Midsole structure for an article of footwear comprising a web

Abstract

A sole structure for an article of footwear is described. In one example, the sole structure includes first and second foam components and one or more web components, such as web textile components. The first foam component includes a first side and an opposite second side, and the second foam component includes a first side and an opposite second side. The first and second foam components form a stack in the sole structure. A web component, such as a web textile component, is positioned in the stack between the second side of the first foam component and the first side of the second foam component, and is bonded to the second side of the first foam component and the first side of the second foam component. This abstract is intended as a scanning tool for purposes of locating subject matter in certain areas and is not intended to be limiting in any way.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 62 / 716,167, filed August 8, 2018, which is incorporated herein by reference in its entirety.

[0003] background

[0004] The design of sports equipment, apparel, and footwear involves a wide range of factors, from aesthetics and comfort to performance and durability. While designs and fashions can change rapidly, the market demand for enhanced performance remains constant. To balance these needs, designers utilize a variety of materials and designs for the various components that make up sports equipment, apparel, and footwear. Brief description of the attached diagram

[0006] Other aspects of this disclosure will be readily understood when viewed in conjunction with the accompanying drawings and upon review of the detailed description described below.

[0007] Figure 1 This is an exemplary perspective view of a footwear article incorporating an exemplary sole structure according to aspects of this disclosure.

[0008] Figure 2 Based on aspects of this disclosure Figure 1 An exemplary exploded perspective view of an exemplary sole structure of a footwear item shown.

[0009] Figure 3 Based on aspects of this disclosure Figure 2 An exemplary cross-sectional side view of the exemplary sole structure shown.

[0010] Figure 4 The illustration shows aspects of this disclosure. Figures 1-3 The image shows a top view of the mesh component and foam component of the shoe sole structure.

[0011] Figure 5 The illustration shows an exemplary mesh textile according to aspects of this disclosure.

[0012] Figures 6A-6B The illustration shows a top view of an example aspect of the present disclosure, each example aspect including different mesh components and foam components arranged in various ways.

[0013] Figure 7 An exploded perspective view of another exemplary midsole structure including a wave pattern, according to aspects of this disclosure, is illustrated.

[0014] Figure 8 The illustration shows aspects of this disclosure. Figure 7 The exemplary shoe sole sandwich structure shown is a cross-sectional side view.

[0015] Figures 9A-9B The illustration shows a top view of an example aspect of the present disclosure, each example aspect including different mesh components and foam components arranged in various ways.

[0016] Figure 10 An exploded perspective view of another exemplary midsole structure including a sawtooth pattern, according to aspects of this disclosure, is illustrated.

[0017] Figure 11 The illustration shows aspects of this disclosure. Figure 10 The exemplary shoe sole sandwich structure shown is a cross-sectional side view.

[0018] Figures 12A-12B The illustration shows a top view of an example aspect of the present disclosure, each example aspect including different mesh components and foam components arranged in various ways.

[0019] Figure 13 An exploded perspective view of another exemplary midsole structure according to an aspect of this disclosure is illustrated, the midsole structure including a first foam component having a cavity and a second foam component fitted into the cavity.

[0020] Figures 14A-14F The illustration shows a view of another exemplary midsole structure according to an aspect of the present disclosure, the midsole structure including a first foam component having an undulating surface in a cavity and a second foam component having a corresponding undulating surface fitted into the cavity.

[0021] Figures 15A-15B The illustration depicts a method for forming a sole interlayer for footwear articles according to aspects of this disclosure.

[0022] Figures 16A-16B The diagram illustrates the test angles for the mesh component. Figure 16A Representative test samples are shown for determining tensile strength and / or elongation along the indicated angle. Figure 16B The orientation of the test angle relative to a representative mesh component is shown in the test sample.

[0023] Detailed description

[0024] The following paragraphs describe a sole structure for footwear articles. In one example, the sole structure includes a first foam component and a second foam component, as well as one or more mesh components. The first foam component includes a first side and an opposing second side, and the second foam component includes a first side and an opposing second side. The first and second foam components form a stack in the sole structure. The mesh components are positioned in the stack between the second side of the first foam component and the first side of the second foam component, and are coupled to the second side of the first foam component and the first side of the second foam component. In one aspect, the mesh components are stretched by a first percentage and a second percentage in a first direction and a second direction, respectively. Depending on the number and orientation of the mesh components, one or both of the compressive strength and shear strength of the sole structure may be increased in certain areas of the sole structure.

[0025] Example aspects will now be described more fully with reference to the accompanying drawings. Example aspects are provided so that this disclosure will be thorough and will fully convey the scope to those skilled in the art. Numerous specific details, such as examples of specific components, apparatuses, and methods, are set forth to provide a thorough understanding of aspects of this disclosure. It will be apparent to those skilled in the art that specific details are not required, example aspects may be implemented in many different forms, and neither specific details nor example aspects should be construed as limiting the scope of this disclosure. In some example aspects, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.

[0026] Shoe sole structure.

[0027] Figure 1 The illustration shows a perspective view of a footwear article 10 incorporated into an exemplary sole structure 14 according to various aspects described herein. Footwear article 10 is a representative example illustrating the use of one or more mesh components (e.g., mesh textiles) in a sole structure to increase compressive and / or shear strength in certain areas of the sole structure. That is, in some aspects, the mesh component may be a mesh textile component as disclosed below. Footwear article 10 in… Figure 1 The figures are not drawn to any particular scale. Similarly, in the remaining figures, the components of the footwear article 10 are not necessarily drawn to scale, but rather the focus is on showing the various ways in which compressive strength and / or shear strength is increased in certain areas of the sole structure.

[0028] like Figure 1As shown, footwear article 10 includes an upper 12 and a sole structure 14 attached to the upper 12. Footwear article 10 includes multiple areas, including a forefoot area 16, a midfoot area 18, and a heel area 20. The forefoot area 16 may correspond to the toes and the joints connecting the metatarsal and phalangeal bones of the foot. The midfoot area 18 may correspond to the arch of the foot, and the heel area 20 may correspond to the posterior portion of the foot, including the calcaneus. Footwear article 10 also includes medial side 22 and lateral side 24, which correspond to opposite sides of the footwear article, respectively.

[0029] As described in further detail below, the sole structure 14 may include one or more mesh components, such as one or more mesh textiles. In several aspects, the mesh components may be stretched in one or both directions. The mesh components may be stretched to the same degree or percentage in either direction, or the mesh components may be stretched by a first percentage in a first direction and by a different second percentage in a second direction. The mesh components may be knitted, crocheted, braided, or woven from one or more yarns, each yarn being formed from one or more individual fibers. The compressive strength and / or shear strength of the sole structure 14 may be increased in certain areas based on the number, placement, and orientation of the mesh components in the sole structure 14. Therefore, the characteristics of the footwear article 10 can be adapted for use in a variety of types of activities.

[0030] Figure 2 The diagram illustrates several aspects described in this article. Figure 1 An exploded perspective view of an exemplary sole structure 14 of the footwear article 10 shown. Figure 2 As shown, the sole structure 14 includes an outsole 30 and a midsole 40. The outsole 30 includes a first side 32 contacting the midsole, a second side 34 opposite to the first side 32, and sidewalls 36 extending around the periphery of the first side 32 and the second side 34. The outsole 30 provides abrasion resistance and traction with the ground surface. The outsole 30 can be formed of any suitable material, including rubber or other materials that impart durability and abrasion resistance as well as enhanced traction with the ground surface. When the footwear article 10 is assembled, the midsole 40 is disposed between the outsole 30 and the upper 12.

[0031] The midsole 40 includes a first foam component 50, a second foam component 60, and a mesh component 70. The first foam component 50 includes a first side 52, a second side 54 opposite to the first side 52, and sidewalls 56 extending around the peripheries of the first and second sides 52 and 54. The second foam component 60 includes a first side 62, a second side 64 opposite to the first side 62, and sidewalls 66 extending around the peripheries of the first and second sides 62 and 64. During assembly, the mesh component 70 is positioned in the stack between the second side 54 of the first foam component 50 and the first side 62 of the second foam component 60, and is coupled to the second side 54 of the first foam component 50 and the first side 62 of the second foam component 60. The form and characteristics of the first foam component 50, the second foam component 60, and the mesh component 70 will be described in further detail below.

[0032] As described herein, the compressive and / or shear strength of the midsole 40 can be increased by including the mesh component 70 compared to a midsole 40 that omits or excludes the mesh component 70. The compressive and / or shear strength can be increased in one or more regions of the midsole 40, such as the forefoot region 16, midfoot region 18, heel region 20, medial side 22, and lateral side 24, depending on the size and placement of the mesh component 70. The compressive and / or shear strength can also be increased to a greater or lesser extent in one or more directions A', B', and C', depending on certain characteristics of the mesh component 70, such as the type and orientation of the mesh component 70, as described below.

[0033] Figure 3 The diagram illustrates several aspects described in this article. Figure 2 The exemplary sole structure 14 shown is a cross-sectional side view. As shown, a first foam component 50 and a second foam component 60 form a stack in the sole interlayer 40. Furthermore, a mesh component 70 is positioned in the stack between the second side 54 of the first foam component 50 and the first side 62 of the second foam component 60, and is bonded to the second side 54 of the first foam component 50 and the first side 62 of the second foam component 60. In some cases, the second side 54 of the first foam component 50 and the first side 62 of the second foam component 60 may also be bonded to each other in certain areas where they meet. Depending on the characteristics of the mesh component 70, the second side 54 of the first foam component 50 and the first side 62 of the second foam component 60 may also be bonded to each other through openings or holes in the mesh component 70.

[0034] like Figure 2 and Figure 3As shown, the first side 52 and second side 54 of the first foam component 50, from the inner side 22 to the outer side 24, and on the forefoot region 16, midfoot region 18, and heel region 20 of the first foam component 50, may be generally flat or planar. In other words, neither the first side 52 nor the second side 54 of the first foam component 50 includes undulations. Similarly, the first side 62 and second side 64 of the second foam component 60, from the inner side 22 to the outer side 24, and on the forefoot region 16, midfoot region 18, and heel region 20 of the second foam component 60, may be generally flat or planar. In other words, neither the first side 62 nor the second side 64 of the second foam component 60 includes undulations. Examples of other aspects of foam components in the sole interlayer including undulations (such as undulations formed as a serrated pattern and / or a wavy pattern) are described below.

[0035] Depending on the design, style, and intended use of the footwear article 10, the first foam component 50 can be formed to any suitable thickness T1. Similarly, depending on the design, style, and intended use of the footwear article 10, the second foam component 60 can be formed to any suitable thickness T2. Although the first side 52 and the second side 54 of the first foam component 50 can be generally flat, the thickness T1 of the first foam component 50 can vary in the forefoot region 16, the midfoot region 18, and the heel region 20. As an example, the thickness T1 of the first foam component 50 can be larger in the heel region 20 and tapers to a smaller thickness T1 in the forefoot region 16. Similarly, the thickness T2 of the second foam component 60 can vary in the forefoot region 16, the midfoot region 18, and the heel region 20. The thickness of the mesh component 70, in Figure 3 Not mentioned separately, the thickness of the mesh component 70 can vary depending on the type of mesh textile used, and the thickness of the mesh component 70 is... Figure 3 It is not drawn to scale.

[0036] In other aspects described below, the first side 62 of the second foam component 60 may include at least one corrugated region. Additionally or alternatively, the second side 54 of the first foam component 50 may include at least one corrugated region. When both the second side 54 of the first foam component 50 and the first side 62 of the second foam component 60 include corrugated regions, the corrugated regions may correspond to each other (e.g., be mirror images of each other). References below... Figure 7 , Figure 8 , Figure 10 , Figure 11 and Figures 14A-14FExamples of these types of wave zones are described in further detail. In those respects, the thickness of the foam component in the sole interlayer 40 (e.g., thicknesses T1 and T2) can also vary due to one or more wave zones formed on the sides of the foam component.

[0037] In several examples, one or both of the first foam component 50 and the second foam component 60 may be formed from the foam composition. In various aspects, the foam composition may have an Asker C hardness of about 30C to 65C. The foam composition may also have an energy return of about 60% to 90%. The foam composition may include olefin polymers or copolymers, thermoplastic polymers or copolymers, and / or polymers selected from the group consisting of: ethylene-vinyl acetate (EVA) copolymers, styrene-butadiene copolymers, polyurethane homopolymers or copolymers, and blends thereof.

[0038] In some cases, the first foam component 50 and the second foam component 60 may be formed from the same foam composition. In other cases, the first foam component 50 and the second foam component 60 may be formed from different foam compositions. In this case, the first foam component 50 may be formed from a first foam composition, and the second foam component 60 may be formed from a different second foam composition. When formed from different foam compositions, the first foam component 50 may have a different stiffness than the second foam component 60.

[0039] The mesh component 70 may be embodied in a mesh textile material, such as a flexible mesh textile material. The mesh component 70 may be knitted, crocheted, braided, or formed by any other suitable process or technique. The mesh component 70 may be formed from one or more yarns, which are formed from one or more individual fibers. In another example, the mesh component 70 may be embodied in a nonwoven textile comprising one or more individual fibers. The mesh component may have fibers with a first concentration or density in a first region and fibers with a second concentration or density in a second region. The first concentration may be greater than the second concentration. For example, the first concentration may be 10 weight percentages or more greater than the second concentration, although other differences in weight percentages between different regions of the mesh component 70 are also within the scope of various aspects.

[0040] In some cases, the mesh component 70 may include openings, channels, or holes. The size of the holes may vary in various aspects. In one example, the length of the hole at its maximum dimension may range from at least 0.5 mm to 1 mm. In another example, the mesh component 70 may include a plurality of different holes of different sizes, the length of which at its maximum dimension ranges from at least 0.5 mm to 1 mm.

[0041] The channels or openings in the mesh component 70 allow the first foam component 50 and the second foam component 60 to be in direct contact with each other at their interface. In some aspects, one or both of the first foam component 50 and the second foam component 60 may be injection molded around or through each channel or opening in the mesh component 70. Alternatively, an adhesive can be used to adhere the mesh component 70 to the first foam component 50. The first foam component 50 and the mesh component 70 can then be adhered to the second foam component 60 using an adhesive or other suitable adhesion process or step. In another case, an adhesive can be used to adhere the mesh component 70 to the second foam component 60. The first foam component 60 and the mesh component 70 can then be adhered to the first foam component 50 using an adhesive or other suitable adhesion process or step. References are made below. Figures 15A-15B Exemplary methods for forming a first foam component 50 and a second foam component 60, as well as exemplary methods for assembling the first foam component 50 and the second foam component 60 with a mesh component 70, or for forming the first foam component 50 and the second foam component 60 with a mesh component 70, are described in further detail.

[0042] Figure 4 The diagram illustrates several aspects described in this article. Figures 1-3 The top view of the mesh component 70 and the second foam component 60 of the sole structure 14 shown. Figure 4 A representative example of how the mesh component 70 can extend between the first foam component 50 and the second foam component 60 within the sole interlayer 40 is provided. As shown, the mesh component 70 extends on the first side 62 of the second foam component 60 within a distance D1 from the sidewall 66 of the second foam component 60. Therefore, when the first foam component 50 is stacked on the second foam component 60, the mesh component 70 can extend on the second side 54 of the first foam component 50. In one example, the mesh component 70 can extend within approximately 1 mm to 5 mm from the sidewall 66 of the second foam component 60 (i.e., the distance D1 can be 1 mm to 5 mm), although other distances are also within the range in various aspects. Similarly, the mesh component 70 can extend within approximately 1 mm to 5 mm from the sidewall 56 of the first foam component 50, although other distances are also within the range in various aspects.

[0043] exist Figure 4In this design, the mesh component 70 extends uniformly around the periphery of the second foam component 60 on the first side 62 of the second foam component 60, extending within a distance D1 from the sidewall 66. In other aspects, the mesh component 70 may extend on any suitable portion or area of ​​the first side 62 of the second foam component 60 and the second side 54 of the first foam component 50. When the mesh component 70 extends around the periphery of the second foam component 60, it may also extend to different distances from the sidewall 66. For example, the mesh component 70 may extend closer to the sidewall 66 in the heel area 20 than in the midfoot area 18 or the forefoot area 16. As another example, the mesh component 70 may extend closer to the sidewall 66 in the heel area 20 and the midfoot area 18 than in the forefoot area 16. As yet another example, the mesh component 70 may extend closer to the sidewall 66 in the forefoot area 16 than in the heel area 20 and the midfoot area 18.

[0044] As mentioned above, the compressive strength and / or shear strength of the sole structure 14 can be increased in certain areas based on the number, placement, and orientation of the mesh components in the sole structure 14. Aspects regarding the different numbers and placements of the mesh components are described below. In particular, regarding the orientation of the mesh components, Figure 5 An exemplary mesh textile 80 is illustrated. The mesh components described herein, such as... Figures 1-4 The mesh component 70 shown, as well as others, can be cut from a mesh textile similar to the mesh textile 80.

[0045] The mesh textile 80 can be stretched in one direction (e.g., a unidirectional stretch textile) or in two directions (e.g., a bidirectional stretch textile). If it is a unidirectional stretch textile, when a tensile force or tension is applied to the mesh textile 80 in directions 82A and 82B, the mesh textile 80 can be stretched to a certain extent in direction A, but even though a tensile force or tension is applied in directions 84A and 84B, the mesh textile 80 may not be stretched in direction B (or may be stretched significantly less). Alternatively, when a tensile force or tension is applied to the mesh textile 80 in directions 84A and 84B, the mesh textile 80 can be stretched to a certain extent in direction B, but even though a tensile force or tension is applied in directions 82A and 82B, the mesh textile 80 may not be stretched in direction A (or may be stretched significantly less). Therefore, the degree of stretching (or resistance to stretching) of the mesh textile 80 can be directionally related to the type or type of material forming the mesh textile 80, the manner in which the mesh textile 80 is formed, and other factors.

[0046] If it is a biaxially oriented textile, the mesh textile 80 can be stretched in direction A when tensile forces or tensions are applied in directions 82A and 82B, and can also be stretched in direction B when tensile forces or tensions are applied in directions 84A and 84B. For biaxially oriented textiles, the mesh textile 80 can be stretched by a first percentage in direction A, and can also be stretched by a different second percentage in direction B. Therefore, even for biaxially oriented textiles, the degree of stretching (or resistance to stretching) of the mesh textile 80 can be directionally related based on the type of material forming the mesh textile 80, the manner in which the mesh textile 80 is formed, and other factors. Furthermore, because the degree of stretching of the mesh textile 80 can be directionally related, the type (e.g., uniaxial or biaxial) and orientation R of the mesh textile 80 can be considered before cutting a piece of mesh textile 80 from it for use in the midsole of a shoe sole.

[0047] Reference Figure 2 Because the midsole 40 includes a mesh component 70, the compressive strength and / or shear strength of the midsole 40 can be increased in one or more directions A', B', and C'. Furthermore, in some cases, the compressive strength and / or shear strength of the midsole 40 can vary to a greater or lesser extent in one or more directions A', B', and C', depending on the type of mesh component 70 (e.g., uniaxial or biaxial tension) and the orientation of the mesh component 70. For example, if... Figure 2 The mesh component 70 shown is from Figure 5 Cut from a mesh textile 80 as shown, the mesh component 70 can be stretched to a greater or lesser extent in one or more directions, A' and B', depending on the orientation R of the mesh textile 80 when the mesh component 70 is cut from it. In one example, the greater the stretch of the mesh component 70 in direction A' compared to direction B', the greater the increase in shear strength of the sole interlayer 40 in direction B' compared to direction A'. On the other hand, the greater the stretch of the mesh component 70 in direction B' compared to direction A', the greater the increase in shear strength of the sole interlayer 40 in direction A' compared to direction B'. Therefore, the shear strength of the sole structure 14 can be increased more or less in certain directions based on the orientation and directionality of the stretching properties of the mesh component 70 in the sole structure 14.

[0048] Depending on other aspects, the sole structure 14 may also include more than one mesh component, and the compressive strength and / or shear strength of the sole structure 14 may be increased based on the number and placement of the mesh components. In this context, Figure 6A The illustration shows a top view of an example including a plurality of mesh components and a second foam component 60. Figure 6A In the example shown, the first mesh component 71, the second mesh component 72, and the third mesh component 73 (collectively referred to as "mesh components 71-73") are each positioned at different locations on the first side 62 of the second foam component 60. The first mesh component 71 is positioned in the forefoot region 16, the second mesh component 72 is positioned in the midfoot region 18, and the third mesh component 73 is positioned in the heel region 20. The size, shape, and relative positions of the mesh components 71-73 are as follows: Figure 6A Provided as an example. In other cases, mesh components other than mesh components 71-73 may be included, or one or more mesh components 71-73 may be omitted.

[0049] exist Figure 6A In this context, each of the mesh components 71-73 can be embodied as a uniaxially stretched textile or a biaxially stretched textile. Furthermore, the degree of stretch of each of the mesh components 71-73 can be direction-dependent as described herein. Therefore, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components 71-73 can be selected to increase the compressive strength and / or shear strength of the sole interlayer 40 in the forefoot region 16, midfoot region 18, and heel region 20. By selecting different types and / or orientations (relative to each other) of the mesh components 71-73, the compressive strength and / or shear strength of the sole interlayer 40 can vary between the forefoot region 16, midfoot region 18, and heel region 20. Furthermore, the compressive strength and / or shear strength in the forefoot region 16 can be increased in one or more directions A', B', or C' (see [link to relevant documentation]). Figure 2 The compressive strength and / or shear strength in both the midfoot region 18 and the heel region 20 may also be increased in one or more directions, namely A', B', or C'.

[0050] exist Figure 6B In the example shown, the first mesh component 74, the second mesh component 75, the third mesh component 76, the fourth mesh component 77, the fifth mesh component 78, and the sixth mesh component 79 (collectively referred to as "mesh components 74-79") are each positioned at different locations on the first side 62 of the second foam component 60. The size, shape, and relative positions of the mesh components 74-79 are as follows: Figure 6B Provided as an example. In other cases, mesh components other than mesh components 74-79 may be included, or one or more mesh components 74-79 may be omitted.

[0051] like Figure 6BAs shown, the first mesh component 74 and the second mesh component 75 are both positioned in the forefoot region 16 and overlap each other in region A1 of the forefoot region 16. Furthermore, the third mesh component 76 and the fourth mesh component 77 are both positioned in the midfoot region 18 and overlap each other in region A2 of the midfoot region 18. Additionally, the fifth mesh component 78 and the sixth mesh component 79 are both positioned in the heel region 20 and overlap each other in region A3 of the heel region 20. In region A1 where the first mesh component 74 and the second mesh component 75 overlap, the compressive strength and / or shear strength of the midsole 40 can be increased compared to their non-overlapping regions. The compressive strength and / or shear strength of the midsole 40 can also be increased in regions A2 and A3 in a similar manner. The dimensions of regions A1-A3 are... Figure 6B The dimensions shown are representative and can vary compared to the dimensions indicated.

[0052] exist Figure 6B In this context, each of the mesh components 74-79 can be embodied as a uniaxially stretched textile or a biaxially stretched textile. Furthermore, the degree of stretch of each of the mesh components 74-79 can be direction-dependent as described herein. Therefore, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components 74-79 can be selected to increase the compressive strength and / or shear strength of the sole interlayer 40 in the forefoot region 16, midfoot region 18, and heel region 20. By selecting different types and / or orientations (relative to each other) of the mesh components 74-79, the compressive strength and / or shear strength of the sole interlayer 40 can vary between the forefoot region 16, midfoot region 18, and heel region 20. Furthermore, the compressive strength and / or shear strength in the forefoot region 16 can be increased in one or more directions A', B', or C' (see [link to relevant documentation]). Figure 2 The compressive strength and / or shear strength in both the midfoot region 18 and the heel region 20 may also be increased in one or more directions, namely A', B', or C'.

[0053] Figure 7An exploded perspective view of another exemplary midsole layer 100 including a wave pattern, according to various aspects described herein, is illustrated. As shown, the midsole layer 100 includes a first foam component 110, a second foam component 120, and a mesh component 130. The first foam component 110 includes a first side 112, a second side 114 opposite to the first side 112, and sidewalls 116 extending around the peripheries of the first side 112 and the second side 114. The second foam component 120 includes a first side 122, a second side 124 opposite to the first side 122, and sidewalls 126 extending around the peripheries of the first side 122 and the second side 124. When the midsole layer 100 is assembled, the mesh component 130 is positioned in the stack between the second side 114 of the first foam component 110 and the first side 122 of the second foam component 120, and is coupled to the second side 114 of the first foam component 110 and the first side 122 of the second foam component 120. The first foam component 110 and the second foam component 120 may be formed of one or more materials that are the same as those used in other foam components described herein. The mesh component 130 may be formed of one or more materials that are the same as those used in other mesh components described herein.

[0054] like Figure 7 As shown, the surface of the second side 114 of the first foam component 110 is corrugated and transitions with a wavy pattern. The surface of the first side 122 of the second foam component 120 is also corrugated and transitions with a wavy pattern. The wavy pattern of the second side 114 of the first foam component 110 can vary in one or more regions according to one or more dimensional aspects, which define the shape of the wavy pattern when extended on the second side 114. The wavy pattern of the first side 122 of the second foam component 120 can also vary in one or more regions according to one or more dimensional aspects, which define the shape of the wavy pattern when extended on the first side 122. See below for further details. Figure 8 Examples regarding dimensions are described in further detail.

[0055] Figure 8 The diagram shows Figure 7The exemplary sole interlayer 100 shown is a cross-sectional side view. As shown, a first foam component 110 and a second foam component 120 form a stack in the sole interlayer 100. Furthermore, a mesh component 130 is positioned in the stack between the second side 114 of the first foam component 110 and the first side 122 of the second foam component 120, and is coupled to the second side 114 of the first foam component 110 and the first side 122 of the second foam component 120. In some cases, the second side 114 of the first foam component 110 and the first side 122 of the second foam component 120 may also be coupled to each other in certain areas where they meet. Depending on the characteristics of the mesh component 130, the second side 114 of the first foam component 110 and the first side 122 of the second foam component 120 may also be coupled to each other through openings or holes in the mesh component 130.

[0056] As in Figure 8 As best viewed, the wavy surface of the second side 114 of the first foam component 110 corresponds to or complements the wavy surface of the first side 122 of the second foam component 120, and the mesh component 130 is positioned in the stack between them. The relative position of the mesh component 130 varies within the stack along the wavy surface of the second side 114 of the first foam component 110 and the wavy surface of the first side 122 of the second foam component 120. The wave patterns of the wavy surface of the second side 114 and the wavy surface of the first side 122 have amplitude A4 and wavelength W1. Amplitude A4 and wavelength W1 are dimensional aspects that define the shape and size of the wave patterns of the wavy surfaces of the second side 114 and the first side 122.

[0057] The amplitude A4 and wavelength W1 can remain substantially constant in the forefoot region 16, midfoot region 18, and heel region 20, such as Figure 8 As shown in the diagram. Alternatively, the amplitude A4 and / or wavelength W1 may differ from those shown. A larger amplitude A4 may result in an increase in the compressive and / or shear strength of the midsole 100. Similarly, a shorter wavelength W1 may result in an increase in the compressive and / or shear strength of the midsole 100. The amplitude A4 and / or wavelength W1 may vary in one or more zones, such as in the forefoot zone 16, the midfoot zone 18, and the heel zone 20. For example, the amplitude A4 may be larger in the heel zone 20, smaller in the midfoot zone 18, and still smaller in the forefoot zone 16. As another example, the wavelength W1 may be larger in the heel zone 20, smaller in the midfoot zone 18, and still smaller in the forefoot zone 16.

[0058] Figure 9A The illustration shows a top view of an example including a plurality of mesh components and a second foam component 120. Figure 9AIn the example shown, the first mesh component 171, the second mesh component 172, and the third mesh component 173 (collectively referred to as "mesh components 171-173") are each positioned at different locations on the first side 122 of the second foam component 120. The first mesh component 171 is positioned in the forefoot area 16, the second mesh component 172 is positioned in the midfoot area 18, and the third mesh component 173 is positioned in the heel area 20. The size, shape, and relative positions of the mesh components 171-173 are as follows: Figure 9A Provided as an example. In other cases, mesh components other than mesh components 171-173 may be included, or one or more mesh components 171-173 may be omitted.

[0059] exist Figure 9A In this context, each of the mesh components 171-173 can be embodied as a uniaxially stretched textile or a biaxially stretched textile. Furthermore, the degree of stretch of each of the mesh components 171-173 can be direction-dependent as described herein. Therefore, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components 171-173 can be selected to increase the compressive strength and / or shear strength of the sole interlayer 100 in the forefoot region 16, midfoot region 18, and heel region 20. By selecting different types and / or orientations (relative to each other) of the mesh components 171-173, the compressive strength and / or shear strength of the sole interlayer 40 can vary between the forefoot region 16, midfoot region 18, and heel region 20. Furthermore, by selecting a specific orientation of the mesh components 171-173, the compressive strength and / or shear strength in the forefoot region 16 can be increased in one or more directions A', B', or C' (see [reference needed]). Figure 2 The compressive strength and / or shear strength in both the midfoot region 18 and the heel region 20 may also increase in one or more directions, respectively, A', B', or C'. The increase in compressive strength and / or shear strength of the sole interlayer 100 due to the inclusion of mesh components 171-173 may be an increase other than any increase caused by the wavy surface of the second side 114 of the first foam component 110 and the wavy surface of the first side 122 of the second foam component 120.

[0060] exist Figure 9B In the example shown, the first mesh component 174, the second mesh component 175, the third mesh component 176, the fourth mesh component 177, the fifth mesh component 178, and the sixth mesh component 179 (collectively referred to as "mesh components 174-179") are each positioned at different locations on the first side 122 of the second foam component 120. The size, shape, and relative positions of the mesh components 174-179 are as follows: Figure 9BProvided as an example. In other cases, mesh components other than mesh components 174-179 may be included, or one or more mesh components 174-179 may be omitted.

[0061] like Figure 9B As shown, the first mesh component 174 and the second mesh component 175 are both positioned in the forefoot region 16 and overlap each other in region A5 of the forefoot region 16. Furthermore, the third mesh component 176 and the fourth mesh component 177 are both positioned in the midfoot region 18 and overlap each other in region A6 of the midfoot region 18. Additionally, the fifth mesh component 178 and the sixth mesh component 179 are both positioned in the heel region 20 and overlap each other in region A7 of the heel region 20. In region A5 where the first mesh component 174 and the second mesh component 175 overlap, the compressive strength and / or shear strength of the midsole 100 can be increased compared to their non-overlapping regions. The compressive strength and / or shear strength of the midsole 100 can also be increased in regions A6 and A7 in a similar manner. The dimensions of regions A5-A7 are... Figure 9B The dimensions shown are representative and can vary compared to the dimensions indicated.

[0062] exist Figure 9B In this context, each of the mesh components 174-179 can be embodied as a uniaxially stretched textile or a biaxially stretched textile. Furthermore, the degree of stretch of each of the mesh components 174-179 can be direction-dependent as described herein. Therefore, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components 174-179 can be selected to increase the compressive strength and / or shear strength of the sole interlayer 100 in the forefoot region 16, midfoot region 18, and heel region 20. By selecting different types and / or orientations (relative to each other) of the mesh components 174-179, the compressive strength and / or shear strength of the sole interlayer 100 can vary between the forefoot region 16, midfoot region 18, and heel region 20. Furthermore, by selecting a specific orientation of the mesh components 174-179, the compressive strength and / or shear strength in the forefoot region 16 can be increased in one or more directions A', B', or C' (see [link to relevant documentation]). Figure 2 The compressive and / or shear strength in the midfoot region 18 and heel region 20 can also be customized to increase in one or more directions A', B', or C', respectively. The increase in compressive and / or shear strength of the midsole 100 due to the inclusion of mesh components 174-179 can be an increase other than any increase caused by the wavy surface of the second side 114 of the first foam component 110 and the wavy surface of the first side 122 of the second foam component 120.

[0063] Figure 10 An exploded perspective view of another exemplary sole interlayer 200 including a serrated pattern, according to several aspects described herein, is illustrated. As shown, the sole interlayer 200 includes a first foam component 210, a second foam component 220, and a mesh component 230. The first foam component 210 includes a first side 212, a second side 214 opposite to the first side 212, and sidewalls 216 extending around the peripheries of the first side 212 and the second side 214. The second foam component 220 includes a first side 222, a second side 224 opposite to the first side 222, and sidewalls 226 extending around the peripheries of the first side 222 and the second side 224. When the sole interlayer 200 is assembled, the mesh component 230 is positioned in the stack between the second side 214 of the first foam component 210 and the first side 222 of the second foam component 220, and is coupled to the second side 214 of the first foam component 210 and the first side 222 of the second foam component 220. The first foam component 210 and the second foam component 220 may be formed of one or more materials that are the same as those used in other foam components described herein. The mesh component 230 may be formed of one or more materials that are the same as those used in other mesh components described herein.

[0064] like Figure 10 As shown, the surface of the second side 214 of the first foam component 210 is corrugated and transitions with a serrated pattern. The surface of the first side 222 of the second foam component 220 is also corrugated and transitions with a serrated pattern. The serrated pattern of the second side 214 of the first foam component 210 can vary in one or more regions according to one or more dimensional aspects, which define the shape of the serrated pattern when extended on the second side 214. The serrated pattern of the first side 222 of the second foam component 220 can also vary in one or more regions according to one or more dimensional aspects, which define the shape of the serrated pattern when extended on the first side 222. See below for further details. Figure 11 Examples regarding dimensions are described in further detail.

[0065] Figure 11 The diagram shows Figure 10The diagram shows a cross-sectional side view of an exemplary sole interlayer 200. As shown, a first foam component 210 and a second foam component 220 form a stack in the sole interlayer 200. Furthermore, a mesh component 230 is positioned in the stack between the second side 214 of the first foam component 210 and the first side 222 of the second foam component 220, and is bonded to the second side 214 of the first foam component 210 and the first side 222 of the second foam component 220. In some cases, the second side 214 of the first foam component 210 and the first side 222 of the second foam component 220 may also be bonded to each other in certain areas where they meet. Depending on the characteristics of the mesh component 230, the second side 214 of the first foam component 210 and the first side 222 of the second foam component 220 may also be bonded to each other through openings or holes in the mesh component 230.

[0066] As in Figure 11 As best viewed, the wavy surface of the second side 214 of the first foam component 210 conforms to or complements the wavy surface of the first side 222 of the second foam component 220, and the mesh component 230 is positioned in the stack between them. The serrated pattern of the wavy surface of the second side 214 and the serrated pattern of the wavy surface of the first side 222 have an amplitude A8 and a wavelength W2. The amplitude A8 and the wavelength W2 are dimensional aspects that define the shape and size of the serrated patterns of the wavy surfaces of the second side 214 and the first side 222.

[0067] The amplitude A8 and wavelength W2 can remain substantially constant in the forefoot region 16, midfoot region 18, and heel region 20, such as Figure 11 As shown in the diagram. Alternatively, the amplitude A8 and / or wavelength W2 may differ from those shown. A larger amplitude A8 may result in an increase in the compressive and / or shear strength of the midsole 200. Similarly, a shorter wavelength W2 may result in an increase in the compressive and / or shear strength of the midsole 200. The amplitude A8 and / or wavelength W2 may vary over one or more zones, such as the forefoot zone 16, the midfoot zone 18, and the heel zone 20. For example, the amplitude A8 may be larger in the heel zone 20, smaller in the midfoot zone 18, and still smaller in the forefoot zone 16. As another example, the wavelength W2 may be larger in the heel zone 20, smaller in the midfoot zone 18, and still smaller in the forefoot zone 16.

[0068] Figure 12A The illustration shows a top view of an example including a plurality of mesh components and a second foam component 220. Figure 12AIn the example shown, the first mesh component 271, the second mesh component 272, and the third mesh component 273 (collectively referred to as "mesh components 271-273") are each positioned at different locations on the first side 222 of the second foam component 220. The first mesh component 271 is positioned in the forefoot region 16, the second mesh component 272 is positioned in the midfoot region 18, and the third mesh component 273 is positioned in the heel region 20. The size, shape, and relative positions of the mesh components 271-273 are as follows: Figure 12A Provided as an example. In other cases, mesh components other than mesh components 271-273 may be included, or one or more mesh components 271-273 may be omitted.

[0069] exist Figure 12A In this context, each of the mesh components 271-273 can be embodied as a uniaxially stretched textile or a biaxially stretched textile. Furthermore, the degree of stretch of each of the mesh components 271-273 can be direction-dependent as described herein. Therefore, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components 271-273 can be selected to increase the compressive strength and / or shear strength of the sole interlayer 200 in the forefoot region 16, midfoot region 18, and heel region 20. By selecting different types and / or orientations (relative to each other) of the mesh components 271-273, the compressive strength and / or shear strength of the sole interlayer 40 can vary between the forefoot region 16, midfoot region 18, and heel region 20. Furthermore, by selecting a specific orientation of the mesh components 271-273, the compressive strength and / or shear strength in the forefoot region 16 can be increased in one or more directions A', B', or C' (see [link to relevant documentation]). Figure 2 The compressive and / or shear strength in both the midfoot region 18 and the heel region 20 may also increase in one or more directions, respectively, A', B', or C'. The increase in compressive and / or shear strength of the sole interlayer 200 due to the inclusion of mesh components 271-273 may be an increase other than any increase caused by the wavy surface of the second side 214 of the first foam component 210 and the wavy surface of the first side 222 of the second foam component 220.

[0070] exist Figure 12B In the example shown, the first mesh component 274, the second mesh component 275, the third mesh component 276, the fourth mesh component 277, the fifth mesh component 278, and the sixth mesh component 279 (collectively referred to as "mesh components 274-279") are each positioned at different locations on the first side 222 of the second foam component 220. The size, shape, and relative positions of the mesh components 274-279 are as follows: Figure 12BProvided as an example. In other cases, mesh components other than mesh components 274-279 may be included, or one or more mesh components 274-279 may be omitted.

[0071] like Figure 12B As shown, the first mesh component 274 and the second mesh component 275 are both positioned in the forefoot region 16 and overlap each other in region A9 of the forefoot region 16. Furthermore, the third mesh component 276 and the fourth mesh component 277 are both positioned in the midfoot region 18 and overlap each other in region A9 of the midfoot region 16. 10 They overlap each other. Furthermore, the fifth mesh component 278 and the sixth mesh component 279 are both positioned in the heel area 20, and in region A of the heel area 20. 11 The first mesh component 274 and the second mesh component 275 overlap each other. In region A9 where the first mesh component 274 and the second mesh component 275 overlap, the compressive strength and / or shear strength of the sole interlayer 200 can be increased compared to regions where they do not overlap. The compressive strength and / or shear strength of the sole interlayer 200 can also be increased in region A in a similar manner. 10 and A 11 Add to area A9-A. 11 Size in Figure 12B The dimensions shown are representative and can vary compared to the dimensions indicated.

[0072] exist Figure 12B In this context, each of the mesh components 274-279 can be embodied as a uniaxially stretched textile or a biaxially stretched textile. Furthermore, the degree of stretch of each of the mesh components 274-279 can be direction-dependent as described herein. Therefore, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components 274-279 can be selected to increase the compressive strength and / or shear strength of the sole interlayer 200 in the forefoot region 16, midfoot region 18, and heel region 20. By selecting different types and / or orientations (relative to each other) of the mesh components 274-279, the compressive strength and / or shear strength of the sole interlayer 200 can vary between the forefoot region 16, midfoot region 18, and heel region 20. Furthermore, by selecting a specific orientation of the mesh components 274-279, the compressive strength and / or shear strength in the forefoot region 16 can be increased in one or more directions A', B', or C' (see [link to relevant documentation]). Figure 2The compressive and / or shear strength in both the midfoot region 18 and the heel region 20 can also be customized to increase in one or more directions A', B', or C', respectively. The increase in compressive and / or shear strength of the sole interlayer 200 due to the inclusion of mesh components 274-279 can be an increase other than any increase caused by the wavy surface of the second side 214 of the first foam component 210 and the wavy surface of the first side 222 of the second foam component 220.

[0073] Figure 13 An exploded perspective view of another exemplary midsole 300 according to several aspects described herein is illustrated, the midsole 300 including a first foam component 310 having a cavity 311 and a second foam component 320 fitting into the cavity 311. To provide a view of the cavity 311, the midsole 300 is illustrated in an upside-down orientation compared to how the midsole 300 will be used. That is, when assembled with… Figure 1 When the footwear item 10 shown is similar to other footwear items, the outsole (e.g., similar to...) Figure 1 The outsole 30 shown can be adhered to the second side 324 of the second foam component 320.

[0074] like Figure 13 As shown, the midsole 300 includes a first foam component 310, a second foam component 320, and a mesh component 330. The first foam component 310 includes a first side 312, a second side 314 opposite to the first side 312, and sidewalls 316 extending around the peripheries of the first side 312 and the second side 314. The second foam component 320 includes a first side 322, a second side 324 opposite to the first side 322, and sidewalls 326 extending around the peripheries of the first side 322 and the second side 324. The dimensions and shapes of the first foam component 310, the second foam component 320, and the mesh component 330 are as follows: Figure 13 The dimensions and shapes shown are provided as examples. In other respects, the dimensions and shapes may differ from those shown.

[0075] Figure 13 One difference between the sole interlayer 300 shown and the sole interlayers 40, 100, and 200 described above is that the second foam component 320 fits into the cavity 311 of the first foam component 310. Similarly, the mesh component 330 is positioned within the cavity 311 between the first foam component 310 and the second foam component 320. The cavity 311 is defined by the second side surface 314 of the first foam component 310 and the inner sidewall 318 of the first foam component 310.

[0076] When assembling the sole interlayer 300, the second side 314 of the first foam component 310 and the first side 322 of the second foam component 320 can also be bonded to each other in certain areas where they meet. Depending on the characteristics of the mesh component 330, the second side 314 of the first foam component 310 and the first side 322 of the second foam component 320 can also be bonded to each other through openings or holes in the mesh component 330. Furthermore, the sidewall 326 of the second foam component 320 can be bonded to the inner sidewall 318 of the first foam component 310 within the cavity 311. The first foam component 310 and the second foam component 320 can be formed of one or more materials similar to the other foam components described herein.

[0077] The mesh component 330 may be formed of one or more materials identical to the other mesh components described herein. The mesh component 330 may be embodied as a uniaxially stretched textile or a biaxially stretched textile. Therefore, the degree of stretch of the mesh component 330 may be direction-dependent as described herein. Thus, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components 330 can be selected to increase the compressive strength and / or shear strength of the sole interlayer 300 in the forefoot region 16, midfoot region 18, and heel region 20. By selecting a specific type and orientation of the mesh component 330, the compressive strength and / or shear strength of the sole interlayer 300 can be tailored for a specific purpose as described herein. Furthermore, the compressive strength and / or shear strength of the sole interlayer 300 may be increased in one or more directions A', B', or C' (see [link to relevant documentation]). Figure 2 ).

[0078] In other examples, a number of individual mesh components can be used instead of mesh component 330. For example, with Figure 6A Mesh components similar to those shown (71-73) can be positioned at different locations between the first foam component 310 and the second foam component 320. In this case, the first mesh component can be positioned in the forefoot area 16, the second mesh component can be positioned in the midfoot area 18, and the third mesh component can be positioned in the heel area 20. In another example, similar to... Figure 6B Similar mesh components 74-79 shown can be positioned at different locations between the first foam component 310 and the second foam component 320. The mesh components can overlap in certain areas or zones.

[0079] When relying on more than one mesh component, each of the mesh components can be embodied as a uniaxially stretched textile or a biaxially stretched textile. In this case, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components can be selected to increase the compressive strength and / or shear strength of the sole interlayer 300 to different degrees in one of the forefoot region 16, midfoot region 18, and heel region 20. By selecting different types and / or orientations of the mesh components (relative to each other), the compressive strength and / or shear strength of the sole interlayer 300 can vary between the forefoot region 16, midfoot region 18, and heel region 20. Furthermore, the compressive strength and / or shear strength in the forefoot region 16 can be increased in one or more directions A', B', or C' (see [reference needed]). Figure 2 The compressive strength and / or shear strength in both the midfoot region 18 and the heel region 20 may also be increased in one or more directions, namely A', B', or C'.

[0080] like Figure 13 As shown, the second side 314 of the first foam component 310 (i.e., within the cavity 311) and the first side 322 of the second foam component 320 can be generally flat or planar in the forefoot region 16, midfoot region 18, and heel region 20. In other words, neither the first side 322 nor the second side 314 includes a wavy portion. As an example of a sole interlayer including a foam component with wavy sides, Figures 14A-14F The illustration shows a view of another exemplary sole interlayer 400. Specifically, Figure 14A The illustration shows a top view of the 400mm midsole. Figure 14B The illustration shows a bottom view of the 400mm midsole, and... Figure 14C The illustration shows a cross-sectional side view of the sole interlayer 400. Figures 14D-14F The diagram shows Figure 14A The cross-sectional view specified in the text.

[0081] like Figure 14C As best shown in the diagram, the midsole includes a first foam component 410 having a first side 412 and a second side 414 opposite to the first side 412. A second foam component 420 includes a first side 422 and a second side 424 opposite to the first side 422. The first foam component 410 fits within a cavity formed in the second foam component 420, similar to... Figure 13 As shown in the figure. The sole interlayer 400 also includes a mesh component 430 positioned within a cavity between the first foam component 410 and the second foam component 420.

[0082] In addition, such as Figure 14CAs shown, the second side 414 of the first foam component 410 and the first side 422 of the second foam component 420 include wavy surfaces. The wavy surface of the second side 414 of the first foam component 410 corresponds to the wavy surface of the first side 422 of the second foam component 420. The patterns of the wavy surfaces of the second side 414 and the first side 422 have an amplitude A. 12 Wavelength W3. Amplitude A 12 Wavelength W3 is an example of the dimensional aspects of the shape and size of the wave pattern on the waveform surfaces defining the second side 414 and the first side 422. Larger amplitude A 12 This can lead to an increase in the compressive strength and / or shear strength of the midsole 400. Similarly, a shorter wavelength W3 can lead to an increase in the compressive strength and / or shear strength of the midsole 400.

[0083] AmplitudeA 12 Wavelength W3 can remain substantially constant across the forefoot region 16, midfoot region 18, and heel region 20. Alternatively, amplitude A 12 And / or wavelength W3 can vary between the forefoot region 16, the midfoot region 18, and the heel region 20. For example, as Figure 14C As shown, amplitude A 12 It can be larger in the heel area 20, smaller in the midfoot area 18, and still smaller in the forefoot area 16.

[0084] When assembling the midsole 400, the second side 414 of the first foam component 410 and the first side 422 of the second foam component 420 can also be bonded to each other in certain areas where they meet. Depending on the characteristics of the mesh component 430, the second side 414 of the first foam component 410 and the first side 422 of the second foam component 420 can also be bonded to each other through openings or holes in the mesh component 430. The first foam component 410 and the second foam component 420 can be formed of one or more materials similar to the other foam components described herein.

[0085] The mesh component 430 may be formed of one or more materials identical to the other mesh components described herein. The mesh component 430 may be embodied as a uniaxially stretched textile or a biaxially stretched textile. Therefore, the degree of stretch of the mesh component 430 may be direction-dependent as described herein. Thus, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components 430 can be selected to increase the compressive and / or shear strength of the sole interlayer 400 in the forefoot region 16, midfoot region 18, and heel region 20. By selecting a specific type and orientation of the mesh component 430, the compressive and / or shear strength of the sole interlayer 400 can be tailored for a specific purpose as described herein. Furthermore, the compressive and / or shear strength of the sole interlayer 400 may be increased in one or more directions A', B', or C' (see [link to relevant documentation]). Figure 2 ).

[0086] In other examples, a number of individual mesh components can be used instead of mesh component 430. For example, with Figure 6A Mesh components similar to those shown (71-73) can be positioned at different locations between the first foam component 410 and the second foam component 420. In this case, the first mesh component can be positioned in the forefoot area 16, the second mesh component can be positioned in the midfoot area 18, and the third mesh component can be positioned in the heel area 20. In another example, similar to... Figure 6B Similar mesh components 74-79 shown can be positioned at different locations between the first foam component 410 and the second foam component 420. The mesh components can overlap in certain areas or zones.

[0087] When relying on more than one mesh component, each of the mesh components can be embodied as a uniaxially stretched textile or a biaxially stretched textile. In this case, the type (e.g., uniaxial or biaxially stretched) and orientation of each of the mesh components can be selected to increase the compressive strength and / or shear strength of the sole interlayer 400 to different degrees in one of the forefoot region 16, midfoot region 18, and heel region 20. By selecting different types and / or orientations of the mesh components (relative to each other), the compressive strength and / or shear strength of the sole interlayer 400 can vary between the forefoot region 16, midfoot region 18, and heel region 20. Furthermore, the compressive strength and / or shear strength in the forefoot region 16 can be increased in one or more directions A', B', or C' (see [reference needed]). Figure 2 The compressive strength and / or shear strength in both the midfoot region 18 and the heel region 20 may also be increased in one or more directions, namely A', B', or C'.

[0088] Turn to other aspects, Figures 15A-15B The illustration shows a method for forming a sole interlayer for footwear. Figures 15A-15B The process illustrated in the diagram provides an example of a series of steps that can be used to form one or more sole interlayers similar to those described above (including sole interlayers 40, 100, 200, 300, and 400, and others). Figures 15A-15B The arrangement of steps shown is provided through representative examples. In other respects, the order of steps may differ from the depicted order. For example, one or more steps may be omitted. Furthermore, the order of two or more steps may be interchanged or rearranged relative to the shown order. Additionally, in some cases, two or more steps may be performed simultaneously or partially simultaneously. Although the method shown in Figure 15 is described in conjunction with the above-described sole interlayers 40, 100, 200, 300, and 400, this method can be used to form other sole interlayers that differ from sole interlayers 40, 100, 200, 300, and 400.

[0089] At step 500, the method includes providing a first foam component having a first side and a second side opposite to the first side. As an example, first foam components 50, 110, 210, 310, and 410, and any of the others, may be provided at step 500, each of these first foam components including a first side and an opposite second side as described above. As described herein, the first foam component provided at step 500 may include a surface having one or more wavy areas on at least one side. Providing the first foam component at step 500 can be achieved in various ways, such as by injection molding the first foam component in a mold 600, by cutting the first foam component from a foam sheet 700, or by other suitable techniques. In any case, the first foam component may be formed from a foam composition as described herein.

[0090] When provided by injection molding, a first foam component without any wavy surface areas can be provided using mold 602. Mold 602 does not include a wavy surface. In this case, the first foam component can be formed without any wavy surface areas, similar to the first foam components 50 and 310 described above. Alternatively, the first foam component can be provided with wavy surface areas, such as one or more areas including a serrated pattern and / or a wavy pattern. For this purpose, step 500 may include injection molding the first foam component using mold 604 having one or more wavy surface areas. In this case, the first foam component can be formed with one or more wavy surface areas, similar to the first foam components 50, 110, 210 and 410 described above. Therefore, step 500 may include forming wavy areas on a second side of the first foam component.

[0091] When provided by cutting the first foam component from the foam sheet 700, the foam sheet 700 can be cut using a knife, wire, laser, jetted water, or other suitable cutting tool and / or technique. Regardless of the type of cutting tool or technique used, the first foam component can be formed without any wavy surface areas, similar to the first foam components 50 and 310 described above. Alternatively, the first foam component can be formed with one or more wavy surface areas, similar to the first foam components 50, 110, 210, and 410 described above. Therefore, step 500 may include forming a wavy portion in the second side of the first foam component by cutting the foam sheet using a knife, wire, laser, jetted water, or other cutting tool.

[0092] At step 502, the method includes providing a second foam component having a first side and a second side opposite to the first side. As an example, second foam components 60, 120, 220, 320, and 420, and any of the others, may be provided at step 502, each of these second foam components including a first side and an opposite second side as described above. As described herein, the first foam component provided at step 502 may include a surface having one or more wavy areas on at least one side. Providing the second foam component at step 502 can be achieved in various ways, such as by injection molding the second foam component in mold 610, by cutting the second foam component from foam sheet 702, or by other suitable techniques. In any case, the second foam component may be formed from a foam composition as described herein.

[0093] When provided by injection molding, a mold 612 without a wavy surface can be used to provide a second foam component without any wavy surface areas. In this case, the second foam component can be formed without any wavy surface areas, similar to the second foam components 60 and 320 described above. Alternatively, the second foam component can be provided with wavy surface areas, such as one or more areas including serrated patterns and / or wavy patterns. For this purpose, step 502 may include injection molding the second foam component using a mold 614 having one or more wavy surface areas. In this case, the second foam component can be formed with one or more wavy surface areas, similar to the second foam components 60, 120, 220 and 420 described above. Therefore, step 502 may include forming wavy areas on a first side of the second foam component.

[0094] When provided by cutting the second foam component from the foam sheet 702, the foam sheet 702 can be cut using a knife, wire, laser, water jet, or other suitable cutting tool and / or technique. Regardless of the type of cutting tool or technique used, the second foam component can be formed without any wavy surface areas, similar to the second foam components 60 and 320 described above. Alternatively, the second foam component can be formed with one or more wavy surface areas, similar to the second foam components 60, 120, 220, and 420 described above. Therefore, step 502 may include forming a wavy portion in the first side of the second foam component using a knife, wire, laser, water jet, or other cutting tool.

[0095] Turn Figure 15B At step 504, the method includes providing one or more mesh components. As shown, providing one or more mesh components may include cutting mesh components from a sheet of mesh textile. At step 504, mesh components of any number, size, and shape may be provided. As described herein, a single mesh component may be provided to extend over multiple areas of the midsole structure, such as across the forefoot area, midfoot area, and heel area, and from the inner side of the midsole to the outer side. In other cases, a number of different mesh components may be provided at step 504. Each of the mesh components may extend over different areas in the forefoot area, midfoot area, and heel area and / or from the inner side of the midsole to the outer side.

[0096] Depending on the properties of the mesh textile, the mesh component can be stretched in one direction or in both directions. The mesh component can be stretched to the same degree or percentage in each direction, or stretched by a first percentage in the first direction and a different second percentage in the second direction. The mesh component can be knitted, crocheted, braided, or woven from one or more yarns, each yarn being formed from one or more individual fibers. The mesh textile can be knitted, crocheted, braided, or formed by any other suitable process or technique. The mesh textile can also be formed from one or more yarns, which are formed from one or more individual fibers.

[0097] At step 506, the method includes combining the foam component provided at steps 500 and 502 with one or more mesh components provided at step 504. The series of combinations at step 506 can occur in many different ways, but generally results in the mesh component provided at step 504, the second side of the first foam component provided at step 500, and the first side of the second foam component provided at step 502 being combined with each other. Following the combination at step 506, the result is that the first side of the first foam component forms the first side of the resulting sole structure, the second side of the second foam component forms the second side of the sole structure opposite to the first side of the sole structure, and the mesh component is positioned and combined between the second side of the first foam component and the first side of the second foam component, as described herein.

[0098] In one example scenario, the bonding at step 506 includes applying an adhesive to one or more mesh components provided at step 504 and adhering the mesh components to a second side of the first foam component provided at step 500. Here, any number, size, and shape of mesh components can be adhered to the second side of the first foam component. For example, a single mesh component can be adhered to the second side of the first foam component to extend over the forefoot, midfoot, and heel areas and / or from the inner side of the sole interlayer to the outer side. In another example, at step 506, a number of different mesh components can be adhered to the second side of the first foam component. In this case, each of the mesh components can extend over different areas in the forefoot, midfoot, and heel areas and / or from the inner side of the first foam component to the outer side. In some cases, the mesh components can be in a similar manner to... Figure 6B , Figure 9B and Figure 12B The arrangements shown overlap each other in certain areas or regions. The bonding at step 506 also includes adhering the second side of the first foam component together with the mesh component to the first side of the second foam component provided at step 502.

[0099] As another example, the bonding at step 506 may include applying an adhesive to one or more mesh components provided at step 504 and adhering the mesh components to a first side of a second foam component provided at step 502. A single mesh component may be adhered to the first side of the second foam component to extend over the forefoot, midfoot, and heel areas and / or from the inner side of the sole interlayer to the outer side. In another example, at step 506, a number of different mesh components may be adhered to the first side of the second foam component. In this case, each of the mesh components may extend over different areas in the forefoot, midfoot, and heel areas and / or from the inner side of the second foam component to the outer side. In some cases, the mesh components may be in a manner similar to... Figure 6B , Figure 9B and Figure 12B The arrangements shown overlap each other in certain areas or regions. The bonding at step 506 also includes adhering the first side of the second foam component together with the mesh component to the second side of the first foam component provided at step 500.

[0100] Instead of using an adhesive (or other than an adhesive), the bonding at step 506 can be performed using a mold. For example, bonding at step 506 may include placing a first foam component provided at step 500 and one or more mesh components provided at step 504 into a mold, with the second side of the first foam component contacting the mesh component. Once in the mold, bonding at step 506 may include using heat to compress and mold the first foam component and the mesh component together, thereby bonding one or more mesh components to the second side of the first foam component. After the mesh components are bonded to the second side of the first foam component, the first side of the second foam component may be bonded to the second side of the first foam component using an adhesive and / or an additional compression molding step.

[0101] As an alternative, the bonding at step 506 may include placing the second foam component provided at step 502 and one or more mesh components provided at step 504 into a mold, wherein a first side of the second foam component contacts the mesh component. Once in the mold, the bonding at step 506 may include compression molding the second foam component and the mesh component together, thereby bonding one or more mesh components to the first side of the second foam component. After the mesh components are bonded to the first side of the second foam component, a second side of the first foam component may be bonded to the first side of the second foam component using an adhesive and / or additional compression molding steps.

[0102] As another alternative, the joining at step 506 may include placing the first foam component provided at step 500, one or more mesh components provided at step 504, and the second foam component provided at step 502 into a mold, wherein the second side of the first foam component and the first side of the second foam component contact the mesh component. Joining may then include compressing the first foam component, the mesh component, and the second foam component together such that the mesh component is positioned and joined between the second side of the first foam component and the first side of the second foam component.

[0103] After step 506 is completed, a sole interlayer for use in footwear articles is constructed. Once the sole interlayer is constructed, the method may include the additional step of attaching the outsole to the sole interlayer at step 508. Figure 2 and Figure 3 The outsole 30 shown is similar to an outsole that can be attached to the sole interlayer using, for example, adhesives or other suitable techniques. Alternatively, the method may include attaching the upper to the sole interlayer structure at step 510 to form a footwear article. The upper can be similar to, for example... Figure 1 The upper 12 shown is an example of an upper that can be attached to the midsole, although any suitable upper can be attached to the midsole.

[0104] As discussed herein, the mesh component 70 can be associated with certain properties such as tensile strength and / or elongation. The associated properties, such as tensile strength and / or elongation, can be determined using standard test methods on a shear testing apparatus (e.g., an Instron 8501 testing machine) capable of providing stress / strain curves in both tensile and compressive modes. Tensile strength and / or elongation can be determined along lines corresponding to... Figure 16A The axes shown are defined by specific angles (e.g., axes at 0°, 45°, and 90° relative to the axis perpendicular to the width dimension of the test sample). These axes are referred to herein as the 0°, 45°, and 90° axes. The test sample has a length dimension of 75 mm 900 and a width dimension of 25.4 mm 901. Figure 16B It shows Figure 16A The relative orientation of the test sample with respect to the test angle of the mesh component 70.

[0105] Elongation can be expressed as a percentage of elongation. The percentage of elongation represents the amount of stretch a material, such as a test sample corresponding to mesh component 70, can undergo along axes such as 0°, 45°, and 90° before fracture. The percentage of elongation is given by the following equation:

[0106] Elongation percentage = 100(LR-L0) / L0.

[0107] Here, LR represents the length of the material at the moment of fracture, while L0 represents the initial length of the material. These measurements are preferably taken relative to the central axis.

[0108] Methods for manufacturing foam components.

[0109] In some examples, the disclosed foam parts can be prepared by a variety of methods as disclosed herein and as known in the art. Thus, as known to those skilled in the art, foam parts comprising the disclosed polymeric material can be formed by molding the polymeric material, for example, by compression molding or injection molding, into a desired shape. The foam parts can be foamed during or after the molding process.

[0110] For example, foamed components can be prepared by injection molding a melt of the polymer material described herein using a suitable extruder with physical and / or chemical blowing agents. An extruder (e.g., a single-screw or twin-screw extruder) can be used to provide the composition. The extruder may have a motor to rotate the screw inside the extruder. The extruder may be a single-screw or twin-screw extruder made of various elements of different sizes and pitches suitable for mixing or kneading the specific material used. In some examples, the extruder has a twin-screw design.

[0111] The polymeric materials and optional additives disclosed herein can be added to the extruder through one or more ports. Multiple components can be added as a melt or as appropriately sized solid particles, such as fragments or spheres, which are melted in stages as they are mixed in the extruder barrel. The contents of the extruder can be heated to melt the composition. Supercritical fluids can be added to the melt as physical blowing agents. In specific examples, foamed components can be prepared using a physical blowing agent that foams the composition after it leaves the extruder, and thus the thermoplastic copolyester elastomer foam is substantially free of chemical blowing agents or their decomposition products.

[0112] In some examples, the disclosed polymeric material can be added as a melt at temperatures close to or at temperatures that cause dissociation of ionic crosslinks between polymer chains. At lower temperatures, the ionic moieties can reform or reassociate. Due to ionic crosslinking, the degree of crosslinking of the composition during processing can be controlled by controlling the temperature; by inducing a temperature decrease at a desired point to increase crosslinking, this results in an increase in the modulus or viscosity of the molten resin as the ionic moieties reassociate.

[0113] If a chemical foaming agent is used, the processing (melting) temperature used can be sufficiently lower than the temperature at which the foaming agent will be triggered. To foam the polymer material, the temperature near the extruder exit can be raised to near or at the trigger temperature of the chemical foaming agent, thereby producing a chemically foamed polymer material foam as the composition leaves the extruder (e.g., as the composition is injected into an injection mold).

[0114] Alternatively or additionally, physical foaming agents can be used to form physically foamed foam components, or physically and chemically foamed polymer foam components. For example, supercritical fluids such as supercritical carbon dioxide or supercritical nitrogen can be mixed with molten polymer material in the barrel of an extruder. As the mixture of molten polymer material containing one or more polymer materials and supercritical fluid exits the extruder, the pressure drop between the higher pressure inside the extruder and the lower pressure outside the extruder causes the supercritical fluid to transition into the gas phase and foams the molten polymer composition.

[0115] Non-limiting examples of suitable compounds that can be used as supercritical fluids include carbon dioxide (critical temperature 31.1°C, critical pressure 7.38 MPa), nitrous oxide (critical temperature 36.5°C, critical pressure 7.24 MPa), ethane (critical temperature 32.3°C, critical pressure 4.88 MPa), ethylene (critical temperature 9.3°C, critical pressure 5.12 MPa), nitrogen (critical temperature -147°C, critical pressure 3.39 MPa), and oxygen (critical temperature -118.6°C, critical pressure 5.08 MPa).

[0116] Carbon dioxide is frequently used as a supercritical fluid in various processes. By mixing supercritical carbon dioxide with polar fluids such as methanol, ethanol, propanol, or isopropanol, its compatibility with polar thermoplastic elastomers (especially thermoplastic polyurethanes, polyurea, and polyamide elastomers) can be improved. The polar fluid used should have a strength equal to or greater than 9 MPa. -1 / 2 The Hildebrand solubility parameter. Increasing the weight fraction of polar fluid increases the amount of carbon dioxide absorbed, but polar fluid is also absorbed, and at some point, there is a transition from the maximum absorption of supercritical carbon dioxide to the increase in the amount of non-foaming polar fluid being absorbed by thermoplastic elastomer articles. In some respects, particularly when used for injection into polyurethane elastomers, polyurea elastomers, or polyamide elastomers, polar fluid is included in the supercritical fluid at a rate of from about 0.1 mol percent to about 7 mol percent based on the total fluid.

[0117] Supercritical fluids can be used in combination. In some cases, supercritical nitrogen can be used as a nucleating agent in small weight percentages along with supercritical carbon dioxide or another supercritical fluid that acts as a blowing agent. Nanoscale particles such as nanoclay, carbon black, crystals, immiscible polymers, and inorganic crystals such as salts can be included as nucleating agents.

[0118] In several aspects, methods for manufacturing foam parts include injection molding the polymeric materials described herein to produce foam parts. Injection molding can utilize a screw-type syringe, which allows for maintaining and controlling the pressure within the syringe barrel. An injection molding machine can allow for the metering and delivery of supercritical fluids, such as carbon dioxide or nitrogen, into the composition prior to injection. The supercritical fluid can be mixed into the composition within the syringe barrel and then injected into a mold. The supercritical fluid can then expand to create cell nuclei to form a physical foam within the mold. Injection molding can also include physically foaming the compositions described herein using microporous foam injection molding processes such as, for example, the MuCell process (Trexcel Inc., Royal Oak, Michigan, USA).

[0119] In some examples, the foam components described herein are manufactured using a process involving impregnating the foam component with a physical blowing agent at a first concentration or pressure (e.g., at or above the softening temperature of the composition). As used herein, the term "impregnation" generally means dissolving or suspending a physical blowing agent in a polymer material. The impregnated polymer material can then be foamed, or can be cooled (where applicable) and re-softened (where applicable) for blowing at a later time.

[0120] In some cases, the impregnated polymer material is foamed by reducing the solubility of the physical blowing agent in the polymer matrix through pressure or temperature changes. The reduction in the solubility of the physical blowing agent can release additional amounts of the impregnated physical blowing agent from the composition (e.g., for secondary expansion to create initially formed micropores in the composition) to further blow the composition to form foam parts (e.g., foam parts with microporous structures).

[0121] Foamed parts can be foamed after a molding process using a method that involves injecting the molded part with a supercritical fluid, preferably until saturated. For example, the part can be placed in a container capable of withstanding high pressure. The container is sealed, and a foaming agent, such as carbon dioxide, nitrogen, a mixture of carbon dioxide and nitrogen, or other types of foaming agents, is introduced. The container temperature and pressure are maintained above the critical temperature and pressure of the foaming agent. Once the part is saturated with the foaming agent, the container is rapidly depressurized (the depressurization process can last up to about one minute). The part is then removed from the container and heated to produce the foamed part. When using a co-solvent, the co-solvent, along with the foaming agent such as carbon dioxide, nitrogen, a mixture of carbon dioxide and nitrogen, or other types of foaming agents, can be introduced into the container containing the part before sealing the container. The part can be immersed in the supercritical fluid under certain conditions—temperature and pressure—for a period of time to allow it to absorb the desired amount of supercritical fluid.

[0122] In several ways, components can be immersed in conditions that cause them to become saturated with a supercritical fluid. The components are then removed from the chamber and immediately heated to a temperature in a medium with suitable thermal properties to induce foaming, or exposed to microwave or infrared radiation in a pipe or oven to induce foaming. In microwave heating, the material is exposed to electromagnetic waves, which cause the molecules in the material to vibrate, thereby generating heat. The system can be designed to operate as a batch or continuous process. In a batch process, components saturated with a supercritical fluid are placed in a microwave oven or a device equipped with one or more IR lamps. Preferably, when the component size is sufficiently small, the component is rotated or agitated to ensure rapid and uniform heating. When foaming is complete, the item is removed from the system. Heating can also be performed in a continuous process. Components can be placed on a flat surface, such as a belt, which moves them through a pipe or tube. The system is designed such that the heating elements (IR lamps or microwave generators) can apply power to achieve rapid and uniform heating. The heating time is controlled by the speed at which the component moves through the pipe or tube.

[0123] Water is a suitable medium in which foaming readily occurs at appropriate temperatures due to its high heat capacity and heat transfer rate. In some preferred aspects, thermoplastic elastomer articles injected or saturated with a supercritical fluid are immersed in water at a temperature at which the water is at least about 80 degrees Celsius higher than, and preferably at least about 100 degrees Celsius higher than, the glass transition temperature of the elastomer (soft segments), but lower than the melting temperature of the elastomer (hard segments). Other suitable media are steam or pressurized hot air.

[0124] The time, temperature, and pressure in the solubilization step using supercritical fluids, as well as the decompression rate, temperature, and medium in the foaming step, all affect the degree of foaming achieved. Generally, thicker articles must be held in supercritical fluids for a longer period to become saturated with the fluid.

[0125] Foamed components can be annealed at elevated temperatures after the foaming process. While not wishing to be bound by theory, it is believed that annealing articles allows for phase separation of the elastomer placed under strain (e.g., mold) and stress (external pressure distribution just balanced by the moderate internal pressure following rapid foaming). Cooling under balanced forces allows the increased modulus to maintain its shape once at room temperature and atmospheric pressure.

[0126] Foam components can be used in temperatures ranging from above ambient to just below the Tf of thermoplastic elastomers. m (T m It can be determined by a generally appropriate thermal method, in which differential scanning calorimetry (DSC) is used, where the temperature is annealed for a period of time sufficient to stabilize the foam.

[0127] In addition to injection molding, the foam components of this disclosure can be foamed and molded using a variety of processes known in the art. For example, polymer material foams can be formed into various shapes and sizes, such as sheet foam, filament foam, or strand foam, and granular (e.g., bead) foam. These various forms of foam components can then be used in different ways. For example, like injection-molded foam, sheet foam and filament or strand foam can be used directly as finished foam articles, or they can be shaped (e.g., cut, polished, or trimmed) to form finished foam articles, or they can be compression molded to form finished foam articles. Optionally, the foam components can undergo an annealing process as part of forming finished foam articles. Polymer material pellets can be used to form individual granular foams, or they can be foamed and molded to form monolithically molded foam articles comprising individual portions of foam attached to each other.

[0128] The foam parts described herein, representing several examples, can be further shaped or molded using any known method for forming articles from thermoplastic materials. Optionally, foam parts of this disclosure that have been foamed using any suitable blow molding process (e.g., blow molding using physical and / or chemical blowing agents), including those foamed by injection molding using only physical blowing agents, can then be compression molded to form compression-molded foam.

[0129] In some examples, the foam component of this disclosure can be prepared by a process comprising: (i) softening a polymer material (e.g., by heating at or above the softening temperature of the composition); (ii) contacting the polymer material simultaneously with or sequentially (where applicable) with a physical blowing agent at a first concentration or a first pressure sufficient to drive a certain amount of physical blowing agent into the composition or to combine the physical blowing agent with the composition; (iii) changing the concentration or pressure of the physical blowing agent (e.g., reducing the pressure or concentration) to a second concentration or a second pressure that effectively foams the composition, thereby forming a foam component (e.g., a polymer material having a microporous structure); and (iv) cooling (where applicable) the foam component (e.g., cooling to a temperature below the softening temperature of the composition) after the change to form a cured thermoplastic foam component.

[0130] In other examples, the foam component of this disclosure is prepared by: (i) in some examples, contacting (e.g., dissolving or suspending) the composition with a first concentration of a chemical blowing agent at or above the softening temperature of the composition; (ii) triggering the chemical blowing agent to foam the polymer material, thereby forming a foam component (e.g., a foam component with a microporous structure); and (iii) after triggering, in some examples, cooling the foam component to a temperature, for example, below its softening temperature, to form a cured thermoplastic copolyester elastomer foam. In some examples, 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 composition, thereby forming a foam component (e.g., a foam component with a microporous structure). In some examples, contact includes pressure contact ranging 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).

[0131] Chemical blowing agents can be endothermic or exothermic, referring to the type of decomposition they undergo to produce gases used for foaming. Decomposition may be a result of thermal energy in the system. Endothermic blowing agents absorb energy and typically release gases, such as carbon dioxide, upon decomposition. Exothermic blowing agents release energy and produce gases, such as nitrogen, upon decomposition. Regardless of the chemical blowing agent used, the thermal variables of the molded polymer composition and the thermal variables of the blowing agent to be decomposed are linked, such that process parameters are selected to allow the polymer to be molded and the blowing agent to decompose at an appropriate stage of the molding operation.

[0132] Polymer materials.

[0133] In several aspects, polymeric materials may include one or more polymers such as polyurethanes, polyureas, polyamides, polyesters, ethylene and metallocene-catalyzed block copolymers of α-olefins having 4 to about 8 carbon atoms, styrene block copolymers such as poly(styrene-butadiene-styrene), poly(styrene-ethylene-co-butene-styrene), and poly(styrene-isoprene-styrene) and combinations thereof.

[0134] In another aspect, the polymer material may include one or more polyesters. In this aspect, the polymer may include polyesters. Polyesters can be formed by reacting one or more carboxylic acids or their ester-forming derivatives with one or more divalent or polyvalent aliphatic alcohols, alicyclic alcohols, aromatic alcohols, or arylaliphatic alcohols or bisphenols. The polyester may be a polyester homopolymer of repeating polyester segments having the same chemical structure. Alternatively, the polyester may comprise a number of polyester segments with different polyester chemical structures (e.g., polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, etc.). Polyester segments with different chemical structures may be arranged randomly or as repeating blocks.

[0135] In several aspects, polymeric materials may include one or more polymers such as polyurethanes, polyureas, polyamides, polyesters, ethylene and metallocene-catalyzed block copolymers of α-olefins having 4 to about 8 carbon atoms, styrene block copolymers such as poly(styrene-butadiene-styrene), poly(styrene-ethylene-co-butene-styrene), and poly(styrene-isoprene-styrene) and combinations thereof.

[0136] Exemplary carboxylic acids that can be used to prepare polyesters include, but are not limited to, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, terephthalic acid, isophthalic acid, alkyl-substituted or halogenated terephthalic acid, alkyl-substituted or halogenated isophthalic acid, nitro-terephthalic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfide dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenylalkylene dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, and cyclohexane-1,3-dicarboxylic acid. Exemplary diols or phenols suitable for preparing polyesters include, but are not limited to, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, and bisphenol A.

[0137] In some respects, the polyester is polybutylene terephthalate (PBT), polypropylene terephthalate, polyhexamethylene terephthalate, poly(1,4-dimethylcyclohexane) terephthalate, polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, or blends or mixtures of two or more of the foregoing.

[0138] The polyester can be a copolyester (i.e., a copolymer comprising polyester segments and non-polyester segments). The copolyester can be an aliphatic copolyester (i.e., a copolyester in which both polyester and non-polyester segments are aliphatic). Alternatively, the copolyester can contain aromatic segments. The polyester segments of the copolyester can include or consist of the following: polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, or any combination thereof. The polyester segments of the copolyester can be arranged randomly or as repeating blocks.

[0139] For example, the polyester can be a block copolyester having repeating blocks (hard segments) of polymer units that are relatively stiff and have the same chemical structure (segment) and repeating blocks (soft segments) of polymer segments that are relatively soft. In block copolyesters that include block copolyesters with repeating hard and soft segments, physical crosslinking can exist within or between blocks, or both. In a particular example, the material may comprise an elastic copolyester having repeating hard and soft segments, or substantially composed of such an elastic copolyester.

[0140] The non-polyester segments of a copolyester may include or consist of polyether segments, polyamide segments, or both. The copolyester may be a block copolyester or a random copolyester. The copolyester may be formed by the polycondensation of a polyester oligomer or prepolymer with a second oligomer prepolymer to form a block copolyester. Optionally, the second prepolymer may be a hydrophilic prepolymer. For example, the copolyester may be formed by the polycondensation of terephthalic acid or naphthalene with ethylene glycol, 1,4-butanediol, or 1,3-propanediol. Examples of copolyesters include polyethylene adipate, polybutylene succinate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and combinations thereof. In specific examples, the copolyamide may include or consist of polyethylene terephthalate.

[0141] In some aspects, a polyester is a block copolymer comprising one or more segments of: polybutylene terephthalate (PBT), polypropylene terephthalate, polyhexamethylene terephthalate, poly(1,4-dimethylcyclohexane) terephthalate, polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylate (PAR), polybutylene naphthalate (PBN), and liquid crystal polyester. For example, suitable polyesters as block copolymers may be PET / PEI copolymers, polybutylene terephthalate / tetraethylene glycol copolymers, polyoxyethylene diacid / polybutylene terephthalate copolymers, or blends or mixtures of any of the aforementioned copolymers.

[0142] In some respects, polyesters are biodegradable resins, such as copolyesters in which poly(α-hydroxy acids) such as polyglycolic acid or polylactic acid are included as the main repeating unit.

[0143] The disclosed polyester can be prepared by a variety of polycondensation methods known to those skilled in the art, such as solvent polymerization or melt polymerization.

[0144] In several aspects, the polymeric materials of this disclosure may include one or more thermoplastic copolyester elastomers. The thermoplastic copolyester elastomer may comprise chain units derived from one or more olefins and chain units derived from one or more olefinic unsaturated acid groups. The polymeric material may also comprise more than one cation in the anionic form of the acid groups in the ionically crosslinked thermoplastic copolyester elastomer. The thermoplastic copolyester elastomer may 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.

[0145] Various thermoplastic copolyester elastomers can be processed into foam structures as described herein. In some aspects, the thermoplastic copolyester elastomer is a terpolymer of ethylene, acrylic acid, and methyl acrylate or butyl acrylate. In some aspects, the ratio III of the total weight parts of acrylic acid in the thermoplastic copolyester elastomer to the total weight of the thermoplastic copolyester elastomer 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.

[0146] The polymeric materials provided herein may include thermoplastic copolyester elastomers comprising: (a) more than one first segment, each first segment derived from a dihydroxy-terminated polydiol; (b) more than one second segment, each second segment derived from a diol; and (c) more than one third segment, each third segment derived from an aromatic dicarboxylic acid. In several aspects, the thermoplastic copolyester elastomer is a block copolymer. In some aspects, the thermoplastic copolyester elastomer is a segment copolymer. In other aspects, the thermoplastic copolyester elastomer is a random copolymer. In still other aspects, the thermoplastic copolyester elastomer is a condensation copolymer.

[0147] In another aspect, the thermoplastic copolyester elastomer may have a weight-average molecular weight of about 50,000 Daltons to about 1,000,000 Daltons, about 50,000 Daltons to about 500,000 Daltons, about 75,000 Daltons to about 300,000 Daltons, about 100,000 Daltons to about 200,000 Daltons; or one or more values ​​of weight-average molecular weight within any of the foregoing ranges or a range of weight-average molecular weight covering any of the foregoing ranges.

[0148] In another aspect, the thermoplastic copolyester elastomer may have a first segment to third segment ratio based on the weight of each of the first and third segments, ranging from about 1:1 to about 1:5, from about 1:1 to about 1:3, from about 1:1 to about 1:2, or from about 1:1 to about 1:3; or have one or more values ​​of the first segment to third segment ratio within any of the foregoing ranges, or have a range of first segment to third segment ratios covering subranges of any of the foregoing ranges.

[0149] In another aspect, the thermoplastic copolyester elastomer may have a second segment to third segment ratio from about 1:1 to about 1:2 based on the weight of each of the first and third segments, and from about 1:1 to about 1:52 based on the weight of each of the first and third segments; or have one or more values ​​of the second segment to third segment ratio within any of the foregoing ranges or have a range of the second segment to third segment ratio covering any of the foregoing ranges.

[0150] In another aspect, the thermoplastic copolyester elastomer may have a first segment derived from a poly(epoxy)diol having a weight-average molecular weight of about 250 Daltons to about 6,000 Daltons, about 400 Daltons to about 6,000 Daltons, about 350 Daltons to about 5,000 Daltons, or about 500 Daltons to about 3,000 Daltons; or one or more values ​​of weight-average molecular weight within any of the foregoing ranges or a range of weight-average molecular weight covering any of the foregoing ranges.

[0151] In another aspect, the thermoplastic copolyester elastomer may have a first segment derived from a poly(epoxide) glycol, such as 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 mixtures thereof. In yet another aspect, the thermoplastic copolyester elastomer may have a first segment derived from a poly(epoxide) glycol, such as poly(ethylene ether) glycol; poly(propylene ether) glycol; poly(tetramethylene ether) glycol; poly(pentamethylene ether) glycol; poly(hexamethylene ether) glycol. In another aspect, thermoplastic copolyester elastomers may have a first segment derived from poly(tetramethylene ether) glycol.

[0152] In another aspect, the thermoplastic copolyester elastomer may 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 may be a C2-C8 diol. In yet another aspect, the second segment may be derived from ethylene glycol; propylene glycol; butanediol; pentanediol; 2-methylpropanediol; 2,2-dimethylpropanediol; hexanediol; 1,2-dihydroxycyclohexane; 1,3-dihydroxycyclohexane; 1,4-dihydroxycyclohexane; and mixtures thereof. In yet another aspect, the second segment may be derived from 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and mixtures thereof. In yet another aspect, the second segment may be derived from 1,2-ethylene glycol. In yet another aspect, the second segment may be derived from 1,4-butanediol.

[0153] In another aspect, the thermoplastic copolyester elastomer may have a third segment derived from an aromatic C5-C16 dicarboxylic acid. The aromatic C5-C16 dicarboxylic acid may have a molecular weight of less than about 300 Daltons, about 120 Daltons to about 200 Daltons; or one or more values ​​within any of the foregoing ranges or a molecular weight range covering any of the foregoing ranges. In some cases, the aromatic C5-C16 dicarboxylic acid is terephthalic acid, phthalic acid, isophthalic acid, or a derivative thereof. In yet another aspect, the aromatic C5-C16 dicarboxylic acid is a diester derivative of terephthalic acid, phthalic acid, or isophthalic acid. In yet another aspect, the aromatic C5-C16 dicarboxylic acid is a dimethyl ester derivative of terephthalic acid or a dimethyl ester derivative thereof.

[0154] In another aspect, the thermoplastic copolyester elastomer comprises: (a) more than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxy-terminated polydiol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0155]

[0156] Wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of 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 (b) more than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from the diol and a third segment derived from the aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0157]

[0158] R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of the diol, wherein the diol is a diol having a molecular weight of less than about 250; and R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment.

[0159] In another aspect, the thermoplastic copolyester elastomer comprises more than one first copolyester unit having a structure represented by Equation 3:

[0160]

[0161] Wherein R is H or methyl; where y is an integer having a value from 1 to 10; 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 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; 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 other 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 a methyl group and y is an integer with a value of 1.

[0162] In another aspect, the thermoplastic copolyester elastomer comprises more than one first copolyester unit having a structure represented by Equation 4:

[0163]

[0164] 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 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; 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 ​​covering a subrange of the foregoing range of integer values.

[0165] In another aspect, the thermoplastic copolyester elastomer comprises 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; or one or more values ​​of weight-average molecular weight within any of the foregoing ranges, or a weight-average molecular weight range covering any of the foregoing ranges.

[0166] In another aspect, the thermoplastic copolyester elastomer comprises more than one second copolyester unit, each of the more than one second copolyester unit having a structure represented by Equation 5:

[0167]

[0168] Where x is an integer having a value from 1 to 20; wherein the foam article has a microporous 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 ​​covering a subrange of the foregoing range of integer values. In other aspects, x is an integer having a value of 2, 3, or 4.

[0169] In another aspect, the thermoplastic copolyester elastomer comprises more than one second copolyester unit, each of the more than one second copolyester unit having a structure represented by Equation 6:

[0170]

[0171] In another aspect, the thermoplastic copolyester elastomer comprises more than one first copolyester unit within a weight percentage range based on the total weight of the thermoplastic copolyester elastomer, such that the weight percentage range is 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 aforementioned weight percentage ranges, or any range of weight percentage values ​​covering any subset of the aforementioned ranges.

[0172] In several aspects, the thermoplastic copolyester elastomer comprises more than one first copolyester unit based on about 30 to about 80% of the total weight of the thermoplastic copolyester elastomer; or alternatively, it comprises more than one second copolyester unit based on about 40 to about 65% of the total weight of the thermoplastic copolyester elastomer.

[0173] In another aspect, when determined using the cyclic tensile test as described herein, the thermoplastic copolyester elastomer may have a maximum load of about 10 N to about 100 N, about 15 N to about 50 N, about 20 N to about 40 N; or any load value or set of load values ​​within any of the aforementioned load value ranges, or any range of load values ​​covering a subset of any of the aforementioned ranges.

[0174] In another aspect, when determined using the cyclic tensile test as described herein, the thermoplastic copolyester elastomer may have an energy efficiency greater than or equal to about 50 percent, greater than or equal to about 60 percent, greater than or equal to about 70 percent, about 50 percent to about 90 percent, about 60 percent to about 90 percent, about 70 percent to about 90 percent; or any energy efficiency value or set of energy efficiency values ​​within any of the aforementioned energy efficiency ranges, or any range of energy efficiency values ​​covering any subset of the aforementioned ranges.

[0175] In another aspect, when determined using the cyclic tensile test as described herein, the thermoplastic copolyester elastomer may have an energy return of about 1 J to 15 J, about 2 J to 12 J, about 4 J to 10 J; or any energy return value or set of energy return values ​​within any of the aforementioned energy return ranges, or any range of energy return values ​​covering any subset of the aforementioned ranges.

[0176] In another aspect, when determined using the cyclic tensile test as described herein, the thermoplastic copolyester elastomer may have a tensile modulus of about 1 MPa to 15 MPa, about 300 kPa to 3 MPa, about 500 kPa to about 2 MPa, and about 100 MPa to about 10 MPa; or any tensile modulus value or set of tensile modulus values ​​within any of the foregoing tensile modulus ranges, or any range of tensile modulus values ​​covering any subset of any of the foregoing ranges.

[0177] In another aspect, thermoplastic copolyester elastomers can possess zero-shear viscosity values, which can be determined as described below. In short, viscosity measurements can be collected using a flat parallel plate on a suitable rheometer, such as the TA Instruments DHR-3 rheometer. Typically, circular samples with a 25 mm cross-section and approximately 2 mm thickness are punched from a solid injection-molded substrate. The samples are dried before being placed in the rheometer. All samples are equilibrated at 180°C for 2–5 minutes and trimmed to obtain a final gap of <1 mm. Shear rates are performed from 0.01 s⁻¹. -1 up to 100s -1 Flow scanning experiments were conducted. Data were fitted to the Carreau, Carreau-Yasuda, and Williamson models, and the best fit was selected to record the zero-shear viscosity values. Polymer melt flow profiles were determined at temperatures, for example, 20°C above the melting point as described above by DSC. In several respects, the thermoplastic copolyester elastomer can have zero-shear viscosity values ​​of about 10 Pa·s to about 10,000 Pa·s; about 100 Pa·s to about 7,000 Pa·s; and about 1,000 Pa·s to about 5,000 Pa·s.

[0178] In some aspects, thermoplastic copolyester elastomers may include phase-separated domains. For example, more than one first segment derived from a dihydroxyl-terminated polydiol may be phase-separated into a domain primarily comprising the first segment. Furthermore, more than one second segment derived from the diol may be phase-separated into a domain primarily comprising the second segment. In other aspects, thermoplastic copolyester elastomers may include phase-separated domains primarily comprising more than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxyl-terminated polydiol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0179]

[0180] Wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of 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 other phase-separated domains mainly comprising more than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from the diol and a third segment derived from the aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0181]

[0182] Wherein R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of 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 group from the aromatic dicarboxylic acid of the third segment. In other aspects, the thermoplastic copolyester elastomer may include phase-separated domains comprising primarily more than one first copolyester unit, each of the more than one first copolyester unit having a structure represented by Formula 4:

[0183]

[0184] Where 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 unit is from about 300 Daltons to about 7,000 Daltons; and other phase-separated domains mainly comprising more than one second copolyester unit, each of the more than one second copolyester unit having a structure represented by Equation 5:

[0185]

[0186] Where x is an integer with values ​​from 1 to 20.

[0187] Exemplary, but not limiting, thermoplastic polyester elastomers, including thermoplastic copolyester elastomers, that can be used in the disclosed methods, foams, and articles, include... 3078 4068 and 4556 (DuPont, Wilmington, Delaware, USA); Pelprene TM P30B, P40B and P40H (Toyobo USA Inc., New York, New York, USA); 5300 5400 and its blends (Samyang Corporation, Korea); Keyflex BT1028D, BT1033D, BT1035D, BT1040D, BT1045D and BT1047D (LG Chem, Korea); and KP3340, KP3346, KP3347, KP3942 (Kolon Plastics, Inc., Korea).

[0188] In some aspects, the disclosed foamed polymeric materials may also include one or more ionomers, such as any Polymer (DuPont, Wilmington, Delaware, USA). The ionic 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 elastomer foam having a density of about 0.7 g / cm³ or less, or 0.5 g / cm³ or less, or 0.4 g / cm³ or less, or 0.3 g / cm³ or less. The process may include blowing the composition to produce an article or part comprising the thermoplastic copolyester elastomer foam. In some examples, the process for forming the thermoplastic copolyester elastomer foam comprises injection molding a mixture comprising the composition described herein and a supercritical fluid (e.g., supercritical carbon dioxide or supercritical nitrogen) in a mold and removing the thermoplastic copolyester elastomer foam from the mold.

[0189] In some aspects, the disclosed foamed polymeric materials may also include one or more thermoplastic polyurethanes, such as Fortimopolymer. TM (Mitsui Chemicals, Inc., Tokyo, Japan); (Covestro LLC, Pittsburgh, Pennsylvania, USA); and BounCell-X TM (Lubrizol Advanced Materials, Inc., Brecksville, Ohio, USA).

[0190] In some aspects, the disclosed foamed polymeric material may further include one or more olefin polymers. The olefin polymers may include ethylene-based copolymers, propylene-based copolymers, and butene-based copolymers. In some aspects, the olefin polymers are ethylene-based copolymers, such as styrene-ethylene / butene-styrene (SEBS) copolymers; ethylene-propylene diene monomer (EPDM) copolymers; ethylene-vinyl acetate (EVA) copolymers; ethylene alkyl acrylate (EAA) copolymers; ethylene alkyl methacrylate (EAMA) copolymers; any copolymers thereof; and any blends thereof. In some aspects, the ratio V of the total weight parts of the olefin polymers present in the composition to the total weight parts of the thermoplastic copolyester elastomer in the composition is about 0.0 to about 0.6, about 0.0 to about 0.4, about 0.01 to about 0.4, or about 0.01 to about 0.6, or about 0.1 to about 0.4.

[0191] In some aspects, the disclosed polymeric materials may also include ethylene-vinyl acetate (EVA) copolymers. The ethylene-vinyl acetate (EVA) copolymers may have a range of vinyl acetate contents, for example, about 50 percent to about 90 percent, about 50 percent to about 80 percent, about 5 percent to about 50 percent, about 10 percent to about 45 percent, about 10 percent to about 30 percent, about 30 percent to about 45 percent, or about 20 percent to about 35 percent.

[0192] In several aspects, the polymeric materials of this disclosure may include suitable thermoplastic elastomers. For example, the thermoplastic elastomer may be selected from thermoplastic polyurethane elastomers, thermoplastic polyurea elastomers, thermoplastic polyether elastomers, thermoplastic copolyether ester elastomers, thermoplastic polyamide elastomers, thermoplastic polystyrene elastomers, thermoplastic polyolefin elastomers, thermoplastic copolyether amide elastomers, thermoplastic styrene diene copolymer elastomers, thermoplastic styrene block copolymer elastomers, thermoplastic polyamide elastomers, thermoplastic polyimide elastomers, any copolymers thereof, and any blends thereof.

[0193] In several aspects, thermoplastic elastomers used to prepare foam components include thermoplastic copolyether ester elastomers. It should be understood that, as used herein, "thermoplastic copolyether ester elastomer" can be used interchangeably with "thermoplastic polyether-polyester block copolymer," "thermoplastic polyester / polyether block copolymer," "copolyester elastomer," "poly-ether-ester block copolymer," "block poly-ether-ester," "polyester elastomer," "thermoplastic poly-ether-ester," "copoly(ether ester)," and "copolyester thermoplastic elastomer." In another aspect, thermoplastic copolyether ester elastomers comprise hard (or crystalline) polyester segments dispersed in soft (or amorphous) polyether segments. In yet another aspect, thermoplastic copolyether ester elastomers are block copolymers. In still another aspect, thermoplastic copolyether ester elastomers are segment block copolymers. In some respects, thermoplastic coether ester elastomers are block copolymers comprising segments or blocks of polyester and segments or blocks of polyether.

[0194] In several aspects, thermoplastic copolyether ester elastomers used to prepare foam components include polyester segments and polyether segments (such as polyalkylene (ether) glycols or polyalkylene (ether) polyols) produced by the reaction of dicarboxylic acid derivatives (such as terephthalates) and diols (such as butanediol).

[0195] In several aspects, the polyester segment includes polybutylene terephthalate (PBT). In another aspect, the polyester segment has a segment molecule with a molecular weight of about 3,000 Daltons to about 9,000 Daltons. In yet another aspect, the polyester segment has a segment molecule with a molecular weight of about 5,000 Daltons to about 7,000 Daltons.

[0196] In several aspects, the polyether segment includes long-chain polyols. In other aspects, it includes polyethylene glycol (PEG), polypropylene glycol (PPG) or polypropylene ether glycol (PPEG), polytetramethylene glycol (PTMG or PTHF), polytetramethylene ether glycol, and combinations thereof. In still other aspects, the polyether segment has a segment molecule with a length of about 200 Daltons to about 4000 Daltons. In yet another aspect, the polyether segment has a segment molecule with a length of about 1000 Daltons to about 3000 Daltons.

[0197] In several aspects, thermoplastic coether ester elastomers include soft segments of polytetramethylene ether terephthalate and hard segments of polybutylene terephthalate. Thermoplastic coether ester elastomers are commercially available, and non-limiting examples are available under the trade names HYTREL (DuPont Company, Wilmington, Delaware), ARNITEL (DSM Engineering Plastics, Evansville, Indiana), and PELPRENE (Toyobo Co., Ltd., Osaka, Japan).

[0198] In several respects, thermoplastic coether ester elastomer polymers include polyether segments obtained by polymerization of tetrahydrofuran (i.e., poly(tetramethylene ether)) and polyester segments obtained by polymerization of tetramethylene glycol and phthalic acid (i.e., 1,4-butanediol terephthalate). The more polyether units incorporated into the coether ester, the softer the polymer. The poly(tetramethylene ether) glycol used to prepare the coether ester can have a molecular weight from about 500 Daltons to about 3500 Daltons, or from about 800 Daltons to about 2500 Daltons.

[0199] In several aspects, the thermoplastic copolyether ester elastomer polymer comprises repeating units derived from 30 to 70 wt% of 1,4-butylene terephthalate and 10 to 70 wt% of poly(tetramethylene ether) terephthalate. In another aspect, the thermoplastic copolyether ester elastomer polymer comprises repeating units derived from 55 to 60 wt% of 1,4-butylene terephthalate, 23 to 27 wt% of 1,4-butylene isophthalate, 10 to 15 wt% of poly(tetramethylene ether) terephthalate, and 3 to 7 wt% of poly(tetramethylene ether) isophthalate. The poly(tetramethylene ether) glycol used to prepare the copolyether ester can have a molecular weight from about 800 to about 1200.

[0200] In several aspects, the thermoplastic copolyether ester elastomer polymer comprises repeating units derived from 30 to 40 wt% butylene terephthalate and 60 to 70 wt% poly(tetramethylene ether) terephthalate. The poly(tetramethylene ether) glycol used to prepare the copolyether ester preferably has a molecular weight from 1500 to about 2500.

[0201] In several respects, thermoplastic coether ester elastomers are block copolymers of short-chain terephthalate glycol esters and long-chain terephthalate glycol esters, comprising approximately 60 weight percent of hard segments of polybutylene terephthalate and approximately 40 weight percent of soft segments of polytetramethylene terephthalate. These thermoplastic coether ester elastomers possess a Shore hardness of 55D (ASTM D-2240), a melting point of 211°C (ASTM D-2117), a Vicat softening point of 180°C (ASTM D1525), and a flexural modulus of 207 MPa (ASTM D790). Suitable materials possessing the aforementioned properties are available under the trade name HYTRELO 5556 (DuPont Company, Wilmington, Delaware).

[0202] In several respects, thermoplastic coether ester elastomers are block copolymers of short-chain terephthalate glycol esters and long-chain terephthalate polyether glycol esters, comprising approximately 42 weight percent of hard segments of polybutylene terephthalate and approximately 58 weight percent of soft segments of polytetramethylene terephthalate. These thermoplastic coether ester elastomers have a hardness of 92A / 40D, a melting point of 168°C, a Vicat softening point of 112°C, and a flexural modulus of 48.3 MPa. Suitable materials possessing the aforementioned properties are available under the trade name HYTREL 4056 (DuPont Company, Wilmington, Delaware).

[0203] In several respects, the thermoplastic coether ester elastomer is a block copolymer of short-chain terephthalate glycol ester and long-chain terephthalate polyether glycol ester, comprising about 80 weight percent of hard segments of polybutylene terephthalate and about 20 weight percent of soft segments of polytetramethylene terephthalate. This thermoplastic coether ester elastomer has a hardness of about 72D, a melting point of 219°C, a Vicat softening point of 207°C, and a flexural modulus of 585 MPa. Suitable materials possessing the aforementioned properties are available under the trade name HYTRELO 7246 (DuPont Company, Wilmington, Delaware).

[0204] In several respects, thermoplastic coether ester elastomers comprise long-chain ester units of formula 7:

[0205]

[0206] The short-chain ester unit of formula 8:

[0207]

[0208] Where R 1 Includes divalent groups remaining after removing terminal hydroxyl groups from the poly(alkylene ether), said poly(alkylene ether) having a carbon-to-oxygen ratio from about 2.0 to about 4.3 and a weight-average molecular weight from about 400 Daltons to about 6000 Daltons; wherein R 2 This includes the divalent group remaining after removing the carboxyl group from a dicarboxylic acid having a molecular weight of less than about 300 Daltons; wherein R 3 This includes the divalent groups remaining after removing the hydroxyl groups from low molecular weight diols having a molecular weight of less than about 250 Daltons; wherein R 4 It includes the divalent group remaining after removing the carboxyl group from a dicarboxylic acid having a molecular weight of less than about 300 Daltons; wherein the long-chain ester unit represented by Formula 7 constitutes about 5% to about 95% by weight of the thermoplastic coether ester elastomer; and wherein the short-chain ester unit represented by Formula 8 constitutes about 95% to about 5% by weight of the thermoplastic coether ester elastomer.

[0209] In another respect, R 1 This includes the divalent groups remaining after removing the terminal hydroxyl groups from poly(tetramethylene ether). In yet another aspect, R... 1 It has a weight-average molecular weight ranging from about 500 Daltons to about 3,500 Daltons; about 600 Daltons to about 3,000 Daltons; about 800 Daltons to about 1,200 Daltons; about 800 Daltons to about 2,000 Daltons; about 800 Daltons to about 2,500 Daltons; about 800 Daltons to about 3,000 Daltons; about 800 Daltons to about 3,500 Daltons; about 800 Daltons to about 4,000 Daltons; about 1,000 Daltons to about 3,000 Daltons; or about 1,500 Daltons to about 2,500 Daltons.

[0210] In another respect, R 2 This includes the divalent group remaining after removing the carboxyl group from an aromatic dicarboxylic acid. In another aspect, R... 2 This includes the divalent groups remaining after removing the carboxyl group from 1,4-phthalic acid.

[0211] In another respect, R 3 This includes the divalent groups remaining after removing the hydroxyl group from C2-C6 alkyl diols. In another aspect, R... 3 This includes the divalent groups remaining after the hydroxyl groups are removed from 1,4-butanediol.

[0212] In another respect, R 4 It is the divalent group remaining after removing the carboxyl group from an aromatic dicarboxylic acid. In another aspect, R... 4It is the divalent group remaining after removing the carboxyl group from 1,4-phthalic acid.

[0213] In another aspect, the long-chain ester units represented by Formula 7 constitute about 10 to about 60 wt% of the thermoplastic coether ester elastomer; about 20 to about 60 wt% of the thermoplastic coether ester elastomer; about 30 to about 60 wt% of the thermoplastic coether ester elastomer; about 10 to about 70 wt% of the thermoplastic coether ester elastomer; about 20 to about 70 wt% of the thermoplastic coether ester elastomer; about 30 to about 70 wt% of the thermoplastic coether ester elastomer; about 10 to about 80 wt% of the thermoplastic coether ester elastomer; about 20 to about 80 wt% of the thermoplastic coether ester elastomer; or about 30 to about 80 wt% of the thermoplastic coether ester elastomer.

[0214] In another aspect, the short-chain ester units represented by Formula 8 constitute about 20 to about 90% by weight of the thermoplastic coether ester elastomer; about 40 to about 90% by weight of the thermoplastic coether ester elastomer; about 20 to about 80% by weight of the thermoplastic coether ester elastomer; about 40 to about 80% by weight of the thermoplastic coether ester elastomer; about 20 to about 70% by weight of the thermoplastic coether ester elastomer; about 40 to about 70% by weight of the thermoplastic coether ester elastomer; about 40 to about 60% by weight of the thermoplastic coether ester elastomer; or about 20 to about 60% by weight of the thermoplastic coether ester elastomer.

[0215] In another respect, at least about 50% by weight of the short-chain ester units represented by Formula 8 are identical.

[0216] In another aspect, the thermoplastic coether ester elastomer comprises a polybutylene terephthalate block and a poly(tetramethylene ether) terephthalate block, wherein the polybutylene terephthalate block constitutes from about 95% by weight to about 5% by weight of the thermoplastic coether ester elastomer, wherein the poly(tetramethylene ether) terephthalate block constitutes from about 5% by weight to about 95% by weight of the thermoplastic coether ester elastomer, and wherein the poly(tetramethylene ether) terephthalate block has a weight-average molecular weight from about 200 Daltons to about 6000 Daltons.

[0217] In another aspect, the thermoplastic coether ester elastomer comprises a polybutylene terephthalate block and a poly(tetramethylene ether) terephthalate block, wherein the polybutylene terephthalate block constitutes from about 70% to about 20% by weight of the thermoplastic coether ester elastomer, wherein the poly(tetramethylene ether) terephthalate block constitutes from about 5% to about 95% by weight of the thermoplastic coether ester elastomer, and wherein the poly(tetramethylene ether) terephthalate block has a weight-average molecular weight from about 200 Daltons to about 6000 Daltons.

[0218] In another aspect, the thermoplastic coether ester elastomer comprises a polybutylene terephthalate block and a poly(tetramethylene ether) terephthalate block, wherein the polybutylene terephthalate block constitutes from about 80% to about 30% by weight of the thermoplastic coether ester elastomer, wherein the poly(tetramethylene ether) terephthalate block constitutes from about 5% to about 95% by weight of the thermoplastic coether ester elastomer, and wherein the poly(tetramethylene ether) terephthalate block has a weight-average molecular weight from about 200 Daltons to about 6000 Daltons.

[0219] In another aspect, the thermoplastic coether ester elastomer comprises a polybutylene terephthalate block and a poly(tetramethylene ether) terephthalate block, wherein the polybutylene terephthalate block constitutes from about 70% to about 20% by weight of the thermoplastic coether ester elastomer, wherein the poly(tetramethylene ether) terephthalate block constitutes from about 30% to about 80% by weight of the thermoplastic coether ester elastomer, and wherein the poly(tetramethylene ether) terephthalate block has a weight-average molecular weight from about 200 Daltons to about 6000 Daltons.

[0220] In another aspect, the poly(tetramethylene ether) terephthalate block has a weight-average molecular weight from about 800 Daltons to about 1200 Daltons; from about 1500 Daltons to about 2500 Daltons; or from about 1000 Daltons to about 3000 Daltons.

[0221] In several aspects, the thermoplastic elastomer used to prepare foam components includes thermoplastic polyurethane elastomers. In yet another aspect, the thermoplastic polyurethane elastomer is selected from thermoplastic polyester-polyurethane elastomers, thermoplastic polyether-polyurethane elastomers, thermoplastic polycarbonate-polyurethane elastomers, thermoplastic polyolefin-polyurethane elastomers, any copolymers thereof, and any blends thereof. In yet another aspect, the thermoplastic polyurethane elastomer is a thermoplastic polyester-polyurethane elastomer. In yet another aspect, the thermoplastic polyurethane elastomer is a thermoplastic polyether-polyurethane elastomer. In yet another aspect, the thermoplastic polyurethane elastomer is a thermoplastic polycarbonate-polyurethane elastomer.

[0222] The thermoplastic polyurethane used to prepare the foam components may have a melt index (also referred to as melt flow index or melt flow rate) of at least about 160 g / 10 min (at 190°C, 21.6 kg), as measured according to ASTM D1238. In various embodiments, the melt index may be from about 160 g / 10 min to about 250 g / 10 min (at 190°C, 21.6 kg) or from about 160 g / 10 min to about 220 g / 10 min (at 190°C, 21.6 kg), in each case as measured according to ASTM D1238.

[0223] Thermoplastic polyurethanes can be produced via (a) the reaction of a diisocyanate with a bifunctional compound reactive to isocyanates. Typically, the bifunctional compound has two hydroxyl groups (diols) and can have a molar mass from 62 Daltons (molar mass of ethylene glycol) to about 10,000 Daltons, although bifunctional compounds with other isocyanate groups (e.g., secondary amines) can generally be used in small amounts, and trifunctional and monofunctional isocyanate-reactive compounds in limited molar fractions can be used. Preferably, the polyurethane is linear. Including a bifunctional compound having a molar mass of about 400 or greater introduces soft segments into the polyurethane. The increased ratio of soft to hard segments in the polyurethane causes it to become increasingly flexible and eventually elastic. In some aspects, such as when the molded article is for the outsole of footwear, the particles can be advantageously prepared using rigid thermoplastic polyurethanes or combinations of thermoplastic polyurethanes. In several other respects, such as when the molded article is for the sole interlayer of footwear, the particles can be advantageously prepared using elastic thermoplastic polyurethane or a combination of elastic thermoplastic polyurethane.

[0224] Suitable thermoplastic polyurethanes include thermoplastic polyester-polyurethanes, polyether-polyurethanes, and polycarbonate-polyurethanes. Non-limiting suitable examples of these include, but are not limited to, polyurethanes polymerized using the following as diol reactants: polyester diols prepared from diols and dicarboxylic acids or anhydrides; polylactone polyester diols (e.g., polycaprolactone diol); polyester diols prepared from hydroxy acids of monocarboxylic acids containing a hydroxyl group; polytetrahydrofuran diol; polyether diols prepared from ethylene oxide, propylene oxide, or a combination of ethylene oxide and propylene oxide; and polycarbonate diols such as polyhexamethylene carbonate diol and poly(hexamethylene-co-pentamethylene) carbonate diol. Elastic thermoplastic polyurethanes can be prepared by reacting one or more of these polymeric diols (polyester diols, polyether diols, polylactone diols, polytetrahydrofuran diol, or polycarbonate diol), one or more polyisocyanates, and optionally one or more monomeric chain extenders. The chain-extended compound is a compound having two or more functional groups that react with isocyanate groups, preferably two functional groups. Preferably, the elastic thermoplastic polyurethane is substantially linear (i.e., substantially all reactants are bifunctional).

[0225] Non-limiting examples of polyester diols used to form elastic thermoplastic polyurethanes include polyester diols prepared by polycondensation of dicarboxylic acid compounds, their anhydrides, and their polymerizable esters (e.g., methyl esters) with diol compounds. Preferably, all reactants are bifunctional, although small amounts of monofunctional, trifunctional, and higher-functionality materials (possibly up to a few molar percentages) may be included. Suitable dicarboxylic acids include, but are not limited to, glutaric acid, succinic acid, malonic acid, oxalic acid, phthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, anhydrides of these dicarboxylic acids, and mixtures thereof. Suitable polyols include, but are not limited to, wherein the chain extender is selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, cyclohexanediol, 2-ethyl-1,6-hexanediol, 1,4-butanediol, 1,5-pentanediol, 1,3-propanediol, butanediol, neopentanediol, and combinations thereof. Sometimes, small amounts of triols or higher-functionality polyols, such as trimethylolpropane or pentaerythritol, are included. In preferred aspects, the carboxylic acid includes adipic acid, and the diol includes 1,4-butanediol. Typical catalysts for esterification polymerization are protic acids, Lewis acids, titanium alkoxides, and dialkyltin oxides.

[0226] Hydroxycarboxylic acid compounds such as 12-hydroxystearic acid can also be polymerized to produce polyester diols. Such reactions can be carried out with or without an initiating diol, such as one of the diols already mentioned.

[0227] Polylactone diol reactants can also be used to prepare elastic thermoplastic polyurethanes. Polylactone diols can be prepared by reacting a diol initiator, such as a diol like ethylene glycol or propylene glycol, or another of the diols already mentioned, with a lactone. Lactones that can be ring-opened by active hydrogen can be polymerized, such as, but not limited to, ε-caprolactone, γ-caprolactone, β-butyrolactone, β-propiolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-decylactone, δ-decylactone, γ-nonylactone, γ-octylactone, and combinations thereof. The lactone ring can be substituted with an alkyl group having 1 to 7 carbon atoms. In a preferred aspect, the lactone is ε-caprolactone. Useful catalysts include those mentioned above regarding polyester synthesis. Alternatively, the reaction can be initiated by forming a sodium salt of the hydroxyl group on the molecule that will react with the lactone ring.

[0228] Tetrahydrofuran can be produced by using counterions such as SbF6. - AsF6 - PF6 - SbCl6 - BF4 - CF3SO3 - FSO3 - and ClO4 - Polymerization is achieved through a cationic ring-opening reaction. Initiation occurs via the formation of tertiary oxonium ions. Polytetrahydrofuran segments can be prepared as “living polymers” and terminated by reaction with the hydroxyl groups of a diol, such as any of the diols mentioned above.

[0229] Aliphatic polycarbonates can be prepared by polycondensation of aliphatic diols with dialkyl carbonates (such as diethyl carbonate), cyclic diol carbonates (such as cyclic carbonates with five- and six-membered rings), or diphenyl carbonate in the presence of catalysts such as alkali metals, tin catalysts, or titanium compounds. Another method of producing aliphatic polycarbonates is the ring-opening polymerization of cyclic aliphatic carbonates catalyzed by organometallic catalysts. Polycarbonate diols can also be produced by copolymerization of epoxides with carbon dioxide. Aliphatic polycarbonate diols are prepared by reacting diols with dialkyl carbonates (such as diethyl carbonate), diphenyl carbonate, or dioxolanones (such as cyclic carbonates with five- and six-membered rings) in the presence of catalysts such as alkali metals, tin catalysts, or titanium compounds. Useful diols include, but are not limited to, any diols already mentioned. Aromatic polycarbonates are typically prepared by reacting bisphenols, such as bisphenol A, with phosgene or diphenyl carbonate.

[0230] Polymer diols used for the synthesis of elastic thermoplastic polyurethanes, such as the polymeric polyester diols and polyether diols described above, preferably have a weight-average molecular weight (e.g., determined by the ASTM D-4274 method) ranging from about 300 Daltons to about 8,000 Daltons, or from about 300 Daltons to about 5,000 Daltons, or from about 300 Daltons to about 3,000 Daltons.

[0231] The synthesis of thermoplastic polyurethane can be carried out by reacting one or more compounds of polymeric diol, one or more compounds having at least two (preferably two) isocyanate groups, and optionally one or more chain extenders. The elastic thermoplastic polyurethane is preferably linear, and therefore the polyisocyanate component is preferably substantially bifunctional. Useful diisocyanate compounds for the preparation of elastic thermoplastic polyurethanes include, but are not limited to, methylene bis-4-cyclohexyl isocyanate; cyclohexyl diisocyanate (CHDI); isophorone diisocyanate (IPDI); m-tetramethylxylyl diisocyanate (m-TMXDI); p-tetramethylxylyl diisocyanate (p-TMXDI); ethylene diisocyanate; 1,2-diisocyanatopropane; 1,3-diisocyanatopropane; 1,6-diisocyanatohexane (hexamethylene diisocyanate or HDI); 1,4-butylene diisocyanate; lysine diisocyanate; 1,4-methylene bis(cyclohexyl isocyanate); 2,4-methylphenylene (“toluene”) diisocyanate and 2,6-methylphenylene diisocyanate (TDI); 2,4'-methylene diphenyl diisocyanate (MDI); 4,4'-methylene... Methyl diphenyl diisocyanate (MDI); o-xylene diisocyanate, m-xylene diisocyanate, and p-xylene diisocyanate (XDI); 4-chloro-1,3-phenylene diisocyanate; naphthylene diisocyanates, including 1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, and 2,6-naphthylene diisocyanate. Esters; 4,4'-dibenzyl diisocyanate; 4,5'-diphenyl diisocyanate; 4,4'-diisocyanatodibenzyl; 3,3'-dimethoxy-4,4'-biphenyl diisocyanate; 3,3'-dimethyl-4,4'-biphenyl diisocyanate; 1,3-diisocyanobenzene, 1,4-diisocyanobenzene, and combinations thereof. Particularly useful is diphenylmethane diisocyanate (MDI).

[0232] Useful chain extenders containing active hydrogen typically contain at least two active hydrogen groups, such as glycols, dithiols, diamines, or compounds having a mixture of hydroxyl, thiol, and amine groups, such as alkanolamines, aminoalkyl thiols, and hydroxyalkyl thiols, among others. The molecular weight of the chain extender can range from about 60 g / mol to about 400 g / mol. In some respects, alcohols and amines are preferred. Typical examples of useful diols used as polyurethane chain extenders include, but are not limited to, 1,6-hexanediol; cyclohexanediol (sold by Eastman Chemical Co. as CHDM); 2-ethyl-1,6-hexanediol; 1,4-butanediol; lower oligomers of ethylene glycol and ethylene glycol, including diethylene glycol, triethylene glycol, and tetraethylene glycol; lower oligomers of propylene glycol and propylene glycol, including dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; 1,3-propanediol; neopentyl glycol; dihydroxyalkylated aromatic compounds, such as hydroquinone and resorcinol bis(2-hydroxyethyl) ethers; p-xylene-α,α′-diol; p-xylene-α,α′-diol bis(2-hydroxyethyl) ethers; m-xylene-α,α′-diol and bis(2-hydroxyethyl) ethers; 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropionate; and mixtures thereof. Suitable diamine chain extenders include, but are not limited to, p-phenylene diamine, m-phenylene diamine, benzidine, 4,4'-methylenediphenylamine, 4,4'-methylenebis(2-chloroaniline), ethylenediamine, and combinations thereof. Other typical chain extenders are amino alcohols, such as ethanolamine, propanolamine, butanolamine, and combinations thereof. Preferred chain extenders include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and combinations thereof.

[0233] In addition to the bifunctional chain extenders described above, small amounts of trifunctional chain extenders such as trimethylolpropane, 1,2,6-hexanetriol, and glycerol, and / or monofunctional active hydrogen compounds such as butanol or dimethylamine may also be present. The amount of trifunctional chain extenders and / or monofunctional compounds used will preferably be based on a few equivalent percentages or less of the total weight of the reaction products and active hydrogen-containing groups used.

[0234] The reaction of polyisocyanate, polymeric glycol, and optionally chain extender is typically carried out by heating the components in the presence of a catalyst. Typical catalysts used for this reaction include organotin catalysts, such as stannous octoate or dibutyltin dilaurate. Generally, the ratio of polymeric glycol, such as polyester glycol, to chain extender can vary over a relatively wide range, depending heavily on the desired stiffness of the elastomer thermoplastic polyurethane. For example, the equivalence ratio of polyester glycol to chain extender can range from 1:0 to 1:12, and more preferably from 1:1 to 1:8. Preferably, the diisocyanate used is proportioned such that the overall ratio of the isocyanate equivalence to the equivalence of the hydrogen-containing material is in the range of 0.95:1 to 1.10:1, and more preferably from 0.98:1 to 1.04:1. The polymeric glycol segment is typically from about 25 wt% to about 65 wt% of the elastomer thermoplastic polyurethane, and preferably from about 25 wt% to about 50 wt% of the elastomer thermoplastic polyurethane.

[0235] In several aspects, the thermoplastic polyurethane elastomer used to prepare foam components comprises a long-chain polyol. In yet another aspect, the long-chain polyol is selected from polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polypropylene polyols, and any copolymers thereof. In yet another aspect, the long-chain polyol is a polyether polyol, a polyester polyol, and any copolymer thereof. In one aspect, the long-chain polyol is a polyether polyol. In another aspect, the long-chain polyol is a polyester polyol. In another aspect, the long-chain polyol has a weight-average molecular weight of not less than about 500 Daltons. In yet another aspect, the long-chain polyol has a weight-average molecular weight of about 500 Daltons to about 10,000 Daltons; about 600 Daltons to about 6,000 Daltons; or about 800 Daltons to about 4,000 Daltons.

[0236] A non-limiting example of a commercially available elastic thermoplastic polyurethane suitable for manufacturing thermoplastic polyurethane foam parts, having a melt flow index from about 160 g / 10 min to about 220 g / 10 min (at 190 degrees Celsius, 21.6 kg), is ELASTOLLAN SP9213 (200 g / 10 min melt flow index (at 190 degrees Celsius, 21.6 kg)) available from BASF Polyurethanes GmbH.

[0237] More rigid thermoplastic polyurethanes can be synthesized in the same manner but with a lower content of polymeric diol segments. Rigid thermoplastic polyurethanes can, for example, contain from about 0% by weight to about 25% by weight polyester diol segments, polyether diol segments, or polycarbonate diol segments. The synthesis of rigid polyurethanes is well known in the art and has been described in numerous references. Rigid thermoplastic polyurethanes having a melt index of at least about 160 g / 10 min (at 190°C, 21.6 kg) as measured according to ASTM D 1238 are commercially available and include those marketed under the trade name Lubrizol Corp., Wickliffe, Ohio. Those sold by ETPU.

[0238] Suitable thermoplastic polyurea elastomers can be prepared by reacting one or more polymeric diamines or polyols with one or more of the polyisocyanates already mentioned and one or more diamine chain extenders. Non-limiting examples of suitable diamine chain extenders include ethylenediamine, 1,3-propanediamine, 2-methylpentanediamine, hexamethylenediamine, 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl-1,6-hexanediamine, imino-bis(propylamine), imide-bis(propylamine), N-(3-aminopropyl)-N-methyl-1,3-propanediamine, 1,4-bis(3-aminopropoxy)butane, diethylene glycol-di(aminopropyl) ether, 1-methyl-2,6-diamino-cyclohexane, 1,4-diamino-cyclohexane... Alkane, 1,3-bis(methylamino)-cyclohexane or 1,4-bis(methylamino)-cyclohexane, isophorone diamine, 1,2-bis(sec-butylamino)-cyclohexane or 1,4-bis(sec-butylamino)-cyclohexane, N,N'-diisopropyl-isophorone diamine, 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, N,N'-dialkylamino-dicyclohexylmethane, and 3,3'-diethyl-5,5'-dimethyl-4,4'-diamino-dicyclohexylmethane. Polymer diamines include polyoxyethylene diamine, polyoxypropylene diamine, poly(ethylene-oxypropylene) diamine, and poly(tetramethylene ether) diamine. Amine-functionalized chain extenders and hydroxyl-functionalized chain extenders already mentioned may also be used. Typically, as in the past, trifunctional reactants are restricted and can be used in combination with monofunctional reactants to prevent cross-linking.

[0239] In several aspects, thermoplastic elastomers include thermoplastic polyamide elastomers. In other aspects, thermoplastic polyamide elastomers include nylon 6, nylon 12, or combinations thereof.

[0240] Suitable thermoplastic polyamide elastomers can be obtained by: (1) (a) polycondensation of dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid or any other dicarboxylic acid mentioned with (b) diamines such as ethylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine or decanediamine, 1,4-cyclohexanediamine, m-xylenyldiamine or any other diamine mentioned; (2) ring-opening polymerization of cyclic lactams such as ε-caprolactam or ω-laurolactam; (3) polycondensation of aminocarboxylic acids such as 6-aminohexanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid or 12-aminododecanoic acid; or (4) copolymerization of cyclic lactams with dicarboxylic acids and diamines to prepare carboxylic acid-functionalized polyamide blocks, followed by polymerization with polymeric ether glycols. Poly(polyoxyalkylene glycol) is reacted with any polymeric ether glycol already mentioned. Polymerization can be carried out, for example, at temperatures ranging from about 180 degrees Celsius to about 300 degrees Celsius. Specific examples of suitable polyamide blocks include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, copolymers of nylon, nylon MXD6, and nylon 46.

[0241] In several aspects, thermoplastic elastomers include at least one thermoplastic polystyrene elastomer. In another aspect, the thermoplastic polystyrene elastomer is a styrene block copolymer elastomer. In yet another aspect, the thermoplastic styrene block copolymer elastomer is a styrene-ethylene-butene-styrene block copolymer. In still another aspect, the styrene block copolymer elastomer is poly(styrene-butadiene-styrene), poly(styrene-ethylene-co-butene-styrene), poly(styrene-isoprene-styrene), any copolymer thereof, and any blend thereof.

[0242] In several aspects, when determined using differential scanning calorimetry, the thermoplastic elastomer used to prepare foam components is characterized by a broad peak indicating the melting temperature (T0). m The melting temperature is characterized by a melting range of about 15 degrees Celsius to about 200 degrees Celsius or about 50 degrees Celsius to about 90 degrees Celsius. In yet another aspect, the melting temperature is characterized by a melting range of about 30 degrees Celsius to about 150 degrees Celsius from the initial melting point to the peak melting temperature. In yet another aspect, the melting temperature is characterized by a melting range of at least about 30 degrees Celsius or by a melting range of at least about 50 degrees Celsius.

[0243] In several respects, the polymeric material can be a polyolefin polymer, such as an ethylene-vinyl acetate (EVA) polymer. The polyolefin polymer can be a polymer containing styrene repeating units and non-styrene repeating units; C4-C 100Unsaturated olefins; ethylene-vinyl acetate copolymers; olefin block copolymers; and mixtures thereof. In some aspects, the polyolefin polymer is an ABA block copolymer, wherein each A block has a styrene repeating unit, the B block is a random copolymer of ethylene and a first α-olefin having 3 to 8 carbon atoms (e.g., 3, 4, 5, 6, 7, or 8 carbon atoms), and wherein the ABA block copolymer comprises, by weight, about 10 percent to 50 percent, about 10 percent to 40 percent, about 15 percent to 40 percent, or about 15 percent to 30 percent of A blocks based on the total weight of the ABA block copolymer; an olefin block copolymer, wherein the olefin block copolymer is a copolymer of ethylene and a second α-olefin having about 4 to 14, about 6 to 12, or about 6 to 10 carbon atoms, and wherein the olefin block copolymer has one or more ethylene-rich blocks and one or more second α-olefin-rich blocks; and an ethylene-vinyl acetate copolymer.

[0244] Elastic ethylene-vinyl acetate copolymers can be prepared by free radical emulsion polymerization of ethylene and vinyl acetate up to about 50 percent by weight. The vinyl acetate monomer is typically at least about 10 percent by weight of the monomers used, preferably at least about 25 percent by weight. The ethylene-vinyl acetate copolymer has a vinyl acetate content preferably from about 25 percent by weight to about 50 percent by weight, and more preferably from about 35 percent by weight to about 50 percent by weight. Ethylene-vinyl acetate (EVA) copolymers can have a vinyl acetate content of about 5 percent to 55 percent, about 5 percent to 50 percent, about 10 percent to 50 percent, about 10 percent to 45 percent, or about 15 percent to 40 percent by weight based on the weight of the ethylene-vinyl acetate copolymer. Ethylene-vinyl acetate copolymers can have a melt flow index ranging from about 0.5 g / 10 min to about 50 g / 10 min (at 190°C, 2.16 kg), preferably from 2.5 g / 10 min to 10 g / 10 min (at 190°C, 2.16 kg), as measured using the procedure of ASTM D1238. Non-limiting examples of suitable commercially available ethylene-vinyl acetate copolymers include ELVAX 265 and ELVAX 40L-3 from DuPont (Midland, ML, USA) and LAVAPRENE 400 from Langxess (Cologne, Germany). Ethylene-vinyl acetate copolymers can be used in combination. In some aspects, EVA can be formed from a combination of high melt flow index materials and low melt flow index materials. For example, EVA can have a melt flow index between about 1 and about 50.

[0245] In another aspect, the polyolefin polymer can be a homopolymer of vinyl esters and an olefin-vinyl ester copolymer, such as polyvinyl acetate, ethylene-vinyl acetate copolymer and propylene-vinyl acetate copolymer, which can be used as vinyl ester polymers.

[0246] In several aspects, the polymeric material can be a block copolymer comprising a first block and a third block, each of the first and third blocks independently comprising a straight-chain or branched aliphatic polymer having more than one side-attached aromatic group, a second block of an aliphatic polymer located between the first and third blocks and comprising more than one aliphatic side chain attached thereto, and more than one first olefin unsaturated group present on one or more of the first, second, and third blocks, wherein the block copolymer comprises about 60 percent to about 90 percent by weight of the second block based on the weight of the block copolymer; an olefin copolymer comprising more than one first olefin segment and more than one second olefin segment, the second olefin segment having a different chemical structure from the first olefin segment; or one or more linking polymers, each linking polymer comprising one or more third olefin segments. ; and ethylene-vinyl acetate (EVA) copolymer; wherein the sum of ratios I, II, III, IV and V is from about 1.00 to about 10.00; wherein ratio I is the ratio of the total weight parts of olefin copolymers present in the composition to the total weight parts of block copolymers present in the composition; wherein ratio II is the ratio of the total weight parts of linking polymers present in the composition to the total weight parts of block copolymers present in the composition; wherein ratio III is the ratio of the total weight parts of EVA copolymers present in the composition to the total weight parts of block copolymers present in the composition; wherein ratio IV is the ratio of the total weight parts of linking polymers present in the composition to the total weight parts of block copolymers present in the composition, and wherein ratio V is the ratio of the total weight parts of one or more EVA copolymers present in the composition to the total weight parts of one or more olefin copolymers present in the composition.

[0247] In several aspects, the polymeric material can be a block copolymer comprising a first block and a third block, each of the first and third blocks independently comprising a straight-chain or branched aliphatic polymer having more than one aliphatic side chain attached thereto; a second block located between the first and third blocks and comprising an aliphatic polymer having more than one aliphatic side chain attached thereto; and more than one first olefinic unsaturated group present on one or more of the first, second, and third blocks, wherein the block copolymer comprises about 60 percent to about 90 percent of the second block by weight based on the weight of the block copolymer; an olefin copolymer comprising more than one first olefin segment and more than one second olefin segment having a different chemical structure from the first olefin segment; and one or more linking polymers, each linking polymer comprising one or more third olefin segments.

[0248] In several aspects, the polymeric material can be a composition comprising: an ABA block copolymer, wherein each A block comprises a styrene repeating unit, the B block is a random copolymer of ethylene and an α-olefin having about 3 to 8 carbon atoms, and wherein the ABA block copolymer comprises about 10 percent to about 40 percent of A blocks based on the weight of the ABA block copolymer; an olefin block copolymer, wherein the olefin block copolymer is a copolymer of ethylene and an α-olefin having about 6 to 12 carbon atoms, and wherein the olefin block copolymer has one or more carbon-rich... The ethylene block and one or more α-olefin-rich blocks; an α-olefin linker polymer, wherein the α-olefin linker polymer is a copolymer of ethylene and an α-olefin having about 3 to 8 carbon atoms, and wherein the α-olefin linker polymer has an α-olefin monomer content of about 15 percent to about 40 percent by weight based on the weight of the α-olefin linker polymer; and an ethylene-vinyl acetate copolymer, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of about 10 percent to about 40 percent by weight based on the weight of the ethylene-vinyl acetate copolymer.

[0249] In several aspects, the polymeric material can be a composition comprising: a partially hydrogenated thermoplastic elastic block copolymer comprising one or more A blocks containing aromatic repeating units, one or more B blocks containing aliphatic repeating units, and one or more first olefinic unsaturated groups present on one or both of the aromatic and aliphatic repeating units; an olefin block copolymer, wherein the olefin block copolymer is a copolymer of a first α-olefin and a second α-olefin different from the first α-olefin, and wherein the olefin block copolymer comprises one or more second olefinic unsaturated groups; an α-olefin-linked polymer, wherein the α-olefin-linked polymer comprises one or more aliphatic side chains; and an ethylene-vinyl acetate copolymer; wherein the sum of ratios I, II, III, IV, and V is from about 1.00 to about 10.00; wherein ratio I is The ratio of the total weight parts of olefin copolymers present in the composition to the total weight parts of partially hydrogenated thermoplastic elastic block copolymers present in the composition; wherein ratio II is the ratio of the total weight parts of α-olefin-linked polymers present in the composition to the total weight parts of partially hydrogenated thermoplastic elastic block copolymers present in the composition; wherein ratio III is the ratio of the total weight parts of ethylene-vinyl acetate copolymers present in the composition to the total weight parts of partially hydrogenated thermoplastic elastic block copolymers present in the composition; wherein ratio IV is the ratio of the total weight parts of α-olefin-linked polymers present in the composition to the total weight parts of partially hydrogenated thermoplastic elastic block copolymers present in the composition; and wherein ratio V is the ratio of the total weight parts of one or more ethylene-vinyl acetate copolymers present in the composition to the total weight parts of one or more olefin copolymers present in the composition.

[0250] In several aspects, the polymeric material can be a composition comprising: a partially hydrogenated thermoplastic elastic block copolymer comprising one or more A blocks containing aromatic repeating units, one or more B blocks containing aliphatic repeating units, and one or more first olefinic unsaturated groups present on one or both of the aromatic and aliphatic repeating units; an olefin block copolymer, wherein the olefin block copolymer is a copolymer of a first α-olefin and a second α-olefin different from the first α-olefin, and wherein the olefin block copolymer comprises one or more second olefinic unsaturated groups; an α-olefin-linked polymer, wherein the α-olefin-linked polymer comprises one or more aliphatic side chains; and an ethylene-vinyl acetate copolymer.

[0251] In several aspects, the polymeric material can be a composition comprising: one or more partially hydrogenated thermoplastic elastic block copolymers, each of which independently comprises one or more aromatic blocks, one or more aliphatic blocks, and one or more first olefin unsaturated units; one or more olefin block copolymers, each of which comprises a second olefin unsaturated unit; one or more α-olefin linked polymers; and one or more ethylene-vinyl acetate copolymers; wherein the sum of ratios I, II, III, IV, and V is from about 1.00 to about 10.00; wherein ratio I is the total weight parts of the olefin block copolymers present in the composition and the partially hydrogenated thermoplastic elastic block copolymers present in the composition. The ratio of the total weight parts of the plastic elastic block copolymers; wherein ratio II is the ratio of the total weight parts of the α-olefin-linked polymers present in the composition to the total weight parts of the partially hydrogenated thermoplastic elastic block copolymers present in the composition; wherein ratio III is the ratio of the total weight parts of the ethylene-vinyl acetate copolymers present in the composition to the total weight parts of the partially hydrogenated thermoplastic elastic block copolymers present in the composition; wherein ratio IV is the ratio of the total weight parts of the α-olefin-linked polymers present in the composition to the total weight parts of the partially hydrogenated thermoplastic elastic block copolymers present in the composition; and wherein ratio V is the ratio of the total weight parts of one or more ethylene-vinyl acetate copolymers present in the composition to the total weight parts of one or more olefin copolymers present in the composition.

[0252] In several aspects, the polymeric material can be a composition comprising: one or more partially hydrogenated thermoplastic elastic block copolymers, each of which independently comprises one or more aromatic blocks, one or more aliphatic blocks, and one or more first olefin unsaturated units; one or more olefin block copolymers, each of which comprises a second olefin unsaturated unit; one or more α-olefin linked copolymers; and one or more ethylene-vinyl acetate copolymers.

[0253] In many respects, the polymeric material can be a polyurethane elastomer, a polyurea elastomer, a polyamide elastomer (PEBA or polyether block polyamide), a polyester elastomer, a metallocene-catalyzed block copolymer of ethylene and an α-olefin having 4 to about 8 carbon atoms, a styrene block copolymer, such as poly(styrene-butadiene-styrene), poly(styrene-ethylene-co-butene-styrene), and poly(styrene-isoprene-styrene) and combinations thereof.

[0254] Polyurethanes can be selected from polyester-polyurethanes, polyether-polyurethanes, and polycarbonate-polyurethanes, including but not limited to polyurethanes polymerized using polyether glycols and polyester (including polycaprolactone polyester) glycols as polymer glycol reactants. These polymer glycol-based polyurethanes are prepared by reacting a polymer glycol (polyester glycol, polyether glycol, polycaprolactone glycol, polytetrahydrofuran glycol, or polycarbonate glycol), one or more polyisocyanates, and optionally one or more chain extenders. When this term is used, the chain extender is a compound having two or more functional groups reactive with isocyanate groups, such as glycols, amino alcohols, and diamines. Preferably, the polymer glycol-based polyurethane is substantially linear (i.e., substantially all reactants are bifunctional).

[0255] Diisocyanates used in the manufacture of polyurethanes can be aromatic or aliphatic. Useful diisocyanate compounds for the preparation of thermoplastic polyurethanes include, but are not limited to, isophorone diisocyanate (IPDI), methylene bis-4-cyclohexyl isocyanate (H... 12 MDI, cyclohexyl diisocyanate (CHDI), m-tetramethylxylene diisocyanate (m-TMXDI), p-tetramethylxylene diisocyanate (p-TMXDI), 4,4'-methylene diphenyl diisocyanate (MDI, also known as 4,4'-diphenylmethane diisocyanate), 2,4-toluene diisocyanate or 2,6-toluene diisocyanate (TDI), ethylene diisocyanate, 1,2-diisocyanate propane 1,3-Diisocyanate propane, 1,6-Diisocyanate hexane (hexamethylene diisocyanate or HDI), 1,4-butylene diisocyanate, lysine diisocyanate, m-xylene diisocyanate and p-xylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 1,5-tetrahydro-naphthalene diisocyanate, 4,4'-dibenzyl diisocyanate and xylene diisocyanate (XDI), and combinations thereof. Non-limiting examples of higher-functionality polyisocyanates that can be used in limited quantities to produce branched thermoplastic polyurethanes (optionally with monofunctional alcohols or monofunctional isocyanates) include 1,2,4-phenyltriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,6,11-undecanetriisocyanate, bicycloheptanetriisocyanate, triphenylmethane-4,4',4”-triisocyanate, isocyanurates of diisocyanates, biuret of diisocyanates, urethane of diisocyanates, and the like.

[0256] Non-limiting examples of suitable diols that can be used as chain extenders include ethylene glycol and lower oligomers of ethylene glycol, including diethylene glycol, triethylene glycol, and tetraethylene glycol; propylene glycol and lower oligomers of propylene glycol, including dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; cyclohexanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,3-propanediol, butanediol, neopentanediol, bis(2-hydroxyethyl) ethers of dihydroxyalkylated aromatic compounds such as hydroquinone and resorcinol; p-xylene-α,α'-diol; p-xylene-α,α'-diol bis(2-hydroxyethyl) ethers; m-xylene-α,α'-diol; and combinations thereof. Thermoplastic polyurethanes can be manufactured using small amounts of triols or higher-functionality polyols such as trimethylolpropane or pentaerythritol, optionally together with monomeric alcohols such as C2-C8 monools or monoisocyanates such as butyl isocyanate.

[0257] Useful chain extenders containing active hydrogen typically contain at least two active hydrogen groups, such as glycols, dithiols, diamines, or compounds having a mixture of hydroxyl, thiol, and amine groups, such as alkanolamines, aminoalkylthiols, and hydroxyalkylthiols, among others. The molecular weight of the chain extender is preferably in the range of about 60 to about 400. Alcohols and amines are preferred. Examples of useful glycols include those already mentioned. Suitable diamine chain extenders include, but are not limited to, ethylenediamine, diethylenetriamine, triethylenetetramine, and combinations thereof. Other typical chain extenders are amino alcohols, such as ethanolamine, propanolamine, butanolamine, and combinations thereof. Dithiols and diamine reactants can also be included in the preparation of inelastic polyurethanes.

[0258] In addition to bifunctional chain extenders, small amounts of trifunctional chain extenders such as trimethylolpropane, 1,2,6-hexanetriol, and glycerol, or monofunctional active hydrogen compounds such as butanol or dimethylamine may also be present. The amounts of trifunctional chain extenders and monofunctional compounds used may be, for example, 5.0 equivalent percentages or less based on the total weight of the reaction products and active hydrogen-containing groups used.

[0259] Polyester diols used to form polyurethanes are typically prepared by polycondensation of one or more polyacid compounds with one or more polyol compounds. Preferably, the polyacid and polyol compounds are bifunctional, meaning the diacid and diol are used to prepare a generally linear polyester diol, but may contain small amounts of monofunctional, trifunctional, and higher-functionality materials (potentially up to 5 mole percent) to provide a slightly branched but uncrosslinked polyester polyol component. Suitable dicarboxylic acids include, but are not limited to, glutaric acid, succinic acid, malonic acid, oxalic acid, phthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, octanoic acid, azelaic acid, dodecanoic acid, their anhydrides and polymerizable esters (e.g., methyl esters) and acid halides (e.g., acyl chlorides), and mixtures thereof. Suitable polyols include those already mentioned, particularly diols. In a preferred aspect, the carboxylic acid component includes one or more of adipic acid, octanoic acid, azelaic acid, phthalic acid, dodecanoic acid, or maleic acid (or their anhydrides or polymerizable esters), and the diol component includes one or more of 1,4-butanediol, 1,6-hexanediol, 2,3-butanediol, or diethylene glycol. Typical catalysts for esterification polymerization are protic acids, Lewis acids, titanium alkoxides, and dialkyltin oxides.

[0260] Polymer polyethers or polycaprolactone diol reactants for the preparation of thermoplastic polyurethanes can be obtained by reacting a diol initiator, such as 1,3-propanediol, ethylene glycol, or propylene glycol, with a lactone or an epoxide chain extender. Lactones that can be ring-opened by active hydrogen are well known in the art. Examples of suitable lactones include, but are not limited to, ε-caprolactone, γ-caprolactone, β-butyrolactone, β-propiolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-decylactolactone, δ-decylactolactone, γ-nonylactolactone, γ-octylactolactone, and combinations thereof. In a preferred aspect, the lactone is ε-caprolactone. Useful catalysts include those mentioned above regarding polyester synthesis. Alternatively, the reaction can be initiated by forming a sodium salt of a hydroxyl group on the molecule that will react with the lactone ring.

[0261] In other respects, diol initiators can react with oxirane-containing compounds to produce polyether diols that will be used in the polymerization of polyurethane elastomers. Oxirane polymer segments include, but are not limited to, polymerization products of ethylene oxide, propylene oxide, 1,2-epoxycyclohexane, 1-butene oxide, 2-butene oxide, 1-hexene oxide, tert-butylethylene oxide, phenyl glycidyl ether, 1-decene oxide, isobutylene oxide, cyclopentane oxide, 1-pentene oxide, and combinations thereof. Oxirane-containing compounds are preferably selected from ethylene oxide, propylene oxide, butane oxide, tetrahydrofuran, and combinations thereof. Oxirane polymerization is typically base-catalyzed. For example, polymerization can be carried out by loading a hydroxyl-functionalized initiator compound and a catalytic amount of a caustic agent such as potassium hydroxide, sodium methoxide, or potassium tert-butoxide, and adding the oxirane at a rate sufficient to keep the monomer usable for the reaction. Two or more different alkyl oxide monomers can be randomly copolymerized by coincident addition or block polymerized by sequential addition. Homopolymers or copolymers of ethylene oxide or propylene oxide are preferred. Tetrahydrofuran can be synthesized by using counterions such as SbF6. - AsF6 - PF6 - SbCl6 - BF4 - CF3SO3 - FSO3 - and ClO4 - Polymerization is achieved through a cationic ring-opening reaction. Initiation occurs via the formation of tertiary oxonium ions. Polytetrahydrofuran segments can be prepared as “living polymers” and terminated by reaction with the hydroxyl groups of a diol such as any of the diols mentioned above. Polytetrahydrofuran is also known as polytetramethylene ether glycol (PTMEG).

[0262] Aliphatic polycarbonate diols that can be used to manufacture polyurethanes are prepared by reacting diols with dialkyl carbonates (such as diethyl carbonate), diphenyl carbonate, or dioxapentane ketones (such as cyclic carbonates having five- or six-membered rings) in the presence of catalysts such as alkali metals, tin catalysts, or titanium compounds. Useful diols include, but are not limited to, any diols already mentioned. Aromatic polycarbonates are typically prepared by reacting bisphenols, such as bisphenol A, with phosgene or diphenyl carbonate.

[0263] In several aspects, the polymeric diol preferably has a weight-average molecular weight of at least about 500, more preferably at least about 1000, and even more preferably at least about 1800, and a weight-average molecular weight of up to about 10,000, but polymeric diols having a weight-average molecular weight of up to about 5000, particularly up to about 4000, are also preferred. The polymeric diol advantageously has a weight-average molecular weight in the range of about 500 to about 10,000, preferably from about 1000 to about 5000, and more preferably from about 1500 to about 4000. Weight-average molecular weight can be determined using suitable methods, such as those known in the art, for example by gel permeation chromatography according to ASTM D4001-13 (ASTM D4001-13, Standard Test Method for Determination of Weight-Average Molecular Weight of Polymers By Light Scattering, ASTM International, West Conshohocken, PA, 2013), or according to Schmitt, MT, “Methods for Polymer Molecular Weight Measurement” (see MNL17-2ND-EB Paint and Coating Testing Manual: 15th Edition of the Gardner-Sward Handbook, edited by Joseph Koleske (pp. 908-913). West Conshohocken, PA: ASTM International, 2012. doi:10.1520 / MNL12254M).

[0264] The reaction of polyisocyanates, polymeric glycols, and glycols or other chain extenders is typically carried out at elevated temperatures in the presence of a catalyst. Typical catalysts used for this reaction include organotin catalysts such as stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide, tertiary amines, zinc salts, and manganese salts. Generally, the ratio of polymeric glycols, such as polyester glycols, to chain extenders can vary over a relatively wide range, depending heavily on the desired hardness of the final polyurethane elastomer. For example, the equivalent ratio of polyester glycol to chain extender can range from 1:0 to 1:12, and more preferably from 1:1 to 1:8. Preferably, the diisocyanate used is proportioned such that the overall ratio of the isocyanate equivalent to the equivalent of the hydrogen-containing material is in the range of 1:1 to 1:1.05, and more preferably from 1:1 to 1:1.02. The polymer diol segments are typically from about 35 percent to about 65 percent by weight of the polyurethane polymer, and preferably from about 35 percent to about 50 percent by weight of the polyurethane polymer.

[0265] The selection of diisocyanates, chain extenders, and polymeric diols, along with the weight percentage of the polymeric diols used, takes into account the desired density and stability of the foam. Generally, a higher content of polymeric polyols with Hildenbrand solubility parameters closer to those of supercritical fluids allows for higher supercritical fluid uptake, resulting in lower density foams. Furthermore, shorter polymeric diols typically provide foams that shrink less after they are initially foamed. Using polymeric diols with higher number-average molecular weights allows for a greater degree of swelling, but too high a molecular weight may result in less stable foams.

[0266] Suitable polyureas can be prepared by reacting one or more polymeric diamines or polyols with one or more of the polyisocyanates already mentioned and one or more diamine chain extenders. Non-limiting examples of suitable diamine chain extenders include ethylenediamine, 1,3-propanediamine, 2-methyl-pentanediamine, hexamethylenediamine, 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl-1,6-hexanediamine, imino-bis(propylamine), imide-bis(propylamine), N-(3-aminopropyl)-N-methyl-1,3-propanediamine, 1,4-bis(3-aminopropoxy)butane, diethylene glycol-di(aminopropyl)ether, 1-methyl-2,6-diamino-cyclohexane, 1,4-diamino- Cyclohexane, 1,3-bis(methylamino)cyclohexane or 1,4-bis(methylamino)cyclohexane, isophorone diamine, 1,2-bis(sec-butylamino)cyclohexane or 1,4-bis(sec-butylamino)cyclohexane, N,N'-diisopropyl-isophorone diamine, 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, N,N'-dialkylamino-dicyclohexylmethane, and 3,3'-diethyl-5,5'-dimethyl-4,4'-diamino-dicyclohexylmethane. Polymer diamines include polyoxyethylene diamine, polyoxypropylene diamine, poly(ethylene oxide-oxypropylene) diamine, and poly(tetramethylene ether) diamine. Amine-functionalized chain extenders and hydroxyl-functionalized chain extenders already mentioned may also be used. Typically, as in the past, trifunctional reactants are restricted and can be used in combination with monofunctional reactants to prevent cross-linking.

[0267] Suitable polyamides can be obtained by: (1) (a) polycondensation of dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid or any other dicarboxylic acid mentioned with (b) diamines such as ethylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine or decanediamine, 1,4-cyclohexanediamine, m-xylylenediamine or any other diamine mentioned; (2) ring-opening polymerization of cyclic lactams such as ε-caprolactam or ω-laurolactam; (3) polycondensation of aminocarboxylic acids such as 6-aminohexanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid or 12-aminododecanoic acid; or (4) copolymerization of cyclic lactams with dicarboxylic acids and diamines to prepare carboxylic acid-functionalized polyamide blocks, followed by reaction with polymeric ether diols (polyoxyalkylene diols) such as any polymeric ether diols mentioned. Polymerization can be carried out, for example, at temperatures ranging from about 180 degrees Celsius to about 300 degrees Celsius. Specific examples of suitable polyamide blocks include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, copolymerized nylon, nylon MXD6, and nylon 46.

[0268] The influence of the type and molecular weight of the soft segment polymer polyols used in the manufacture of thermoplastic polyurea elastomers and polyamide elastomers is similar to that in the manufacture of thermoplastic polyurethane elastomers.

[0269] Polyesters can have blocks of monomer units with low chain length that form crystalline regions, as well as blocks of softened segments with monomer units with relatively high chain lengths. In some aspects, polyesters can be thermoplastic polyester elastomers, such as those commercially available from DuPont under the trade name HYTREL.

[0270] Metallocene-catalyzed block copolymers of ethylene and α-olefins having 4 to about 8 carbon atoms are prepared by single-site metallocene catalysis of ethylene with softening comonomers such as 1-hexane or 1-octene, for example, in a high-pressure process in the presence of a catalyst system comprising a cyclopentadienyl-transition metal compound and an aluminoxane. 1-Octene is the preferred comonomer. These materials are commercially available from ExxonMobil (Irving, TX, USA) under the trade name EXACT and from Dow Chemical Company (Midland, ML, USA) under the trade name ENGAGE.

[0271] Styrene block copolymers such as poly(styrene-butadiene-styrene), poly(styrene-ethylene-co-butene-styrene), and poly(styrene-isoprene-styrene) can be prepared by anionic polymerization, wherein the polymer segments are first reacted with styrene via an alkyllithium initiator, then polymerization is continued by adding an olefin monomer, and finally polymerization is completed by adding styrene again. S-EB-S and S-EP-S block copolymers are produced by hydrogenation of SBS and SIS block copolymers, respectively.

[0272] additive.

[0273] In several aspects, the disclosed foam components also include additives. Additives may be directly incorporated into the disclosed foam components or alternatively applied to them. Additives that may be used in the disclosed foam components include, but are not limited to, dyes, pigments, colorants, UV absorbers, hindered amine light stabilizers, antioxidants, processing aids or processing agents, plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, rheological additives, catalysts, flow control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke suppressants, flameproofing agents, antistatic agents, fillers, or mixtures of two or more of the foregoing. When used, additives may be present in amounts from about 0.01 weight percent to about 10 weight percent, from about 0.025 weight percent to about 5 weight percent, or from about 0.1 weight percent to 3 weight percent, wherein the weight percentages are based on the total amount of material components in the thermoplastic composition, fiber, filament, yarn, or fabric.

[0274] Individual components can be blended with other components of a thermoplastic composition in a continuous or batch mixer, such as in intermeshing rotor mixers like intermix mixers, twin-screw extruders, tangential rotor mixers like Banbury mixers using twin-roll mills, or combinations of these mixers, to produce a composition containing a thermoplastic polymer and additives. The mixer can blend the components together via a single step or multiple steps, and can combine the components via dispersion mixing or distribution mixing to form the resulting thermoplastic composition. This step is often referred to as "compounding".

[0275] In some respects, the additive is an antioxidant, such as ascorbic acid, alkylated monophenols, alkylthiomethylphenols, hydroquinone or alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylene bisphenols, benzyl compounds, hydroxylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, benzylphosphonates, acylaminophenols, esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, amine antioxidants, or mixtures of two or more of the foregoing.

[0276] Exemplary alkylated monophenols include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-ethylcyclohexyl)-4,6-dimethylphenol, 2,6-bis(octadecyl)-4-methylphenol, and 2, 4,6-Tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols with straight or branched side chains such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundecane-1-yl)phenol, 2,4-dimethyl-6-(1-methylheptadecane-1-yl)phenol, 2,4-dimethyl-6-(1-methyltetrazane-1-yl)phenol, and mixtures of two or more of the foregoing.

[0277] Exemplary alkylthiomethylphenols include, but are not limited to, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol, and mixtures of two or more of the foregoing.

[0278] Exemplary hydroquinones and alkylated hydroquinones include, but are not limited to, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-pentylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate, and mixtures of two or more of the foregoing.

[0279] Exemplary tocopherols include, but are not limited to, α-tocopherol, p-tocopherol, 7-tocopherol, 6-tocopherol, and mixtures of two or more of the foregoing.

[0280] Exemplary hydroxylated thiodiphenyl ethers include, but are not limited to, 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-disec-pentylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide, and mixtures of two or more of the foregoing.

[0281] Exemplary alkylene bisphenols include, but are not limited to, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), and 2,2'-alkylene bisphenol. 2,2'-Ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2'-Methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-Methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylenebis(2,6-di-tert-butylphenol), 4,4'-Methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenol) 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl mercaptobutane, ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3-tert-butyl)butane] [2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-dodecyl mercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, and mixtures of two or more of the foregoing.

[0282] Exemplary benzyl compounds include, but are not limited to, 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, and 3,5-di-tert-butyl -4-hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphate dioctadecyl ester and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphate monoethyl ester, and mixtures of two or more of the foregoing.

[0283] Exemplary hydroxybenzyl malonates include, but are not limited to, bis(octadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, bis(octadecyl-2-(3-tert-butyl-4-hydroxy-5-ethylbenzyl)malonate, bis(dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, and mixtures of two or more of the foregoing.

[0284] Exemplary aromatic hydroxybenzyl compounds include, but are not limited to, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and mixtures of two or more of the foregoing.

[0285] Exemplary triazine compounds include, but are not limited to, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, and 1,3,5-tris(3 5-Di-tert-butyl-4-hydroxy-benzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, and mixtures of two or more of the foregoing.

[0286] Exemplary benzylphosphonates include, but are not limited to, calcium salts of dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, monoethyl esters of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and mixtures of two or more of the foregoing.

[0287] Exemplary acylaminophenols include, but are not limited to, 4-hydroxy-lauricoaniline, 4-hydroxy-stearicoaniline, 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyaniline)-s-triazine and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate, and mixtures of two or more of the foregoing.

[0288] Exemplary esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0289] Exemplary esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0290] Exemplary esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N ester bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0291] Exemplary esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid include, but are not limited to, esters with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, and mixtures of esters derived from two or more of the aforementioned monohydric or polyhydric alcohols.

[0292] Exemplary amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid include, but are not limited to, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxalamide, and mixtures of two or more of the foregoing.

[0293] Exemplary amine antioxidants include, but are not limited to, N,N′-diisopropyl-p-phenylene diamine, N,N′-disec-butyl-p-phenylene diamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylene diamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylene diamine, N,N′-bis(1-methylheptyl)-p-phenylene diamine, N,N′-dicyclohexyl-p-phenylene diamine, N,N′-diphenyl-p-phenylene diamine, N,N′-bis(2-naphthyl)-p-phenylene diamine, N-isopropyl-N′-phenyl-p-phenylene diamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylene diamine, and N-(1-methylheptyl)-N′-phenyl-p-phenylene diamine. N-cyclohexyl-N′-phenyl-p-phenylene diamine, 4-(p-toluenesulfonyl)diphenylamine, N,N′-dimethyl-N,N′-disec-butyl-p-phenylene diamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p,p′-ditert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-ditert-butyl-4-dimethylaminomethylphenol, 2, 4′-Diaminodiphenylmethane, 4,4′-Diaminodiphenylmethane, N,N,N′,N′-Tetramethyl-4,4′-Diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanidine, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of monoalkylated and dialkylated tert-butyldiphenylamine / tert-octyldiphenylamine, mixtures of monoalkylated and dialkylated nonyldiphenylamine, mixtures of monoalkylated and dialkylated dodecyldiphenylamine, mixtures of monoalkylated and dialkylated isopropyldiphenylamine / isohexyldiphenylamine, monoalkylated and... Mixtures of dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of monoalkylated and dialkylated tert-butylphenothiazine / tert-octylphenothiazine, mixtures of monoalkylated and dialkylated tert-octylphenothiazine, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethyl-piperidin-4-yl)-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol, and mixtures of two or more of the foregoing.

[0294] In some respects, the additive is a UV absorber and / or light stabilizer, including but not limited to 2-(2-hydroxyphenyl)-2H-benzotriazole compounds, 2-hydroxybenzophenone compounds, esters of substituted and unsubstituted benzoic acids, acrylate or malonic acid ester compounds, sterically hindered amine stabilizer compounds, oxamide compounds, triaryl-o-hydroxyphenyl-s-triazine compounds, or mixtures of two or more of the foregoing.

[0295] Exemplary 2-(2-hydroxyphenyl)-2H-benzotriazole compounds include, but are not limited to, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, and 2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole. 2-(2-hydroxy-4-octoxyphenyl)-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-(ω)-hydroxy-octa(ethyleneoxy)carbonyl-ethyl)-phenyl)-2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octoxycarbonyl)ethylphenyl)-2H-benzotriazole, deca- Dialkylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-)-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-)-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-(2-)-hydroxyphenyl)-2H-benzotriazole, (2-Ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole, 2,2′-methylene-bis(4-tert-octyl-(6-2H-benzotriazole-2-yl)phenol, 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-octyl-5-α-cumylphenyl)-2H-benzotriazole, 5-fluoro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole,5-Di-α-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole, 3-(5-trifluoromethyl-2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamon Methyl benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, and mixtures of two or more of the foregoing.

[0296] Exemplary 2-hydroxybenzophenone compounds include, but are not limited to, 4-hydroxy derivatives, 4-methoxy derivatives, 4-octoxy derivatives, 4-decoxy derivatives, 4-dodecoxy derivatives, 4-benzyloxy derivatives, 4,2′,4′-trihydroxy derivatives and 2′-hydroxy-4,4′-dimethoxy derivatives of 2-hydroxybenzophenone, as well as mixtures of two or more such derivatives.

[0297] Exemplary esters of substituted and unsubstituted benzoic acid include, but are not limited to, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and mixtures of two or more of the foregoing.

[0298] Exemplary acrylate or malonic acid ester compounds include, but are not limited to, ethyl α-cyano-β,β-diphenylacrylate or isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbonylmethoxy-cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate or butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbonylmethoxy-p-methoxycinnamate, N-(β-carbonylmethoxy-β-cyanovinyl)-2-methyl-indoline, dimethyl-p-methoxybenzylmalonic acid ester, di(1,2,2,6,6-pentamethylpiperidin-4-yl)-p-methoxybenzylmalonic acid ester, and mixtures of two or more of the foregoing.

[0299] Exemplary sterically hindered amine stabilizer compounds include, but are not limited to, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, and bis(1,2,2,6,6-pentamethyl-4-piperidine). 1,2,2,6,6-Tetramethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, tris(2,2,6,6-tetramethyl-4-piperidinyl)hydantoin triacetate, tetra(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane-tetracarboxylic acid ester, 1,1′-(1,2- Ethylenediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearoyl-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidinyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]dec-2,4-dione, bis (1-Octoxy-2,2,6,6-Tetramethylpiperidinyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-piperidinyl) succinate, straight-chain or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4].5] Dec-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidinyl)pyrrolidine-2,5-dione, N-(2,2,6,6-tetramethyl-4-piperidinyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3 ,8-diaza-4-oxo-spiro[4,5]decane, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyl)-2-(4-methoxyphenyl)ethylene, N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidinyl)]siloxane, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl Piperidin-4-yl) adipate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate, and 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethyl-amino)-s-triazine, and mixtures of two or more of the foregoing.

[0300] Exemplary oxamide compounds include, but are not limited to, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-bis(dodecyloxy-5,5′-di-tert-butoxanilide, 2-ethyl Oxy-2′-ethyloxalaniline, N,N′-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2′-ethyloxalaniline and mixtures thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxalaniline, mixtures of o-methoxydisubstituted oxalaniline and p-methoxydisubstituted oxalaniline, mixtures of o-ethoxydisubstituted oxalaniline and p-ethoxydisubstituted oxalaniline, and mixtures of two or more of the foregoing.

[0301] Exemplary triaryl-o-hydroxyphenyl-s-triazine compounds include, but are not limited to, 4,6-bis(2,4-dimethylphenyl)-2-(2-hydroxy-4-octoxyphenyl)-s-triazine, 4,6-bis(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, and 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl) 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis(4-biphenyl)-6-(2-hydroxy-4-octyloxycarbonylethyleneoxyphenyl)-s-triazine, 2-phenyl-4-[2-hydroxy-4-(3-sec-butoxy-2-hydroxypropoxy)phenyl]-6-2-hydroxy-4-(3-sec-pentoxy-2- [2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropoxy)phenyl]-s-triazine, 2,4-bis(2-hydroxy-4-n-butoxyphenyl)-6-(2,4-di-n-butoxyphenyl)-s-triazine, methylenebis{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)-phenyl]-s-triazine}, 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropyloxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6- (2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine, 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-s-triazine, 2,4,6-tris[2-hydroxy-4-(3-sec-butoxy-2-hydroxypropoxy)phenyl-s-triazine, 4,6-bis(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine, 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine, and mixtures of two or more of the foregoing.

[0302] In some respects, the additive is a peroxide scavenger, such as esters of β-thiodipropionic acid, such as lauryl ester, stearyl ester, myristyl ester, or tridecyl ester; mercaptobenzimidazole; and zinc salts of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate, or mixtures of any of the foregoing.

[0303] In some respects, the additives are polyamide stabilizers, such as halogens like copper salts of iodine, and / or phosphorus compounds and salts of divalent manganese.

[0304] In some cases, the additives are alkaline stabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate, or zinc pyrocatecholate.

[0305] 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. Alternatively, the nucleating agent can be a monocarboxylic acid 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 herein.

[0306] In some respects, rheological modifiers can be nanoparticles, nanoclays, nanocarbons, graphite, nanosilica, and the like with a fairly high aspect ratio.

[0307] In some applications, additives are fillers or reinforcing agents, such as clay, kaolin, talc, asbestos, graphite, and glass (such as glass fiber, glass particles, and glass bubbles). Bulbs, glass spheres or glass-like spheres, mica, calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide, silicates, diatomaceous earth, carbonates (such as calcium carbonate, magnesium carbonate and the like), metals (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, granular synthetic plastics (such as high molecular weight polyethylene, polypropylene, polystyrene, polyethylene ionomer resin, polyamide, polyester, polyurethane, polyimide and the like), synthetic fibers (such as fibers containing high molecular weight polyethylene, polypropylene, polystyrene, polyethylene ionomer resin, polyamide, polyester, polyurethane, polyimide and the like), granular carbonaceous materials (such as carbon black and the like), powders or fibers of wood flour and other natural products, as well as cotton lint, cellulose lint, cellulose pulp, leather fibers, and combinations thereof. Non-limiting examples of heavy filler components that can be used to increase the specific gravity of cured elastomeric compositions may 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 filler components that can be used to reduce the specific gravity of elastomeric compounds may include granular plastics, hollow glass spheres, ceramics and hollow spheres, re-ground materials, and foams, which may be used in combination.

[0308] In some respects, the additive is a crosslinking agent. A variety of crosslinking agents are available that can be used in the disclosed polymer materials. For example, the crosslinking agent can be a free radical initiator. Free radical initiators can generate free radicals through thermal decomposition or UV radiation. Free radical initiators can be present in amounts from about 0.001 weight percent to about 1.0 weight percent. A variety of free radical initiators can be used as free radical sources to produce polymer materials with crosslinked structures. Suitable free radical initiators applied include peroxides, sulfur, and sulfides. Exemplary peroxides include, but are not limited to, aliphatic and aromatic peroxides, such as diacetyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, dibenzoyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(butylperoxy)-3-hexyne, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 1,4-bis(tert-butylperoxyisopropyl)benzene, tert-butylperoxybenzoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and bis(2,4-dichlorobenzoyl), or combinations of two or more of the foregoing.

[0309] In some aspects, the additive is a colorant. As used herein, the term "colorant" refers to a compound that provides color to a substrate (e.g., the disclosed thermoplastic composition), including but not limited to dyes, pigments, and the like, and combinations thereof. A colorant can be an organic pigment or an inorganic pigment, dye, or a mixture or combination thereof. In other aspects, the pigment or dye is an inorganic material such as a metal oxide, such as iron oxide or titanium dioxide. Alternatively, the inorganic pigment or dye can be a metal compound such as strontium chromate or barium sulfate, or a metallic pigment such as aluminum flakes or aluminum particles. Other exemplary inorganic pigments include carbon black, talc, and the like. In some cases, the metal compound is not a cadmium-containing metal compound. In some cases, it may be desirable that the inorganic pigment or dye is not an inorganic pigment or dye containing lead compounds, cadmium compounds, and chromium (VI) compounds.

[0310] In another aspect, the pigment or dye is an organic compound, such as perylene, phthalocyanine derivatives (e.g., copper phthalocyanine), indigoanthraquinone, benzimidazolone, quinacridone, perinone, and methylimine derivatives. For example, the colorant can be added to the thermoplastic composition directly or otherwise via a masterbatch in a mixing apparatus such as an extruder. In several aspects, the disclosed thermoplastic composition can constitute between about 0.005% and about 5% by weight relative to the weight of the composition.

[0311] In another aspect, the disclosed thermoplastic composition may be constituted in amounts between about 0.01 weight percent and about 3 weight percent relative to the weight of the composition.

[0312] The foam component and / or bonding material may contain one or more colorants. In some aspects, the foam component may contain a first colorant, and the bonding material may contain a second colorant. In this case, it should be understood that the first colorant may include one or more dyes or pigments. Similarly, it should be understood that the second colorant may include one or more dyes or pigments.

[0313] There are at least two types of metal complex dyes that can be used as colorants. Acidic metal complex dyes are soluble in water and are therefore dissolved in an aqueous solvent system before use. Solvent-based metal complex dyes are insoluble in water and are therefore dissolved in an aqueous / organic solvent system before use.

[0314] Solvent systems for metal complex dyes should both dissolve the dye and facilitate the diffusion of dye molecules into the elastic matrix under mild conditions. Therefore, it has been found that certain organic solvents not only dissolve water-insoluble dyes, such as solvent metal complex dyes, but also promote or facilitate the diffusion of dyes into the polymer matrices of both acid metal complex dyes and solvent metal complex dyes.

[0315] Suitable organic solvents include ethylene glycol phenyl ether (EGPE) and isopropanol. Relatively small amounts of organic solvent are typically required.

[0316] Suitable solvent systems for acid metal complex dyes comprise, for example, 90 to 100 vol percent water and 0 to 10 vol percent organic solvent. Typical amounts of organic solvent are 0.5 to 7 vol percent or 1 to 5 vol percent.

[0317] Suitable solvent systems for solvent-metal complex dyes include a third component, typically an organic solvent, in addition to water and ethylene glycol phenyl ether, to increase the dye's solubility. For example, the solvent system may contain 40 to 80 vol% water and 60 to 20 vol% organic solvent. Suitable organic solvents include, but are not limited to, alcohols, ethers, esters, and ketones. Suitable solvent-metal complex dyes include Orasol Yellow 2RLN, OrasolYellow2GLN-M, Pylam Solvent Red, Pylam Brilliant Yellow, and Resofast Orange M2Y.

[0318] Alternatively, a two-phase solvent system can be used, wherein the dye is soluble in an organic solvent but insoluble in water, and the organic solvent is only partially miscible with water or insoluble or practically insoluble in water. Suitable organic solvents for forming a two-phase system include polar organic solvents that are insoluble in water, such as suitable hydrocarbons, alcohols, aldehydes, ketones, ethers, esters, amides, acids, and halogenated compounds. Examples include, but are not limited to, n-butanol, cyclohexanol, butyl acetate, and ethylene glycol phenyl ether.

[0319] In a two-phase solvent system, a solution containing a large amount of water and a small amount of organic solvent is prepared. The organic solvent is partially miscible with water or almost insoluble in water, thus forming a two-phase system. Two-phase solvent compositions allow for rapid and uniform dyeing, for example, of foam components.

[0320] The dye can first be dissolved in an organic solvent to form a homogeneous solution, and then the solution can be dispersed as droplets in water under agitation or stirring. Alternatively, the organic solvent can be combined with water to form a two-phase solvent. The dye is then added to the two-phase solvent under agitation or stirring to form droplets.

[0321] Two-phase solvent compositions may contain 1 to 30 volume percent, for example 1 to 25 volume percent, of an organic solvent and 70 to 99 volume percent, for example 75 to 99 volume percent, of water. These two-phase solvent compositions are particularly suitable for solvent dyes that have high solubility in organic solvents. Typically, dyes suitable for use in this embodiment include dyes that are highly soluble in organic solvents but practically insoluble in water.

[0322] When a suitable substrate is immersed in a two-phase solvent-dye system, droplets of both organic solvent and dye are preferentially adsorbed onto the substrate surface. This creates a thin layer of organic solvent with a high concentration of dye on the substrate surface. Furthermore, the organic solvent causes the substrate to swell, providing an open polymer structure. This combination of an open structure in the substrate and a high concentration of dye facilitates rapid diffusion of dye molecules into the substrate.

[0323] Therefore, the two-phase solvent composition both dissolves the dye and facilitates the diffusion of dye molecules into the flexible substrate under mild conditions. Compared to conventional dyeing systems, the two-phase solvent dye system offers rapid dyeing, uses less organic solvent, employs mild dyeing conditions, and provides the potential for efficient dye recovery / removal from the solvent.

[0324] In some respects, the dye can be a metal complex dye, such as, but not limited to, Bezanyl Black, Bezanyl Red, Bezanyl Yellow, Orasol Black, Orasol Blue GN, Orasol Red G, Orasol Yellow 2GLN, Isolan Blue, SP-R, Isolan Grey SP-G, Isolan Red SP-G, Isolan Yellow SP-2RL, Pylam Solvent Blue, Pylam Solvent Red, Pylam Solvent Yellow, Resofast Blue, Resofast Orange, and Resofast Yellow.

[0325] In some respects, foam components may be dyed with nonionic or anionic (“acidic”) dyes by: (1) prior to injection of a supercritical fluid, (2) during injection of a supercritical fluid by dissolving or dispersing a nonionic or anionic dye in the supercritical fluid, which optionally contains a polar liquid, (3) during immersion in a heated fluid containing the dye, or (4) after foaming.

[0326] In some applications, colorants can be acid dyes, such as water-soluble anionic dyes. A wide variety of acid dyes are available, ranging from dull tones to brilliant shades. Chemically, acid dyes include azo compounds, anthraquinone compounds, and triarylmethane compounds.

[0327] The Color Index (CI), jointly published by the Society of Dyers and Colourists (UK) and the American Association of Textile Chemists and Colorists (USA), is a comprehensive compilation of the most extensive range of dyes and pigments for large-scale coloring purposes, encompassing 12,000 products under 2,000 CI common names. In the CI, each compound is provided with two numbers, referring to both its color classification and chemical classification. The "common name" indicates the application area and / or coloring method, while the other number is the "constitution number." Non-limiting examples of acid dyes include Acid Yellow 1, 17, 23, 25, 34, 42, 44, 49, 61, 79, 99, 110, 116, 127, 151, 158, 1, 159, 166, 169, 194, 199, 204, 220, 232, 241, 246, and 250; Acid Red 1, 14, 17, 18, 42, 57, 88, 97, 118, 119, 151, 183, 184, 186, and 1 94, 195, 198, 211, 225, 226, 249, 251, 257, 260, 266, 278, 283, 315, 336, 337, 357, 359, 361, 362, 374, 405, 407, 414, 418, 419 and 447; Acid Violet 3, 5, 7, 17, 54, 90 and 92; Acid Brown 4, 14, 15, 45, 50, 58, 75, 97, 98, 147, 160: 1, 161, 165, 191, 235, 239, 248, 282, 283, 289, 298, 322, 343, 349, 354, 355, 357, 365, 384, 392, 402, 414, 420, 422, 425, 432 and 434; Acid Orange 3, 7, 10, 19, 33, 56, 60, 61, 67, 74, 80, 86, 94, 139, 142, 144, 154 and 162 Acid Blue 1, 7, 9, 15, 92, 133, 158, 185, 193, 277, 277:1, 314, 324, 335, and 342; Acid Green 1, 12, 68:1, 73, 80, 104, 114, and 119; Acid Black 1, 26, 52, 58, 60, 64, 65, 71, 82, 84, 107, 164, 172, 187, 194, 207, 210, 234, and 235, and combinations thereof. Acid dyes can be used alone or in any combination in dye solutions.

[0328] Acid dyes and nonionic disperse dyes are commercially available from a number of sources, including Dystar LP, Charlotte, North Carolina, under the trademark TELON; Huntsman Corporation, Woodlands, Texas, under the trademarks ERIONYL and TECTILON; BASF SE, Ludwigshafen, Germany, under the trademark BASACID; Clariant International Ltd., Muttenz, Switzerland, under the trademarks SOLVAPERM, HOSTASOL, POLYSYNTHREN, and SAVINYL; and Bezema AG, Montlingen, Switzerland, under the trade name Bemacid.

[0329] Nonionic disperse dyes are also commercially available in many colors, including fluorescent dyes.

[0330] In some aspects, the foam components may be dyed before foaming. The acidic disperse dye solution or nonionic disperse dye solution in which the spheres or other articles are dyed may include, for example, from about 0.001 g / L to about 5.0 g / L, preferably from about 0.01 g / L to about 2 g / L, an acidic disperse dye compound or a combination of acidic disperse dye compounds or nonionic disperse dye compounds. The amount of acidic disperse dye compound or nonionic disperse dye compound used will determine how strong the color is and how quickly the spheres or other articles are dyed, and can be optimized in a direct manner; generally, a more concentrated dye solution can provide a stronger (deeper, darker, more intense) dyeing color and can dye spheres or other articles containing thermoplastic elastomers more quickly.

[0331] Dye solutions may include water-soluble organic solvents. The water solubility of a particular organic solvent used in a specific amount in the dye solution is determined by the concentration at 20°C and 1 atm pressure in the alcohol used in the dye solution; an organic solvent is water-soluble if it is completely soluble or completely miscible in water at a concentration at 20°C and 1 atm pressure in the alcohol used in the dye solution and does not form any separate phase or layer. Suitable non-limiting examples of water-soluble organic solvents that may be used include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and glycerol; ketones such as acetone and methyl ethyl ketone; esters such as butyl acetate, which is soluble in water in limited amounts; and glycol ethers and glycol ether esters (especially acetate esters), such as ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate. Water-soluble organic solvents may be contained in an aqueous medium used to manufacture the dye solution at concentrations of up to about 50 percent by volume, or up to about 25 percent by volume, or from about 1 percent to about 50 percent by volume, or from about 5 percent to about 40 percent by volume, or from about 10 percent to about 30 percent by volume, or from about 15 percent to about 25 percent by volume. Whether and how much organic solvent is used may vary depending on the type of dye used and the application method used to contact the dye solution with the pellets or other articles.

[0332] When the foam component or bonding material comprises a thermoplastic polyurethane elastomer or a thermoplastic polyurea elastomer, the anionic dye solution also advantageously comprises a quaternary (tetraalkyl)ammonium salt selected from soluble tetrabutylammonium compounds and tetrahexylammonium compounds. Such articles are advantageously dyed in an acidic dye solution comprising an anionic dye compound, a quaternary ammonium salt selected from soluble tetrabutylammonium compounds and tetrahexylammonium compounds, and optionally a water-soluble organic solvent.

[0333] The counterion of the quaternary ammonium salt should be selected such that the quaternary ammonium salt forms a stable solution with the anionic dye. The quaternary ammonium compound can be, for example, a halide (such as chloride, bromide, or iodide), hydroxide, sulfate, sulfite, carbonate, perchlorate, chlorate, bromate, iodate, nitrate, nitrite, phosphate, phosphite, hexafluorophosphite, borate, tetrafluoroborate, cyanide, isocyanate, azide, thiosulfate, thiocyanate, or carboxylate (such as acetate or oxalate). In some embodiments, the anion of a weaker Lewis base can be selected for the tetraalkylammonium compound to produce a darker color for use in a cover layer or coating for dyeing. In many embodiments, the tetraalkylammonium compound is or includes tetrabutylammonium halide or tetrahexylammonium halide, particularly tetrabutylammonium bromide or tetrabutylammonium chloride or tetrahexylammonium bromide or tetrahexylammonium chloride.

[0334] When the foam component comprises thermoplastic polyurethane elastomer or thermoplastic polyurea elastomer, the acidic dye solution used to dye the foam component may contain from about 0.1 equivalents to about 5 equivalents of a soluble tetraalkylammonium compound per equivalent dye compound. In various embodiments, the acidic dye solution may contain from about 0.5 equivalents to about 4 equivalents, preferably from about 1 equivalent to about 4 equivalents of a tetraalkylammonium compound per equivalent dye compound. The amount of tetraalkylammonium compound used with a particular acidic dye compound depends on the rate at which the dye diffuses into and within the capping or coating layer, and can be optimized in a direct manner. The process of dyeing foam components comprising thermoplastic polyurethane elastomer or thermoplastic polyurea elastomer with this dye solution containing a soluble tetraalkylammonium compound can produce strong color intensity in the dyed foam component.

[0335] The foamed parts can be dyed with nonionic or anionic dyes before the supercritical fluid is injected. The microspheres can also be dyed simultaneously with the injection of supercritical fluid by dissolving or dispersing nonionic or anionic dyes in the supercritical fluid, which optionally contains a polar liquid. The microspheres can also be dyed while immersed in a heated fluid containing dye. Specifically, the heated fluid can be a heated aqueous dye solution, which may contain quaternary ammonium salts and organic solvents as described. Finally, the foamed parts can be dyed after foaming using a dyeing process as described.

[0336] definition

[0337] 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 pertains. It will also be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having the meaning consistent with their meaning in the context of the specification and in the relevant field, and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0338] The terms “comprises,” “comprising,” “including,” and “having” are inclusive and therefore specify the presence of the designed features, integers, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Unless specifically identified as the order of execution, the method steps, processes, and operations described herein should not be construed as requiring them to be performed in the specific order discussed or illustrated. It should also be understood that additional or alternative steps may be employed.

[0339] As used in this specification and the appended claims, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” include plural indicators. Thus, for example, references to “polymer,” “mold,” or “preform” include, but are not limited to, two or more such polymers, molds, preforms, and the like.

[0340] As used herein, the term “foam component” includes both the first foam component and the second foam component; that is, “foam component” can be used to refer to any disclosed foam component, including the first foam component and the second foam component.

[0341] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items.

[0342] As used herein, substantially means at least 50 percent, 60 percent, 75 percent, 90 percent, 95 percent or more, as determined based on weight or volume.

[0343] The terms first, second, third, etc., may be used herein to describe different elements, components, areas, layers, and / or segments. These elements, components, areas, layers, and / or segments should not be limited by these terms. These terms may be used only to distinguish one element, component, area, layer, or segment from another. Terms such as “first,” “second,” and other numerical terms do not imply a sequence or order unless the context clearly indicates otherwise. Therefore, the first element, first component, first area, first layer, or first segment discussed below may be referred to as a second element, second component, second area, second layer, or second segment without departing from the teachings of the embodiment configuration.

[0344] As used herein, the modifiers “up,” “down,” “top,” “bottom,” “upward,” “downward,” “vertical,” “horizontal,” “longitudinal,” “lateral,” “front,” “back,” etc., unless otherwise defined or clearly stated from this disclosure, are relative terms referring to the various structures or orientations of footwear placed in the context of footwear worn by a user standing on a flat, horizontal surface.

[0345] For ease of description, this document uses spatially relative terms such as “inside,” “outside,” “below,” “below,” “lower,” “above,” “upper,” etc., to describe the relationship between one element or feature and another element or feature illustrated in the figures. In addition to the orientations depicted in the figures, spatially relative terms may be intended to cover different orientations of the device in use or operation. For example, if the device in the figures is flipped, an element or feature described as “below” or “below” will then be oriented as an element or feature “above.” Thus, the exemplary term “below” can cover both above and below orientations. The device may be otherwise oriented (rotated 90 degrees or otherwise), and the spatially relative descriptive terms used herein are interpreted accordingly.

[0346] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed in range format herein. Where a stated range contains one or both extreme values, the range excluding any one or both of those extreme values ​​is also included in this disclosure; for example, the phrase “x to y” includes the range from 'x' to 'y' as well as the range greater than 'x' and less than 'y'. Ranges may also be expressed as upper limits, such as 'about x, y, z, or less' and should be interpreted as including the specific ranges of 'about x', 'about y', and 'about z', as well as the ranges of 'less than x', 'less than y', and 'less than z'. Similarly, the phrase 'about x, y, z, or greater' should be interpreted as including the specific ranges of 'about x', 'about y', and 'about z', as well as the ranges of 'greater than x', 'greater than y', and 'greater than z'. Furthermore, the phrase “about 'x' to 'y'”, where 'x' and 'y' are numerical values, includes “about 'x' to about 'y'”. It should be understood that this range format is used for convenience and brevity, and therefore should be interpreted flexibly to include not only the values ​​explicitly stated as extreme values ​​of the range, but also all individual values ​​or subranges covered within that range, as if each value and subrange were explicitly stated. For example, the range of numbers “about 0.1% to 5%” should be interpreted to include not only the explicitly stated values ​​of about 0.1% to about 5%, but also individual values ​​(e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.5%, 1.1%, 2.4%, 3.2%, and 4.4%) within the indicated range.

[0347] As used herein, the terms “about,” “approximate,” “at or about,” and “generally” mean that the quantity or value in question can be an exact value or a value that provides an equivalent result or effect to that described in the claims or taught herein. That is, it should be understood that quantities, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximately and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art, resulting in an equivalent result or effect. In some cases, the value providing an equivalent result or effect cannot be reasonably determined. In such cases, it should generally be understood that, as used herein, “about” and “at or about” mean a variation of ±10% of the indicated nominal value, unless otherwise indicated or inferred. Generally, quantities, sizes, formulations, parameters, or other quantities or characteristics are “about,” “approximately,” or “at or about,” whether or not explicitly stated as such. It should be understood that when “about,” “approximately,” or “in or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless otherwise specifically stated.

[0348] The reference to “a(a)” to a chemical compound refers to one or more molecules of the chemical compound, and is not limited to a single molecule of that chemical compound. Furthermore, the one or more molecules may be identical or may not be identical, as long as they fall under the category of that chemical compound. Thus, for example, “a” polyamide is interpreted as including one or more polymer molecules of polyamide, wherein the polymer molecules may be identical or may not be identical (e.g., different molecular weights and / or isomers).

[0349] The terms "at least one" and "one or more" are used interchangeably and have the same meaning, including both single and multiple elements, and may also be indicated by a suffix at the end of the element. For example, "at least one polyamide," "one or more polyamides," and "(one or more) polyamides" are used interchangeably and have the same meaning.

[0350] As used herein, the terms “optional” or “optionally” mean that a component, event, or condition described below may or may not occur, and the description includes both cases in which said component, event, or condition occurs and cases in which said component, event, or condition does not occur.

[0351] When used in the claims, the term "receive," such as in "receive uppers for footwear articles," is not intended to require any specific delivery or receipt of the received items. Rather, the term "receive" is used merely to describe items that will be referred to in subsequent elements of the claims for clarity and readability purposes.

[0352] As used herein, the interchangeable terms "percentage by weight," "weight percentage," "wt%," and "wt.%" 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 equals 100. Similarly, the interchangeable terms "percentage by volume," "vol%," and "vol.%" 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, formulation, or article equals 100.

[0353] Compounds are described using standard nomenclature. 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 attachment point for a substituent. For example, -CHO is attached by the carbonyl group. Unless otherwise defined, the 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 pertains.

[0354] As used herein, the term "effective amount" refers to an amount sufficient to achieve the desired change in the physical properties of a composition or material. For example, the "effective amount" of a thermoplastic polymer refers to an amount sufficient to achieve the desired improvement in properties regulated by the formulation components, such as an amount to achieve a desired modulus level. The specific level of the composition required as an effective amount in wt% will depend on a variety of factors, including the amount and type of thermoplastic polymer, the amount of polymer and the type of foaming during the manufacture of the part or article, and the end use of the article manufactured using the composition.

[0355] As used herein, the terms “optional” or “optionally” mean that an event or situation described below may or may not occur, and the description includes both scenarios in which the event or situation occurs and scenarios in which the event or situation does not occur.

[0356] As used herein, the term "unit" can be used to refer to a single (co)monomer unit, such that, for example, a styrene repeating unit refers to a single styrene (co)monomer unit in the polymer. Furthermore, the term "unit" can be used to refer to a polymer block unit, such that, for example, "styrene repeating unit" can also refer to a polystyrene block; "polyethylene unit" refers to a polyethylene block unit; "polypropylene unit" refers to a polypropylene block unit; "polybutene unit" refers to a polybutene block unit, and so on. Such usage will be clear from the context.

[0357] The term "polymer" refers to a polymer having two or more monomeric substances, and includes terpolymers (i.e. copolymers having three monomeric substances).

[0358] Unless otherwise specified, the temperatures mentioned in this article are determined at standard atmospheric pressure (i.e., 1 atm).

[0359] The components of the polymeric materials used to prepare the contents of this disclosure and the polymeric materials themselves used in the methods disclosed herein are disclosed. These and other materials are disclosed herein, and it should be understood that when combinations, subsets, interactions, groups, etc., of these materials are disclosed, while specific references cannot be explicitly disclosed for every variety of individual and collective combinations and arrangements of these compounds, each is specifically anticipated and described herein. For example, if a particular compound is disclosed and discussed, and many modifications that can be made to a number of molecules including that compound are discussed, then each and every combination and arrangement of that compound, and possible modifications, is specifically anticipated unless otherwise specifically indicated. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and an example of the combination molecule AD is disclosed, then even though each is not described individually, each is considered to be a combination of meanings individually and collectively anticipated, and thus AE, AF, BD, BE, BF, CD, CE, and CF are considered disclosed. Similarly, any subsets or combinations of these are also disclosed. Thus, for example, subgroups of AE, BF, and CE would be considered disclosed. This concept applies to all aspects of this application, including but not limited to steps in methods of manufacturing and using the polymeric materials of this disclosure. Therefore, if multiple additional steps are possible, it should be understood that each of these additional steps can be performed using any particular aspect or combination of aspects of the methods of this disclosure.

[0360] In this specification and concluding claims, references to specific elements or components in a composition or article indicate a weight relationship between that element or component and any other element or component in the composition or article whose weight percentage is indicated. Therefore, in a compound comprising 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5, and in such a ratio regardless of whether other components are contained in the compound.

[0361] As used herein, the term "weight percentage" indicates a percentage by weight of a given component based on the total weight of the composition, 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 is equal to 100.

[0362] aspect.

[0363] The following list of exemplary aspects supports and is supported by the disclosures provided herein.

[0364] Aspect 1. A sole structure for footwear articles, comprising: a first foam component having a first side and a second side opposite to the first side; a second foam component having a first side and a second side opposite to the first side, wherein the first foam component and the second foam component form a stack in the sole structure; and a mesh component positioned in the stack between the second side of the first foam component and the first side of the second foam component, and coupled to the second side of the first foam component and the first side of the second foam component.

[0365] Aspect 2. The sole structure as described in Aspect 1, wherein: the first foam component includes a cavity; a second side of the first foam component is defined within the cavity; the second foam component is at least partially positioned within the cavity; an interface between the second side of the first foam component and the first side of the second foam component is within the cavity; and the mesh component is positioned between the second side of the first foam component and the first side of the second foam component, and is coupled to the second side of the first foam component and the first side of the second foam component.

[0366] Aspect 3. The sole structure as described in aspect 1 or aspect 2, wherein: the sole structure includes a forefoot region, a midfoot region, and a heel region; and the mesh component is incorporated in at least one of the forefoot region, the midfoot region, and the heel region between the second side of the first foam component and the first side of the second foam component.

[0367] Aspect 4. The sole structure of any one of Aspects 1-3, wherein the mesh component extends from the inner side of the first foam component and the second foam component across to the outer side of the first foam component and the second foam component between the second side of the first foam component and the first side of the second foam component.

[0368] Aspect 5. The sole structure of any one of Aspects 1-3, wherein: the mesh component extends between the second side of the first foam component and the first side of the second foam component within about 1 mm to 5 mm from the edge of the second side of the first foam component, and extends within about 1 mm to 5 mm from the edge of the first side of the second foam component; and the sole structure includes an interface between the second side of the first foam component and the first side of the second foam component along at least a portion of the edge of the second side of the first foam component and the edge of the first side of the second foam component.

[0369] Aspect 6. The sole structure of any one of Aspects 1-5, wherein the second side of the first foam component includes a wave-shaped region, or the first side of the second foam component includes a wave-shaped region, or both include a wave-shaped region.

[0370] Aspect 7. The sole structure as described in aspect 6, wherein the second side of the first foam component includes the wave-shaped region.

[0371] Aspect 8. The sole structure as described in aspect 6, wherein the first side of the second foam component includes the wave-shaped region.

[0372] Aspect 9. The sole structure as described in aspect 6, wherein the wave region includes a pattern selected from at least one of serrated patterns and wavy patterns.

[0373] Aspect 10. The sole structure as described in aspect 9, wherein the pattern varies according to the size aspect of the pattern.

[0374] Aspect 11. The sole structure as described in aspect 10, wherein the dimensional aspect of the pattern includes at least one of amplitude and wavelength.

[0375] Aspect 12. The sole structure of any one of Aspects 6-11, wherein: the mesh component is bonded to the second side of the first foam component and the first side of the second foam component in the wave region; and the relative position of the mesh component varies within the wave region within the stacked portion of the sole structure.

[0376] Aspect 13. The sole structure as described in aspect 6, wherein the first side of the second foam component includes a first wave region; the second side of the second foam component includes a second wave region; and the first wave region and the second wave region are complementary to each other.

[0377] Aspect 14. The sole structure of any one of Aspects 1-13, wherein the mesh component has fibers of a first density in a first region and fibers of a second density in a second region, wherein the first density is at least 10 weight percent greater than the second density.

[0378] Aspect 15. The sole structure of any one of Aspects 1-14, wherein: the mesh component comprises at least two mesh components; and the at least two mesh components overlap each other between the second side of the first foam component and the first side of the second foam component.

[0379] Aspect 16. The sole structure of any one of Aspects 1-14, wherein: the mesh component comprises at least two mesh components; and the at least two mesh components are spaced apart from each other in the stacked portion between the second side of the first foam component and the first side of the second foam component.

[0380] Aspect 17. The sole structure of any one of Aspects 1-16, wherein: the mesh component comprises at least two mesh components; at least one of the at least two mesh components is coupled at a first position between the second side of the first foam component and the first side of the second foam component; and at least another of the at least two mesh components is coupled at a second position between the second side of the first foam component and the first side of the second foam component.

[0381] Aspect 18. The sole structure of any one of Aspects 1-17, wherein: the mesh component comprises at least two mesh components; at least one of the at least two mesh components comprises fibers of a first density, and at least another of the at least two mesh components comprises fibers of a second density.

[0382] Aspect 19. The sole structure of any one of Aspects 1-18, wherein the mesh component comprises a mesh textile.

[0383] Aspect 20. The sole structure as described in aspect 19, wherein the mesh textile is a knitted textile, crocheted textile, braided textile or woven textile comprising one or more yarns, wherein each of the one or more yarns is formed from one or more individual fibers.

[0384] Aspect 21. The sole structure as described in aspect 19, wherein the mesh textile is a nonwoven textile comprising more than one fiber.

[0385] Aspect 22. The sole structure of any one of Aspects 19-21, wherein the mesh textile comprises one or more fibers or yarns comprising a fiber / yarn polymer material, the fiber / yarn polymer material comprising a polymer material of any one of Aspects 44-188.

[0386] Aspect 23. The sole structure as described in any one of Aspects 1-22, wherein: the mesh component comprises a mesh textile; and the mesh textile has fibers of a first density in a first region and fibers of a second density in a second region.

[0387] Aspect 24. The sole structure of any one of Aspects 1-23, wherein: the mesh component comprises a mesh textile; and the mesh textile has an elongation of at least 20 percent along at least one of the 0°, 45° or 90° axes of the test sample as defined herein.

[0388] Aspect 25. The sole structure of any one of Aspects 1-23, wherein the mesh component comprises a mesh textile; and the mesh textile has an elongation of at least 20 percent along at least two of the 0°, 45° or 90° axes of the test sample as defined herein.

[0389] Aspect 26. The sole structure of any one of Aspects 1-23, wherein the mesh component comprises a mesh textile; and the mesh textile has an elongation of at least 20 percent along each of the 0°, 45° or 90° axes of the test sample as defined herein.

[0390] Aspect 27. The sole structure as described in any one of Aspects 24-26, wherein the elongation is at least 35 percent.

[0391] Aspect 28. The sole structure as described in any one of Aspects 24-26, wherein the elongation is at least 50 percent.

[0392] Aspect 29. The sole structure as described in any one of Aspects 24-26, wherein the elongation is at least 75 percent.

[0393] Aspect 30. The sole structure as described in any one of Aspects 24-26, wherein the elongation is at least 100 percent.

[0394] Aspect 31. The sole structure as described in any one of Aspects 24-26, wherein the elongation is at least 150 percent.

[0395] Aspect 32. The sole structure as described in aspect 26 or aspect 27, wherein the first stretch percentage is at least 5 percentage points greater than the second stretch percentage.

[0396] Aspect 33. The sole structure of any one of Aspects 1-32, wherein the mesh component comprises a mesh textile having more than one hole, at least one of the more than one hole having a size of at least 0.5 mm.

[0397] Aspect 34. The sole structure of any one of Aspects 1-33, wherein the mesh component comprises a mesh textile having more than one hole, at least one of the more than one hole having a size of at least 1.0 mm.

[0398] Aspect 35. The sole structure of any one of Aspects 1-34, wherein the mesh component comprises a mesh textile having more than one hole, at least one of the more than one hole having a size of less than 5 mm.

[0399] Aspect 36. The sole structure of any one of Aspects 1-35, wherein the mesh component comprises a mesh textile having more than one hole, at least one of the more than one hole having a size of less than 10 mm.

[0400] Aspect 37. The sole structure of any one of Aspects 1-36, wherein the mesh component comprises a mesh textile having more than one hole, at least one of the more than one hole having at least one size from about 0.5 mm to about 3.0 mm.

[0401] Aspect 38. The sole structure of any one of Aspects 1-37, wherein the mesh component comprises a mesh component polymer material, the mesh component polymer material comprising any one of Aspects 45-188.

[0402] Aspect 39. The sole structure of any one of Aspects 1-38 further includes an adhesive applied between the second side of the first foam member and the first side of the second foam member.

[0403] Aspect 40. The sole structure of any one of Aspects 1-38, wherein at least one of the compressive strength and shear strength of the sole structure in which the mesh component is positioned and incorporated is at least 5 percentage points greater than the compressive strength and shear strength of any area of ​​the sole structure in which the mesh component is not positioned and incorporated.

[0404] Aspect 41. The sole structure of any one of Aspects 1-40, wherein: in a first region of the sole structure, the mesh component is positioned and bonded between a second side of the first foam component and a first side of the second foam component; in a second region of the sole structure, the mesh component is not positioned and bonded between a second side of the first foam component and a first side of the second foam component; and the first region of the sole structure has at least one greater than the compressive strength and shear strength of the second region of the sole structure by at least 5 percentage points.

[0405] Aspect 42. The sole structure of any one of Aspects 1-41, wherein at least one of the first foam component and the second foam component comprises a foam composition having an Asker C hardness of about 30C to 65C.

[0406] Aspect 43. The sole structure of any one of Aspects 1-42, wherein at least one of the first foam component and the second foam component comprises a foam composition having an energy return of about 60% to 90%.

[0407] Aspect 44. The sole structure of any one of Aspects 1-43, wherein the first foam component comprises a first foam component polymer material comprising a polymer material; and wherein the second foam component comprises a second foam component polymer material independently comprising a polymer material.

[0408] Aspect 45. The sole structure as described in aspect 44, wherein the polymer material includes olefin polymers or copolymers, thermoplastic polymers or copolymers, thermosetting polymers or copolymers, ionomer polymers or copolymers, or combinations thereof.

[0409] Aspect 46. The sole structure as described in aspect 44, wherein the polymer material comprises one or more aliphatic polymers, aromatic polymers, or mixtures thereof.

[0410] Aspect 47. The sole structure as described in aspect 44, wherein the polymer material includes homopolymers, copolymers, terpolymers, or mixtures thereof.

[0411] Aspect 48. The sole structure as described in aspect 44, wherein the polymer material includes random copolymers, block copolymers, alternating copolymers, periodic copolymers, or graft copolymers.

[0412] Aspect 49. The sole structure as described in aspect 44, wherein the polymer material comprises an ionomer polymer.

[0413] Aspect 50. The sole structure as described in aspect 49, wherein the ionomer polymer comprises a polycarboxylic acid or a derivative thereof.

[0414] Aspect 51. The sole structure as described in aspect 49 or aspect 50, wherein the ionomer polymer is a salt of sodium, magnesium, potassium or another metal ion.

[0415] Aspect 52. The sole structure as described in aspects 49-51, wherein the ionomer polymer includes a fatty acid-modified ionomer polymer.

[0416] Aspect 53. The sole structure as described in aspect 49, wherein the ionomer polymer comprises polystyrene sulfonate, ethylene-methacrylic acid copolymer, or a mixture thereof.

[0417] Aspect 54. The sole structure as described in aspect 44, wherein the polymer material includes an olefin polymer or copolymer.

[0418] Aspect 55. The sole structure as described in aspect 54, wherein the olefin polymer or copolymer is a cross-linked polyolefin.

[0419] Aspect 56. The sole structure as described in aspect 54 or aspect 55, wherein the olefin polymer or copolymer includes ethylene vinyl acetate polymer or copolymer, butane-based polymer or copolymer, or octane-based polymer or copolymer.

[0420] Aspect 57. The sole structure as described in aspect 56, wherein the polymer is a copolymer.

[0421] Aspect 58. The sole structure as described in aspect 57, wherein the copolymer is a block copolymer.

[0422] Aspect 59. The sole structure as described in aspect 54, wherein the olefin polymer or copolymer is an olefin homopolymer, an olefin copolymer, or a mixture thereof.

[0423] Aspect 60. The sole structure as described in any one of Aspects 44-48 or Aspect 54, wherein the olefin polymer includes polyethylene, polypropylene, or combinations thereof.

[0424] Aspect 61. The sole structure as described in any one of Aspects 54 or 60, wherein the olefin polymer includes a polyethylene polymer.

[0425] Aspect 62. The sole structure as described in aspect 61, wherein the polyethylene polymer is a polyethylene homopolymer.

[0426] Aspect 63. The sole structure as described in any one of Aspects 60-62, wherein the polyethylene includes low-density polyethylene, high-density polyethylene, low molecular weight polyethylene, ultra-high molecular weight polyethylene, linear polyethylene, branched polyethylene, or combinations thereof.

[0427] Aspect 64. The sole structure as described in aspect 60 or aspect 61, wherein the polyethylene comprises an ethylene copolymer.

[0428] Aspect 65. The sole structure as described in aspect 64, wherein the polyethylene comprises ethylene-vinyl acetate (EVA) copolymer, ethylene-vinyl alcohol (EVOH) copolymer, ethylene-ethyl acrylate copolymer, ethylene-unsaturated monofatty acid copolymer, or combinations thereof.

[0429] Aspect 66. The sole structure as described in any one of Aspects 54-65, wherein the olefin polymer or copolymer comprises polyacrylate.

[0430] Aspect 67. The sole structure as described in aspect 66, wherein the polyacrylate comprises polyacrylic acid, esters of polyacrylic acid, polyacrylonitrile, polyacrylate acetate, polymethacrylate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polyvinyl acetate, derivatives thereof, copolymers thereof, or any mixture thereof.

[0431] Aspect 68. The sole structure as described in aspect 44, wherein the polymer material includes a thermoplastic polymer or a copolymer.

[0432] Aspect 69. The sole structure as described in aspect 68, wherein the thermoplastic polymer or copolymer is a thermoplastic elastomer.

[0433] Aspect 70. The sole structure as described in aspect 68 or 69, wherein the thermoplastic polymer or copolymer is selected from thermoplastic polyurethane, thermoplastic polyurea, thermoplastic polyether, thermoplastic polyester, thermoplastic copolyether ester, thermoplastic copolyester, thermoplastic polyamide, thermoplastic polystyrene, thermoplastic polyolefin, thermoplastic copolyether amide, thermoplastic styrene diene copolymer, thermoplastic styrene block copolymer, thermoplastic polyamide, thermoplastic polyimide, any copolymer thereof, and any blend thereof.

[0434] Aspect 71. The sole structure as described in aspect 69 or 70, wherein the thermoplastic elastomer comprises a thermoplastic polyamide elastomer.

[0435] Aspect 72. The sole structure as described in aspect 71, wherein the thermoplastic polyamide elastomer comprises nylon 6, nylon 12, or a combination thereof.

[0436] Aspect 73. The sole structure as described in aspect 69 or 70, wherein the thermoplastic elastomer comprises a thermoplastic copolyester elastomer.

[0437] Aspect 74. The sole structure as described in aspect 73, wherein the thermoplastic copolyester elastomer comprises a thermoplastic copolyester elastomer comprising: (a) more than one first segment, each first segment being derived from a dihydroxy-terminated polydiol; (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.

[0438] Aspect 75. The sole structure as described in aspect 74, wherein the thermoplastic copolyester elastomer is a block copolymer; a segment copolymer; a random copolymer; or a condensation copolymer.

[0439] Aspect 76. The sole structure as described in aspect 74 or 75, wherein the thermoplastic copolyester elastomer has a weight-average molecular weight of about 50,000 Daltons to about 1,000,000 Daltons.

[0440] Aspect 77. The sole structure as described in aspect 76, wherein the thermoplastic copolyester elastomer has a weight-average molecular weight of about 50,000 Daltons to about 500,000 Daltons; about 75,000 Daltons to about 300,000 Daltons; or about 100,000 Daltons to about 200,000 Daltons.

[0441] Aspect 78. The sole structure as described in any one of Aspects 74-77, wherein the thermoplastic copolyester elastomer has a first segment to third segment ratio from about 1:1 to about 1:5 based on the weight of each of the first segment and the third segment.

[0442] Aspect 79. The sole structure as described in aspect 78, wherein the thermoplastic copolyester elastomer has a ratio of the first segment to the third segment based on the weight of each of the first segment and the third segment, from about 1:1 to about 1:3 or from about 1:1 to about 1:2.

[0443] Aspect 80. The sole structure as described in any one of Aspects 74-79, wherein the thermoplastic copolyester elastomer has a ratio of a second segment to a third segment from about 1:1 to about 1:3 based on the weight of each of the first segment and the third segment.

[0444] Aspect 81. The sole structure as described in aspect 80, wherein the thermoplastic copolyester elastomer has a ratio of a second segment to a third segment based on the weight of each of the first and third segments, ranging from about 1:1 to about 1:2 or from about 1:1 to about 1:1.52.

[0445] Aspect 82. The sole structure of any one of Aspects 74-81, wherein the first segment of the dihydroxy-terminated polydiol comprises a segment derived from a poly(epoxy)diol having a weight-average molecular weight of about 250 Daltons to about 6000 Daltons.

[0446] Aspect 83. The sole structure as described in aspect 82, wherein the weight-average molecular weight is about 400 Daltons to about 6,000 Daltons; about 350 Daltons to about 5,000 Daltons; or about 500 Daltons to about 3,000 Daltons.

[0447] Aspect 84. The sole structure as described in any one of Aspects 82-83, wherein the poly(epoxy) 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.

[0448] Aspect 85. The sole structure as described in aspect 84, wherein the poly(epoxy) glycol is poly(ethylene ether) glycol; poly(propylene ether) glycol; poly(tetramethylene ether) glycol; poly(pentamethylene ether) glycol; or poly(hexamethylene ether) glycol.

[0449] Aspect 86. The sole structure as described in aspect 84, wherein the poly(epoxy) glycol is poly(tetramethylene ether) glycol.

[0450] Aspect 87. The sole structure as described in any one of Aspects 74-86, wherein the second segment derived from the diol comprises a diol having a molecular weight of less than about 250.

[0451] Aspect 88. The sole structure as described in aspect 87, wherein the diol is a C2-C8 diol.

[0452] Aspect 89. The sole structure as described in aspect 88, wherein the second segment derived from the diol comprises a diol selected from the group consisting of: ethylene glycol; propylene glycol; butanediol; pentanediol; 2-methylpropanediol; 2,2-dimethylpropanediol; hexanediol; 1,2-dihydroxycyclohexane; 1,3-dihydroxycyclohexane; 1,4-dihydroxycyclohexane; and mixtures thereof.

[0453] Aspect 90. The sole structure as described in aspect 89, wherein the diol is selected from 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and mixtures thereof.

[0454] Aspect 91. The sole structure as described in any one of Aspects 74-90, wherein the third segment derived from an aromatic dicarboxylic acid comprises an aromatic C5-C16 dicarboxylic acid.

[0455] Aspect 92. The sole structure as described in aspect 91, wherein the aromatic C5-C16 dicarboxylic acid has a molecular weight of less than about 300 Daltons or about 120 Daltons to about 200 Daltons.

[0456] Aspect 93. The sole structure as described in aspect 91, wherein the aromatic C5-C16 dicarboxylic acid is terephthalic acid, phthalic acid, isophthalic acid or a derivative thereof.

[0457] Aspect 94. The sole structure as described in aspect 93, wherein the aromatic C5-C16 dicarboxylic acid is terephthalic acid or a dimethyl ester derivative thereof.

[0458] Aspect 95. The sole structure of any one of Aspects 74-94, wherein the thermoplastic copolyester elastomer comprises: (a) more than one first copolyester unit, each of the more than one first copolyester unit comprising a first segment derived from a dihydroxy-terminated polydiol and a third segment derived from an aromatic dicarboxylic acid, wherein the first copolyester unit has a structure represented by Formula 1:

[0459]

[0460] Wherein R1 is the group remaining after removing the terminal hydroxyl group from the poly(epoxy)diol of the first segment, wherein the poly(epoxy)diol of the first segment is a poly(epoxy)diol having a number average molecular weight of 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 (b) more than one second copolyester unit, each of the more than one second copolyester unit comprising a second segment derived from the diol and a third segment derived from the aromatic dicarboxylic acid, wherein the second copolyester unit has a structure represented by Formula 2:

[0461]

[0462] R3 is the group remaining after removing the hydroxyl group from the diol derived from the second segment of the diol, wherein the diol is a diol having a molecular weight of less than about 250; and R2 is the group remaining after removing the carboxyl group from the aromatic dicarboxylic acid of the third segment.

[0463] Aspect 96. The sole structure as described in aspect 95, wherein the first copolyester unit has a structure represented by formula 3:

[0464]

[0465] Wherein R is H or methyl; where y is an integer having a value from 1 to 10; 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 unit is from about 300 Daltons to about 7,000 Daltons.

[0466] Aspect 97. The sole structure as described in aspect 96, wherein y is an integer having a value of 1, 2, 3, 4 or 5.

[0467] Aspect 98. The sole structure as described in aspect 96 or aspect 97, 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.

[0468] Aspect 99. The sole structure as described in aspect 95, wherein the first copolyester unit has a structure represented by formula 4:

[0469]

[0470] Where z is an integer having a value from 2 to 60; and the weight-average molecular weight of each of the more than one first copolyester unit is from about 300 Daltons to about 7,000 Daltons.

[0471] Aspect 100. The sole structure as described in any one of Aspects 96-99, 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.

[0472] Aspect 101. The sole structure of any one of aspects 96-100, wherein the weight-average molecular weight of each of the more than one first copolyester unit 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.

[0473] Aspect 102. The sole structure as described in any one of Aspects 95-101, wherein the second copolyester unit has a structure represented by Formula 5:

[0474]

[0475] Where x is an integer with values ​​from 1 to 20.

[0476] Aspect 103. The sole structure as described in aspect 102, wherein x is an integer having a value from 2 to 18; a value from 2 to 17; a value from 2 to 16; a value from 2 to 15; a value from 2 to 14; a value from 2 to 13; a value from 2 to 12; a value from 2 to 11; a value from 2 to 10; a value from 2 to 9; a value from 2 to 8; a value from 2 to 7; a value from 2 to 6; or a value of 2, 3, or 4.

[0477] Aspect 104. The sole structure as described in aspect 102, wherein the second copolyester unit has a structure represented by formula 6:

[0478]

[0479] Aspect 105. The sole structure of any one of Aspects 95-104, wherein the thermoplastic copolyester elastomer comprises more than one first copolyester unit in weight percentages of about 30% to about 80% based on the total weight of the thermoplastic copolyester elastomer; about 40% to about 80% based on the total weight of the thermoplastic copolyester elastomer; about 50% to about 80% based on the total weight of the thermoplastic copolyester elastomer; about 30% to about 70% based on the total weight of the first copolyester unit; about 40% to about 70% based on the total weight of the first copolyester unit; or about 50% to about 70% based on the total weight of the first copolyester unit.

[0480] Aspect 106. The sole structure of any one of Aspects 95-105, wherein the thermoplastic copolyester elastomer comprises about 40% to about 65% by weight based on the total weight of the thermoplastic copolyester elastomer; about 45% to about 65% by weight; about 50% to about 65% by weight; about 55% to about 65% by weight; about 40% to about 60% by weight; about 45% to about 60% by weight; about 50% to about 60% by weight; or about 55% to about 60% by weight of the more than one second copolyester unit.

[0481] Aspect 107. The sole structure as described in any one of Aspects 74-106, wherein the thermoplastic copolyester elastomer composition further comprises additives.

[0482] Aspect 108. The sole structure as described in aspect 107, wherein the additive is present in an amount from about 0.1% by weight to about 10% by weight based on the total weight of the foamed polymer material.

[0483] Aspect 109. The sole structure as described in aspect 107 or aspect 108, wherein the additive is a wax, an antioxidant, a UV absorber, a colorant, or a combination thereof.

[0484] Aspect 110. The sole structure as described in any one of Aspects 74-109 further comprises at least one ionomer.

[0485] Aspect 111. The sole structure as described in any one of Aspects 74-109 further comprises at least one thermoplastic polyurethane.

[0486] Aspect 112. The sole structure as described in any one of Aspects 74-111, wherein the thermoplastic copolyester elastomer composition is substantially free of thermoplastic polyamide polymers, including polyamide copolymers such as polyether block amide copolymers.

[0487] Aspect 113. The sole structure as described in any one of Aspects 74-111, wherein the thermoplastic copolyester elastomer composition is substantially free of thermoplastic polyolefin polymers, including polyethylene and polypropylene and / or polyolefin copolymers such as ethylene-vinyl acetate copolymers.

[0488] Aspect 114. The sole structure of any one of Aspects 74-113, wherein the thermoplastic copolyester elastomer has a maximum load of about 10 N to about 100 N; about 15 N to about 50 N; or about 20 N to about 40 N when determined using a cyclic tensile test as described herein.

[0489] Aspect 115. The sole structure of any one of Aspects 74-114, wherein the thermoplastic copolyester elastomer has an energy efficiency of more than or equal to about 50 percent; more than or equal to about 60 percent; or more than or equal to about 70 percent when determined using a cyclic tensile test as described herein.

[0490] Aspect 116. The sole structure as described in any one of Aspects 74-115, wherein the thermoplastic copolyester elastomer has an energy return of about 1 J to 15 J; about 2 J to 12 J; or about 4 J to 10 J when determined using a cyclic tensile test as described herein.

[0491] Aspect 117. The sole structure as described in any one of Aspects 74-116, wherein the thermoplastic copolyester elastomer has a tensile modulus of about 1 MPa to 15 MPa when determined using a cyclic tensile test as described herein.

[0492] Aspect 118. The sole structure of any one of Aspects 74-117, wherein the thermoplastic copolyester elastomer has a zero shear viscosity of about 10 Pascal-second to about 10,000 Pascal-second; about 100 Pascal-second to about 7,000 Pascal-second; or about 1,000 Pascal-second to about 5,000 Pascal-second when determined using a cyclic tensile test as described herein.

[0493] Aspect 119. The sole structure as described in aspect 69 or aspect 70, wherein the thermoplastic elastomer material comprises a thermoplastic styrene block copolymer elastomer.

[0494] Aspect 120. The sole structure as described in aspect 75, wherein the thermoplastic styrene block copolymer elastomer is a styrene-ethylene-butene-styrene block copolymer.

[0495] Aspect 121. The sole structure as described in aspect 69 or 70, wherein the thermoplastic elastomer material comprises a thermoplastic copolyether ester elastomer.

[0496] Aspect 122. The sole structure as described in aspect 121, wherein the thermoplastic coether ester elastomer is a block copolymer.

[0497] Aspect 123. The sole structure as described in any one of Aspects 121-122, wherein the block copolymer is a segmental block copolymer.

[0498] Aspect 124. The sole structure as described in any one of Aspects 121-123, wherein the thermoplastic coether ester elastomer comprises a long-chain ester unit of Formula 7:

[0499]

[0500] The short-chain ester unit of formula 8:

[0501]

[0502] R1 comprises a divalent group remaining after removing terminal hydroxyl groups from a poly(alkylene ether), the poly(alkylene ether) having a carbon-oxygen ratio of about 2.0 to about 4.3 and a number-average molecular weight of about 400 to about 6000; R2 comprises a divalent group remaining after removing carboxyl groups from a dicarboxylic acid having a molecular weight of less than about 300; R3 comprises a divalent group remaining after removing hydroxyl groups from a low molecular weight diol having a molecular weight of less than about 250; R4 comprises a divalent group remaining after removing carboxyl groups from a dicarboxylic acid having a molecular weight of less than about 300; wherein the long-chain ester unit represented by Formula 7 constitutes about 5% to about 95% by weight of the thermoplastic coether ester elastomer; and wherein the short-chain ester unit represented by Formula 8 constitutes about 95% to about 5% by weight of the thermoplastic coether ester elastomer.

[0503] Aspect 125. The sole structure as described in aspect 124, wherein R1 comprises the divalent group remaining after the terminal hydroxyl group has been removed from the poly(tetramethylene ether).

[0504] Aspect 126. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 500 to about 3500.

[0505] Aspect 127. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 600 to about 3000.

[0506] Aspect 128. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 800 to about 1200.

[0507] Aspect 129. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 800 to about 2000.

[0508] Aspect 130. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 800 to about 2500.

[0509] Aspect 131. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 800 to about 3000.

[0510] Aspect 132. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 800 to about 3500.

[0511] Aspect 133. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 800 to about 4000.

[0512] Aspect 134. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 1,000 to about 3,000.

[0513] Aspect 135. The sole structure as described in any one of Aspects 124-125, wherein R1 has a number-average molecular weight from about 1,500 to about 2,500.

[0514] Aspect 136. The sole structure as described in any one of Aspects 124-135, wherein R2 comprises the divalent group remaining after the carboxyl group has been removed from the aromatic dicarboxylic acid.

[0515] Aspect 137. The sole structure as described in aspect 136, wherein the aromatic dicarboxylic acid is 1,4-phthalic acid.

[0516] Aspect 138. The sole structure as described in any one of Aspects 124-136, wherein R3 comprises the divalent group remaining after the hydroxyl group has been removed from the C2-C6 alkyl diol.

[0517] Aspect 139. The sole structure as described in aspect 138, wherein the C2-C6 alkyl diol is 1,4-butanediol.

[0518] Aspect 140. The sole structure as described in any one of Aspects 124-139, wherein R4 is a divalent group remaining after removing the carboxyl group from an aromatic dicarboxylic acid.

[0519] Aspect 141. The sole structure as described in aspect 140, wherein the aromatic dicarboxylic acid is 1,4-phthalic acid.

[0520] Aspect 142. The sole structure as described in any one of Aspects 124-141, wherein the long-chain ester units represented by Formula 7 constitute about 10 to about 60% by weight of the thermoplastic coether ester elastomer.

[0521] Aspect 143. The sole structure as described in any one of Aspects 124-141, wherein the long-chain ester units represented by Formula 7 constitute about 20 to about 60% by weight of the thermoplastic coether ester elastomer.

[0522] Aspect 144. The sole structure as described in any one of Aspects 124-141, wherein the long-chain ester units represented by Formula 7 constitute about 30 to about 60% by weight of the thermoplastic coether ester elastomer.

[0523] Aspect 145. The sole structure as described in any one of Aspects 124-141, wherein the long-chain ester units represented by Formula 7 constitute about 10 to about 70% by weight of the thermoplastic coether ester elastomer.

[0524] Aspect 146. The sole structure as described in any one of Aspects 124-141, wherein the long-chain ester units represented by Formula 7 constitute about 20 to about 70% by weight of the thermoplastic coether ester elastomer.

[0525] Aspect 147. The sole structure as described in any one of Aspects 124-141, wherein the long-chain ester units represented by Formula 7 constitute about 30 to about 70% by weight of the thermoplastic coether ester elastomer.

[0526] Aspect 148. The sole structure as described in any one of Aspects 124-141, wherein the long-chain ester units represented by Formula 7 constitute about 10 to about 80% by weight of the thermoplastic coether ester elastomer.

[0527] Aspect 149. The sole structure as described in any one of Aspects 124-141, wherein the long-chain ester units represented by Formula 7 constitute about 20 to about 80% by weight of the thermoplastic coether ester elastomer.

[0528] Aspect 150. The sole structure of any one of aspects 124-141, wherein the long-chain ester units represented by Formula 7 constitute about 30 to about 80% by weight of the thermoplastic coether ester elastomer.

[0529] Aspect 151. The sole structure as described in any one of Aspects 124-150, wherein the short-chain ester units represented by Formula 8 constitute about 20 to about 90% by weight of the thermoplastic coether ester elastomer.

[0530] Aspect 152. The sole structure as described in any one of Aspects 124-150, wherein the short-chain ester units represented by Formula 8 constitute about 40 to about 90% by weight of the thermoplastic coether ester elastomer.

[0531] Aspect 153. The sole structure as described in any one of Aspects 124-150, wherein the short-chain ester units represented by Formula 8 constitute about 20 to about 80% by weight of the thermoplastic coether ester elastomer.

[0532] Aspect 154. The sole structure as described in any one of Aspects 124-150, wherein the short-chain ester units represented by Formula 8 constitute about 40 to about 80% by weight of the thermoplastic coether ester elastomer.

[0533] Aspect 155. The sole structure as described in any one of Aspects 124-150, wherein the short-chain ester units represented by Formula 8 constitute about 20 to about 70% by weight of the thermoplastic coether ester elastomer.

[0534] Aspect 156. The sole structure of any one of Aspects 124-150, wherein the short-chain ester units represented by Formula 8 constitute about 40 to about 70% by weight of the thermoplastic coether ester elastomer.

[0535] Aspect 157. The sole structure of any one of Aspects 124-150, wherein the short-chain ester units represented by Formula 8 constitute about 40 to about 60% by weight of the thermoplastic coether ester elastomer.

[0536] Aspect 158. The sole structure as described in any one of aspects 124-150, wherein short-chain ester units represented by Formula 8 constitute about 20 to about 60% by weight of the thermoplastic coether ester elastomer.

[0537] Aspect 159. The sole structure as described in any one of Aspects 124-158, wherein at least about 50% by weight of the short-chain ester units represented by Formula 8 are identical.

[0538] Aspect 160. The sole structure as described in any one of Aspects 121-123, wherein the thermoplastic coether ester elastomer comprises a polybutylene terephthalate block and a poly(tetramethylene ether) terephthalate block, wherein the polybutylene terephthalate block constitutes from about 95% by weight to about 5% by weight of the thermoplastic coether ester elastomer, wherein the poly(tetramethylene ether) terephthalate block constitutes from about 5% by weight to about 95% by weight of the thermoplastic coether ester elastomer, and wherein the poly(tetramethylene ether) terephthalate block has a weight-average molecular weight from about 200 Daltons to about 6000 Daltons.

[0539] Aspect 161. The sole structure as described in aspect 160, wherein the polybutylene terephthalate block constitutes a thermoplastic copolyether ester elastomer from about 20% to about 70% by weight.

[0540] Aspect 162. The sole structure as described in any one of Aspects 160-161, wherein the poly(tetramethylene ether) terephthalate block constitutes a thermoplastic copolyether ester elastomer from about 30 percent to about 80 percent by weight.

[0541] Aspect 163. The sole structure as described in aspect 160, wherein the polybutylene terephthalate block constitutes from about 70 percent to about 20 percent of the thermoplastic copolyether ester elastomer, wherein the poly(tetramethylene ether) terephthalate block constitutes from about 30 percent to about 80 percent of the thermoplastic copolyether ester elastomer.

[0542] Aspect 164. The sole structure of any one of Aspects 160-163, wherein the poly(tetramethylene ether) terephthalate block has a weight-average molecular weight from about 800 Daltons to about 1200 Daltons.

[0543] Aspect 165. The sole structure as described in any one of Aspects 160-163, wherein the poly(tetramethylene ether) terephthalate block has a weight-average molecular weight from about 1,500 Daltons to about 2,500 Daltons.

[0544] Aspect 166. The sole structure as described in any one of Aspects 160-163, wherein the poly(tetramethylene ether) terephthalate block has a weight-average molecular weight from about 1,000 Daltons to about 3,000 Daltons.

[0545] Aspect 167. The sole structure as described in aspect 69 or 70, wherein the thermoplastic elastomer material includes thermoplastic polyurethane elastomer.

[0546] Aspect 168. The sole structure as described in aspect 167, wherein the thermoplastic polyurethane elastomer is selected from thermoplastic polyester-polyurethane elastomers, thermoplastic polyether-polyurethane elastomers, thermoplastic polycarbonate-polyurethane elastomers, thermoplastic polyolefin-polyurethane elastomers, any copolymers thereof, and any blends thereof.

[0547] Aspect 169. The sole structure as described in aspect 168, wherein the thermoplastic polyurethane elastomer is a thermoplastic polyester-polyurethane elastomer.

[0548] Aspect 170. The sole structure as described in aspect 168, wherein the thermoplastic polyurethane elastomer is a thermoplastic polyether-polyurethane elastomer.

[0549] Aspect 171. The sole structure as described in aspect 168, wherein the thermoplastic polyurethane elastomer is a thermoplastic polycarbonate-polyurethane elastomer.

[0550] Aspect 172. The sole structure as described in aspect 168, wherein the thermoplastic polyurethane elastomer comprises a long-chain polyol.

[0551] Aspect 173. The sole structure as described in aspect 172, wherein the long-chain polyol is selected from polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polypropylene polyols, and any copolymers thereof.

[0552] Aspect 174. The sole structure as described in aspect 172, wherein the long-chain polyol is a polyether polyol, a polyester polyol, or any copolymer thereof.

[0553] Aspect 175. The sole structure as described in aspect 172, wherein the long-chain polyol is a polyether polyol.

[0554] Aspect 176. The sole structure as described in aspect 172, wherein the long-chain polyol is a polyester polyol.

[0555] Aspect 177. The sole structure as described in any one of Aspects 172-176, wherein the long-chain polyol has a weight-average molecular weight of not less than about 500 Daltons.

[0556] Aspect 178. The sole structure as described in any one of Aspects 172-176, wherein the long-chain polyol has a weight-average molecular weight of about 500 Daltons to about 10,000 Daltons.

[0557] Aspect 179. The sole structure as described in any one of Aspects 172-176, wherein the long-chain polyol has a weight-average molecular weight of about 600 Daltons to about 6,000 Daltons.

[0558] Aspect 180. The sole structure as described in any one of Aspects 172-176, wherein the long-chain polyol has a weight-average molecular weight of about 800 Daltons to about 4,000 Daltons.

[0559] Aspect 181. The sole structure as described in aspect 69 or 70, wherein the thermoplastic elastomer material comprises at least one thermoplastic polystyrene elastomer.

[0560] Aspect 182. The sole structure as described in aspect 181, wherein the thermoplastic styrene elastomer is a styrene block copolymer elastomer.

[0561] Aspect 183. The sole structure as described in aspect 182, wherein the styrene block copolymer elastomer is poly(styrene-butadiene-styrene), poly(styrene-ethylene-co-butene-styrene), poly(styrene-isoprene-styrene), any copolymer thereof, and any blend thereof.

[0562] Aspect 184. The sole structure as described in aspect 44, wherein the polymer material includes thermosetting polymers or copolymers.

[0563] Aspect 185. The sole structure as described in aspect 184, wherein the thermosetting polymer or copolymer is thermosetting polyurethane.

[0564] Aspect 186. The sole structure as described in aspect 185, wherein the thermosetting polyurethane is polyester, polyether, or polycaprolactone.

[0565] Aspect 187. The sole structure of any one of Aspects 1-186, wherein the first foam component, the second foam component, or both the first foam component and the second foam component comprise polymers selected from the group consisting of: ethylene-vinyl acetate (EVA) copolymers, styrene-butadiene copolymers, polyurethane homopolymers or copolymers, and blends thereof.

[0566] Aspect 188. The sole structure as described in any one of Aspects 44-187, wherein the polymer material further comprises cross-links.

[0567] Aspect 189. A footwear article comprising a sole structure as described in any one of Aspects 1-188 and an upper attached to said sole structure.

[0568] Aspect 190. A method of manufacturing footwear articles, the method comprising attaching an upper to a sole structure as described in any one of Aspects 1-188, thereby forming footwear articles.

[0569] Aspect 191. A method for forming a sole structure for footwear articles, comprising:

[0570] A first foam component is provided, the first foam component having a first side and a second side opposite to the first side;

[0571] A second foam component is provided, the second foam component having a first side and a second side opposite to the first side;

[0572] Provide mesh components; and

[0573] The mesh component, the second side of the first foam component, and the first side of the second foam component are joined together.

[0574] Aspect 192. The method of aspect 191, wherein the first foam component comprises a first foam component polymer material comprising a polymer material as described in any one of aspects 45-188.

[0575] Aspect 193. The method as described in aspect 191 or aspect 192, wherein the second foam component comprises a second foam component polymer material that independently comprises a polymer material as described in any one of aspects 45-188.

[0576] Aspect 194. The method of any one of aspects 191-193, wherein the mesh component comprises a mesh component polymer material comprising a polymer material of any one of aspects 45-188.

[0577] Aspect 195. The method of any one of Aspects 191-194, wherein a first side of a first foam component forms a first side of a sole structure, a second side of a second foam component forms a second side of a sole structure opposite to the first side of the sole structure, and a mesh component is positioned and coupled between the second side of the first foam component and the first side of the second foam component.

[0578] Aspect 196. The method of any one of Aspects 191-195, wherein forming the first foam component comprises injection molding the first foam component in a mold.

[0579] Aspect 197. The method of aspect 196, wherein injection molding of the first foam component includes injection molding the first foam component in a mold including a corrugated molding surface; thereby forming a corrugated region on a second side of the first foam component.

[0580] Aspect 198. The method of any one of Aspects 191-197, wherein providing the first foam component comprises cutting the first foam component from a foam sheet using at least one of a cutting knife, a wire, a laser, and water jet.

[0581] Aspect 199. The method of aspec...

Claims

1. A sole structure for footwear, comprising: A first foam component, the first foam component including a cavity and having a first side and a second side defined within the cavity opposite to the first side, wherein the first foam component includes an inner sidewall, and the cavity is defined by the second sidewall of the first foam component and the inner sidewall of the first foam component; A second foam component is at least partially positioned within the cavity, the second foam component having a first side and a second side opposite to the first side, wherein the first foam component and the second foam component form a stack in the sole structure and the interface between the second side of the first foam component and the first side of the second foam component is within the cavity, and wherein the sidewall of the second foam component is coupled to the inner sidewall of the first foam component within the cavity; The outsole is adhered to the second side of the second foam component; as well as A mesh textile is positioned in the stack between the second side of the first foam component and the first side of the second foam component, and is bonded to the second side of the first foam component and the first side of the second foam component, wherein the mesh textile comprises at least two mesh components; and the at least two mesh components overlap each other between the second side of the first foam component and the first side of the second foam component.

2. The sole structure according to claim 1, wherein: The sole structure includes a forefoot area, a midfoot area, and a heel area; and The mesh textile is incorporated in at least one of the forefoot area, the midfoot area, and the heel area between the second side of the first foam component and the first side of the second foam component.

3. The sole structure of claim 1, wherein the mesh textile extends from the inner side of the first foam component and the second foam component across to the outer side of the first foam component and the second foam component between the second side of the first foam component and the first side of the second foam component.

4. The sole structure according to claim 1, wherein: The mesh textile extends between the second side of the first foam component and the first side of the second foam component, within approximately 1 mm to 5 mm of the edge of the second side of the first foam component, and also extends within approximately 1 mm to 5 mm of the edge of the first side of the second foam component; and The sole structure includes at least a portion of the edge along the second side of the first foam component and the edge along the first side of the second foam component at the interface between the second side of the first foam component and the first side of the second foam component.

5. The sole structure according to claim 1, wherein the second side of the first foam component includes a wave-shaped area, or the first side of the second foam component includes a wave-shaped area, or both include a wave-shaped area.

6. The sole structure according to claim 5, wherein the second side of the first foam component includes the wave-shaped region.

7. The sole structure of claim 5, wherein the first side of the second foam component includes the wave-shaped region.

8. The sole structure according to claim 5, wherein the wave pattern includes at least one pattern selected from serrated patterns and wavy patterns.

9. The sole structure according to claim 8, wherein the pattern varies in terms of the size of the pattern.

10. The sole structure of claim 9, wherein the dimensional aspect of the pattern includes at least one of amplitude and wavelength.

11. The sole structure according to claim 5, wherein: The mesh textile is bonded to the second side of the first foam component and the first side of the second foam component in the wave region; and The relative position of the mesh textile varies within the wave region of the stacked portion of the sole structure.

12. The sole structure according to claim 5, wherein: The first side of the second foam component includes a first wave-shaped region; The second side of the first foam component includes a second wave-shaped region; and The first waveform region and the second waveform region are complementary to each other.

13. The sole structure of claim 1, wherein the mesh textile has fibers of a first density in a first region and fibers of a second density in a second region, wherein the first density is at least 10% greater by weight than the second density.

14. The sole structure according to claim 1, wherein: The mesh textile includes at least two other mesh components; and The at least two other mesh components are spaced apart from each other in the stack between the second side of the first foam component and the first side of the second foam component.

15. The sole structure according to claim 1, wherein: The mesh textile includes at least two mesh textiles; At least one of the at least two mesh textiles is bonded at a first location between the second side of the first foam component and the first side of the second foam component; and At least one of the at least two mesh textiles is attached at a second position between the second side of the first foam component and the first side of the second foam component.

16. The sole structure of claim 1, wherein the mesh textile comprises one or more individual fibers or yarns comprising a thermoplastic material, said thermoplastic material comprising thermoplastic polyester, thermoplastic polyamide, thermoplastic polyurethane, or any combination thereof.

17. The sole structure of claim 16, wherein the mesh textile is a knitted textile, crocheted textile, braided textile or woven textile comprising one or more yarns, wherein each of the one or more yarns is formed from one or more individual fibers.

18. The sole structure of claim 16, wherein the mesh textile is a nonwoven textile comprising more than one fiber.

Images