a supercritical fluid. In this way, the second thermoplastic composition can be used to form a decorative or protective layer over the thermoplastic foam. One advantage of the method is that the level of detail of the unfoamed polymer layer can be greater because the unfoamed material will retain a greater level of mold detail than the foamed layer. Another advantage of the method is that the second thermoplastic composition can have different physical properties or coloring or both physical properties and coloring compared to the first thermoplastic composition, or the second thermoplastic composition and the first thermoplastic composition can be structurally different as described herein. For example, compared to the thermoplastic foam comprising the first thermoplastic composition, the second thermoplastic composition can have a greater durometer hardness, or a greater level of abrasion resistance, or a greater coefficient of friction so as to provide a greater level of adhesion friction. In another example, compared to the first thermoplastic composition, the second thermoplastic composition can comprise a greater concentration of pigment or dye or both. For example, the second thermoplastic composition can comprise greater than 3 weight percent, or greater than 4 weight percent, or greater than 5 weight percent, or greater than 6 weight percent or greater than 10 weight percent of pigment, while the first thermoplastic composition can be free or substantially free of pigment. This can reduce the total amount of pigment used to impart color to the entire part without including pigment in both the first thermoplastic composition and the second thermoplastic composition, which increases the recyclability of the entire part.

[0141] Optionally or alternatively, a second component comprising a second thermoplastic composition may be disposed on an outer surface of a first component comprising a first thermoplastic composition during a compression molding step or during a vacuum forming step. For example, the first component may be manufactured such as by injection molding, and thereafter the foam component may be compression molded or vacuum formed (optionally with heating) in a mold comprising the second component such that the first component is bonded to the surface of the second component during the compression molding or vacuum forming process. As described above, compared to the thermoplastic foam comprising the first thermoplastic composition, the second thermoplastic composition may have a greater durometer hardness, or a greater level of abrasion resistance, or a greater coefficient of friction to provide a greater level of attachment friction. The second thermoplastic composition and the first thermoplastic composition may be structurally different. In another example, compared to the first thermoplastic composition, the second thermoplastic composition may comprise a greater concentration of pigment or dye or both.

[0142] The second component may be provided to an injection mold or a compression mold as a pre-formed component, e.g., the second component. For example, the second component, such as a film, may be inserted into the injection mold and held in place against the target surface of the mold via a vacuum port, an electrostatic charge, or other means. Before or after the second component is inserted into the mold, the second component may conform to the target surface of the mold, e.g., with the application of heat or vacuum. Then, the first thermoplastic composition for the first component, i.e., the disclosed thermoplastic copolyester composition, may be injected into the mold comprising the film and foamed as described herein. As a result, the second component becomes an integral part of the molded component.

[0143] Optionally or alternatively, the second component may be disposed on the foam component after the foam component has been formed. According to some of the disclosed methods, the second component is provided separately from the first component and is thereafter operatively coupled such that the second component contacts a target portion of the outer surface of the first component. The second component may be coupled to the outer surface of the first component using any suitable method. In one aspect, the second component may be adhesively laminated to the first component. In another aspect, the second component may be coupled to the first component and thermally laminated to the outer surface of the first component. For example, heat may be applied to the outer surface of the first component, the surface of the second component, or both to soften or melt the heated surfaces, and the two surfaces may be joined when one or both surfaces are in a softened or molten state. In one aspect, the second component may be coupled to the first component using a flame lamination process.

[0144] The second component can be provided as a polymer layer. For example, a polymer coating can be formed by applying a liquid second thermoplastic composition to the foam component, such as by spraying, dip coating, roll coating, brush coating, or a combination thereof. The liquid polymer material can then be dried or cured upon contact with the first component.

[0145] The polymer layer can be disposed on at least one outer surface of the foam component. For example, in the case where the foam article is a midsole, the coating can be on all or part of the sidewall of the midsole, or on all or part of the ground-facing surface (bottom surface) of the midsole, or on all or part of the upper-facing surface (top surface) of the midsole, or any combination thereof. The polymer layer can be disposed on at least one surface that can be exposed to moisture during normal use of the finished article, such as a footwear article.

[0146] When disposed on the foam component, the polymer layer has an average thickness of from about 0.01 millimeters to about 3 millimeters, or from about 0.03 millimeters to about 2 millimeters, or from about 0.1 millimeters to about 1 millimeter.

[0147] According to various aspects, a foam component or article having the disclosed polymer layer has similar physical properties when compared to an equivalent foam component or article lacking the polymer layer.

[0148] In certain aspects, when the second thermoplastic composition is a film, the film can be a multilayer film. The multilayer film can include one or more layers of the second thermoplastic composition, and one or more layers of a different (i.e., third) thermoplastic composition. The third thermoplastic composition can be a material having a lower level of oxygen transmission or water vapor transmission or both, compared to the second thermoplastic composition. For example, the third thermoplastic composition can include a barrier polymer such as ethylene-vinyl alcohol (EVOH). An example of a multilayer film includes a first layer and a second layer, the first layer including the second thermoplastic composition comprising TPU, and the second layer including the third thermoplastic composition comprising EVOH. Alternatively, the third thermoplastic composition can be an adhesive layer comprising one or more adhesive polymers such as one or more hot melt adhesive polymers. Another example of a multilayer film includes a first layer including the second thermoplastic composition comprising a first TPU; and a second layer including the third thermoplastic composition comprising a second hot melt adhesive TPU having a lower melting temperature than the first TPU.

[0149] The polymer layer can be formed by applying a powdered second thermoplastic composition to the foam component, such as by spraying, powder coating, electrostatic coating, roll coating, or a combination thereof. In some aspects, an adhesive can be used to attach the powder to the midsole, and / or a coating can be applied over the powder to hold it in place on the foam component. After the powder is attached to the midsole, it can remain in powder form, or it can be processed to form a more uniform coating, such as by heating it to cause melting, by applying a solvent to cause dissolution, etc.

[0150] Alternatively, the polymer layer can be in the form of a separate element that is applied to all or a portion of the outer surface of the foam component when the midsole is incorporated into a footwear item. For example, the foam component can be a midsole component of a footwear item, and the polymer layer can be a welt or foxing tape applied around the perimeter of the midsole. The polymer layer can be an extension of an outsole that covers all or a portion of the bottom surface of the midsole and that wraps around and covers at least a portion of the sidewall of the midsole. The polymer layer can be the "shell" portion of a core-shell sole structure that covers both the bottom surface and the sidewall of the midsole and that is attached to the upper of the footwear item.

[0151] The foam articles and components can be foamed using any of the methods described above.

[0152] In various aspects, the disclosed method of manufacturing an article includes a first component and a second component, where the second component containing the second thermoplastic composition can be produced separately via injection molding with or without the addition of a compressed gas, supercritical fluid, or other foaming agent, and a foam article is produced on the second component.

[0153] In some cases, the disclosed method of manufacturing an article including a first component and a second component includes injection via overmolding. In some cases, overmolding can include sequentially injecting the polymer material for the first component, i.e., the disclosed thermoplastic copolyester, and the second thermoplastic composition in the same process, or where the second thermoplastic composition is produced in a separate process and then inserted into the mold, after which the foam article from the first thermoplastic composition is overmolded. The second component can be produced separately via injection molding with only enough compressed gas, supercritical fluid, or other foaming agent to achieve a density of 0.90 grams per cubic centimeter, 0.85 grams per cubic centimeter, or 0.80 grams per cubic centimeter.

[0154] In some cases, the disclosed method of manufacturing an article including a first component and a second component includes a step of corona treatment. That is, for example, the second component can be a film or an outsole or a welt that is pre-treated with plasma or corona treatment before receiving the overmolding assembly described herein.

[0155] In some cases, the disclosed method of manufacturing an article including a first component and a second component includes a step of pretreatment with a primer. That is, for example, the second component can be a film or an outsole or a welt that is pre-treated with a separate primer or a primer plus an adhesive before receiving the overmolding assembly described herein.

[0156] In some cases, the disclosed method of manufacturing an article including a first component and a second component includes a step of fused deposition 3D printing. That is, for example, the second component can be fused deposition 3D printed onto the first component. In such a case, the second thermoplastic composition can be extruded into a fused deposition 3D printing filament having a diameter of about 1.5 mm, about 1.75 mm, about 1.85 mm, about 2.85 mm, about 3.0 mm or other relevant diameters for deposition and attachment to the first component in such a way that the fused deposition 3D printing filament includes a layer in contact with the ground, a print-on outsole or other external features. Any grade commonly used in injection molding will generally be sufficient for the 3D printing filament used in fused deposition applications.

[0157] The resulting article including the first component and the second component can be characterized by a good bond strength between the first component and the second component. When determined using the interlayer adhesion test method described herein, the interlayer adhesion strength between the polymer layer and the foam component is greater than 2.5 kg force / cm or greater than 3.0 kg force / cm. Alternatively or additionally, the bond strength between the first component and the second component can be determined according to the Hand Pull Test described herein. The disclosed article or component can have a bond between the first component and the second component that has an average hand pull test result greater than or equal to 2.0, or greater than or equal to 2.5, or greater than or equal to 3.0, or greater than or equal to 3.5, or greater than or equal to 4.0, or greater than or equal to 4.5 when determined according to the hand pull test method described herein.

[0158] Each of the first component and / or the second component can be characterized by one or more properties. For example, the first component and / or the second component can have an Akron abrasion loss of less than 0.50 cubic centimeters as determined by the Akron abrasion test, optionally less than 0.40 cubic centimeters loss, less than 0.30 cubic centimeters loss, less than 0.20 cubic centimeters loss, or less than 0.10 cubic centimeters loss. The first component and / or the second component can have an Akron abrasion loss of about 0.05 cubic centimeters loss, about 0.10 cubic centimeters loss, about 0.15 cubic centimeters loss, about 0.20 cubic centimeters loss, about 0.25 cubic centimeters loss, about 0.30 cubic centimeters loss, about 0.35 cubic centimeters loss, about 0.40 cubic centimeters loss, about 0.45 cubic centimeters loss, or about 0.50 cubic centimeters loss as determined by the Akron abrasion test, any range of abrasion values covered by any of the foregoing values, or any combination of the foregoing abrasion values.

[0159] The first component and / or the second component can have an Akron abrasion loss of less than 500 milligrams as determined by the Akron abrasion test, optionally less than 400 milligrams loss, less than 300 milligrams loss, less than 200 milligrams loss, or less than 100 milligrams loss. The first component and / or the second component can have an Akron abrasion loss of about 50 milligrams loss, about 100 milligrams loss, about 150 milligrams loss, about 200 milligrams loss, about 250 milligrams loss, about 300 milligrams loss, about 350 milligrams loss, about 400 milligrams loss, about 450 milligrams loss, or about 500 milligrams loss as determined by the Akron abrasion test, any range of abrasion values covered by any of the foregoing values, or any combination of the foregoing abrasion values.

[0160] The first component and / or the second component can have a DIN abrasion loss of less than 0.30 cubic centimeters as determined by the DIN abrasion test, optionally less than 0.20 cubic centimeters loss, less than 0.10 cubic centimeters loss, less than 0.05 cubic centimeters loss, or less than 0.03 cubic centimeters loss. The first component and / or the second component can have a DIN abrasion loss of about 0.01 cubic centimeters loss, about 0.05 cubic centimeters loss, about 0.10 cubic centimeters loss, about 0.15 cubic centimeters loss, about 0.20 cubic centimeters loss, about 0.25 cubic centimeters loss, or about 0.30 cubic centimeters loss as determined by the DIN abrasion test, any range of abrasion values covered by any of the foregoing values, or any combination of the foregoing abrasion values.

[0161] The first component and / or the second component can have a DIN abrasion loss of less than 300 mg, optionally less than 250 mg, optionally less than 200 mg, optionally less than 150 mg, optionally less than 100 mg, optionally less than 80 mg, optionally less than 50 mg or optionally less than 30 mg as determined using the DIN abrasion test. The first component and / or the second component can have a DIN abrasion of about 10 mg, about 50 mg, about 100 mg, about 150 mg, about 200 mg, about 250 mg or about 300 mg as determined using the DIN abrasion test, any range of abrasion values covered by any of the foregoing values, or any combination of the foregoing abrasion values.

[0162] When the first component and / or the second component described herein are incorporated into an article, the product can have improved adhesion friction properties. In one aspect, the coefficient of friction of the polymer layer can be used to measure the adhesion friction properties.

[0163] The first component and / or the second component can have a dry dynamic coefficient of friction (COF) greater than 0.5, optionally greater than 0.7, greater than 0.8, greater than 0.9, greater than 1.0 on a dry surface (e.g., a smooth, flat or textured surface such as, for example, a wooden parquet court, concrete, asphalt, laminate, brick or tile) as determined using the dry shoe outsole coefficient of friction test. Using the dry shoe upper coefficient of friction test, the polymer layer can have a dry dynamic COF greater than 0.15, optionally greater than 0.2, greater than 0.25 or greater than 0.3.

[0164] The first component and / or the second component can have a wet dynamic COF greater than 0.25, optionally greater than 0.30, greater than 0.35, greater than 0.40 or greater than 0.50 as determined using the wet shoe outsole coefficient of friction test. Using the wet shoe upper coefficient of friction test, the polymer layer can have a wet dynamic COF greater than 0.15, optionally greater than 0.2, greater than 0.25 or greater than 0.3.

[0165] It can be expected that the dynamic coefficient of friction of the same dry and wet surfaces (e.g., smooth concrete or a playing field) is as close as possible. In one aspect, the difference between the dynamic coefficients of friction of the dry and wet surfaces is less than 15 percent. In another aspect, the difference between the dynamic coefficients of friction of the dry and wet surfaces is about 0 percent, about 1 percent, about 2 percent, about 3 percent, about 4 percent, about 5 percent, about 6 percent, about 7 percent, about 8 percent, about 9 percent, about 10 percent, about 11 percent, about 12 percent, about 13 percent, about 14 percent, or about 15 percent, any range of percentage values covered by any of the foregoing values, or any combination of the foregoing percentage values.

[0166] The first component and / or the second component can have a durometer Shore A hardness of less than 90 or less than 85 or less than 80. The polymer layer can have a durometer Shore A hardness of greater than 60 or greater than 65. The polymer layer can have a durometer Shore A hardness of from about 50 Shore A to about 90 Shore A, optionally from about 55 Shore A to about 85 Shore A, from about 60 Shore A to about 80 Shore A, or from about 60 Shore A to about 70 Shore A. The polymer layer can have a durometer Shore A hardness of about 50 Shore A, about 55 Shore A, about 60 Shore A, about 65 Shore A, about 70 Shore A, about 75 Shore A, about 80 Shore A, about 85 Shore A, or about 90 Shore A, any range of Shore A hardness values covered by any of the foregoing values, or any combination of the foregoing Shore A hardness values.

[0167] Thermoplastic copolyester composition

[0168] The thermoplastic composition disclosed herein (i.e., the polymer material of the first component for the foam portion and / or the second thermoplastic composition) can comprise or consist essentially of: one or more thermoplastic copolyesters, including one or more thermoplastic copolyester elastomers. In some aspects, the first thermoplastic composition for the first component comprises at least 90 weight percent or at least 95 weight percent, or at least 99 weight percent, of the thermoplastic copolyesters disclosed herein, based on the total weight of the first thermoplastic composition.

[0169] The thermoplastic copolyester composition comprises one or more thermoplastic copolyesters or consists essentially of one or more thermoplastic copolyesters. The disclosed thermoplastic copolyester composition may comprise at least about 90 weight percent, or at least about 95 weight percent, or at least about 99 weight percent of one or more thermoplastic copolyesters based on the total weight of the thermoplastic copolyester composition. In some aspects, the polymer component of the thermoplastic copolyester composition comprising all of the polymeric materials present in the thermoplastic copolyester composition consists essentially of one or more thermoplastic copolyesters. The thermoplastic copolyester may comprise chain units derived from one or more olefins and chain units derived from one or more ethylenically unsaturated acid groups.

[0170] The thermoplastic copolyester composition may have a melt flow index of from about 5 to about 40, or about 10 to about 20, or about 20 to about 30 as determined at 210 degrees Celsius using a 2.16 kilogram weight. Optionally or additionally, the thermoplastic copolyester composition may have a melt flow index of from about 5 to about 40, or about 10 to about 20, or about 20 to about 30 as determined at 220 degrees Celsius using a 2.16 kilogram weight. Optionally or additionally, the thermoplastic copolyester composition may have a melt flow index of from about 5 to about 40, or about 10 to about 20, or about 20 to about 30 as determined at 230 degrees Celsius using a 2.16 kilogram weight.

[0171] The thermoplastic copolyester may be a terpolymer derived from moieties of ethylene, acrylic acid, and methyl acrylate or butyl acrylate. In some aspects, the ratio of the total weight parts of acrylic acid in the thermoplastic copolyester to the total weight of the thermoplastic copolyester is from about 0.05 to about 0.6, about 0.1 to about 0.6, about 0.1 to about 0.5, about 0.15 to about 0.5, or about 0.2 to about 0.5.

[0172] The thermoplastic composition provided herein may comprise a thermoplastic copolyester comprising: (a) more than one first chain segment, each first chain segment derived from a dihydroxy-terminated polyglycol; (b) more than one second chain segment, each second chain segment derived from a diol; and (c) more than one third chain segment, each third chain segment derived from an aromatic dicarboxylic acid. In various aspects, the thermoplastic copolyester is a block copolymer. In some aspects, the thermoplastic copolyester is a multi-block copolymer. In further aspects, the thermoplastic copolyester is a random copolymer. In still further aspects, the thermoplastic copolyester is a condensation copolymer.

[0173] The thermoplastic copolyester can have a weight-average molecular weight of from about 50,000 Daltons to about 1,000,000 Daltons, from about 50,000 Daltons to about 500,000 Daltons, from about 75,000 Daltons to about 300,000 Daltons, from about 100,000 Daltons to about 250,000 Daltons, from about 100,000 Daltons to about 500,000 Daltons; or one or more values of the weight-average molecular weight within any of the foregoing ranges or a range of weight-average molecular weights that encompasses a subrange of any of the foregoing ranges.

[0174] The thermoplastic copolyester can have a ratio of the first segment to the third segment of from about 1:1 to about 1:5, based on the weight of each of the first and third segments, from about 1:1 to about 1:3, based on the weight of each of the first and third segments, from about 1:1 to about 1:2, based on the weight of each of the first and third segments, from about 1:1 to about 1:3, based on the weight of each of the first and third segments; or one or more values of the ratio of the first segment to the third segment within any of the foregoing ranges or a range of the ratio of the first segment to the third segment that encompasses a subrange of any of the foregoing ranges.

[0175] The thermoplastic copolyester can have a ratio of the second segment to the third segment of from about 1:1 to about 1:2, based on the weight of each of the first and third segments, from about 1:1 to about 1:1.52, based on the weight of each of the first and third segments; or one or more values of the ratio of the second segment to the third segment within any of the foregoing ranges or a range of the ratio of the second segment to the third segment that encompasses a subrange of any of the foregoing ranges.

[0176] The thermoplastic copolyester can have a first segment derived from a poly(alkylene oxide) diol having a weight-average molecular weight of from about 250 Daltons to about 6000 Daltons, from about 400 Daltons to about 6,000 Daltons, from about 350 Daltons to about 5,000 Daltons, from about 500 Daltons to about 3,000 Daltons, from about 2,000 Daltons to about 3,000 Daltons; or one or more values of the weight-average molecular weight within any of the foregoing ranges or a range of weight-average molecular weights that encompasses a subrange of any of the foregoing ranges.

[0177] The thermoplastic copolyester can have a first segment derived from a poly(alkylene oxide) diol such as poly(ethylene ether) diol; poly(propylene ether) diol; poly(tetramethylene ether) diol; poly(pentamethylene ether) diol; poly(hexamethylene ether) diol; poly(heptamethylene ether) diol; poly(octamethylene ether) diol; poly(nonamethylene ether) diol; poly(decamethylene ether) diol; or a mixture thereof. In still further aspects, the thermoplastic copolyester can have a first segment derived from a poly(alkylene oxide) diol such as poly(ethylene ether) diol; poly(propylene ether) diol; poly(tetramethylene ether) diol; poly(pentamethylene ether) diol; poly(hexamethylene ether) diol. In yet further aspects, the thermoplastic copolyester can have a first segment derived from poly(tetramethylene ether) diol.

[0178] The thermoplastic copolyester can have a second segment derived from a diol having a molecular weight of less than about 250. The diol from which the second segment is derived can be a C2-C8 diol. In still further aspects, the second segment can be derived from ethylene glycol; propylene glycol; butylene glycol; pentylene glycol; 2-methylpropylene glycol; 2,2-dimethylpropylene glycol; hexylene glycol; 1,2-dihydroxycyclohexane; 1,3-dihydroxycyclohexane; 1,4-dihydroxycyclohexane; and mixtures thereof. In yet further aspects, the second segment can be derived from 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, and mixtures thereof. In even further aspects, the second segment can be derived from 1,2-ethylene glycol. In still further aspects, the second segment can be derived from 1,4-butylene glycol.

[0179] The thermoplastic copolyester can have a third segment derived from an aromatic C5-C16 dicarboxylic acid. The aromatic C5-C16 dicarboxylic acid can have a molecular weight of less than about 300 daltons, from about 120 daltons to about 200 daltons; or a molecular weight of one or more values within any of the foregoing ranges or a molecular weight range encompassing any of the foregoing ranges and subranges. In some cases, the aromatic C5-C16 dicarboxylic acid is terephthalic acid, phthalic acid, isophthalic acid, or a derivative thereof. In still further aspects, the aromatic C5-C16 dicarboxylic acid is a diester derivative of terephthalic acid, phthalic acid, or isophthalic acid. In yet further aspects, the aromatic C5-C16 dicarboxylic acid is terephthalic acid or a dimethyl ester derivative thereof.

[0180] The thermoplastic copolyester can comprise: (a) more than one first copolyester unit, each of the more than one first copolyester units comprising a first segment derived from a dihydroxy-terminated polyglycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0181]

[0182] wherein R1 is the group remaining after removing the terminal hydroxyl groups from the poly(alkylene oxide) diol of the first segment, wherein the poly(alkylene oxide) diol of the first segment is a poly(alkylene oxide) diol having a number average molecular weight of from about 400 to about 6000; and wherein R2 is the group remaining after removing the carboxyl groups from the aromatic dicarboxylic acid of the third segment; and (b) more than one second copolyester unit, each second copolyester unit of the more than one second copolyester unit comprising a second segment derived from a diol and a third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0183]

[0184] wherein R3 is the group remaining after removing the hydroxyl groups from the diol of the second segment derived from a diol, wherein the diol is a diol having a molecular weight of less than about 250; and wherein R2 is the group remaining after removing the carboxyl groups from the aromatic dicarboxylic acid of the third segment.

[0185] The thermoplastic copolyester can comprise more than one first copolyester unit having a structure represented by Formula 3:

[0186]

[0187] wherein R is H or methyl; wherein y is an integer having a value from 1 to 10; wherein z is an integer having a value from 2 to 60; and wherein the weight average molecular weight of each first copolyester unit of the more than one first copolyester unit is from about 300 daltons to about 7,000 daltons. In some aspects, in the foregoing formula, y can be an integer having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range of the foregoing integer values. In some aspects, in the foregoing formula, z is an integer having a value from 5 to 60; having a value from 5 to 50; having a value from 5 to 40; having a value from 4 to 30; having a value from 4 to 20; having a value from 2 to 10; or z can be any set or range of the foregoing integer values. In some aspects, R is hydrogen. In still further aspects, R is methyl. In some cases, R is hydrogen and y is an integer having a value of 1, 2, or 3. Alternatively, in other cases, R is methyl and y is an integer having a value of 1.

[0188] The thermoplastic copolyester can comprise more than one first copolyester unit having a structure represented by Formula 4:

[0189]

[0190] where z is an integer having a value from 2 to 60; and where the weight average molecular weight of each of the more than one first copolyester units is from about 300 Daltons to about 7,000 Daltons. In some aspects, in the foregoing formula, y can be an integer having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range of the foregoing integer values. In some aspects, in the foregoing formula, z is an integer having a value from 5 to 60; an integer having a value from 5 to 50; an integer having a value from 5 to 40; an integer having a value from 4 to 30; an integer having a value from 4 to 20; an integer having a value from 2 to 10; or z can be any integer value or set of integer values within the foregoing range or values, or any range of integer values that encompasses a subrange of the foregoing integer values.

[0191] The thermoplastic copolyester can comprise more than one first copolyester unit having a weight average molecular weight from about 400 Daltons to about 6,000 Daltons; about 400 Daltons to about 5,000 Daltons; about 400 Daltons to about 4,000 Daltons; about 400 Daltons to about 3,000 Daltons; about 500 Daltons to about 6,000 Daltons; about 500 Daltons to about 5,000 Daltons; about 500 Daltons to about 4,000 Daltons; about 500 Daltons to about 3,000 Daltons; about 600 Daltons to about 6,000 Daltons; about 600 Daltons to about 5,000 Daltons; about 600 Daltons to about 4,000 Daltons; about 600 Daltons to about 3,000 Daltons; about 2,000 Daltons to about 3,000 Daltons; or one or more values of a weight average molecular weight within any of the foregoing ranges or a range of weight average molecular weights that encompasses a subrange of any of the foregoing ranges.

[0192] The thermoplastic copolyester can comprise more than one second copolyester unit, each of the more than one second copolyester units having a structure represented by Formula 5:

[0193]

[0194] where x is an integer having a value from 1 to 20; where the foam article has a porous closed-cell or open-cell foam structure. In some aspects, in the foregoing formula, x is an integer having a value from 2 to 18; 2 to 17; 2 to 16; 2 to 15; 2 to 14; 2 to 13; 2 to 12; 2 to 11; 2 to 10; 2 to 9; 2 to 8; 2 to 7; 2 to 6; 2 to 5; 2 to 4; or x can be any integer value or set of integer values within the foregoing range or values, or any range of integer values that encompasses a subrange of the foregoing integer values. In additional aspects, x is an integer having a value of 2, 3, or 4.

[0195] The thermoplastic copolyester may comprise more than one second copolyester unit, each of the more than one second copolyester units having a structure represented by Formula 6:

[0196]

[0197] The thermoplastic copolyester may comprise more than one first copolyester unit in a weight percentage range based on the total weight of the thermoplastic copolyester, such that the weight percentage range is from about 30 weight percent to about 80 weight percent; from about 40 weight percent to about 80 weight percent; from about 50 weight percent to about 80 weight percent; from about 30 weight percent to about 70 weight percent; from about 40 weight percent to about 70 weight percent; from about 50 weight percent to about 70 weight percent; from about 40 weight percent to about 65 weight percent; from about 45 weight percent to about 65 weight percent; from about 50 weight percent to about 65 weight percent; from about 55 weight percent to about 65 weight percent; from about 40 weight percent to about 60 weight percent; from about 45 weight percent to about 60 weight percent; from about 50 weight percent to about 60 weight percent; from about 55 weight percent to about 60 weight percent; or any weight percentage value or set of weight percentage values within any of the foregoing weight percentage ranges, or any weight percentage value range that encompasses a subset of any of the foregoing ranges.

[0198] In some aspects, when in solid form, the thermoplastic copolyester may include phase-separated domains. For example, more than one first segment derived from a dihydroxy-terminated polyglycol may phase-separate into domains predominantly comprising the first segment. Additionally, more than one second segment derived from a diol may phase-separate into domains predominantly comprising the second segment. In other aspects, the thermoplastic copolyester may include: phase-separated domains predominantly comprising more than one first copolyester unit, each of the more than one first copolyester units including a first segment derived from a dihydroxy-terminated polyglycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0199]

[0200] wherein R1 is the group remaining after removing the terminal hydroxyl groups from the poly(alkylene oxide) diol of the first segment, wherein the poly(alkylene oxide) diol of the first segment is a poly(alkylene oxide) diol having a number average molecular weight of from about 400 to about 6000, and wherein R2 is the group remaining after removing the carboxyl groups from the aromatic dicarboxylic acid of the third segment; and other phase-separated domains mainly comprising more than one second copolyester unit, each of the more than one second copolyester units comprising a second segment derived from a diol and a third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0201]

[0202] wherein R3 is the group remaining after removing the hydroxyl groups from the diol of the second segment derived from a diol, wherein the diol is a diol having a molecular weight of less than about 250; and wherein R2 is the group remaining after removing the carboxyl groups from the aromatic dicarboxylic acid of the third segment.

[0203] In other aspects, when in solid form, the thermoplastic copolyester can include phase-separated domains mainly comprising more than one first copolyester unit, each of the more than one first copolyester units having a structure represented by Formula 3:

[0204]

[0205] wherein R is H or methyl; wherein y is an integer having a value from 1 to 10; wherein z is an integer having a value from 2 to 60; and wherein the weight average molecular weight of each of the more than one first copolyester units is from about 300 daltons to about 7,000 daltons. In some aspects, in the foregoing formula, y can be an integer having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range of the foregoing integer values. In some aspects, in the foregoing formula, z is an integer having a value from 5 to 60; an integer having a value from 5 to 50; an integer having a value from 5 to 40; an integer having a value from 4 to 30; an integer having a value from 4 to 20; an integer having a value from 2 to 10; or z can be any set or range of the foregoing integer values. In some aspects, R is hydrogen. In still further aspects, R is methyl. In some cases, R is hydrogen and y is an integer having a value of 1, 2, or 3. Alternatively, in other cases, R is methyl and y is an integer having a value of 1.

[0206] In other aspects, when in solid form, the thermoplastic copolyester can include phase-separated domains that primarily comprise more than one first copolyester unit, each of the more than one first copolyester units having a structure represented by Formula 4:

[0207]

[0208] where z is an integer having a value from 2 to 60; and where the weight-average molecular weight of each of the more than one first copolyester units is from about 300 Daltons to about 7,000 Daltons. In some aspects, in the foregoing formula, y can be an integer having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any set or range of the foregoing integer values. In some aspects, in the foregoing formula, z is an integer having a value from 5 to 60; an integer having a value from 5 to 50; an integer having a value from 5 to 40; an integer having a value from 4 to 30; an integer having a value from 4 to 20; an integer having a value from 2 to 10; or z can be any integer value or set of integer values within the foregoing ranges or values, or any range of integer values that encompasses a sub-range of the foregoing integer value ranges.

[0209] When in solid form, the thermoplastic copolyester can include phase-separated domains that primarily comprise more than one first copolyester unit having a weight-average molecular weight from about 400 Daltons to about 6,000 Daltons; about 400 Daltons to about 5,000 Daltons; about 400 Daltons to about 4,000 Daltons; about 400 Daltons to about 3,000 Daltons; about 500 Daltons to about 6,000 Daltons; about 500 Daltons to about 5,000 Daltons; about 500 Daltons to about 4,000 Daltons; about 500 Daltons to about 3,000 Daltons; about 600 Daltons to about 6,000 Daltons; about 600 Daltons to about 5,000 Daltons; about 600 Daltons to about 4,000 Daltons; about 600 Daltons to about 3,000 Daltons; about 2,000 Daltons to about 3,000 Daltons; or one or more values of the weight-average molecular weight within any of the foregoing ranges or a range of weight-average molecular weights that encompasses a sub-range of any of the foregoing ranges.

[0210] In other aspects, when in solid form, the thermoplastic copolyester can include phase-separated domains that comprise more than one second copolyester unit, each of the more than one second copolyester units having a structure represented by Formula 5:

[0211]

[0212] where x is an integer having a value from 1 to 20; wherein the foam article has a porous closed-cell or open-cell foam structure. In some aspects, in the foregoing formula, x is an integer having a value from 2 to 18; 2 to 17; 2 to 16; 2 to 15; 2 to 14; 2 to 13; 2 to 12; 2 to 11; 2 to 10; 2 to 9; 2 to 8; 2 to 7; 2 to 6; 2 to 5; 2 to 4; or x can be any integer value or set of integer values within the foregoing ranges or values, or any range of integer values that encompasses a sub-range of the foregoing integer value ranges. In additional aspects, x is an integer having a value of 2, 3, or 4.

[0213] In other aspects, when in solid form, the thermoplastic copolyester can include phase-separated domains that contain more than one second copolyester unit, each of the more than one second copolyester units having a structure represented by Formula 6:

[0214]

[0215] When in solid form, the thermoplastic copolyester can include phase-separated domains that contain more than one first copolyester unit in a weight percentage range based on the total weight of the thermoplastic copolyester, such that the weight percentage range is from about 30 weight percent to about 80 weight percent; about 40 weight percent to about 80 weight percent; about 50 weight percent to about 80 weight percent; about 30 weight percent to about 70 weight percent; about 40 weight percent to about 70 weight percent; about 50 weight percent to about 70 weight percent; about 40 weight percent to about 65 weight percent; about 45 weight percent to about 65 weight percent; about 50 weight percent to about 65 weight percent; about 55 weight percent to about 65 weight percent; about 40 weight percent to about 60 weight percent; about 45 weight percent to about 60 weight percent; about 50 weight percent to about 60 weight percent; about 55 weight percent to about 60 weight percent; or any weight percentage value or set of weight percentage values within any of the foregoing weight percentage ranges, or any range of weight percentage values that encompasses a subset of any of the foregoing ranges.

[0216] The disclosed thermoplastic copolyester compositions, the polymeric components of the compositions, or the thermoplastic copolyesters alone in pure form can be characterized by one or more properties. In some aspects, when determined using the cyclic tensile test method described herein, the thermoplastic copolyester composition or polymeric component or polymer has a maximum load of from about 10 Newtons to about 100 Newtons, or from about 15 Newtons to about 50 Newtons, or from about 20 Newtons to about 40 Newtons; or any load value or set of load values within any of the foregoing load value ranges, or any range of load values that encompasses a subset of any of the foregoing ranges.

[0217] The tensile strength of the thermoplastic copolyester composition or a component of the thermoplastic copolyester composition or a thermoplastic copolyester copolymer in pure form is another important physical property. The thermoplastic copolyester composition or component or copolymer can have a tensile strength of from 5 kilograms per square centimeter to 25 kilograms per square centimeter, or from 10 kilograms per square centimeter to 23 kilograms per square centimeter, or from 15 kilograms per square centimeter to 22 kilograms per square centimeter when determined using the cyclic tensile test method described herein; or any tensile strength value or set of tensile strength values ​​within any of the foregoing ranges of tensile strength values, or any range of tensile strength values ​​covering a subset of any of the foregoing ranges.

[0218] The thermoplastic copolyester composition or a polymeric component of the thermoplastic copolyester composition or a thermoplastic copolyester copolymer in pure form can have a tensile modulus of from about 2 MPa to about 20 MPa, or from about 5 MPa to about 15 MPa, when determined using the cyclic tensile test method described herein; or any tensile modulus value or set of tensile modulus values ​​within any of the foregoing ranges of tensile modulus values, or any range of tensile modulus values ​​encompassing a subset of any of the foregoing ranges.

[0219] Exemplary, but not limiting, thermoplastic polyester elastomers that can be used in the disclosed methods, foams, and articles include thermoplastic copolyesters, including "HYTREL" 3078, "HYTREL" 4068, and "HYTREL" 4556 (DuPont, Wilmington, Delaware, USA); "PELPRENE" P30B, P40B, and P40H (Toyobo USA Inc., New York, New York, USA); "TRIEL" 5300, "TRIEL" 5400, and blends thereof (Samyang Corporation, Korea); "KEYFLEX" BT1028D, BT1033D, BT1035D, BT1040D, BT1045D, and BT1047D (LG Chem, Korea); and "KOPEL" KP3340, KP3346, KP3347, KP3942 (Kolon Plastics, Inc., Korea).

[0220] The disclosed thermoplastic copolyester composition may further comprise one or more ionomers, such as any of the “SURLYN” polymers (DuPont, Wilmington, Delaware, USA). The thermoplastic copolyester foam described herein can be manufactured by a process / method comprising: receiving the composition described herein, and physically foaming the composition to form a thermoplastic copolyester foam having a density of about 0.7 grams per cubic centimeter or less, or 0.5 grams per cubic centimeter or less, or 0.4 grams per cubic centimeter or less, or 0.3 grams per cubic centimeter or less. The process may include blowing the composition to produce an article or component comprising the thermoplastic copolyester foam. In some instances, the process for forming the thermoplastic copolyester foam includes injection molding in a mold a mixture comprising the composition described herein and a supercritical fluid (e.g., supercritical carbon dioxide or supercritical nitrogen), and removing the thermoplastic copolyester foam from the mold.

[0221] The disclosed thermoplastic copolyester composition may further comprise one or more thermoplastic polyurethanes, including thermoplastic polyurethane elastomers, such as “FORTIMO” (Mitsui Chemicals, Inc., Tokyo, Japan); “TEXIN” (Covestro LLC, Pittsburgh, Pennsylvania, USA); and “BOUNCELL-X” (Lubrizol Advanced Materials, Inc., Brecksville, Ohio, USA).

[0222] The disclosed thermoplastic copolyester composition may further comprise one or more olefin polymers. Olefin polymers may include ethylene-based copolymers, propylene-based copolymers, and butene-based copolymers. In some aspects, the olefin polymer is an ethylene-based copolymer, such as a styrene-ethylene / butene-styrene (SEBS) copolymer; an ethylene-propylene-diene monomer (EPDM) copolymer; an ethylene-vinyl acetate (EVA) copolymer; an ethylene alkyl acrylate (EAA) copolymer; an ethylene alkyl methacrylate (EAMA) copolymer; any copolymer thereof, and any blend thereof. In some aspects, the ratio V of the total weight fraction of the olefin polymer present in the composition to the total weight fraction of the thermoplastic copolyester in the composition is from about 0.0 to about 0.6, from about 0.0 to about 0.4, from about 0.01 to about 0.4, or from about 0.01 to about 0.6, or from about 0.1 to about 0.4.

[0223] The disclosed thermoplastic copolyester composition may further comprise an ethylene-vinyl acetate (EVA) copolymer. The ethylene-vinyl acetate (EVA) copolymer may have a vinyl acetate content in a range based on the total weight of the copolymer, such as from about 50 percent to about 90 percent, from about 50 percent to about 80 percent, from about 5 percent to about 50 percent, from about 10 percent to about 45 percent, from about 10 percent to about 30 percent, from about 30 percent to about 45 percent, or from about 20 percent to about 35 percent.

[0224] The disclosed thermoplastic copolyester composition may further comprise an ethylene-vinyl alcohol (EVOH) copolymer. The EVOH copolymer may have a vinyl alcohol content in a range based on the total weight of the copolymer, such as from about 50 percent to about 90 percent, from about 50 percent to about 80 percent, from about 5 percent to about 50 percent, from about 10 percent to about 45 percent, from about 10 percent to about 30 percent, from about 30 percent to about 45 percent, or from about 20 percent to about 35 percent.

[0225] Second thermoplastic composition

[0226] Having described foams and methods of forming foams, we turn to the second thermoplastic composition. According to various aspects, the disclosed foam article has a second thermoplastic composition disposed on at least one outer surface of the foam. For example, the second thermoplastic composition may be a polymer layer or a polymer coating or a polymer film. In some aspects, the second thermoplastic composition has a higher abrasion resistance than the foam component. In another aspect, the second thermoplastic composition has a higher coefficient of friction than the first thermoplastic composition of the foam component. In another aspect, the second thermoplastic composition has a higher durometer hardness than the foam component. In other aspects, the second thermoplastic composition has a higher specific gravity than the foam component. In other aspects, the second thermoplastic composition comprises a higher concentration of non-polymeric components, such as fillers and pigments, than the first thermoplastic composition of the foam component. In yet another aspect, the second thermoplastic composition has two or more of higher abrasion resistance, higher coefficient of friction, higher durometer hardness, higher specific gravity, and higher concentration of non-polymeric components compared to the foam component or the first thermoplastic composition of the foam component. In one aspect, the second thermoplastic composition is structurally different from the first thermoplastic composition, as described below. Alternatively, the second thermoplastic composition is structurally the same as the first thermoplastic composition. The second thermoplastic composition may be integral with the foam component or may be a separate component operably coupled to the foam component, as described herein.

[0227] In one aspect, the first thermoplastic composition may be the same structurally as the second thermoplastic composition or different structurally from the second thermoplastic composition. Here, the first thermoplastic composition has one or more structural chemical features that are the same as or different from those of the second thermoplastic composition. In one aspect, the structural difference is based on the chemical structure of the first thermoplastic elastomer being different from the chemical structures of all the second thermoplastic elastomers present in the second thermoplastic composition (e.g., different positions or stereochemical groups). In another aspect, the structural difference is based on the number-average molecular weight of the first thermoplastic elastomer being different from the number-average molecular weight of the second thermoplastic elastomer, where the first thermoplastic elastomer and the second thermoplastic elastomer have the same chemical structure. In another aspect, the first structural difference is based on the concentration of the first thermoplastic elastomer in the first thermoplastic composition being different from the concentration of the second thermoplastic elastomer in the second thermoplastic composition, where the first thermoplastic elastomer and the second thermoplastic elastomer have the same chemical structure and the same number-average molecular weight. In yet another aspect, the structural difference is based on any combination of different chemical structures, number-average molecular weights, and concentrations. For example, based on the first thermoplastic composition and the second thermoplastic composition comprising thermoplastic elastomers with different chemical structures, the first thermoplastic composition comprising a thermoplastic copolyester elastomer is structurally different from the second thermoplastic composition comprising a thermoplastic styrene copolymer elastomer or a thermoplastic polyurethane elastomer. In another example, based on the number-average molecular weight, the first thermoplastic composition comprising a first 50,000 Dalton thermoplastic copolyester elastomer is structurally different from the second thermoplastic composition comprising a second 100,000 Dalton thermoplastic copolyester elastomer having the same chemical structure as the first 50,000 Dalton thermoplastic copolyester. In another example, due to the presence of the 100,000 Dalton thermoplastic composition in the second thermoplastic composition, the second thermoplastic composition comprising a second 100,000 Dalton thermoplastic copolyester elastomer having the same chemical structure as the first 50,000 Dalton thermoplastic copolyester and further comprising the first 50,000 Dalton thermoplastic copolyester will still be structurally different from the first thermoplastic composition. In yet another example, the first thermoplastic elastomer comprising 5 weight percent of the first 50,000 Dalton thermoplastic copolyester is structurally different from the second thermoplastic elastomer comprising 95 weight percent of the first 50,000 Dalton thermoplastic copolyester.

[0228] In some aspects, the second thermoplastic composition comprises at least 90 weight percent, or at least 95 weight percent, or at least 99 weight percent of the thermoplastic copolyester as disclosed herein, based on the total weight of the second thermoplastic composition. In some cases, the polymer component of the second thermoplastic composition consists essentially of only one or more of the disclosed thermoplastic copolyesters.

[0229] The second thermoplastic composition can be disposed on at least one outer surface of the foam component. For example, in the case where the foam article is a midsole, the second thermoplastic composition can be on all or part of the ground-facing surface (bottom surface) of the midsole, or on all or part of the side surface of the midsole, or any combination thereof.

[0230] In some aspects, the disclosed method includes forming the second thermoplastic composition integrally with the first component. For example, the polymeric materials for the first component, such as the disclosed first thermoplastic copolyester composition and the second thermoplastic composition, can be sequentially added to the mold during an injection molding process to provide an integral component having a foam portion and a second portion comprising the second thermoplastic composition. In this aspect, a mold having a first mold portion with a mold surface can be provided. The second thermoplastic composition can be added to the mold to form a layer of the second thermoplastic composition on at least a portion of the mold surface. The first thermoplastic composition for the first component, such as the disclosed thermoplastic copolyester composition, can be injected into the mold including the second thermoplastic composition and foamed upon contact with the second thermoplastic composition. The resulting injection molded component is an integral component in which the second thermoplastic composition is bonded to the foam component. Alternatively or additionally, the second thermoplastic composition can be disposed on the outer surface of the foam component during a compression molding step. For example, the foam component can be manufactured such as by injection molding, and thereafter the foam component can be compression molded in a mold including the second thermoplastic composition, and the second thermoplastic composition is bonded to the surface of the foam during the compression molding process.

[0231] The second thermoplastic composition can be provided to an injection mold or a compression mold as a discrete layer or film. For example, a layer or film forming the second thermoplastic composition can be inserted into the injection mold and held in place against the target surface of the mold via a vacuum port, an electrostatic charge, or other means. The layer or film can conform to the target surface of the mold with the application of heat or vacuum, for example, before or after the layer or film is inserted into the mold. Then, the first thermoplastic composition can be injected into the mold including the film and foamed as described herein. As a result, the second thermoplastic composition of the layer or film becomes an integral part of the molded component.

[0232] Optionally or alternatively, the second thermoplastic composition can be disposed on the foam component after the foam component has been formed. According to some of the disclosed methods, the second thermoplastic composition is provided as a layer or film provided separately from the foam component and is thereafter operatively coupled such that the second thermoplastic composition forms a layer on a target portion of the outer surface of the foam. The second thermoplastic composition can be coupled to the outer surface of the foam component or article using any suitable method. In one aspect, the second thermoplastic composition can be adhesively laminated to the foam component. In another aspect, the second thermoplastic composition can be coupled to the foam component, such as by thermally laminating to the outer surface of the foam. For example, heat can be applied to the outer surface of the foam component, the surface of the second thermoplastic composition, or both, to soften or melt the respective heated surfaces, and when one or both surfaces are in a softened or molten state, the two surfaces can be joined. In one aspect, the second thermoplastic composition can be coupled to the foam component using a flame lamination process.

[0233] The second thermoplastic composition can be provided as a polymer coating. For example, the polymer coating can be formed by applying a liquid polymer material to the foam component, such as by spraying, dip coating, roll coating, brush coating, or a combination thereof. The liquid second thermoplastic composition can then be dried or cured when in contact with the midsole.

[0234] The polymer coating can be formed by applying a powdered second thermoplastic composition to the foam component, such as by spraying, powder coating, electrostatic coating, roll coating, or a combination thereof. In some aspects, an adhesive can be used to attach the powder to the midsole, and / or a coating can be applied over the powder to hold it in place on the foam component. After the powder is attached to the midsole, it can remain in the form of the powder, or it can be processed to form a more uniform coating, such as by heating it to melt it, by applying a solvent to dissolve it, etc.

[0235] Optionally, the second thermoplastic composition can be in the form of a separate element that is applied to all or a portion of the outer surface of the foam component when the midsole is incorporated into a footwear article. For example, the foam component can be a midsole component of a footwear article, and the second thermoplastic composition can be a welt or a bottom welt applied around the perimeter of the midsole. The second thermoplastic composition can be an extension of an outsole that covers all or a portion of the bottom surface of the midsole and that wraps around and covers at least a portion of the sidewall of the midsole. The second thermoplastic composition can be the "shell" portion of a core-shell sole structure that covers both the bottom surface and the sidewall of the midsole and that is attached to the upper of the footwear article.

[0236] The resulting article comprising the first component and the second thermoplastic composition can be characterized by a good bond strength between the second thermoplastic composition and the foam component. When determined using the interlayer adhesion test method described herein, the interlayer adhesion strength between the second thermoplastic composition and the foam component is greater than 2.5 kg force / cm or greater than 3.0 kg force / cm.

[0237] Properties of the Second Thermoplastic Composition

[0238] The disclosed second thermoplastic composition can be characterized by one or more properties.

[0239] In one aspect, a polymer layer comprising the second thermoplastic composition forms a waterproof barrier over at least a portion of the outer surface of the first foam component. Here, the second thermoplastic composition of the polymer layer reduces or prevents water absorption by the open-cell foam microstructure of the first foam component.

[0240] In one aspect, the foams and articles having a polymer layer described herein exhibit beneficial water absorption capabilities. In other words, a foam article having a polymer layer as disclosed herein does not absorb any water or a significant amount of water during use of the article. For example, when determined using the water absorption test method described herein, a foam article or foam component having a polymer layer has a water absorption of less than 5 percent, or less than 4 percent, or less than 3 percent, or less than 2 percent at 2 hours. In contrast, when determined using the water absorption test method described herein, an equivalent foam article or foam component lacking a polymer layer can have a water absorption of greater than 2 percent, or from about 2 percent to about 30 percent, or from about 3 percent to about 25 percent, or from about 5 percent to about 20 percent at 2 hours. When compared to an equivalent foam component or article lacking a polymer layer, the disclosed foam component or article having the disclosed polymer layer can have reduced water absorption. For example, when determined using the water absorption test method described herein, the disclosed foam component or article can have a water absorption at 2 hours that is about 20 percent less, or about 30 percent less, or about 50 percent less than the water absorption of an equivalent foam component or article lacking a polymer layer at 5 minutes. When determined using the water absorption test method described herein, the disclosed foam component or article can have a water absorption at 5 minutes that is at least 2 percentage points less, or at least 3 percentage points less, or at least 4 percentage points less, or at least 5 percentage points less, or at least 6 percentage points less, or at least 7 percentage points less, or at least 8 percentage points less, or at least 9 percentage points less, or at least 10 percentage points less, or at least 11 percentage points less, or at least 12 percentage points less, or at least 13 percentage points less, or at least 14 percentage points less, or at least 15 percentage points less, or at least 20 percentage points less, or at least 25 percentage points less, or at least 30 percentage points less than the water absorption of an equivalent foam component or article lacking a polymer layer at 5 minutes.

[0241] In some aspects, when determined using the cyclic tensile test method described herein, the second thermoplastic composition or second thermoplastic elastomer has a maximum load of from about 10 Newtons to about 100 Newtons, or from about 15 Newtons to about 50 Newtons, or from about 20 Newtons to about 40 Newtons; or any load value or set of load values within any of the foregoing load value ranges, or any load value range that encompasses a subset of any of the foregoing ranges.

[0242] The tensile strength of the second thermoplastic composition or the second thermoplastic elastomer is another important physical property. When determined using the cyclic tensile test method described herein, the second thermoplastic composition or resin can have a tensile strength from 5 kilograms per square centimeter to 25 kilograms per square centimeter, or from 10 kilograms per square centimeter to 23 kilograms per square centimeter, or from 15 kilograms per square centimeter to 22 kilograms per square centimeter; or any tensile strength value or set of tensile strength values within any of the foregoing tensile strength value ranges, or any tensile strength value range that encompasses a subset of any of the foregoing ranges.

[0243] When determined using the cyclic tensile test method described herein, the second thermoplastic composition or the second thermoplastic elastomer can have a tensile modulus of about 2 megapascals to about 20 megapascals or from about 5 megapascals to about 15 megapascals; or any tensile modulus value or set of tensile modulus values within any of the foregoing tensile modulus value ranges, or any tensile modulus value range that encompasses a subset of any of the foregoing ranges.

[0244] The second thermoplastic composition can have an Akron abrasion loss of less than 0.50 cubic centimeters, optionally less than 0.40 cubic centimeters, less than 0.30 cubic centimeters, less than 0.20 cubic centimeters, or less than 0.10 cubic centimeters, as determined using the Akron abrasion test. The second thermoplastic composition can have an Akron abrasion loss of about 0.05 cubic centimeters, about 0.10 cubic centimeters, about 0.15 cubic centimeters, about 0.20 cubic centimeters, about 0.25 cubic centimeters, about 0.30 cubic centimeters, about 0.35 cubic centimeters, about 0.40 cubic centimeters, about 0.45 cubic centimeters, or about 0.50 cubic centimeters, as determined using the Akron abrasion test, any abrasion value range encompassed by any of the foregoing values, or any combination of the foregoing abrasion values.

[0245] The second thermoplastic composition can have an Akron abrasion loss of less than 500 milligrams, optionally less than 400 milligrams, less than 300 milligrams, less than 200 milligrams, or less than 100 milligrams, as determined using the Akron abrasion test. The second thermoplastic composition can have an Akron abrasion loss of about 50 milligrams, about 100 milligrams, about 150 milligrams, about 200 milligrams, about 250 milligrams, about 300 milligrams, about 350 milligrams, about 400 milligrams, about 450 milligrams, or about 500 milligrams, as determined using the Akron abrasion test, any abrasion value range encompassed by any of the foregoing values, or any combination of the foregoing abrasion values.

[0246] The second thermoplastic composition may have a DIN abrasion loss of less than 0.30 cm³, optionally less than 0.20 cm³, less than 0.10 cm³, less than 0.05 cm³, or less than 0.03 cm³ as determined using the DIN abrasion test. The second thermoplastic composition may have a DIN abrasion of about 0.01 cm³, about 0.05 cm³, about 0.10 cm³, about 0.15 cm³, about 0.20 cm³, about 0.25 cm³, or about 0.30 cm³ as determined using the DIN abrasion test, any range of abrasion values covered by any of the foregoing values, or any combination of the foregoing abrasion values.

[0247] The second thermoplastic composition may have a DIN abrasion loss of less than 300 mg, optionally less than 250 mg, optionally less than 200 mg, optionally less than 150 mg, optionally less than 100 mg, optionally less than 80 mg, optionally less than 50 mg, or optionally less than 30 mg as determined using the DIN abrasion test. The second thermoplastic composition may have a DIN abrasion of about 10 mg, about 50 mg, about 100 mg, about 150 mg, about 200 mg, about 250 mg, or about 300 mg as determined using the DIN abrasion test, any range of abrasion values covered by any of the foregoing values, or any combination of the foregoing abrasion values.

[0248] When the second thermoplastic composition described herein is incorporated into an article, the product has improved adhesion friction properties. In one aspect, the coefficient of friction of the second thermoplastic composition can be used to measure the adhesion friction properties.

[0249] The second thermoplastic composition may have a dry dynamic coefficient of friction (COF) greater than 0.5, optionally greater than 0.7, greater than 0.8, greater than 0.9, greater than 1.0 on a dry surface (e.g., a smooth, flat, or textured surface such as, for example, a wooden parquet court, concrete, asphalt, laminate, brick, or tile) as determined using the dry shoe outsole coefficient of friction test. Using the dry shoe upper coefficient of friction test, the second thermoplastic composition may have a dry dynamic COF greater than 0.15, optionally greater than 0.2, greater than 0.25, or greater than 0.3.

[0250] The second thermoplastic composition may have a wet dynamic COF greater than 0.25, optionally greater than 0.30, greater than 0.35, greater than 0.40, or greater than 0.50 as determined using the wet shoe outsole coefficient of friction test. Using the wet shoe upper coefficient of friction test, the second thermoplastic composition may have a wet dynamic COF greater than 0.15, optionally greater than 0.2, greater than 0.25, or greater than 0.3.

[0251] It can be expected that the dynamic friction coefficients of the same dry and wet surfaces (e.g., smooth concrete or a playing field) are as close as possible. In one aspect, the difference between the dynamic friction coefficients of the dry and wet surfaces is less than 15 percent. In another aspect, the difference between the dynamic friction coefficients of the dry and wet surfaces is about 0 percent, about 1 percent, about 2 percent, about 3 percent, about 4 percent, about 5 percent, about 6 percent, about 7 percent, about 8 percent, about 9 percent, about 10 percent, about 11 percent, about 12 percent, about 13 percent, about 14 percent, or about 15 percent, any percentage value range covered by any of the foregoing values, or any combination of the foregoing percentage values.

[0252] The second thermoplastic composition can have a melting temperature from about 100 degrees Celsius to about 210 degrees Celsius, optionally from about 110 degrees Celsius to about 195 degrees Celsius, from about 120 degrees Celsius to about 180 degrees Celsius, or from about 120 degrees Celsius to about 170 degrees Celsius. The melting temperature of the second thermoplastic composition can be within about 50 degrees Celsius, or about 40 degrees Celsius, or about 30 degrees Celsius, or about 20 degrees Celsius of the first thermoplastic composition.

[0253] The second thermoplastic composition can have a melt flow rate of at least 0.2 grams per 10 minutes, optionally at least 5 grams per 10 minutes, at least 10 grams per 10 minutes, at least 15 grams per 10 minutes, at least 20 grams per 10 minutes, at least 25 grams per 10 minutes, at least 30 grams per 10 minutes, at least 40 grams per 10 minutes, or at least 50 grams per 10 minutes as determined using ASTM D1238-13 at 160 degrees Celsius using a weight of 2.16 kg. The second thermoplastic composition can have a melt flow rate of at least 0.2 grams per 10 minutes, optionally at least 5 grams per 10 minutes, at least 10 grams per 10 minutes, at least 15 grams per 10 minutes, at least 20 grams per 10 minutes, at least 25 grams per 10 minutes, at least 30 grams per 10 minutes, at least 40 grams per 10 minutes, or at least 50 grams per 10 minutes as determined using ASTM D1238-13 at 200 degrees Celsius using a weight of 10 kg.

[0254] The second thermoplastic composition can have a melting temperature from about 100 degrees Celsius to about 210 degrees Celsius, optionally from about 110 degrees Celsius to about 195 degrees Celsius, from about 120 degrees Celsius to about 180 degrees Celsius, or from about 120 degrees Celsius to about 170 degrees Celsius.

[0255] The second thermoplastic composition may have a melt flow index of from about 5 to about 40, or from about 10 to about 20, or from about 20 to about 30 as determined at 210 degrees Celsius using a 2.16 kilogram weight. Optionally or additionally, the second thermoplastic composition may have a melt flow index of from about 5 to about 40, or from about 10 to about 20, or from about 20 to about 30 as determined at 220 degrees Celsius using a 2.16 kilogram weight. Optionally or additionally, the second thermoplastic composition may have a melt flow index of from about 5 to about 40, or from about 10 to about 20, or from about 20 to about 30 as determined at 230 degrees Celsius using a 2.16 kilogram weight.

[0256] The second thermoplastic composition may have a Shore A durometer hardness of less than 90 or less than 85 or less than 80. The second thermoplastic composition may have a Shore A durometer hardness of greater than 60 or greater than 65. The second thermoplastic composition may have a Shore A durometer hardness of from about 50 Shore A to about 90 Shore A, optionally from about 55 Shore A to about 85 Shore A, from about 60 Shore A to about 80 Shore A, or from about 60 Shore A to about 70 Shore A.

[0257] In the foamed article, the second thermoplastic composition may have a specific gravity of from about 0.8 to about 1.5, optionally from about 0.85 to about 1.30, or from about 0.88 to about 1.20. Optionally, in the foamed article, the second thermoplastic composition may be a porous foam having a specific gravity of from about 0.15 to about 0.60, or from about 0.15 to about 0.40, or from about 0.15 to about 0.25.

[0258] The second thermoplastic composition may have two or more of the first properties provided above, or optionally three or more, four or more, five or more, six or more, seven or more, or all ten of the first properties provided above.

[0259] In addition to the first properties, the second thermoplastic composition may have one or more second properties. The second thermoplastic composition may have a glass transition temperature of less than 50 degrees Celsius, optionally less than 30 degrees Celsius, less than 0 degrees Celsius, less than -10 degrees Celsius, or less than -20 degrees Celsius. The second thermoplastic composition may have a fracture stress greater than 7 megapascals, optionally greater than 8 megapascals, as determined using ASTM DE-412 at 25 degrees Celsius. The second thermoplastic composition may have a tensile stress at 300 percent modulus greater than 2 megapascals, optionally greater than 2.5 megapascals or greater than 3 megapascals, as determined using ASTM DE-412 at 25 degrees Celsius. The second thermoplastic composition may have an elongation at break greater than 450 percent, optionally greater than 500 percent or greater than 550 percent, as determined using ASTM DE-412 at 25 degrees Celsius. The second thermoplastic composition may have two or more of the second properties, or optionally three or more, or all four second properties.

[0260] According to various aspects, the disclosed foam article has a polymer layer disposed on at least one outer surface of the foam component. For example, the polymer layer can be a polymer coating or a polymer film. In some aspects, the polymer layer serves as a fluid barrier that controls or prevents water absorption of the foam article. The polymer layer can be integral with the foam component or can be a separate component operably coupled to the foam component, as described herein.

[0261] The polymer layer can be disposed on at least one outer surface of the foam component. For example, in the case where the foam article is a midsole, the coating can be on all or part of the sidewall of the midsole, or on all or part of the ground-facing surface (bottom surface) of the midsole, or on all or part of the upper-facing surface (top surface) of the midsole, or any combination thereof. The polymer layer can be disposed on at least one surface that can be exposed to moisture during normal use of the finished article, such as a footwear article.

[0262] When disposed on the foam component, the polymer layer has an average thickness of from about 0.01 millimeters to about 3 millimeters, or from about 0.03 millimeters to about 2 millimeters, or from about 0.1 millimeters to about 1 millimeter.

[0263] Thermoplastic Elastomer

[0264] The first and second thermoplastic compositions described herein may comprise one or more thermoplastic elastomers. Exemplary thermoplastic elastomers include thermoplastic homopolymer elastomers and thermoplastic copolymer elastomers. The thermoplastic elastomer may be a thermoplastic random copolymer elastomer. The thermoplastic elastomer may be a thermoplastic block copolymer elastomer. The term "polymer" refers to a polymeric molecule having one or more monomeric species and includes homopolymers and copolymers. The term "copolymer" refers to a polymer having two or more monomeric species and includes terpolymers (i.e., copolymers having three monomeric species). For example, the thermoplastic elastomer may be a block copolymer having: repeating blocks (hard blocks) of polymer units of the same relatively hard chemical structure (segments) and repeating blocks of relatively soft polymer segments (soft blocks). In various aspects, in a block copolymer including a block copolymer having repeating hard and soft blocks, physical crosslinks may be present within or between the blocks, or both within and between the blocks. Specific examples of hard blocks include isocyanate segments and polyamide segments. Specific examples of soft blocks include polyether segments and polyester segments. As used herein, a polymer segment may be referred to as a particular type of polymer segment, such as, for example, an isocyanate segment, a polyamide segment, a polyether segment, a polyester segment, and the like. It should be understood that the chemical structure of the segment is derived from the described chemical structure. For example, an isocyanate segment is a polymeric unit including an isocyanate functional group. When referring to a block of a polymer segment of a particular chemical structure, the block may contain up to 10 mol% of segments of other chemical structures. For example, as used herein, a polyether segment is understood to include up to 10 mol% of non-polyether segments.

[0265] The thermoplastic elastomer may include one or more of the following: thermoplastic polyester elastomers, thermoplastic polyurea elastomers, thermoplastic polyimide elastomers, thermoplastic polyamide elastomers, thermoplastic polyether elastomers, thermoplastic polyurethane elastomers, thermoplastic polyolefin elastomers, thermoplastic ionomer elastomers, any copolymers thereof or any blends thereof. It should be understood that other thermoplastic polymer materials not specifically described below are also contemplated for use in the coated and / or uncoated fibers as described herein.

[0266] The second thermoplastic composition may comprise one or more of thermoplastic polyamide elastomers, such as PEBA or polyether block polyamides. The second thermoplastic composition may comprise one or more metallocene-catalyzed block copolymers of ethylene and an α-olefin having 4 to about 8 carbon atoms. The second thermoplastic composition may comprise one or more thermoplastic styrene copolymers, including styrene block copolymers such as poly(styrene-butadiene-styrene), poly(styrene-ethylene-co-butene-styrene), and poly(styrene-isoprene-styrene) and combinations thereof.

[0267] The second thermoplastic composition may comprise at least one thermoplastic polyester, including at least one thermoplastic copolyester. Exemplary but non-limiting, thermoplastic copolyester elastomers that can be used in the disclosed methods, foams, and articles include thermoplastic copolyesters, including "HYTREL" 3078, "HYTREL" 4068, and "HYTREL" 4556 (DuPont, Wilmington, Delaware, USA); "PELPRENE" P30B, P40B, and P40H (Toyobo U.S.A. Inc., New York, New York, USA); "TRIEL" 5300, "TRIEL" 5400, and blends thereof (Samyang Corporation, Korea); "KEYFLEX" BT1028D, BT1033D, BT1035D, BT1040D, BT1045D, and BT1047D (LG Chem, Korea); and "KOPEL" KP3340, KP3346, KP3347, KP3942 (Kolon Plastics, Inc., Korea). The polymer component of the second thermoplastic composition (i.e., the component consisting of all polymers present in the second polymer material) may comprise at least 80 weight percent, or at least 90 weight percent, or at least 95 weight percent of a thermoplastic copolyester elastomer based on the total weight of the second thermoplastic composition.

[0268] The second thermoplastic composition may comprise one or more thermoplastic polyurethanes (TPUs), such as "FORTIMO" (Mitsui Chemicals, Inc., Tokyo, Japan); "TEXIN" (Covestro LLC, Pittsburgh, Pennsylvania, USA); and "BOUNCELL-X" (Lubrizol Advanced Materials, Inc., Brecksville, Ohio, USA). The polymer component of the second thermoplastic composition (i.e., the component consisting of all polymers present in the second thermoplastic composition) may comprise at least 80 weight percent, or at least 90 weight percent, or at least 95 weight percent of a TPU elastomer based on the total weight of the second thermoplastic composition. The second thermoplastic composition may comprise one or more thermoplastic polyurethane hot melt adhesives, such as, for example, "NASA-T" hot melt film (Sambu Fine Chemicals, Gimhae-si, Gyeongsangdam-do, Korea).

[0269] The second thermoplastic composition may comprise a blend of one or more thermoplastic polyurethane elastomers and one or more thermoplastic polymers having different chemical structures. In one aspect, the second thermoplastic composition comprises one or more thermoplastic polyurethane elastomers and one or more ethylene-vinyl alcohol copolymers. In another aspect, the second thermoplastic composition comprises one or more thermoplastic elastomers and one or more thermoplastic styrene elastomers, such as, for example, one or more SEBS copolymer elastomers.

[0270] The thermoplastic composition may comprise one or more olefin polymers. Olefin polymers may include ethylene-based copolymers, propylene-based copolymers, and butene-based copolymers. The olefin polymer may be an ethylene-based copolymer such as styrene-ethylene / butene-styrene (SEBS) copolymer; ethylene-propylene-diene monomer (EPDM) copolymer; ethylene-vinyl acetate (EVA) copolymer; ethylene-vinyl alcohol (EVOH) copolymer; ethylene alkyl acrylate (EAA) copolymer; ethylene alkyl methacrylate (EAMA) copolymer; any copolymer thereof and any blend thereof.

[0271] The thermoplastic composition may comprise one or more olefin polymers. Olefin polymers may include ethylene-based copolymers, propylene-based copolymers, and butene-based copolymers. In some aspects, the olefin polymer is an ethylene-based copolymer such as styrene-ethylene / butene-styrene (SEBS) copolymer; ethylene-propylene-diene monomer (EPDM) copolymer; ethylene-vinyl acetate (EVA) copolymer; ethylene alkyl acrylate (EAA) copolymer; ethylene alkyl methacrylate (EAMA) copolymer; any copolymer thereof and any blend thereof. In some aspects, the ratio of the total weight parts of the olefin polymer present in the composition to the total weight parts of the thermoplastic copolyester or the second thermoplastic composition in the composition is from about 0.0 to about 0.6, from about 0.0 to about 0.4, from about 0.01 to about 0.4, or from about 0.01 to about 0.6, or from about 0.1 to about 0.4.

[0272] The thermoplastic composition may comprise an ethylene-vinyl acetate (EVA) copolymer. The ethylene-vinyl acetate (EVA) copolymer may have a range of vinyl acetate contents, such as, for example, from about 50 percent to about 90 percent, from about 50 percent to about 80 percent, from about 5 percent to about 50 percent, from about 10 percent to about 45 percent, from about 10 percent to about 30 percent, from about 30 percent to about 45 percent, or from about 20 percent to about 35 percent.

[0273] The second thermoplastic composition may include one or more ionomers, such as any of the "SURLYN" polymers (DuPont, Wilmington, Delaware, USA).

[0274] The thermoplastic elastomer may have a melting temperature greater than about 110 °C and less than about 210 °C or less than about 170 °C.

[0275] When determined in accordance with ASTM D3418-97 as described below, the thermoplastic elastomer may have a glass transition temperature less than 50 °C, or less than 20 °C, or less than 0 °C, or less than -10 °C.

[0276] Thermoplastic Polyurethane Elastomer

[0277] The thermoplastic elastomer may be a thermoplastic polyurethane elastomer. The thermoplastic polyurethane elastomer may be a thermoplastic block polyurethane copolymer. The thermoplastic block polyurethane copolymer may be a block copolymer having blocks of hard segments and blocks of soft segments. The hard segments may include or consist of isocyanate segments. The soft segments may include polyether segments, or polyester segments or a combination of polyether segments and polyester segments, or consist of polyether segments, or polyester segments or a combination of polyether segments and polyester segments. The thermoplastic material may include or consist essentially of an elastomeric thermoplastic polyurethane having repeating blocks of hard segments and repeating blocks of soft segments.

[0278] One or more of the thermoplastic polyurethane elastomers may be produced by polymerizing one or more isocyanates with one or more polyols to produce copolymer chains having urethane linkages (-N(CO)O-), as shown in Equation 7 below,

[0279]

[0280] wherein the isocyanates each preferably include two or more isocyanate (-NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups per molecule (although monofunctional isocyanates may also optionally be included, for example as chain terminating units). In these aspects, each R1 and R2 is independently an aliphatic segment or an aromatic segment. Optionally, each R2 may be a hydrophilic segment.

[0281] Unless otherwise indicated, any functional group or compound described herein can be substituted or unsubstituted. A "substituted" group or compound, such as an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxy, ester, ether, or carboxylate, refers to an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heteroaryl group, alkoxy group, ester group, ether group, or carboxylate group having at least one hydrogen group substituted by a non-hydrogen group (i.e., a substituent). Examples of non-hydrogen groups (or substituents) include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ether, aryl, heteroaryl, heterocycloalkyl, hydroxy, oxo (or keto), alkoxy, ester, thioester, acyl, carboxyl, cyano, nitro, amino, amido, sulfur, and halogen. When a substituted alkyl group contains more than one non-hydrogen group, the substituents can be attached to the same carbon atom or two or more different carbon atoms.

[0282] Additionally, the isocyanate can also be chain-extended with one or more chain extenders to bridge two or more isocyanates. This can result in a polyurethane copolymer chain as shown in Formula 8 below,

[0283]

[0284] wherein R3 includes the chain extender. Like each R1 and R2, each R3 is independently an aliphatic segment or an aromatic segment.

[0285] Each segment R1 or the first segment in Formulas 7 and 8 can independently include a straight-chain or branched-chain C 3-30 segment, and can be aliphatic, aromatic, or include a combination of an aliphatic portion and an aromatic portion. The term "aliphatic" refers to a saturated or unsaturated organic molecule that does not include a cyclically conjugated ring system having delocalized π electrons. In contrast, the term "aromatic" refers to a cyclically conjugated ring system having delocalized π electrons, which exhibits greater stability than a hypothetical ring system having localized π electrons.

[0286] Each segment R1 can be present in an amount of from 5 weight percent to 85 weight percent, from 5 weight percent to 70 weight percent, or from 10 weight percent to 50 weight percent based on the total weight of the reactant monomers.

[0287] In the aliphatic aspect (from aliphatic isocyanates), each segment R1 can include a straight-chain aliphatic group, a branched-chain aliphatic group, a cycloaliphatic group, or a combination thereof. For example, each segment R1 can include a straight-chain or branched-chain C 3-20 alkylene segment (e.g., C 4-15Alkylene or C 6-10 alkylene), one or more C 3-8 subcycloalkyl segments (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl) and combinations thereof.

[0288] Examples of suitable aliphatic diisocyanates for generating polyurethane copolymer chains include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), dicyclohexylmethane diisocyanate (HMDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), dicyclohexylmethyl diisocyanate, dicyclohexylmethyl tricyclodecane diisocyanate, norbornane diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), dodecane diisocyanate, lysine diisocyanate and combinations thereof.

[0289] In the aromatic aspect (from aromatic isocyanates), each segment R1 can include one or more aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl, phenanthryl, biphenylenyl, indanyl, indenyl, anthryl and fluorenyl. Unless otherwise indicated, the aromatic group can be an unsubstituted aromatic group or a substituted aromatic group and can also include a heteroaromatic group. "Heteroaromatic" refers to a monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ring system in which one to four ring atoms are selected from oxygen, nitrogen or sulfur and the remaining ring atoms are carbon, and in which the ring system is attached to the remainder of the molecule through any ring atom. Examples of suitable heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, furyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl and benzothiazolyl.

[0290] Examples of suitable aromatic diisocyanates for generating polyurethane copolymer chains include toluene diisocyanate (TDI), a TDI adduct with trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene 1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3,3'-dimethylbiphenyl-4,4'-diisocyanate (DDDI), 4,4'-dibenzyl diisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate and combinations thereof. In some aspects, the copolymer chains are substantially free of aromatic groups.

[0291] The polyurethane copolymer chains can be produced from diisocyanates including HMDI, TDI, MDI, H 12 aliphatic compounds, and combinations thereof. For example, the coated fibers as described herein of the present disclosure can include one or more polyurethane copolymer chains produced from diisocyanates including HMDI, TDI, MDI, H 12 aliphatic compounds, and combinations thereof.

[0292] Commercially available thermoplastic polyurethane elastomers having greater hydrophilicity suitable for the uses herein include, but are not limited to, those sold under the trade names "TECOPHILIC", such as TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60 (Lubrizol, Countryside, IL); "ESTANE" (e.g., 58238, T470A-, 2350-75A-030; Lubrizol, Countryside, IL); and "ELASTOLLAN" (e.g., 9500, B70A; BASF).

[0293] The thermoplastic polyurethane elastomers can be partially covalently crosslinked as previously described herein.

[0294] The second thermoplastic composition can include one or more thermoplastic polyurethanes (TPUs), such as "FORTIMO" (Mitsui Chemicals, Inc., Tokyo, Japan); "TEXIN" (Covestro LLC, Pittsburgh, Pennsylvania, USA); and "BOUNCELL-X" (Lubrizol Advanced Materials, Inc., Brecksville, Ohio, USA). The polymeric component of the second thermoplastic composition (i.e., the component consisting of all the polymers present in the second thermoplastic composition) can include at least 80 weight percent of TPU, or at least 90 weight percent of TPU, or at least 95 weight percent of TPU, based on the total weight of the second thermoplastic composition. The second thermoplastic composition can include one or more thermoplastic polyurethane hot melt adhesives, such as, for example, the "NASA-T" hot melt film (Sambu Fine Chemicals, Gimhae-si, Gyeongsangdam-do, Korea).

[0295] Thermoplastic Block Copolyamide Elastomer

[0296] In various aspects, the second thermoplastic composition as described herein can include one or more thermoplastic elastomers, and the one or more thermoplastic elastomers include thermoplastic block copolyamide elastomers. The thermoplastic block copolyamide can include many polyamide segments having different polyamide chemical structures (e.g., polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, etc.). The polyamide segments having different chemical structures can be arranged randomly, or can be arranged as repeating blocks.

[0297] The block copolyamide can have repeating blocks of hard segments and repeating blocks of soft segments. The hard segments can include polyamide segments, and the soft segments can include non-polyamide segments. The thermoplastic elastomer can be an elastomeric thermoplastic copolyamide that includes or consists of a block copolyamide having repeating blocks of hard segments and repeating blocks of soft segments. In a block copolymer that includes a block copolymer having repeating hard and soft segments, physical crosslinks can be present within the blocks or between the blocks, or both within and between the blocks.

[0298] The polyamide segments of the block copolyamide can include or consist of: polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, or any combination thereof. The polyamide segments of the copolyamide can be arranged randomly, or can be arranged as repeating blocks. In a particular example, the polyamide segments can include or consist of: polyamide 6 segments, or polyamide 12 segments, or both polyamide 6 segments and polyamide 12 segments. In an example where the polyamide segments of the copolyamide include polyamide 6 segments and polyamide 12 segments, the segments can be arranged randomly. The non-polyamide segments of the copolyamide can include or consist of: polyether segments, polyester segments, or both polyether segments and polyester segments. The copolyamide can be a block copolyamide, or can be a random copolyamide. The thermoplastic copolyamide can be formed by the polycondensation of a polyamide oligomer or prepolymer with a second oligomer prepolymer to form a block copolyamide (i.e., a block copolymer including polyamide segments). Optionally, the second prepolymer can be a hydrophilic prepolymer.

[0299] Exemplary commercially available copolymers include but are not limited to copolymers available under the following trade names: (Evonik Industries); (Arkema), such as product code H2694; (Arkema), such as product codes “PEBAX MH1657” and “PEBAX MV1074”; RNEW (Arkema); (EMS-Chemie AG), or other similar materials produced by other various suppliers.

[0300] Thermoplastic Polyolefin Elastomer

[0301] In some aspects, the thermoplastic elastomer can comprise or consist essentially of a thermoplastic polyolefin. Exemplary thermoplastic polyolefins that can be used in the disclosed second thermoplastic composition can include, but are not limited to, thermoplastic olefin elastomers (e.g., metallocene-catalyzed block copolymers of ethylene and α-olefins having 4 to about 8 carbon atoms). The thermoplastic polyolefin can be a polymer comprising: ethylene-α-olefin copolymers, ethylene-propylene rubber (EPDM), polybutene, polyisobutene, poly-4-methylpent-1-ene, polyisoprene, polybutadiene, ethylene-methacrylic acid copolymers, and olefin elastomers such as dynamically cross-linked polymers obtained from polypropylene (PP) and ethylene-propylene rubber (EPDM), and blends or mixtures of the foregoing. Another exemplary thermoplastic polyolefin that can be used in the disclosed second thermoplastic composition is a polymer of a cycloolefin such as cyclopentene or norbornene.

[0302] The polyolefin can be a polyethylene copolymer derived from monomers of monoolefins and diolefins copolymerized with: vinyl, acrylic acid, methacrylic acid, ethyl acrylate, vinyl alcohol, and / or vinyl acetate. The polyolefin copolymer containing vinyl acetate-derived units can be a copolymer with a high vinyl acetate content, e.g., a vinyl acetate-derived composition greater than about 50 wt%.

[0303] The thermoplastic polyolefin can be a mixture of thermoplastic polyolefins, such as a mixture of two or more of the polyolefins disclosed above. For example, a suitable thermoplastic polyolefin mixture can be a mixture of polypropylene and polyisobutene, a mixture of polypropylene and polyethylene (e.g., PP / HDPE, PP / LDPE), or a mixture of different types of polyethylene (e.g., LDPE / HDPE).

[0304] The thermoplastic polyolefin can be a copolymer of suitable monoolefin monomers or a copolymer of suitable monoolefin monomers and vinyl monomers. Exemplary thermoplastic polyolefin copolymers include, but are not limited to, ethylene / propylene copolymers, linear low density polyethylene (LLDPE), and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers, and copolymers thereof with carbon monoxide or ethylene / acrylic acid copolymers, and salts (ionomers) thereof, as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with each other and with the polymers mentioned in 1) above, such as polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA, and alternating or random polyalkylene / carbon monoxide copolymer and mixtures thereof with other polymers such as polyamides.

[0305] The polyolefin can be polypropylene. As used herein, the term "polypropylene" is intended to encompass any polymer composition containing propylene monomers, which are either alone or in mixtures or copolymers with other randomly selected and oriented polyolefins, dienes or other monomers such as ethylene, butene and the like. Such term also encompasses any different configurations and arrangements of the component monomers (such as atactic, syndiotactic, isotactic, etc.). Thus, as applied to fibers, the term is intended to encompass the actual long filaments, tapes, sutures and the like of the drawn polymer. Polypropylene can have any standard melt flow (as tested); however, standard fiber grade polypropylene resins have a melt flow index range between about 1 and 1000.

[0306] The polyolefin can be polyethylene. As used herein, the term "polyethylene" is intended to encompass any polymer composition containing ethylene monomers, which are either alone or in a mixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers (such as propylene, butylene, and the like). Such a term also encompasses any different configurations and arrangements of the constituent monomers (such as atactic, syndiotactic, isotactic, etc.). Thus, as applied to fibers, the term is intended to encompass the actual long strands, tapes, sutures, and the like of the drawn polymer. Polyethylene can have any standard melt flow (as tested); however, standard fiber-grade polyethylene resins have a melt flow index range between about 1 and 1000.

[0307] Thermoplastic Ionomer Elastomer

[0308] In some aspects, the thermoplastic elastomer can be one or more ionomer polymers. The ionomer polymer can contain chain units derived from one or more olefins and chain units derived from one or more ethylenically unsaturated acid groups. The composition can also include more than one cation in the anionic form that ionically crosslinks the acid groups in the ionomer copolymer. The composition can be essentially only the ionomer copolymer and the metal cation. The ionomer copolymer can have a melt flow index of about 30 or less, about 20 or less, about 15 or less, about 10 or less, or about 5 or less.

[0309] The ionomer copolymer can be a terpolymer of ethylene, acrylic acid, and methyl acrylate or butyl acrylate. In some aspects, the ratio III of the total weight fraction of acrylic acid in the ionomer copolymer to the total weight of the ionomer copolymer is about 0.05 to about 0.6, about 0.1 to about 0.6, about 0.1 to about 0.5, about 0.15 to about 0.5, or about 0.2 to about 0.5.

[0310] The second thermoplastic composition can contain one or more ionomers, such as any of the "SURLYN" polymers (DuPont, Wilmington, Delaware, USA).

[0311] The second thermoplastic composition can contain an acrylic block copolymer elastomer, such as a block copolymer containing a first PMMA block, an acrylate block, and a second PMMA block.

[0312] Thermoplastic Styrene Copolymer Elastomer

[0313] In some aspects, the thermoplastic elastomer is a thermoplastic elastomer styrene copolymer. Examples of such copolymers include, but are not limited to, styrene-butadiene-styrene (SBS) block copolymers, styrene-ethylene / butylene-styrene (SEBS) resins, polyoxymethylene resins (POM), or styrene acrylonitrile resins (SAN). Exemplary commercially available thermoplastic elastomer styrene copolymers include MONOPRENE IN5074, SP066070, and SP16975 (Teknor Apex), which are styrene-ethylene / butylene-styrene (SEBS) resins.

[0314] Thermoplastic Vulcanizate Material

[0315] The second thermoplastic composition may include an injection-moldable thermoplastic vulcanizate (TPV) material. Injection-moldable TPV materials are generally crosslinked or partially crosslinked rubbers dispersed in a thermoplastic matrix phase. Exemplary TPV materials include ethylene propylene diene rubber in a polypropylene matrix (EPDM / PP), such as "SARLINK" or "SANTOPRENE" TPV materials. Other exemplary TPV materials include alkyl acrylate copolymer rubber in a polyamide matrix (ACM / PA), such as "ZEOTHERM" TPV. Still other exemplary TPV materials include silicone rubber dispersed in a "HYTREL"-based copolyester (e.g., so-called TSiPV).

[0316] Additives

[0317] In various aspects, the disclosed first and second thermoplastic compositions may also independently include additives. The additives may be directly incorporated into the disclosed first or second thermoplastic composition before foaming the first or second thermoplastic composition, or alternatively, applied to the disclosed first or second thermoplastic composition. Additives that may be used in the disclosed compositions and materials include, but are not limited to, dyes, pigments, colorants, ultraviolet light absorbers, hindered amine light stabilizers, antioxidants, processing aids or agents, plasticizers, lubricants, emulsifiers, optical brighteners, rheological additives, catalysts, flow control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke inhibitors, flameproofing agents, antistatic agents, fillers, or mixtures of two or more of the foregoing. In some aspects, the additives may be waxes, antioxidants, UV absorbers, colorants, or combinations thereof.

[0318] The additive can be present in an amount from about 0.1 weight percent to about 10 weight percent, or from 0.1 weight percent to 6 weight percent, based on the total weight of the first thermoplastic composition or the second thermoplastic composition. In certain aspects, the additive can be present in an amount from about 0.1 weight percent to about 4 weight percent based on the total weight of the first thermoplastic composition or the second thermoplastic composition in the first thermoplastic composition or the second thermoplastic composition. The first thermoplastic composition or the second thermoplastic composition can contain less than 4 weight percent, or less than 3 weight percent, or less than 2 weight percent, or less than 1 weight percent of the additive based on the total weight of the first thermoplastic composition or the second thermoplastic composition.

[0319] The first thermoplastic composition and / or the second thermoplastic composition can be substantially free of the additive, where the amount of the additive is less than about 0.1 weight percent, about 0.08 weight percent, about 0.06 weight percent, about 0.04 weight percent or about 0.02 weight percent of the first thermoplastic composition and / or the second thermoplastic composition. In another aspect, the first thermoplastic composition and / or the second thermoplastic composition is free of any additive (i.e., does not contain an additive).

[0320] In some cases, the additive can be present in an amount from about 0.01 weight percent to about 10 weight percent, about 0.025 weight percent to about 5 weight percent or about 0.1 weight percent to 3 weight percent, where the weight percent is based on the sum of the material components in the first thermoplastic composition or the second thermoplastic composition.

[0321] The individual components can be mixed with other components of the first thermoplastic composition or the second thermoplastic composition in a continuous mixer or a batch mixer, such as in an intermeshing rotor mixer such as an Intermix mixer, a twin-screw extruder, in a tangential rotor mixer such as a Banbury mixer using a two-roll mill, or in some combination of these, to produce a composition comprising a thermoplastic polymer and an additive. The mixer can blend the components together via a single step or multiple steps, and can mix the components via distributive mixing or dispersive mixing to form the resulting thermoplastic composition. This step is generally referred to as "compounding".

[0322] The first thermoplastic composition and the second thermoplastic composition may also independently comprise a solid non-polymeric material such as a chemical blowing agent, a nucleating agent, a filler, a pigment, or a combination thereof. The solid non-polymeric material may be present in an amount from about 0.05 weight percent to about 20 weight percent, based on the total weight of the first thermoplastic composition and / or the second thermoplastic composition; from about 0.1 weight percent to about 10 weight percent, based on the total weight of the first thermoplastic composition and / or the second thermoplastic composition; from 0.5 weight percent to about 5 weight percent, based on the total weight of the first thermoplastic composition and / or the second thermoplastic composition. The first thermoplastic composition or the second thermoplastic composition may comprise about 5 weight percent or less, or about 3 weight percent or less, or about 2 weight percent or less, or about 1 weight percent or less of the solid non-polymeric material, based on the total weight of the first thermoplastic composition and / or the second thermoplastic composition. The foamed polymeric material may comprise less than about 5 weight percent, or less than 4 weight percent, or less than 3 weight percent, or less than 2 weight percent, or less than 1 weight percent of the solid non-polymeric material, based on the total weight of the first thermoplastic composition and / or the second thermoplastic composition.

[0323] The first thermoplastic composition and / or the second thermoplastic composition may substantially not contain or may not contain a non-polymeric material such as a chemical blowing agent, a nucleating agent, a filler, a pigment, or a combination thereof. In other words, the first thermoplastic composition and / or the second thermoplastic composition may be substantially free of non-polymeric materials. In other aspects, the first thermoplastic composition and / or the second thermoplastic composition may comprise 5 weight percent or less of a non-polymeric material such as a chemical blowing agent, a nucleating agent, a filler, a pigment, or a combination thereof. The first thermoplastic composition and / or the second thermoplastic composition may comprise less than 4 weight percent, less than 3 weight percent, less than 2 weight percent, less than 1 weight percent, less than 0.5 weight percent, less than 0.1 weight percent, less than 0.08 weight percent, less than 0.06 weight percent, less than 0.04 weight percent, or less than 0.02 weight percent of the non-polymeric material, based on the total weight of the first thermoplastic composition and / or the second thermoplastic composition. In other aspects, the first thermoplastic composition and / or the second thermoplastic composition does not contain (i.e., does not comprise) a non-polymeric material such as a chemical blowing agent, a nucleating agent, a filler, or a combination thereof.

[0324] In some cases, the solid non-polymeric material is a filler. The filler can be a particulate filler. In other aspects, the filler is a carbonaceous filler. The carbonaceous filler can be carbon black, activated carbon, graphite, carbon fiber, carbon fibril, carbon nanoparticles, or a combination thereof. In various aspects, the carbonaceous filler can be chemically modified. Optionally, the filler can be an inorganic filler. The inorganic filler can be an oxide, hydroxide, salt, silicate, metal, or a combination thereof. Examples of inorganic fillers include, but are not limited to, glass spheres, glass fibers, glass hollow spheres, glass flakes, MgO, SiO2, Sb2O3, Al2O3, ZnO, talc, mica, kaolin, wollastonite, or a combination thereof.

[0325] Nucleating agents are widely used to modify the properties of various polymers. The nucleating agent can assist in reducing the foam specific gravity, increasing the number of pores present in the foam, and decreasing the pore size in the foam by providing a surface for the heterogeneous nucleation of bubbles from the supercritical fluid state. For the first and second thermoplastic compositions of the present disclosure, the nucleating agent can affect the properties of the final foam article by changing the amount, distribution, and rate of conversion of the supercritical fluid from liquid to gas during a foaming process at a lower pressure. The addition of the nucleating agent provides a surface on which the supercritical fluid can transform from liquid to gas. Thus, many nucleation sites will result in many gas pore domains. In certain instances, the nucleating agent can include metal salts of fatty acids. In some aspects, the nucleating agent is zinc stearate. In some aspects, the composition or material contains from about 0.1 weight percent to about 10 weight percent, from about 0.1 weight percent to about 5 weight percent, from about 0.1 weight percent to about 2 weight percent, or from about 0.5 weight percent to about 2 weight percent of the nucleating agent based on the total weight of the composition or material.

[0326] In some aspects, the additive is a nucleating agent such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates, or sulfates of alkaline earth metals, or mixtures thereof. Optionally, the nucleating agent can be a monocarboxylic or polycarboxylic acid and its salts, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate, sodium benzoate, or mixtures thereof. In other aspects, the additive can be a nucleating agent comprising both inorganic and organic materials as disclosed above.

[0327] In some aspects, the rheology modifier can be nanoparticles, nanoclays, nanocarbons, graphite, nanosilicas, and the like having a relatively high aspect ratio.

[0328] In some aspects, the additive is a filler or reinforcing agent such as clay, kaolin, talc, asbestos, graphite, glass (such as glass fiber, glass particles, and glass bulbs, glass spheres or glass-like spheres), mica, calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide, silicate, diatomaceous earth, carbonate (such as calcium carbonate, magnesium carbonate and the like), metal (such as titanium, tungsten, zinc, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron, bronze, cobalt, beryllium and alloys thereof), metal oxides (such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide and the like), metal hydroxides, particulate synthetic plastics (such as polyethylene, polypropylene, polystyrene, polyamide, polyester, polyurethane, polyimide and the like), synthetic fibers (such as fibers containing high molecular weight polyethylene, polypropylene, polystyrene, polyamide, polyester, polyurethane, polyimide and the like), particulate carbonaceous materials (such as carbon black and the like), wood flour and powders or fibers of other natural products, and cotton linter, non-cotton cellulose linter, cellulose pulp, leather fiber, and combinations of any of the foregoing. Non-limiting examples of heavy density filler components that can be used to increase the specific gravity of the cured elastomeric composition can include titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, steel, lead, copper, brass, boron, boron carbide whiskers, bronze, cobalt, beryllium, zinc, tin, metal oxides (such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide and zirconium oxide), metal sulfates (such as barium sulfate), metal carbonates (such as calcium carbonate) and combinations thereof. Non-limiting examples of light density filler components that can be used to reduce the specific gravity of the elastomeric compound can include particulate plastics, hollow glass spheres, ceramics and hollow spheres, regrind and foams, which can be used in combination.

[0329] In some instances, the non-polymeric material may further include nano-fillers. Nano-fillers can be used not only as mechanical reinforcing agents but also as nucleating agents. A variety of nano-fillers can be used in place of or in addition to zinc stearate. Nano-fillers can include nanomaterials having a one-dimensional structure such as plates, flakes and / or shells; two-dimensional structures such as nanotubes and nanofibers having a diameter of less than 0.1 micron; or three-dimensional nanostructures such as nanoparticles or beads. Nano-sheet fillers can be natural clay or synthetic clay, and phosphates of transition metals. Clay-based nanocomposites result in an overall improvement in physical properties. The most widely used nano-fillers are phyllosilicates. Nano-fillers can include nano-oxides such as nanoparticles of titanium dioxide or rutile. Other nano-fillers can include nanoparticles of alumina or aluminum oxide, diatomaceous earth and nano-scale carbon materials such as single-walled carbon nanotubes (SWCNT) or double-walled carbon nanotubes (DWCNT).

[0330] Definition

[0331] Unless otherwise defined, 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 also be 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 the relevant art and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0332] The terms “comprises,” “comprising,” “including,” and “having” are inclusive and thus specify the presence of stated features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof.

[0333] As used in this specification and the appended claims, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” include plural referents. Thus, for example, reference to “foam particles,” “midsole,” or “adhesive” includes but is not limited to two or more such foam particles, midsoles, or adhesives and the like.

[0334] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items.

[0335] As used herein, “in substance” or “substantially” means at least 50 percent, 60 percent, 75 percent, 90 percent, 95 percent or more as determined by weight or volume.

[0336] The terms first, second, third, etc. may be used herein to describe different 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 used only to distinguish one element, component, region, layer, or section from another. Terms such as “first,” “second,” and other numerical terms do not imply a sequence or order unless the context clearly indicates. Thus, a first element, first component, first region, first layer, or first section discussed below may be referred to as a second element, second component, second region, second layer, or second section without departing from the teachings of the exemplary configuration.

[0337] As used herein, modifiers such as "upper", "lower", "top", "bottom", "upward", "downward", "vertical", "horizontal", "longitudinal", "lateral", "front", "back", etc., unless otherwise defined or clear from the present disclosure, are relative terms denoting the orientation of various structures or structures in which a footwear item is placed in the context of a footwear item worn by a user standing on a flat horizontal surface.

[0338] When recited in a claim, the term "receive", such as for "receive an upper for a footwear item", is not intended to require any particular delivery or receipt of the item being received. Rather, the term "receive" is merely used to recite the item that will be referred to in subsequent elements of the claim for purposes of clarity and ease of reading.

[0339] The terms "at least one" element and "one or more" of an element are used interchangeably and have the same meaning, meaning including a single element and more than one element, and may also be indicated by the suffix "(s)" at the end of the element. For example, "at least one polyamide", "one or more polyamides", and "(one or more) polyamide(s)" may be used interchangeably and have the same meaning.

[0340] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. In cases where the stated range includes one or both of the extreme values, ranges excluding either or both of the included extreme values are also included in the present disclosure. For example, the phrase "x to y" includes the range from 'x' to 'y' and ranges greater than 'x' and less than 'y'. A range may also be expressed as an upper limit, such as 'about x, y, z or less' and should be interpreted to include the specific ranges of 'about x', 'about y', and 'about z' as well as ranges 'less than x', 'less than y', and 'less than z'. Similarly, the phrase 'about x, y, z or greater' should be interpreted to include the specific ranges of 'about x', 'about y', and 'about z' as well as ranges 'greater than x', 'greater than y', and 'greater than z'. In addition, the phrase "about 'x' to 'y'", where 'x' and 'y' are numerical values, includes "about 'x' to about 'y'". It should be understood that such range formats are used for convenience and brevity and should, therefore, be interpreted in a flexible manner to include not only the numerical values explicitly recited as the extreme values of the range but also all individual numerical values or sub-ranges subsumed within that range as if each numerical value and sub-range were explicitly recited. By way of illustration, the numerical range of "about 0.1% to 5%" should be interpreted to include not only the explicitly recited values of about 0.1 percent to about 5 percent but also individual values (e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and sub-ranges (e.g., 0.5 percent, 1.1 percent, 2.4 percent, 3.2 percent, and 4.4 percent) within the indicated range.

[0341] The terms "about" and "substantially" are used herein together with respect to measurable values and ranges due to the expected variations known to those of ordinary skill in the art (e.g., limitations and variability in measurements).

[0342] As used herein, the term "optional" or "optionally" means that the subsequently described component, event, or circumstance may or may not occur, and the description includes the case where the said component, event, or circumstance occurs and the case where the said component, event, or circumstance does not occur.

[0343] As used herein, the term "unit" may be used to refer to individual (co)monomer units such that, for example, a styrene repeat unit refers to an individual styrene (co)monomer unit in a polymer. In addition, the term "unit" may be used to refer to polymer block units such that, for example, a "styrene repeat unit" may also refer to a polystyrene block; a "unit of polyethylene" refers to a block unit of polyethylene; a "unit of polypropylene" refers to a block unit of polypropylene; a "unit of polybutene" refers to a block unit of polybutene, and so on. Such usage will be clear from the context.

[0344] The term "copolymer" refers to a polymer having two or more monomeric substances and includes terpolymers (i.e., copolymers having three monomeric substances).

[0345] The mention of "a" chemical compound refers to one or more molecules of the chemical compound and is not limited to a single molecule of the chemical compound. Further, one or more molecules may or may not be the same as long as they fall under the category of the chemical compound. Thus, for example, "a" polyamide is interpreted to include one or more polymer molecules of the polyamide, where the polymer molecules may or may not be the same (e.g., different molecular weights and / or isomers).

[0346] As used herein, the terms "percent by weight" or "weight percent", which may be used interchangeably, indicate the weight percentage of a given component based on the total weight of the composition or article, unless otherwise indicated. That is, unless otherwise indicated, all weight percentage values are based on the total weight of the composition. It should be understood that the sum of the weight percentage values of all components in the disclosed composition or formulation or article equals 100.

[0347] Similarly, the terms "percent by volume" or "volume percent", which may be used interchangeably, indicate the volume percentage of a given component based on the total volume of the composition or article, unless otherwise indicated. That is, unless otherwise indicated, all volume percentage values are based on the total volume of the composition or article. It should be understood that the sum of the volume percentage values of all components in the disclosed composition or formulation or article equals 100.

[0348] Standard nomenclature is used to describe compounds. For example, any position not substituted by any indicated group is understood to have its valence filled by a bond or hydrogen atom as indicated. A dash ("-") not between two letters or symbols is used to indicate the point of attachment for a substituent. For example, -CHO is attached through the carbon of the carbonyl group. Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0349] Unless otherwise indicated, temperatures mentioned herein are based on atmospheric pressure (i.e., one atmosphere).

[0350] Prior to proceeding with the examples, it is to be understood that the present disclosure is not limited to the particular aspects described and may, of course, vary. After reviewing the following figures and detailed description, other systems, methods, features, and advantages of the foam compositions and their components will be apparent or will become apparent to those of ordinary skill in the art. It is intended that all such additional systems, methods, features, and advantages be included within this description, be included within the scope of the present disclosure, and be protected by the appended claims. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Those skilled in the art will recognize many variations and adaptations of the aspects described herein. These variations and adaptations are intended to be included in the teachings of the present disclosure and be covered by the claims herein.

[0351] Test Methods

[0352] The following are certain sampling procedures and test methods cited in the description and examples.

[0353] Sampling Procedures

[0354] Various properties of the compositions, foams, and other articles formed therefrom can be characterized using samples prepared using the following sampling procedures:

[0355] a. Neat Sampling Procedure

[0356] A pure sampling procedure can be used to obtain pure samples of the first thermoplastic composition, either foamed or unfoamed, the second thermoplastic composition, either unfoamed or foamed, or in some cases, samples of the materials (e.g., polymers) used to form the first thermoplastic composition or the second thermoplastic composition. The materials can be provided in a medium form such as sheets, pellets, powders, spheres, and the like. If the source of the first thermoplastic composition or the second thermoplastic composition is not available in pure form, samples can be cut from another component containing the composition or material to isolate a sample of the composition or material.

[0357] b. Substrate Sampling Procedure - Solid Composition or Material

[0358] The first thermoplastic composition or the second thermoplastic composition is molded into a substrate having dimensions of approximately 6 inches by approximately 4 inches and a thickness of approximately 20 millimeters (or as otherwise specified by the test method). Samples are prepared by mixing the components of the composition or material, melting the composition or material, pouring, extruding, or injecting the molten composition into a mold cavity, cooling the molten composition or material to solidify it in the mold cavity to form the substrate, and then removing the substrate from the mold cavity.

[0359] c. Substrate Sampling Procedure - Foam Composition or Material

[0360] The foamed first thermoplastic composition or second thermoplastic composition is foamed into a sheet. The surface layer is removed from a portion of the sheet, and the portion of the sheet with the surface layer is cut into a substrate having dimensions of approximately six inches by approximately four inches and a thickness of about 20 millimeters (mm) (or as otherwise specified by the test method).

[0361] d. Component Sampling Procedure

[0362] When the composition or material is incorporated into a component such as a midsole structure or midsole or outsole of a footwear item, this procedure can be used to obtain samples of the foamed or unfoamed composition or material. Samples of the component including the composition or material are obtained when the component is formed or cut from the footwear item using a blade. The process is carried out by separating the component from the associated footwear upper (if present) and removing any material from the top surface of the item (e.g., corresponding to the top surface). For example, the top surface of the item can be skived, sanded, scraped, or otherwise cleaned to remove any upper adhesives, yarns, fibers, foams, and the like that may potentially interfere with the test results.

[0363] The resulting component sample includes the composition or material. Thus, any test using the component sampling procedure can simulate how the composition or material will perform as part of a footwear item. As specified by the test method, the component can be tested as a complete component (e.g., a complete midsole component), or the component can be extracted as a sample having a certain geometry. Samples of the component are obtained at locations on the component that provide a substantially constant thickness (within plus or minus 10 percent of the average thickness), such as in the forefoot region, midfoot region, or heel region of the item. Unless otherwise indicated, the desired harvested geometry is a cylindrical puck having a 45 - millimeter diameter and a cylindrical height of at least about 10 millimeters, preferably from about 20 millimeters to 25 millimeters. Compression testing of the harvested component sample should be carried out along the length of the cylinder using a compression platen that is at least twice the diameter of the cylindrical disk sample.

[0364] Characterization of solid polymers, thermoplastic copolyester compositions, and second thermoplastic compositions.

[0365] Testing of Glass Transition Temperature, Melting Temperature and Crystallization Temperature

[0366] Dynamic scanning calorimetry (DSC) is performed on samples prepared using a pure sampling procedure, or on a portion of a sample prepared using a substrate sampling procedure or a component sampling procedure. The test is carried out using a DSC system such as a TA Instruments Q2000. A 10 mg - 30 mg sample is cycled from -90 °C to 225 °C at a rate of 20 °C / min and cooled to -90 °C at a rate of 10 °C / min. Each sample is run in duplicate. Melting temperature values, crystallization temperature values, and glass transition temperature values are recorded from the second cycle. The melting "peak", crystallization "peak", or glass transition "peak" is determined as the local maximum of the second heating cycle. If there are more than one melting peaks in the DSC curve, the melting peak occurring at the hotter temperature is selected as the injection temperature or foaming temperature reference. The peak tail is determined as the intersection of the tangent of the line on the higher temperature side of the melting peak with the extrapolated baseline. A schematic diagram showing the method for determining the peak temperature and peak tail temperature is shown in Figure 8 is shown in.

[0367] Cyclic Tensile Test

[0368] The cyclic tensile test is performed on a solid sample prepared using a substrate sampling procedure or a component sampling procedure, the solid sample having a dog-bone shape with a thickness of 2 mm as described in ASTM D638. In the test, the specimen is placed under a preload of 5 N. The strain is controlled to extend the sample to an extension range of 6 percent at a strain rate of 5 Hz. The stiffness is the load at 6 percent strain divided by the extension range at 6 percent strain, giving a value in N / mm. The maximum load (N) observed during the 500-cycle test cycle is also recorded.

[0369] Melt Flow Index Test

[0370] According to the test method detailed in the ASTM D1238-13 standard test method for melt flow rate of thermoplastics by extrusion plastometer, using Procedure A described therein, using samples prepared by a pure sampling procedure, or determining the melt flow index for a portion of samples prepared by a substrate sampling procedure or a component sampling procedure. Briefly, the melt flow index measures the rate at which a thermoplastic extrudes through an orifice at a specified temperature and load. In the test method, approximately 7 grams of the sample is loaded into the barrel of the melt flow apparatus, which has been heated to a specified temperature of 210 degrees Celsius, 220 degrees Celsius, or 230 degrees Celsius. A weight of 2.16 kilograms is applied to the plunger, and the molten sample is forced through the die. The timed extrudate is collected and weighed. The melt flow value is calculated in g / 10 min and is reported at the specified temperature (i.e., 210 degrees Celsius, 220 degrees Celsius, or 230 degrees Celsius) and the weight applied to the plunger (i.e., 2.15 kilograms).

[0371] Aklon Abrasion Test for Solid Polymer

[0372] The abrasion loss is tested for a sample sheet having a thickness of 3 millimeters prepared by a substrate sampling procedure or a component sampling procedure. The sample sheet is adhered to an Akron abrasion test specimen having a JIS-A hardness of 70 using an adhesive to prepare a test specimen. According to JIS K6254, the abrasion loss by volume is measured using an Akron abrasion testing machine at a load of 27 N, an inclination angle of 15 degrees, 500 preliminary abrasions, and 1,000 test abrasions. The mass and / or volume of the sample is measured before and after the test, and the difference is the abrasion loss. The smaller the abrasion loss volume or mass, the better the abrasion resistance.

[0373] DIN Abrasion Test for Solid Polymer

[0374] The abrasion loss is tested for a sample cut from a sheet having a minimum thickness of 6 millimeters to 12 millimeters prepared by a substrate sampling procedure or a component sampling procedure. The cut sample has a cylindrical shape with a diameter of 16 millimeters plus or minus 0.2 millimeters cut from the sheet using an ASTM standard drill and a minimum thickness of 6 mm to 12 mm. The abrasion loss is measured using Method B of ASTM D 5963-97a on a standard abrasion testing machine such as a Gotech GT-7012-D abrasion testing machine. The test is conducted at 22 degrees Celsius, where the abrasion path is 40 meters. The sample is abraded using a standard sandpaper such as VSM-VITEX-KK511X-60P sandpaper (commercially available from VSMAbrasives Corp.) with an abrasion load of 10 Newtons. The mass and / or volume of the sample is measured before and after the test, and the difference is the abrasion loss. The smaller the abrasion loss, the better the abrasion resistance of the material.

[0375] Coefficient of Friction Test for Solid Polymer (Wet & Dry)

[0376] This test measures the coefficient of friction for a coefficient of friction test on a sample (e.g., obtained using the component sampling procedure, substrate sampling procedure, or pure sampling procedure discussed above). The sample is cut into a rectangular shape measuring approximately 3.0 inches by 3.3 inches and having a thickness of approximately 2 millimeters. The sample is permanently adhered to a 1 - centimeter - thick EVA foam piece that has a density of approximately 0.25 grams per cubic centimeter and a durometer hardness of 50C.

[0377] For the dry test (i.e., determining the dry coefficient of friction), the sample is initially equilibrated at 25°C and 20 percent humidity for 24 hours. For the wet test (i.e., determining the wet coefficient of friction), the sample is completely immersed in a deionized water bath maintained at 25°C for 24 hours. After this, the sample is removed from the bath and blotted dry with a cloth to remove surface water.

[0378] The measurement is performed using an aluminum sled mounted on a test track, which is used to perform a sliding friction test on the test sample on the surface of the test track. The surface of the test track can include a specified test track material, such as aluminum, a wooden field surface (wet or dry), a smooth concrete surface (wet or dry). The test track measures 127 millimeters wide by 610 millimeters long. The aluminum sled measures 76.2 millimeters by 76.2 millimeters, with the leading edge cut to have a radius of 9.5 millimeters. The contact area of the aluminum sled with the track is 76.2 millimeters by 66.6 millimeters, or 5,100 square millimeters.

[0379] A room - temperature - curing two - component epoxy adhesive, such as the adhesive commercially available from Henkel, Dusseldorf, Germany under the trade name “LOCTITE 608”, is used to attach the dry or wet sample to the bottom of the sled. The adhesive is used to maintain the planarity of the wet sample, which may curl when saturated. A polystyrene foam having a thickness of approximately 25.4 millimeters is attached to the top surface of the sled (opposite the test sample) for structural support.

[0380] The sliding friction test was conducted using a screw-driven load frame. The tow cable was attached to the sled using mounts supported in a Styrofoam structure and was wrapped around a pulley to pull the sled across an aluminum test track. The sliding force or frictional force was measured using a load transducer with a capacity of 2,000 Newtons. The normal force was controlled by placing weights on top of the aluminum sled supported by the foam structure, with the total sled weight being 1,000 Newtons. The crosshead of the test frame had a speed of 0.4 m / s, and the total test displacement was 250 mm. The coefficient of friction was calculated based on the steady-state force parallel to the direction of motion required to pull the sled at a constant speed. The coefficient of friction itself was obtained by dividing the steady-state tensile force by the applied normal force. Any transient values related to the static coefficient of friction at the start of the test were ignored.

[0381] Interlayer Adhesion Test

[0382] The interlaminar adhesion test was used to determine the adhesion between two bonded material (e.g., a thermoplastic copolyester composition and a second thermoplastic composition) plies using a tensile testing device such as an Instron Electropuls E10000 (Instron, Norwood, Massachusetts, USA). Sample plies of each material could be provided using a neat sampling procedure or a substrate sampling procedure or a component sampling procedure, and the plies were then bonded using a specified method. Alternatively, samples of the bonded plies could be provided by using a component sampling procedure. At one end of the sample, the bond between the plies was carefully separated to provide an unbonded length of approximately 0.5 cm, which could be inserted into the crosshead of the tensile testing device. The first ply was inserted into the first clamp of the tensile testing machine, and the second ply was inserted into the second clamp of the tensile testing machine such that the sample between the clamps was generally straight. The crosshead speed was set at 50 mm per minute. The peel strength was measured throughout the separation of the bonded sample until the bond was completely separated or the sample failed. The force per peel distance (kgf / cm) was reported, and the failure mode (adhesive or cohesive) of each sample was recorded.

[0383] Foam characterization.

[0384] Density Test

[0385] Measure the density of samples obtained using the substrate sampling procedure or the component sampling procedure using a digital balance or a Densicom tester (Qualitest, Plantation, Florida, USA). For each sample, determine the sample volume in cubic centimeters and then weigh each sample (g). The density of the sample is the mass divided by the sample volume, given in grams per cubic centimeter.

[0386] Specific Gravity Test

[0387] Measure the specific gravity (SG) of samples obtained using the substrate sampling procedure or the component sampling procedure using a digital balance or a Densicom tester (Qualitest, Plantation, Florida, USA). Weigh each sample (g) and then immerse it in a distilled water bath (at 22 degrees Celsius plus or minus 2 degrees Celsius). To avoid errors, remove the air bubbles on the surface of the sample, for example, by wiping isopropyl alcohol on the sample before immersing it in water or using a brush after the sample has been immersed. Record the weight of the sample in distilled water. The specific gravity is calculated using the following formula:

[0388]

[0389] Water Absorption Test

[0390] This test measures the water absorption capacity of the foam sample after a soaking duration of 5 minutes. Starting from the side wall of the sole sandwich of a foamed article such as a footwear article, remove a 1 - centimeter core sample from the foam sample prepared using the substrate sampling procedure or the component sampling procedure. Then, cut the core to provide a cylindrical sample with a 1 - centimeter cylinder height, ensuring that the side wall remains part of the core sample. Condition the sample in an oven at 50 degrees Celsius plus or minus 3 degrees Celsius for 24 hours. After conditioning, cool the sample in a laboratory environment at a temperature of 22 degrees Celsius plus or minus 2 degrees Celsius for 30 minutes and then immediately weigh it and record the weight (W_0) in grams. Mask the surface of the side wall with masking tape while sealing all other surfaces with an impermeable coating. When the surface is completely coated, the side wall surface is not masked. Then, condition the coated sample in an oven at 50 degrees Celsius plus or minus 3 degrees Celsius for 24 hours, cool it in a laboratory environment at a temperature of 22 degrees Celsius plus or minus 2 degrees Celsius for 30 minutes, and then immediately weigh it and record the weight (W_i) in grams. Immerse the dry sample completely in a deionized water bath maintained at 22 degrees Celsius plus or minus 2 degrees Celsius for a duration of 2 hours. After the soaking duration, remove the sample from the deionized water bath, blot it dry with a cloth to remove the surface water, and measure the total weight (W_f) of the soaked sample in grams. The water absorption for this period is calculated as follows:

[0391]

[0392] Force / Displacement Test (Cyclic Compression Test)

[0393] The force / displacement behavior of foams and foamed articles is measured using a cyclic compression testing apparatus, such as an Instron Electropuls E10000 (Instron, Norwood, Massachusetts, USA), with a stainless steel circular cross-section impact geometry having a diameter at least twice that of the foam sample (e.g., a 90 mm diameter platen for a 45 mm diameter sample), on samples having a diameter of 45 mm and a thickness of at least 10 mm (preferably 20 mm to 25 mm) prepared using a substrate sampling procedure or a component sampling procedure. Each sample is compressed to 50% strain at 5 Hz for 500 cycles. The stiffness, efficiency, and energy return at cycles 200, 300, 400, and 500 are measured from the force-versus-displacement curve. The stiffness of a particular foam sample is the stress at maximum strain divided by the maximum strain, giving a value in kPa or N / mm. The efficiency of the foam sample is the integral of the unloading force-displacement curve divided by the integral of the loading force-displacement curve. The energy return of the foam sample is the integral of the unloading force-displacement curve, giving a value in mJ. The reported value for each metric is the average of each metric between cycles 200, 300, 400, and 500. All fatigue metrics are defined as the relative difference in a property at the end of the test compared to the same property at the start of the test (i.e., cycle 1).

[0394] In some cases, a shoe form for impact is used instead of a cylindrical tupp to test the complete midsole to more accurately simulate full gate loading. For these tests, midsoles of US men's size 10 and a men's size 9 shoe form for impact were tested, with a load of 2000 N applied to the midsole and shoe form at a loading rate of 5 Hz. As described above, all metrics from the shoe form tests were collected and analyzed.

[0395] As with when using a cylindrical tupp, when using a shoe form, the energy input is considered as the integral of the force-displacement curve during the compressive force load. The energy return is considered as the integral of the force-displacement curve during unloading. Hysteresis is considered as the ratio: (energy return) / (energy input), which can also be considered as the energy efficiency of the foam. Fatigue behavior is judged by the change in foam displacement at the maximum load of the cycle. All measured properties: stiffness, hysteresis, and fatigue were measured for thousands of cycles for both running compression cycles and walking compression cycles.

[0396] Shore A Durometer Hardness Test

[0397] The tests for obtaining the hardness value of a foam article are as follows. A flat foam sample is prepared using a substrate sampling procedure or a component sampling procedure, where the sample has a minimum thickness of 6 mm for Shore A durometer testing. If necessary, the samples are stacked to make up the minimum thickness. The sample is large enough to allow all measurements to be made at least 12 mm from the edge of the sample and at least 12 mm from any other measurement. The area being tested is flat and parallel to an area with a diameter of at least 6 mm. At least five hardness measurements are made and the test is conducted using a 1 kg head weight.

[0398] Delamination Tear Test

[0399] The laminate tear test can determine the internal tear strength of a foam material. Samples can be provided using a substrate sampling procedure or a component sampling procedure. The sample is die cut into a rectangular shape with a width of 1.54 cm and a length of 15.24 cm (1 inch by 6 inches) and a thickness of 10 mm plus or minus 1 mm. At one end, a cut is made in the sample bisecting the thickness, the cut extending across the entire width of the sample and 3 cm from the end of the sample. Starting from the end of the cut, 5 marks are placed at 2 cm intervals along the length of the sample. The cut end of the sample is placed in the jaws of a tensile tester. Each part of the sample is held in the jaws in such a way that the original adjacent cut edges form a straight line connecting the centers of the jaws. The crosshead speed is set at 50 mm per minute. The tear strength is measured throughout the separation of the crosshead. If necessary, a sharp knife can be used to keep the foam in the center of the sample separated, discarding readings caused by the cut of the knife. The lowest laminate tear strength value in each of the five marked sections of the sample (between each of the 2 cm marks) is recorded. The average laminate tear strength value for each sample is recorded. If a section of the sample has a bubble measured as greater than 2 mm, the tear strength of that section is discarded and the bubble is recorded as a test defect. If more than one section of the sample has a bubble measured as greater than 2 mm, the entire sample is discarded.

[0400] Hand Pull Test

[0401] A hand pull test can evaluate the bond strength between two foams, compositions, or materials, such as between a solid and a foam or between two different foams. Depending on the bonding method used, samples of two pre-bonded foams, compositions, or materials can be provided using a substrate sampling procedure or a component sampling procedure. Alternatively, separate samples of the foam, composition, or material can be prepared using a substrate sampling procedure or a component sampling procedure and then bonded together using the bonding method to be evaluated. The samples are die cut into a rectangular shape having a width of 1.54 cm and a length of 15.24 cm (1 inch by 6 inches) and a thickness of 10 mm plus or minus 1 mm. At one end, a cut is made in the sample bisecting the thickness, the cut extending across the entire width of the sample and 3 cm from the end of the sample. Starting at the end of the cut, five marks are placed 2 cm apart along the length of the sample. The cut end of the sample is held in the tester's hand and pulled at a rate of approximately 50 mm per minute. If desired, a sharp knife can be used to keep the material in the center of the sample separated, discarding readings caused by the cut of the knife. The tear strength value of each of the five marked segments of the sample (between each of the 2 cm marks) is recorded using the following scoring rules: easy peel or adhesive failure is given a score of 1; adhesive failure with some resistance is given a score of 2; cohesive foam failure is given a score of 3 to 4.5 based on the level of accompanying foam skin failure, where 3 is the highest level of foam skin failure and 4.5 is the lowest level of foam skin failure; and inability to separate is given a score of 5. The scores for each segment are averaged to give the value recorded for each sample. If a segment of the sample has a bubble measured to be greater than 2 mm, the tear strength of that segment is discarded and the bubble is recorded as a test defect. If more than one segment of the sample has a bubble measured to be greater than 2 mm, the entire sample is discarded.

[0402] Aspect

[0403] The following list of exemplary aspects supports and is supported by the disclosure provided herein.

[0404] Aspect 1. A foam comprising a thermoplastic porous foam having an open cell foam microstructure, an average pore size from about 50 microns to about 500 microns, and a specific gravity from about 0.15 to about 0.25;

[0405] wherein the first foam compositionally comprises a first thermoplastic composition comprising one or more copolyesters; and

[0406] wherein the first thermoplastic composition of the first foam is free or substantially free of a nucleating agent, or free or substantially free of a filler, or free or substantially free of both a nucleating agent and a filler.

[0407] Aspect 2. A foam comprising a thermoplastic porous foam having an open-cell foam microstructure, an average pore size from about 50 microns to about 500 microns, and a specific gravity from about 0.15 to about 0.25;

[0408] wherein the first foam compositionally comprises a first thermoplastic composition comprising one or more copolyesters;

[0409] wherein the first foam is a physically foamed product of a single-phase solution of a supercritical fluid and a first thermoplastic composition in a molten state; and

[0410] wherein the first thermoplastic composition of the first foam contains no or substantially no nucleating agent, or no or substantially no filler, or no or substantially no nucleating agent and filler both.

[0411] Aspect 3. The foam according to Aspect 1-2, wherein the foam is produced by a method comprising:

[0412] forming a single-phase solution of a first thermoplastic composition comprising one or more thermoplastic copolyesters and a supercritical fluid, wherein the first thermoplastic composition is molten in the single-phase solution;

[0413] injecting the single-phase solution into a mold cavity, the single-phase solution having an injection temperature during injection;

[0414] reducing the pressure in the mold cavity and causing the molten first thermoplastic composition to foam, the single-phase solution having a foaming temperature during foaming, thereby forming a first foam, wherein the first foam is a thermoplastic porous foam having an open-cell foam microstructure;

[0415] curing the first foam; and

[0416] removing the cured first foam from the mold cavity to form a buffer element.

[0417] Aspect 4. The foam according to any one of Aspects 1-3, wherein the supercritical fluid comprises supercritical carbon dioxide or supercritical nitrogen.

[0418] Aspect 5. The foam according to any one of Aspects 1-4, wherein the supercritical fluid is present in the single-phase solution in an amount of about 1 percent to about 3 percent by weight based on the total weight of the single-phase solution.

[0419] Aspect 6. The foam according to any one of Aspects 1-5, wherein the foaming temperature is from about the melting temperature of the thermoplastic copolyester as determined by dynamic scanning calorimetry to about 50 °C above the peak tail temperature of the thermoplastic copolyester as determined by dynamic scanning calorimetry.

[0420] Aspect 7. The foam according to any one of aspects 1-6, wherein the thermoplastic copolyester is a block copolymer; a multi-block copolymer; a random copolymer; or a condensation copolymer.

[0421] Aspect 8. The foam according to any one of aspects 1-7, wherein the thermoplastic copolyester has a weight average molecular weight of from about 50,000 Daltons to about 1,000,000 Daltons.

[0422] Aspect 9. The foam according to any one of aspects 1-8, wherein the thermoplastic copolyester has a weight average molecular weight of from about 50,000 Daltons to about 500,000 Daltons; from about 75,000 Daltons to about 300,000 Daltons; or from about 100,000 Daltons to about 200,000 Daltons.

[0423] Aspect 10. The foam according to any one of aspects 1-9, wherein the thermoplastic copolyester has a ratio of the first segment to the third segment of from about 1:1 to about 1:5 based on the weight of each of the first segment and the third segment.

[0424] Aspect 11. The foam according to any one of aspects 1-10, wherein the thermoplastic copolyester has a ratio of the first segment to the third segment of from about 1:1 to about 1:3 or from about 1:1 to about 1:2 based on the weight of each of the first segment and the third segment.

[0425] Aspect 12. The foam according to any one of aspects 1-11, wherein the thermoplastic copolyester has a ratio of the second segment to the third segment of from about 1:1 to about 1:3 based on the weight of each of the first segment and the third segment.

[0426] Aspect 13. The foam according to any one of aspects 1-12, wherein the thermoplastic copolyester has a ratio of the second segment to the third segment of from about 1:1 to about 1:2 or from about 1:1 to about 1:1.52 based on the weight of each of the first segment and the third segment.

[0427] Aspect 14. The foam according to any one of aspects 1-13, wherein the first segment derived from a dihydroxy-terminated polyglycol comprises a segment derived from a poly(alkylene oxide) glycol having a weight average molecular weight of from about 250 Daltons to about 6000 Daltons.

[0428] Aspect 15. The foam according to aspect 14, wherein the weight average molecular weight is from about 400 Daltons to about 6,000 Daltons; from about 350 Daltons to about 5,000 Daltons; or from about 500 Daltons to about 3,000 Daltons.

[0429] Aspect 16. The foam according to any one of aspects 14-15, wherein the poly(alkylene oxide) diol is poly(ethylene ether) diol; poly(propylene ether) diol; poly(tetramethylene ether) diol; poly(pentamethylene ether) diol; poly(hexamethylene ether) diol; poly(heptamethylene ether) diol; poly(octamethylene ether) diol; poly(nonamethylene ether) diol; poly(decamethylene ether) diol; or a mixture thereof.

[0430] Aspect 17. The foam according to aspect 16, wherein the poly(alkylene oxide) diol is poly(ethylene ether) diol; poly(propylene ether) diol; poly(tetramethylene ether) diol; poly(pentamethylene ether) diol; or poly(hexamethylene ether) diol.

[0431] Aspect 18. The foam according to aspect 16, wherein the poly(alkylene oxide) diol is poly(tetramethylene ether) diol.

[0432] Aspect 19. The foam according to any one of aspects 1-18, wherein the second segment derived from the diol comprises a diol having a molecular weight of less than about 250.

[0433] Aspect 20. The foam according to aspect 19, wherein the diol is a C2-C8 diol.

[0434] Aspect 21. The foam according to aspect 20, wherein the second segment derived from the diol comprises a diol selected from the group consisting of: ethylene glycol; propylene glycol; butylene glycol; pentylene glycol; 2-methylpropylene glycol; 2,2-dimethylpropylene glycol; hexylene glycol; 1,2-dihydroxycyclohexane; 1,3-dihydroxycyclohexane; 1,4-dihydroxycyclohexane; and mixtures thereof.

[0435] Aspect 22. The foam according to aspect 21, wherein the diol is selected from 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, and mixtures thereof.

[0436] Aspect 23. The foam according to any one of aspects 1-22, wherein the third segment derived from the aromatic dicarboxylic acid comprises an aromatic C5-C16 dicarboxylic acid.

[0437] Aspect 24. The foam according to aspect 23, wherein the aromatic C5-C16 dicarboxylic acid has a molecular weight of less than about 300 daltons or from about 120 daltons to about 200 daltons.

[0438] Aspect 25. The foam according to aspect 23, wherein the aromatic C5-C16 dicarboxylic acid is terephthalic acid, phthalic acid, isophthalic acid, or a derivative thereof.

[0439] Aspect 26. The foam according to aspect 25, wherein the aromatic C5-C16 dicarboxylic acid is terephthalic acid or a dimethyl ester derivative thereof.

[0440] Aspect 27. The foam according to any one of Aspects 1-26, wherein the first thermoplastic composition of the first foam further comprises a non-polymer component, the non-polymer component comprising all non-polymeric ingredients present in the first thermoplastic composition, and based on the total weight of the first thermoplastic composition, the non-polymer component constitutes less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt% or less than 0.5 wt% of the first thermoplastic composition.

[0441] Aspect 28. The foam according to any one of Aspects 1-27, wherein the first thermoplastic composition of the first foam comprises a polymer component, the polymer component comprising all polymers present in the first thermoplastic composition, and based on the total weight of the first thermoplastic composition, the polymer component constitutes at least 95 wt% of the first thermoplastic composition.

[0442] Aspect 29. The foam according to any one of Aspects 1-28, wherein the first thermoplastic composition of the first foam comprises a polymer component, the polymer component comprising all polymers present in the first thermoplastic composition, and based on the total weight of the first thermoplastic composition, the polymer component constitutes at least 97 wt%, at least 98 wt% or at least 99 wt% of the first thermoplastic composition.

[0443] Aspect 30. The foam according to any one of Aspects 1-29, wherein the first thermoplastic composition of the first foam comprises a polymer component, the polymer component comprising all polymers present in the first thermoplastic composition, and in addition to one or more copolyesters, the polymer component further comprises a polyester, a polyolefin or both.

[0444] Aspect 31. The foam according to any one of Aspects 1-30, wherein the first thermoplastic composition of the first foam comprises a polymer component, the polymer component comprising all polymers present in the first thermoplastic composition, and the polymer component consists essentially of one or more copolyesters.

[0445] Aspect 32. The foam according to any one of Aspects 1-31, wherein the thermoplastic copolyester comprises:

[0446] More than one first segment, each first segment being derived from a dihydroxy-terminated polyglycol;

[0447] More than one second segment, each second segment being derived from a diol; and

[0448] More than one third segment, each third segment being derived from an aromatic dicarboxylic acid.

[0449] Aspect 33. The foam according to any one of aspects 1-32, wherein one or more thermoplastic copolyesters comprise at least one thermoplastic copolyester elastomer.

[0450] Aspect 34. The foam according to any one of aspects 1-33, wherein the thermoplastic copolyester comprises:

[0451] (a) More than one first copolyester unit, each of the more than one first copolyester units comprising a first segment derived from a dihydroxy-terminated polyglycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0452]

[0453] wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(alkylene oxide) glycol of the first segment, wherein the poly(alkylene oxide) glycol of the first segment is a poly(alkylene oxide) glycol having a number average molecular weight of from about 400 to about 6000; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment; and

[0454] (b) More than one second copolyester unit, each of the more than one second copolyester units comprising a second segment derived from a diol and a third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0455]

[0456] wherein R3 is the group remaining after removing the hydroxyl group from the diol of the second segment derived from a diol, wherein the diol is a diol having a molecular weight of less than about 250; and wherein R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment.

[0457] Aspect 35. The foam according to aspect 34, wherein the first copolyester unit has a structure represented by Formula 3:

[0458]

[0459] wherein R is H or methyl; wherein y is an integer having a value from 1 to 10; wherein z is an integer having a value from 2 to 60; and wherein the weight average molecular weight of each of the more than one first copolyester units is from about 300 daltons to about 7,000 daltons.

[0460] Aspect 36. The foam according to aspect 35, wherein y is an integer having a value of 1, 2, 3, 4 or 5.

[0461] Aspect 37. The foam according to aspect 35 or 36, wherein R is hydrogen; wherein R is methyl; wherein R is hydrogen and y is an integer having a value of 1, 2 or 3; or wherein R is methyl and y is an integer having a value of 1.

[0462] Aspect 38. The foam according to aspect 35, wherein the first copolyester unit has a structure represented by Formula 4:

[0463]

[0464] wherein z is an integer having a value from 2 to 60; and wherein the weight average molecular weight of each of the more than one first copolyester units is from about 300 daltons to about 7,000 daltons.

[0465] Aspect 39. The foam according to any one of aspects 35 - 38, wherein z is an integer having a value from 5 to 60; from 5 to 50; from 5 to 40; from 4 to 30; from 4 to 20; or from 2 to 10.

[0466] Aspect 40. The foam according to any one of aspects 35 - 39, wherein the weight average molecular weight of each of the more than one first copolyester units is from about 400 daltons to about 6,000 daltons; from about 400 daltons to about 5,000 daltons; from about 400 daltons to about 4,000 daltons; from about 400 daltons to about 3,000 daltons; from about 500 daltons to about 6,000 daltons; from about 500 daltons to about 5,000 daltons; from about 500 daltons to about 4,000 daltons; from about 500 daltons to about 3,000 daltons; from about 600 daltons to about 6,000 daltons; from about 600 daltons to about 5,000 daltons; from about 600 daltons to about 4,000 daltons; from about 600 daltons to about 3,000 daltons.

[0467] Aspect 41. The foam according to any one of aspects 35 - 40, wherein the second copolyester unit has a structure represented by Formula 5:

[0468]

[0469] wherein x is an integer having a value from 1 to 20.

[0470] Aspect 42. The foam according to aspect 41, wherein x is an integer having a value from 2 to 18; from 2 to 17; from 2 to 16; from 2 to 15; from 2 to 14; from 2 to 13; from 2 to 12; from 2 to 11; from 2 to 10; from 2 to 9; from 2 to 8; from 2 to 7; from 2 to 6; or an integer having a value of 2, 3 or 4.

[0471] Aspect 43. The foam according to aspect 41, wherein the second copolyester unit has a structure represented by formula 6:

[0472]

[0473] Aspect 44. The foam according to any one of aspects 1-43, wherein the thermoplastic copolyester comprises from about 30 weight percent to about 80 weight percent; from about 40 weight percent to about 80 weight percent; from about 50 weight percent to about 80 weight percent; from about 30 weight percent to about 70 weight percent; from about 40 weight percent to about 70 weight percent; or from about 50 weight percent to about 70 weight percent, based on the total weight of the thermoplastic copolyester, of more than one first copolyester unit by weight percentage.

[0474] Aspect 45. The foam according to any one of aspects 1-44, wherein the thermoplastic copolyester comprises from about 40 weight percent to about 65 weight percent; from about 45 weight percent to about 65 weight percent; from about 50 weight percent to about 65 weight percent; from about 55 weight percent to about 65 weight percent; from about 40 weight percent to about 60 weight percent; from about 45 weight percent to about 60 weight percent; from about 50 weight percent to about 60 weight percent; or from about 55 weight percent to about 60 weight percent, based on the total weight of the thermoplastic copolyester, of more than one second copolyester unit by weight percentage.

[0475] Aspect 46. The foam according to any one of aspects 1-45, wherein the thermoplastic copolyester comprises from about 40 weight percent to about 65 weight percent, based on the total weight of the thermoplastic copolyester, of more than one second copolyester unit by weight percentage.

[0476] Aspect 47. The foam according to any one of aspects 1-46, wherein the thermoplastic copolyester has a ratio of the first segment to the third segment of from about 1:1 to about 1:5 based on the weight of each of the first segment and the third segment, or wherein the thermoplastic copolyester has a ratio of the second segment to the third segment of from about 1:1 to about 1:3 based on the weight of each of the first segment and the third segment.

[0477] Aspect 48. The foam according to any one of aspects 1-47, wherein the thermoplastic copolyester has a weight average molecular weight of from about 50,000 daltons to about 1,000,000 daltons.

[0478] Aspect 49. The foam according to any one of aspects 1-48, wherein the thermoplastic copolyester composition further comprises an additive.

[0479] Aspect 50. The foam according to aspect 49, wherein the additive is present in an amount from about 0.1 weight percent to about 10 weight percent based on the total weight of the foamed polymeric material.

[0480] Aspect 51. The foam according to aspect 49 or 50, wherein the additive is wax, antioxidant, UV absorber, colorant, or a combination thereof.

[0481] Aspect 52. The foam according to any one of aspects 1 - 51, wherein the thermoplastic copolyester composition consists essentially of one or more thermoplastic copolyesters.

[0482] Aspect 53. The foam according to any one of aspects 1 - 52, further comprising at least one ionomer.

[0483] Aspect 54. The foam according to any one of aspects 1 - 53, further comprising at least one thermoplastic polyurethane.

[0484] Aspect 55. The foam according to any one of aspects 1 - 54, wherein the thermoplastic copolyester composition is substantially free of thermoplastic polyamide polymers, including polyamide copolymers such as polyether block amide copolymers.

[0485] Aspect 56. The foam according to any one of aspects 1 - 55, wherein the thermoplastic copolyester composition is substantially free of thermoplastic polyolefin polymers, including polyethylene and polypropylene and / or polyolefin copolymers such as ethylene - vinyl acetate copolymer.

[0486] Aspect 57. The foam according to any one of aspects 1 - 56, wherein the thermoplastic copolyester has a zero - shear viscosity of about 10 Pascal - seconds to about 10,000 Pascal - seconds; about 100 Pascal - seconds to about 7,000 Pascal - seconds; or about 1,000 Pascal - seconds to about 5,000 Pascal - seconds when determined using the cyclic tensile test described herein.

[0487] Aspect 58. The foam according to any one of aspects 1 - 57, wherein the first thermoplastic composition of the first foam further comprises one or more dyes or pigments.

[0488] Aspect 59. The foam according to any one of aspects 1 - 58, wherein the first thermoplastic composition of the first foam comprises 5 weight percent or less, 4 weight percent or less, 3 weight percent or less, 2 weight percent or less, or 1 weight percent or less of dyes or pigments.

[0489] Aspect 60. The foam according to any one of aspects 1 - 59, wherein the first thermoplastic composition of the first foam is substantially free of dyes or pigments.

[0490] Aspect 61. The foam according to any one of aspects 1 - 60, wherein the single - phase solution does not contain or substantially does not contain a chemical blowing agent, and the first foam does not contain or substantially does not contain decomposition products of the chemical blowing agent.

[0491] Aspect 62. The foam according to any one of aspects 1 - 61, wherein the porous foam does not contain a chemical blowing agent or decomposition products of the chemical blowing agent.

[0492] Aspect 63. The foam according to aspect 62, wherein the chemical blowing agent comprises an inorganic substance.

[0493] Aspect 64. The foam according to aspect 62, wherein the chemical blowing agent comprises an organic substance.

[0494] Aspect 65. The foam according to any one of aspects 1 - 63, wherein the single - phase solution is substantially free of a cross - linker.

[0495] Aspect 66. The foam according to any one of aspects 1 - 64, wherein the porous foam structure comprises less than 10 percent of pores having a closed - cell microstructure.

[0496] Aspect 67. The foam according to any one of aspects 1 - 64, wherein the porous foam structure comprises less than 5 percent of pores having a closed - cell microstructure.

[0497] Aspect 68. The foam according to any one of aspects 1 - 64, wherein the porous foam structure comprises less than 1 percent of pores having a closed - cell microstructure.

[0498] Aspect 69. The foam according to any one of aspects 1 - 68, wherein the porous foam has an average pore size ranging from about 50 microns to about 5 millimeters; from about 100 microns to about 1 millimeter; or from about 50 microns to about 1 millimeter.

[0499] Aspect 70. The foam according to any one of aspects 1 - 69, wherein up to 80% of the open cells in the first foam have an average diameter ranging from about 50 microns to about 200 microns.

[0500] Aspect 71. The foam according to any one of aspects 1 - 70, wherein the first foam has a split - layer tear greater than or equal to about 2.0 kg / cm, or an energy efficiency greater than or equal to about 60 percent, or both.

[0501] Aspect 72. A method for manufacturing a foam article, the method comprising:

[0502] Forming a mixture of a molten first thermoplastic composition comprising a thermoplastic elastomer and a blowing agent;

[0503] Injecting the mixture into a mold cavity;

[0504] Foam the molten first thermoplastic composition to form a foamed molten first thermoplastic composition;

[0505] Solidify the foamed molten first thermoplastic composition to form a porous foam article having a porous foam structure; and

[0506] Remove the foam article from the mold cavity.

[0507] Aspect 73. The method according to aspect 72, wherein the blowing agent is a physical blowing agent.

[0508] Aspect 74. The method according to aspect 73, wherein the physical blowing agent is a supercritical fluid.

[0509] Aspect 75. The method according to aspect 74, wherein the supercritical fluid comprises nitrogen or its supercritical fluid.

[0510] Aspect 76. The method according to aspect 75, wherein the supercritical fluid comprises nitrogen or its supercritical fluid or consists essentially of nitrogen or its supercritical fluid.

[0511] Aspect 77. The method according to aspect 75, wherein the supercritical fluid further comprises carbon dioxide or its supercritical fluid.

[0512] Aspect 78. The method according to aspect 75, wherein the carbon dioxide is present in an amount of about 1% to about 3% or about 1% to about 5% by weight based on the total weight of the mixture.

[0513] Aspect 79. The method according to any one of aspects 75-78, wherein the nitrogen is present in an amount of about 1% to about 3% or about 1% to about 5% by weight based on the total weight of the mixture.

[0514] Aspect 80. The method according to any one of aspects 72-79, wherein forming a mixture of the molten first thermoplastic composition and the physical blowing agent comprises adding the physical blowing agent to the molten first thermoplastic composition and forming a single-phase solution of the physical blowing agent dissolved in the molten first thermoplastic composition.

[0515] Aspect 81. The method according to any one of aspects 72-79, wherein forming a mixture of the molten first thermoplastic composition and the physical blowing agent comprises injecting the physical blowing agent into a solid resin comprising a polymeric material to form an injected resin and melting the injected resin to form a single-phase solution of the physical blowing agent dissolved in the molten first thermoplastic composition.

[0516] Aspect 82. The method according to any one of aspects 72 - 81, wherein injecting the mixture into the mold cavity includes injecting the mixture into a pressurized mold cavity having a first pressure greater than atmospheric pressure; and foaming the molten first thermoplastic composition includes reducing the first pressure to a second pressure and initiating the formation of bubbles by a physical blowing agent, thereby foaming the molten first thermoplastic composition.

[0517] Aspect 83. The method according to any one of aspects 72 - 82, wherein injecting the mixture into the mold cavity includes injecting the mixture into a pressurized mold cavity having a first pressure greater than atmospheric pressure.

[0518] Aspect 84. The method according to aspect 83, wherein the method includes applying a gas backpressure to the mold cavity from about 100 psi to about 3,000 psi, or from about 550 psi to about 1500 psi, or from about 650 psi to about 1000 psi, and wherein the gas backpressure is applied to the mold cavity before the foaming.

[0519] Aspect 85. The method according to aspect 82, wherein the second pressure is atmospheric pressure; and wherein reducing the first pressure to the second pressure includes venting the pressurized mold cavity to atmospheric pressure.

[0520] Aspect 86. The method according to aspect 82, wherein the second pressure is atmospheric pressure; and wherein reducing the first pressure to the second pressure includes using a controlled pressure reduction rate until the mold cavity has a pressure substantially equal to atmospheric pressure.

[0521] Aspect 87. The method according to aspect 86, wherein the controlled pressure reduction rate is from about 10 psi per second to about 600 psi per second, or from about 15 psi per second to about 300 psi per second, or from about 20 psi per second to about 150 psi per second.

[0522] Aspect 88. The method according to any one of aspects 72 - 87, wherein the foam article is substantially free of chemical blowing agents or their decomposition products.

[0523] Aspect 89. The method according to any one of aspects 72 - 88, wherein the mixture has an injection temperature; and wherein the injection temperature is from about the melting temperature of the first thermoplastic composition to about 50 °C above the peak tail temperature of the first thermoplastic composition.

[0524] Aspect 90. The method according to aspect 89, wherein the injection temperature is a temperature from about the melting temperature of the first thermoplastic composition to about 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C or 50 °C above the peak tail temperature of the first thermoplastic composition.

[0525] Aspect 91. The method according to any one of aspects 72 - 90, wherein the foaming occurs at a foaming temperature; and wherein the foaming temperature is from about the melting temperature of the thermoplastic elastomer to about 50 °C higher than the peak tail temperature of the thermoplastic elastomer.

[0526] Aspect 92. The method according to aspect 91, wherein the foaming temperature is a temperature from about the melting temperature of the first thermoplastic composition to about 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C or 50 °C higher than the peak tail temperature of the first thermoplastic composition.

[0527] Aspect 93. The method according to any one of aspects 72 - 92, wherein the foam article is a thermoplastic foam article.

[0528] Aspect 94. The method according to any one of aspects 72 - 93, wherein the curing comprises cooling the mold cavity; or wherein the curing comprises cooling the foamed first thermoplastic composition.

[0529] Aspect 95. The method according to any one of aspects 72 - 94, wherein the foaming comprises releasing pressure from the mold cavity at a mold cavity pressure release rate.

[0530] Aspect 96. The method according to aspect 95, wherein the mold cavity pressure release rate is from about 10 psi per second to about 600 psi per second, or from about 15 psi per second to about 300 psi per second, or from about 20 psi per second to about 150 psi per second.

[0531] Aspect 97. The method according to any one of aspects 72 - 96, wherein the foaming comprises providing a gas back pressure to the mold cavity.

[0532] Aspect 98. The method according to aspect 97, wherein the gas back pressure is at least about 550 psi, from about 550 psi to about 1500 psi, or from about 650 psi to about 1000 psi.

[0533] Aspect 99. The method according to aspect 98, wherein the blowing agent is a physical blowing agent; or wherein the blowing agent is supercritical nitrogen.

[0534] Aspect 100. The method according to any one of aspects 72 - 99, the method further comprising placing a textile element in the mold cavity before injecting the mixture, and foaming the molten first thermoplastic composition in contact with the textile element.

[0535] Aspect 101. The method according to aspect 100, wherein the textile element comprises thermoplastic polyester fibers, thermoplastic polyester yarns, thermoplastic polyurethane fibers, thermoplastic polyurethane yarns, thermoplastic polyamide fibers, thermoplastic polyamide yarns, or a combination thereof.

[0536] Aspect 102. The method according to aspect 100 or 101, wherein the textile element is a component of an upper for a footwear item.

[0537] Aspect 103. The method according to any one of aspects 72 - 102, wherein the foam article is a component of a footwear item.

[0538] Aspect 104. The method according to aspect 103, wherein the foam article is a midsole.

[0539] Aspect 105. The method according to any one of aspects 72 - 103, wherein the foam article is a component of a clothing item.

[0540] Aspect 106. The method according to any one of aspects 72 - 103, wherein the foam article is a component of a sports equipment item.

[0541] Aspect 107. The method according to any one of aspects 72 - 106, wherein the injection comprises monitoring the injection pressure of the mixture before or during the injection and controlling the injection based on the injection pressure of the mixture.

[0542] Aspect 108. The method according to any one of aspects 72 - 106, wherein the injection comprises controlling the injection temperature of the mixture before the mixture enters the mold cavity.

[0543] Aspect 109. The method according to any one of aspects 72 - 106, wherein the injection comprises controlling the mold cavity temperature before the mixture enters the mold cavity.

[0544] Aspect 110. The method according to any one of aspects 72 - 109, wherein the mixture has an expansion ratio of 1 compared to the volume of the mold cavity.

[0545] Aspect 111. The method according to any one of aspects 72 - 109, wherein after removing the foam article from the mold cavity, the foam article is cooled to about 25°C, and the foam article is pressure - balanced at about 25°C and about 1 atm, and the volume of the balanced foam article is within plus or minus 5 percent of the volume of the mold cavity.

[0546] Aspect 112. The method according to any one of aspects 72 - 111, wherein the porous foam article comprises less than 1 percent of pores having a closed - cell microstructure.

[0547] Aspect 113. The method according to any one of aspects 72 - 112, wherein the porous foam article has an average pore size of from about 50 microns to about 5 millimeters; from about 100 microns to about 1 millimeter; or from about 50 microns to about 1 millimeter.

[0548] Aspect 114. The method according to any one of aspects 72 - 113, wherein the porous foam article does not include a chemical blowing agent.

[0549] Aspect 115. The method according to aspect 114, wherein the chemical blowing agent comprises an inorganic substance.

[0550] Aspect 116. The method according to aspect 115, wherein the chemical blowing agent comprises an organic substance.

[0551] Aspect 117. The method according to any one of aspects 72 - 116, wherein the thermoplastic copolyester is a block copolymer; a multi - block copolymer; a random copolymer; or a condensation copolymer.

[0552] Aspect 118. The method according to any one of aspects 72 - 117, wherein the thermoplastic copolyester has a weight - average molecular weight of from about 50,000 Daltons to about 1,000,000 Daltons.

[0553] Aspect 119. The method according to aspect 118, wherein the thermoplastic copolyester has a weight - average molecular weight of from about 50,000 Daltons to about 500,000 Daltons; from about 75,000 Daltons to about 300,000 Daltons; or from about 100,000 Daltons to about 200,000 Daltons.

[0554] Aspect 120. The method according to any one of aspects 72 - 119, wherein the thermoplastic copolyester has a ratio of the first segment to the third segment of from about 1:1 to about 1:5 based on the weight of each of the first segment and the third segment.

[0555] Aspect 121. The method according to aspect 120, wherein the thermoplastic copolyester has a ratio of the first segment to the third segment of from about 1:1 to about 1:3 or from about 1:1 to about 1:2 based on the weight of each of the first segment and the third segment.

[0556] Aspect 122. The method according to any one of aspects 72 - 121, wherein the thermoplastic copolyester has a ratio of the second segment to the third segment of from about 1:1 to about 1:3 based on the weight of each of the first segment and the third segment.

[0557] Aspect 123. The method according to aspect 122, wherein the thermoplastic copolyester has a ratio of the second segment to the third segment of from about 1:1 to about 1:2 or from about 1:1 to about 1:1.52 based on the weight of each of the first segment and the third segment.

[0558] Aspect 124. The method according to any one of aspects 72 - 123, wherein the first segment derived from the dihydroxy-terminated polyglycol comprises segments derived from a poly(alkylene oxide) glycol having a weight average molecular weight of from about 250 daltons to about 6000 daltons.

[0559] Aspect 125. The method according to aspect 124, wherein the weight average molecular weight is from about 400 daltons to about 6,000 daltons; from about 350 daltons to about 5,000 daltons; or from about 500 daltons to about 3,000 daltons.

[0560] Aspect 126. The method according to any one of aspects 124 - 125, wherein the poly(alkylene oxide) glycol is poly(ethylene ether) glycol; poly(propylene ether) glycol; poly(tetramethylene ether) glycol; poly(pentamethylene ether) glycol; poly(hexamethylene ether) glycol; poly(heptamethylene ether) glycol; poly(octamethylene ether) glycol; poly(nonamethylene ether) glycol; poly(decamethylene ether) glycol; or a mixture thereof.

[0561] Aspect 127. The method according to aspect 126, wherein the poly(alkylene oxide) glycol is poly(ethylene ether) glycol; poly(propylene ether) glycol; poly(tetramethylene ether) glycol; poly(pentamethylene ether) glycol; or poly(hexamethylene ether) glycol.

[0562] Aspect 128. The method according to aspect 126, wherein the poly(alkylene oxide) glycol is poly(tetramethylene ether) glycol.

[0563] Aspect 129. The method according to any one of aspects 72 - 128, wherein the second segment derived from the diol comprises a diol having a molecular weight of less than about 250.

[0564] Aspect 130. The method according to aspect 129, wherein the diol is a C2 - C8 diol.

[0565] Aspect 131. The method according to aspect 130, wherein the second segment derived from the diol comprises a diol selected from the group consisting of: ethylene glycol; propylene glycol; butylene glycol; pentylene glycol; 2 - methylpropylene glycol; 2,2 - dimethylpropylene glycol; hexylene glycol; 1,2 - dihydroxycyclohexane; 1,3 - dihydroxycyclohexane; 1,4 - dihydroxycyclohexane; and mixtures thereof.

[0566] Aspect 132. The method according to aspect 130, wherein the diol is selected from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and mixtures thereof.

[0567] Aspect 133. The method according to any one of aspects 72 - 132, wherein the third segment derived from the aromatic dicarboxylic acid comprises an aromatic C5 - C16 dicarboxylic acid.

[0568] Aspect 134. The method according to aspect 133, wherein the aromatic C5 - C16 dicarboxylic acid has a molecular weight of less than about 300 Daltons or from about 120 Daltons to about 200 Daltons.

[0569] Aspect 135. The method according to aspect 133, wherein the aromatic C5 - C16 dicarboxylic acid is terephthalic acid, phthalic acid, isophthalic acid, or a derivative thereof.

[0570] Aspect 136. The method according to aspect 135, wherein the aromatic C5 - C16 dicarboxylic acid is terephthalic acid or a dimethyl ester derivative thereof.

[0571] Aspect 137. The method according to any one of aspects 72 - 136, wherein the thermoplastic copolyester comprises:

[0572] a. More than one first copolyester unit, each first copolyester unit of the more than one first copolyester unit comprising a first segment derived from a dihydroxy - terminated polyalkylene glycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0573]

[0574] wherein R1 is the group remaining after removing the terminal hydroxyl groups from the poly(alkylene oxide) glycol of the first segment, wherein the poly(alkylene oxide) glycol of the first segment is a poly(alkylene oxide) glycol having a number - average molecular weight of about 400 to about 6000; and wherein R2 is the group remaining after removing the carboxyl groups from the aromatic dicarboxylic acid of the third segment; and

[0575] b. More than one second copolyester unit, each second copolyester unit of the more than one second copolyester unit comprising a second segment derived from a diol and a third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0576]

[0577] wherein R3 is the group remaining after removing the hydroxyl groups from the diols of the second segment derived from the diol, wherein the diol is a diol having a molecular weight of less than about 250; and wherein R2 is the group remaining after removing the carboxyl groups from the aromatic dicarboxylic acids of the third segment.

[0578] Aspect 138. The method according to aspect 137, wherein the first copolyester unit has a structure represented by formula 3:

[0579]

[0580] wherein R is H or methyl; wherein y is an integer having a value from 1 to 10; wherein z is an integer having a value from 2 to 60; and wherein the weight average molecular weight of each of the more than one first copolyester units is from about 300 daltons to about 7,000 daltons.

[0581] Aspect 139. The method according to aspect 138, wherein y is an integer having a value of 1, 2, 3, 4 or 5.

[0582] Aspect 140. The method according to aspect 138 or 139, wherein R is hydrogen; wherein R is methyl; wherein R is hydrogen and y is an integer having a value of 1, 2 or 3; or wherein R is methyl and y is an integer having a value of 1.

[0583] Aspect 141. The method according to aspect 137, wherein the first copolyester unit has a structure represented by formula 4:

[0584]

[0585] wherein z is an integer having a value from 2 to 60; and wherein the weight average molecular weight of each of the more than one first copolyester units is from about 300 daltons to about 7,000 daltons.

[0586] Aspect 142. The method according to any one of aspects 137 - 141, wherein z is an integer having a value from 5 to 60; from 5 to 50; from 5 to 40; from 4 to 30; from 4 to 20; or from 2 to 10.

[0587] Aspect 143. The method according to any one of aspects 137 - 142, wherein the weight - average molecular weight of each of the more than one first copolyester units is from about 400 Daltons to about 6,000 Daltons; from about 400 Daltons to about 5,000 Daltons; from about 400 Daltons to about 4,000 Daltons; from about 400 Daltons to about 3,000 Daltons; from about 500 Daltons to about 6,000 Daltons; from about 500 Daltons to about 5,000 Daltons; from about 500 Daltons to about 4,000 Daltons; from about 500 Daltons to about 3,000 Daltons; from about 600 Daltons to about 6,000 Daltons; from about 600 Daltons to about 5,000 Daltons; from about 600 Daltons to about 4,000 Daltons; from about 600 Daltons to about 3,000 Daltons.

[0588] Aspect 144. The method according to any one of aspects 137 - 143, wherein the second copolyester unit has a structure represented by Formula 5:

[0589]

[0590] where x is an integer having a value from 1 to 20.

[0591] Aspect 145. The method according to aspect 144, wherein x is an integer having a value from 2 to 18; from 2 to 17; from 2 to 16; from 2 to 15; from 2 to 14; from 2 to 13; from 2 to 12; from 2 to 11; from 2 to 10; from 2 to 9; from 2 to 8; from 2 to 7; from 2 to 6; or a value of 2, 3 or 4.

[0592] Aspect 146. The method according to aspect 144, wherein the second copolyester unit has a structure represented by Formula 6:

[0593]

[0594] Aspect 147. The foam according to any one of aspects 137 - 146, wherein the thermoplastic copolyester comprises from about 30 weight percent to about 80 weight percent; from about 40 weight percent to about 80 weight percent; from about 50 weight percent to about 80 weight percent; from about 30 weight percent to about 70 weight percent; from about 40 weight percent to about 70 weight percent; or from about 50 weight percent to about 70 weight percent, based on the total weight of the thermoplastic copolyester, of the more than one first copolyester unit.

[0595] Aspect 148. The method according to any one of Aspects 72 - 147, wherein the thermoplastic copolyester comprises from about 40 weight percent to about 65 weight percent; from about 45 weight percent to about 65 weight percent; from about 50 weight percent to about 65 weight percent; from about 55 weight percent to about 65 weight percent; from about 40 weight percent to about 60 weight percent; from about 45 weight percent to about 60 weight percent; from about 50 weight percent to about 60 weight percent; or from about 55 weight percent to about 60 weight percent, by weight, of more than one second copolyester unit, based on the total weight of the thermoplastic copolyester.

[0596] Aspect 149. The method according to any one of Aspects 72 - 148, wherein the thermoplastic copolyester composition further comprises an additive.

[0597] Aspect 150. The method according to Aspect 149, wherein the additive is present in an amount from about 0.1 weight percent to about 10 weight percent, based on the total weight of the foamed polymeric material.

[0598] Aspect 151. The method according to Aspect 149 or 150, wherein the additive is a wax, antioxidant, UV absorber, colorant, or a combination thereof.

[0599] Aspect 152. The method according to any one of Aspects 72 - 151, wherein the thermoplastic copolyester composition consists essentially of one or more thermoplastic copolyesters.

[0600] Aspect 153. The method according to any one of Aspects 72 - 151, further comprising at least one ionomer.

[0601] Aspect 154. The method according to any one of Aspects 72 - 151, further comprising at least one thermoplastic polyurethane.

[0602] Aspect 155. The method according to any one of Aspects 72 - 154, wherein the thermoplastic copolyester composition is substantially free of thermoplastic polyamide polymers, including polyamide copolymers such as polyether block amide copolymers.

[0603] Aspect 156. The method according to any one of Aspects 72 - 154, wherein the thermoplastic copolyester composition is substantially free of thermoplastic polyolefin polymers, including polyethylene and polypropylene and / or polyolefin copolymers such as ethylene - vinyl acetate copolymers.

[0604] Aspect 157. The method according to any one of aspects 72 - 156, wherein when determined using the cyclic tensile test described herein, the thermoplastic copolyester has a zero shear viscosity of from about 10 Pascal - seconds to about 10,000 Pascal - seconds; from about 100 Pascal - seconds to about 7,000 Pascal - seconds; or from about 1,000 Pascal - seconds to about 5,000 Pascal - seconds.

[0605] Aspect 158. The method according to any one of aspects 72 - 157, wherein when determined using the cyclic tensile test described herein, the foam article has a maximum load of from about 100 N to about 4000 N.

[0606] Aspect 159. The method according to aspect 158, wherein when determined using the cyclic tensile test described herein, the foam article has a maximum load of from about 100 N to about 4000 N.

[0607] Aspect 160. The method according to any one of aspects 72 - 159, wherein when determined using the cyclic compression test described herein, the foam article has an energy efficiency of greater than or equal to about 50 percent.

[0608] Aspect 161. The method according to aspect 160, wherein when determined using the cyclic compression test described herein, the foam article has an energy efficiency of greater than or equal to about 60 percent.

[0609] Aspect 162. The method according to aspect 160, wherein when determined using the cyclic compression test described herein, the foam article has an energy efficiency of greater than or equal to about 70 percent.

[0610] Aspect 163. The method according to aspect 160, wherein when determined using the cyclic compression test described herein, the foam article has an energy efficiency of from about 50 percent to about 97 percent.

[0611] Aspect 164. The method according to any one of aspects 72 - 163, wherein when determined using the cyclic compression test described herein, the foam article has an energy return of from about 200 millijoules (mJ) to 1200 mJ.

[0612] Aspect 165. The method according to aspect 164, wherein when determined using the cyclic compression test described herein, the foam article has an energy return of from about 400 mJ to 1000 mJ.

[0613] Aspect 166. The method according to aspect 164, wherein when determined using the cyclic compression test described herein, the foam article has an energy return of from about 600 mJ to 800 mJ.

[0614] Aspect 167. The method according to any one of aspects 72 - 166, wherein using the delamination tear test as described herein, the foam article has a delamination tear value of about 1.0 kg / cm to 4.5 kg / cm, about 1.6 kg / cm to 4.0 kg / cm, about 2.0 kg / cm to 4.0 kg / cm, about 2.0 kg / cm to 3.5 kg / cm, about 2.5 kg / cm to 3.5 kg / cm, about 0.07 kg / cm to 2.0 kg / cm, or about 0.8 kg / cm to 1.5 kg / cm, or about 0.9 kg / cm to 1.2 kg / cm, about 1.5 kg / cm to 2.2 kg / cm, about 0.08 kg / cm to 4.0 kg / cm, about 0.9 kg / cm to 3.0 kg / cm, about 1.0 kg / cm to 2.0 kg / cm, about 1.0 kg / cm to 1.5 kg / cm, or about 2 kg / cm.

[0615] Aspect 168. The method according to any one of aspects 72 - 167, wherein when determined using the delamination tear test as described herein, the foam article has a delamination tear value greater than or equal to about 1.5 kg / cm, greater than or equal to about 2.0 kg / cm, or greater than or equal to about 2.5 kg / cm.

[0616] Aspect 169. The method according to any one of aspects 72 - 168, wherein the foam article has a specific gravity less than or equal to 0.9, less than or equal to 0.7, less than or equal to 0.5, or less than or equal to 0.3.

[0617] Aspect 170. The method according to aspect 169, wherein the foam article has a specific gravity from about 0.02 to about 0.22; from about 0.03 to about 0.12; from about 0.04 to about 0.10; from about 0.11 to about 0.12; from about 0.10 to about 0.12; from about 0.15 to about 0.2; 0.15 to about 0.30; 0.01 to about 0.10; from about 0.02 to about 0.08; from about 0.03 to about 0.06; 0.08 to about 0.15; from about 0.10 to about 0.12; from about 0.15 to about 0.2; from about 0.10 to about 0.12; from about 0.1 to about 0.35; from about 0.12 to about 0.20; from 0.02 to about 0.22; from about 0.02 to about 0.20; from about 0.02 to about 0.18; or from about 0.02 to about 0.16.

[0618] Aspect 171. The method according to any one of aspects 72 - 170, wherein for a cylindrical sample having a diameter of about 45 mm, the foam article has a stiffness of about 200 kPa to about 1000 kPa as determined using the cyclic compression test.

[0619] Aspect 172. The method according to aspect 171, wherein for a cylindrical sample having a diameter of about 45 millimeters, the foam article has a stiffness of about 400 kilopascals to about 900 kilopascals as determined using a cyclic compression test.

[0620] Aspect 173. The method according to any one of aspects 72 - 172, wherein when measured on a foam board having a thickness of about 1 centimeter, the foam article has a displacement change of about 1 millimeter to about 5 millimeters at maximum load, wherein the foam board is compressed for about 5000 compression cycles, each cycle from 0 Newtons to 300 Newtons and back to 0 N, using a 45 mm diameter cylindrical tupp as the compression head.

[0621] Aspect 174. The method according to any one of aspects 72 - 172, wherein when measured on a foam board having a thickness of about 1 centimeter, the foam article has a displacement change of about 2 millimeters to about 4 millimeters at maximum load, wherein the foam board is compressed for about 5000 compression cycles, each cycle from 0 Newtons to 300 Newtons and back to 0 Newtons, using a 45 mm diameter cylindrical tupp as the compression head.

[0622] Aspect 175. The method according to any one of aspects 72 - 174, further comprising disposing a layer comprising a second thermoplastic composition on an outer surface of the foam article.

[0623] Aspect 176. The method according to aspect 175, further comprising the step of removing the foam article from the mold cavity after the disposing step.

[0624] Aspect 177. The method according to aspect 175, further comprising the step of removing the foam article from the mold cavity before the disposing step.

[0625] Aspect 178. The method according to any one of aspects 175 - 177, wherein the thermoplastic composition comprises a thermoplastic elastomer or a thermoplastic vulcanizate material for one type of ground contact, reinforcement surface layer, containment layer, shoe outsole, welt, or other applications.

[0626] Aspect 179. The method according to any one of aspects 175 - 178, wherein the second thermoplastic composition comprises a thermoplastic elastomer (TPE) from the polymer chemistry family, such as copolyesters; thermoplastic polyurethanes (TPU); styrene copolymers such as styrene - butadiene rubber (SBR), styrene - ethylene - butadiene - styrene (SEBS), styrene - ethylene - propylene - styrene (SEPS); ethylene copolymers such as ethylene - propylene copolymers, olefin block copolymers, Surlyn; and other ionomers; and / or acrylic copolymer elastomers, where they are block copolymers comprising PMMA block - acrylate block - PMMA block; and so on.

[0627] Aspect 180. The method according to any one of aspects 175 - 179, wherein the second thermoplastic composition comprises an injection - processable thermoplastic vulcanizate (TPV) material, which is generally a cross - linked or partially cross - linked rubber dispersed in a thermoplastic matrix phase, such as ethylene - propylene - diene rubber (EPDM / PP) in polypropylene, examples of which include Sarlink or Santoprene TPV trade names; or alkyl acrylate copolymer rubber (ACM / PA) in a polyamide matrix, examples of which include Zeotherm TPV; or silicone rubber dispersed in a Hytrel - based copolyester (e.g., so - called TSiPV).

[0628] Aspect 181. The method according to any one of aspects 175 - 180, wherein if used as a solid polymer material without adding a compressed gas, supercritical fluid, or other foaming agent, the second thermoplastic composition has a hardness less than Shore A 90, optionally less than Shore A 85, and preferably less than Shore A 80, but greater than Shore A 60 and optionally greater than Shore A 65.

[0629] Aspect 182. The method according to any one of aspects 175 - 181, wherein if used as a solid polymer, the thermoplastic composition comprises a TPE or TPV having a density less than 1.25 g / cc, optionally less than 1.1 g / cc, or less than 0.95 g / cc, and preferably less than 0.9 g / cc.

[0630] Aspect 183. The method according to any one of aspects 175 - 182, wherein the second thermoplastic composition is produced separately via injection molding with or without adding a compressed gas, supercritical fluid, or other foaming agent, or a foam article is produced via overmolding on the second thermoplastic composition.

[0631] Aspect 184. The method according to any one of aspects 175 - 183, wherein the second thermoplastic composition (TPE or TPV) is extruded into a fused deposition 3D printing filament with a diameter of 1.5 mm, 1.75 mm, 1.85 mm, 2.85 mm, 3.0 mm, or other relevant diameters for deposition and attachment to a foamed article comprising the first thermoplastic composition in such a way as to include a layer in contact with the ground, print - on outsole on a shoe outsole, or other external features.

[0632] Aspect 185. The method according to aspect 184, wherein the second thermoplastic composition is produced via sequential injection in the same process, or wherein the second thermoplastic composition is produced in a separate process and subsequently inserted into the mold, after which the foam article is overmolded with the first thermoplastic composition.

[0633] Aspect 186. The method according to any one of aspects 175 - 185, wherein the second thermoplastic composition is produced solely by injection molding with just enough compressed gas, supercritical fluid, or other foaming agent to achieve a density of 0.9 g / cc or less, 0.85 g / cc or less, or 0.8 g / cc or less.

[0634] Aspect 187. The method according to any one of aspects 175 - 185, wherein the second thermoplastic composition is a film or an outsole or a welt that is pretreated with plasma or corona treatment before receiving the overmolding assembly method.

[0635] Aspect 188. The method according to any one of aspects 175 - 187, wherein the second thermoplastic composition is a film or an outsole or a welt that is pretreated with a separate primer or a primer plus an adhesive before receiving the overmolding assembly method described in the above aspects.

[0636] Aspect 189. The method according to any one of aspects 175 - 188, wherein the interfacial adhesion strength between the second thermoplastic composition and the first thermoplastic composition that constitutes the overmolded foam article exceeds 2.5 kilogram - force per centimeter.

[0637] Aspect 190. The method according to aspect 189, wherein the interfacial adhesion strength between the second thermoplastic composition and the first thermoplastic composition that constitutes the foam article exceeds 3.0 kilogram - force per centimeter.

[0638] Aspect 191. The method according to any one of aspects 72 - 190, wherein the foam article comprises a thermoplastic copolyester greater than about 90 weight percent based on the total weight of the first thermoplastic composition.

[0639] Aspect 192. The method according to aspect 191, wherein the foam article comprises a thermoplastic copolyester greater than about 95 weight percent based on the total weight of the first thermoplastic composition.

[0640] Aspect 193. The method according to aspect 191, wherein the foam article comprises a thermoplastic copolyester greater than about 97 weight percent based on the total weight of the first thermoplastic composition.

[0641] Aspect 194. The method according to aspect 191, wherein the foam article comprises a thermoplastic copolyester greater than about 98 weight percent based on the total weight of the first thermoplastic composition.

[0642] Aspect 195. The method according to aspect 191, wherein the foam article comprises a thermoplastic copolyester greater than about 99 weight percent based on the total weight of the first thermoplastic composition.

[0643] Aspect 196. A foam article comprising a foamed polymeric material, the foamed polymeric material constituting the foam according to any one of aspects 1-71; wherein the foam article has a porous foam structure.

[0644] Aspect 197. The foam article according to aspect 196, wherein the foam article is an extruded foam article.

[0645] Aspect 198. The foam article according to aspect 196, wherein the foam article is an injection molded foam article.

[0646] Aspect 199. The foam article according to aspect 198, wherein the foam article is a compression molded foam article.

[0647] Aspect 200. The foam article according to any one of aspects 196-199, wherein the porous foam structure has a closed cell foam microstructure.

[0648] Aspect 201. The foam article according to any one of aspects 196-200, wherein the porous foam structure comprises less than 5 percent of pores having a closed cell microstructure.

[0649] Aspect 202. The foam article according to any one of aspects 196-200, wherein the porous foam structure comprises less than 1 percent of pores having a closed cell microstructure.

[0650] Aspect 203. The foam article according to any one of aspects 196-202, wherein the porous foam has an average pore size from about 50 microns to about 5 millimeters; from about 100 microns to about 1 millimeter; or from about 50 microns to about 1 millimeter.

[0651] Aspect 204. The foam article according to any one of aspects 196-203, wherein when determined using the interlayer adhesion test method described herein, the foam article has an interlayer adhesion strength between the polymer layer and the foam component greater than 2.5 kg force / cm or greater than 3.0 kg force / cm.

[0652] Aspect 205. The foam article according to any one of aspects 196 - 204, wherein when determined according to the hand - pull test method described herein, the foam article has an average hand - pull test result between the polymer layer and the foam component that is greater than or equal to 2.0, or greater than or equal to 2.5, or greater than or equal to 3.0, or greater than or equal to 3.5, or greater than or equal to 4.0, or greater than or equal to 4.5.

[0653] Aspect 206. The foam article according to any one of aspects 196 - 205, wherein the layer has an Akron abrasion loss of less than 0.50 cubic centimeters as determined using the Akron abrasion test, optionally less than 0.40 cubic centimeters loss, less than 0.30 cubic centimeters loss, less than 0.20 cubic centimeters loss, or less than 0.10 cubic centimeters loss.

[0654] Aspect 207. The foam article according to any one of aspects 196 - 206, wherein the layer has an Akron abrasion loss of less than 500 milligrams as determined using the Akron abrasion test, optionally less than 400 milligrams loss, less than 300 milligrams loss, less than 200 milligrams loss, or less than 100 milligrams loss.

[0655] Aspect 208. The foam article according to any one of aspects 196 - 207, wherein the layer has a DIN abrasion loss of less than 0.30 cubic centimeters as determined using the DIN abrasion test, optionally less than 0.20 cubic centimeters loss, less than 0.10 cubic centimeters loss, less than 0.05 cubic centimeters loss, or less than 0.03 cubic centimeters loss.

[0656] Aspect 209. The foam article according to any one of aspects 196 - 208, wherein the layer has a DIN abrasion loss of less than 300 milligrams, optionally less than 250 milligrams, optionally less than 200 milligrams, optionally less than 150 milligrams, optionally less than 100 milligrams, optionally less than 80 milligrams, optionally less than 50 milligrams, or optionally less than 30 milligrams as determined using the DIN abrasion test.

[0657] Aspect 210. The foam article according to any one of aspects 196 - 209, wherein...

Claims

1. A cushioning element for a footwear item, the cushioning element comprising: a first foam, wherein the first foam is an injection molded thermoplastic porous foam having an open cell foam microstructure, an average pore size from 50 microns to 500 microns, and a specific gravity from 0.15 to 0.25; and a second component of a second thermoplastic composition, the second component of the second thermoplastic composition being thermally bonded to the first foam, the second thermoplastic composition having a specific gravity of at least 0.85 and comprising a thermoplastic copolyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic styrene copolymer elastomer, or a thermoplastic vulcanizate material; wherein the first foam compositionally comprises a first thermoplastic composition, the first thermoplastic composition comprising one or more copolyesters; wherein the first foam is a physically foamed product of a single-phase solution of a supercritical fluid and the first thermoplastic composition in a molten state; and wherein the first thermoplastic composition of the first foam contains no or substantially no solid non-polymeric material, or contains less than one weight percent of solid non-polymeric material based on the total weight of the first thermoplastic composition.

2. The cushioning element according to claim 1, wherein the first foam is produced by a method comprising: forming a single-phase solution of the first thermoplastic composition comprising the one or more copolyesters and the supercritical fluid, wherein the first thermoplastic composition is molten in the single-phase solution; injecting the single-phase solution into a mold cavity, the single-phase solution having an injection temperature during injection; reducing the pressure in the mold cavity and causing the molten first thermoplastic composition to foam, the single-phase solution having a foaming temperature during foaming, thereby forming a first foam, wherein the first foam is a thermoplastic porous foam having an open cell foam microstructure; curing the first foam; and removing the cured first foam from the mold cavity.

3. The cushioning element according to claim 2, wherein the foaming temperature is from about the melting temperature of the copolyester determined by dynamic scanning calorimetry to about 50 degrees Celsius above the peak tail temperature of the copolyester determined by dynamic scanning calorimetry.

4. The cushioning element according to any one of claims 1-3, wherein the supercritical fluid comprises supercritical carbon dioxide or supercritical nitrogen.

5. The cushioning element according to any one of claims 1-3, wherein the supercritical fluid is present in the single-phase solution in an amount of from 1 percent to 3 percent by weight based on the total weight of the single-phase solution.

6. The cushioning element according to any one of claims 1-3, wherein the first foam has a split tear of greater than or equal to about 2.0 kg / cm and / or an energy efficiency of greater than or equal to about 60 percent.

7. The cushioning element according to any one of claims 1-3, wherein the first thermoplastic composition of the first foam contains less than 5 weight percent of a dye.

8. The cushioning element according to any one of claims 1 - 3, wherein the first thermoplastic composition of the first foam comprises a polymer component, and the polymer component has an amount of at least 95 weight percent based on the total weight of the first thermoplastic composition.

9. The cushioning element according to any one of claims 1 - 3, wherein the first thermoplastic composition of the first foam comprises a polymer component, and in addition to the one or more copolyesters, the polymer component further comprises a polyester and / or a polyolefin.

10. The cushioning element according to any one of claims 1 - 3, wherein the first thermoplastic composition of the first foam comprises a polymer component, and the polymer component consists essentially of the one or more copolyesters.

11. The cushioning element according to any one of claims 1 - 3, wherein the copolyester comprises: (a) More than one first segment, each first segment being derived from a dihydroxy - terminated polyglycol; (b) More than one second segment, each second segment being derived from a diol; and (c) More than one third segment, each third segment being derived from an aromatic dicarboxylic acid.

12. The cushioning element according to any one of claims 1 - 3, wherein the open - cell foam microstructure of the first foam comprises less than 10 percent of pores having a closed - cell foam microstructure.

13. The cushioning element according to any one of claims 1 - 3, wherein the open - cell foam microstructure of the first foam comprises less than 5 percent of pores having a closed - cell foam microstructure.

14. The cushioning element according to any one of claims 1 - 3, wherein the open - cell foam microstructure of the first foam comprises less than 1 percent of pores having a closed - cell foam microstructure.

15. The cushioning element according to any one of claims 1 - 3, wherein up to 80% of the open - cells in the first foam have an average diameter ranging from 50 microns to 200 microns.

16. The cushioning element according to any one of claims 1 - 3, wherein the copolyester comprises: (a) More than one first copolyester unit, each first copolyester unit in the more than one first copolyester unit comprises a first segment derived from a dihydroxy - terminated polyglycol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1: wherein R1 is the group remaining after removing the terminal hydroxyl groups from the polyglycol of the first segment, wherein the polyglycol of the first segment is a poly(alkylene oxide) glycol having a number - average molecular weight of 400 to 6000; and wherein R2 is the group remaining after removing the carboxyl groups from the aromatic dicarboxylic acid of the third segment; and (b) More than one second copolyester unit, each second copolyester unit in the more than one second copolyester unit comprises a second segment derived from a diol and the third segment derived from an aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2: wherein R3 is the group remaining after removing the hydroxyl groups from the diol of the second segment derived from the diol, wherein the diol is a diol having a molecular weight of less than about 250; and wherein R2 is the group remaining after removing the carboxyl groups from the aromatic dicarboxylic acid of the third segment.

17. The cushioning element according to any one of claims 1-3, wherein the one or more copolyesters comprise at least one thermoplastic copolyester elastomer.

18. The cushioning element according to any one of claims 1-3, wherein the cushioning element is a midsole or a heel cushion.

19. An article of footwear comprising the cushioning element according to any one of claims 1-18.

20. The cushioning element according to any one of claims 1-3 or the article of footwear according to claim 19, wherein the first thermoplastic composition for the first foam and the second thermoplastic composition are sequentially added to the mold during an injection molding process to provide an integral part having the first foam and the second component.

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