FOOTWEAR ARTICLE WITH IMPROVED BONDING BETWEEN UPPER AND SOLE

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority benefit of U.S. Provisional Patent Application No. 63/627,796 (filed on Jan. 31, 2024), which is hereby incorporated herein by reference in its entirety.

TECHNICAL FIELD

The present disclosure generally relates to a footwear article with improved bonding strength between a footwear upper and a sole structure.

BACKGROUND

The design and manufacture of footwear and sporting equipment involves a variety of factors from the aesthetic examples, to the comfort and feel, to the performance and durability. While design and fashion may be rapidly changing, the demand for increasing performance in the footwear and sporting equipment market is unchanging. In addition, the market has shifted to demand lower-cost and recyclable materials still capable of meeting increasing performance demands. To balance these demands, designers of footwear and sporting equipment employ a variety of materials and designs for the various components.

BRIEF DESCRIPTION OF THE DRAWINGS

Further examples of the present disclosure will be readily appreciated upon review of the detailed description, described below, when taken in conjunction with the accompanying drawings.

FIG. 1 is a lateral side perspective view of a footwear article, and FIG. 1 includes a reference view of a cross section A-A.

FIG. 2 is a top plan view of a footwear article, and FIG. 2 includes a reference view of a cross section B-B.

FIG. 3 is a partially deconstructed view of a footwear article with the upper partially cut away.

FIG. 4 is a pictorial flow diagram illustrating some steps/operations related to manufacturing a footwear article.

FIG. 5A is a cross sectional view that shows an upper with a surface texture.

FIG. 5B is a cross sectional view that shows a strobel bonded to the upper.

FIG. 6A illustrates a first material that can form an upper.

FIG. 6B illustrates another material that can form an upper.

FIG. 7A illustrates another material that can form an upper.

FIG. 7B illustrates another material that can form an upper.

DETAILED DESCRIPTION

The present disclosure is related to a footwear article (and method of making a footwear article) associated with improved bonding (e.g., reduced likelihood of delamination) between a footwear upper and a sole structure and along at least a portion of the biteline. For example, the footwear upper can include an outer-facing surface (e.g., externally-facing side) that faces away from the foot-receiving cavity. In addition, the outer-facing surface can include a first zone that overlaps with, and is bonded to, the sole structure (e.g., a plate or midsole or outsole or other portion of the sole structure) and a second zone that does not overlap with the sole structure (e.g., at least part of the second zone includes portions of the upper that enclose the foot-receiving space, such as the quarter(s), instep, vamp, heel, etc.). Examples of the present disclosure are directed to various features of the first zone that improve bonding to the sole structure (and that might not be present in the second zone or that might be different in the second zone), such as bonding via thermal bonding, adhesive bonding, mechanical bonding, chemical bonding, and the like. In at least some examples, the bonding between the first zone of the upper and the sole structure can include a bond that arises from the sole being molded directly onto the upper, such that the material of the sole and/or the material of the first zone are (due to heat) at least partially softened (e.g., can be melted) and fused to one another (e.g., the materials can at least partially mix in a softened state and solidify in a comingled state to form the bond). This is one example of bonding, and the properties of the first zone can improve bonding to the sole structure via one or more other types of bonding methods (e.g., mechanical, chemical, adhesive, etc.).

A footwear upper can include a material (e.g., synthetic leather material) having properties (e.g., chemical composition) that are configured to bond with a sole structure. For example, the sole structure can include a first thermoplastic composition and the footwear-upper material can include a second thermoplastic composition, which is configured to bond with the first thermoplastic composition (e.g., via a thermal bond) and resists delamination when subjected to forces associated with a user wearing the footwear article during athletic-related activities. Conventional techniques often include applying additional or different properties (e.g., surface properties, including surface chemical composition) to the footwear-upper material (e.g., the first zone and the second zone), such as by applying cleaning agents, corona treatment, printed components (e.g., ink or other colorant carriers), surface texture (e.g., surface with varied relief or other z-height dimensional offset), and the like. However, it has been discovered in association with this present disclosure that these additional and/or different properties of the footwear-upper material can (e.g., when associated with the first zone that overlaps with the sole structure) reduce the strength of the bond between the footwear-upper material and the sole structure. For example, if the first zone of the upper that overlaps with the sole structure includes a surface chemistry that is different from the sole structure, then a bond between the two structures might not be as strong and might have a higher risk of delamination (e.g., might have a lower peel strength based on a peel strength test).

In contrast to conventional approaches, examples of the present disclosure can include the first zone of the outer-facing surface (e.g., that overlaps with, and is bonded to, the sole structure) having different properties as compared to the second zone of the outer-facing surface (e.g., that does not overlap with the sole structure). The properties of the first zone that are different from the properties of the second zone can improve the bond strength between the first zone and the sole. For example, the first zone can include, on the outermost surface of the outer-facing surface, a first property, and the first property is different from a second property, which is on the outermost surface of the outer-facing surface in the second zone. The first property and the second property can include, among other things, a chemical composition (e.g., surface chemistry, which can include a thermoplastic composition), a surface texture (or lack thereof), or a combination thereof, or any other surface property that might differ. In some examples, the first property and second property are respective chemical compositions, and the first property includes a thermoplastic polyolefin resin composition, which is different from the second property. For instance, the surface in the second zone might not include any amount of the thermoplastic polyolefin resin composition, or might include less than some threshold amount (e.g., less than 5% percentage composition, such as by weight). In some examples, the second property can include (on a surface in the second zone and in contrast to the surface in the first zone) a cleaning-solution composition, a more oxidized surface, a primer composition, an ink composition, a surface texture (e.g., deeper relief features as compared to the first zone), or any and all combinations thereof. In examples, the first property (e.g., the thermoplastic composition on the surface of the first zone) can contribute to improved bond strength between the footwear upper and the sole structure.

The first zone (e.g., with properties that are different from the second zone and that contribute to improved bonding with the sole) can include a width that extends from a terminal edge of the upper (e.g., the terminal edge that is at least partially wrapped beneath the footbed) to a position aligned with a biteline (e.g., the position or juncture at which a terminal edge of the sole structure aligns with the upper where the two are bonded to one another). In at least some examples, the width can vary depending on a position of the first zone around the periphery of the footwear article. For example, a first width of the first zone along the midfoot can differ from a second width of the first zone in the forefoot. In some examples, the varied widths associated with the first zone can contribute to enhanced strength in select areas (e.g., where the width is larger) and reduced weight in other areas (e.g., where the width is smaller), and in this respect, the varied widths can contribute to balancing of various overall (and sometimes competing or conflicting) properties. That is, at some positions, the first zone can include a larger width where increased bond strength is desired between the upper and other underfoot structures (e.g., the sole, lasting board, strobel, etc.), whereas in other positions the first zone can include a smaller width where sufficient bond strength can be achieved with less bonding surface area and the smaller width can contribute to less overall materials and a lower overall weight (of the footwear article).

In at least some examples, the outer-facing surface can include a transition zone that is positioned between the first zone and the second zone. For example, the upper can include the first zone that is adjacent to the transition zone, which is adjacent to the second zone. In examples, the outermost surface of the transition zone is not bonded to the sole structure. For example, the transition zone can extend from the biteline and to the second zone (e.g., to a position at which the outer-facing surface transitions from having the first property to having the second property). In addition, the transition zone can include properties that can contribute to a stronger bond with the sole structure (e.g., a chemical composition, a surface texture (or lack thereof), or a combination thereof, or any other surface property) and that are similar to the first zone and that are different from the second zone. In examples, the transition zone can include (or form) a buffer zone that safeguards against properties of the second zone being associated with a surface bonded to the sole structure, and in this respect, the buffer zone can reduce the likelihood of bonding failure and delamination between the upper (in the first zone) and the sole structure. In at least some instances, the transition zone can extend around the entire periphery of the footwear article. In some examples, a width of the transition zone (e.g., from the biteline to the second zone) is the same at two or more positions around the periphery. In some examples, a width of the transition zone (e.g., from the biteline to the second zone) can vary depending on a position around the periphery.

Surface chemistry can be assessed (e.g., for one or more zones associated with the upper) using one or more various known surface analysis techniques, such as X-ray Photoelectron Spectroscopy (XPS) or similar techniques. For example, the surface chemistry of the second zone of the upper (that does not overlap with the sole and is not bonded to the sole) can be analyzed using one or more surface analysis techniques to assess whether the surface of the second zone is different from the transition zone and/or different from the first zone. In at least some examples, the surface analysis technique can be used to determine whether the second zone includes one or more properties that are less conducive to bonding with the sole structure (as compared to the properties of the first zone and/or the transition zone). In at least some examples, the surface analysis technique can be used to determine whether the second zone includes, as compared to the first zone and/or the second zone, higher amounts of a polymeric material (e.g., PU, such as in an ink or other surface layer) that is different from the thermoplastic composition (e.g., thermoplastic polyolefin resin composition) of the sole structure. In at least some examples, the surface analysis technique can be used to determine whether the second zone is, as compared to the first zone and/or the second zone, more oxidized.

At least some examples of this disclosure relate to a strength of a bond between an upper and a sole structure. The strength of the bond can be assed in various manners that measure the ability of the bond to resist delamination when subjected to forces. In some examples, these tests can be referred to as a “peel strength test.” In at least some instances, peel strength can be measured based on SATRA TM411.

“A,” “an,” “the,” “at least one,” and “one or more” might be used interchangeably to indicate that at least one of the items is present. When such terminology is used, a plurality of such items might be present unless the context clearly indicates otherwise. All numerical values of parameters (e.g., of quantities or conditions) in this specification, unless otherwise indicated expressly or clearly in view of the context, including the appended claims, are to be understood as being modified in all instances by the term “about” whether or not “about” actually appears before the numerical value. “About” indicates that the stated numerical value allows some slight imprecision (with some approach to exactness in the value; approximately or reasonably close to the value; nearly). If the imprecision provided by “about” is not otherwise understood in the art with this ordinary meaning, then “about” as used herein indicates at least variations that may arise from ordinary methods of measuring and using such parameters. The term “about” can include +/−10% of a given element, if that numerical definition is necessary to understand the scope of a claimed element. In addition, a disclosure of a range is to be understood as specifically disclosing all values and further divided ranges within the range.

The terms “comprising,” “including,” and “having” are inclusive and therefore specify the presence of stated features, steps, operations, elements, or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, or components. Orders of steps, processes, and operations may be altered when possible, and additional or alternative steps may be employed. As used in this specification, the term “or” includes any one and all combinations of the associated listed items. The term “any of” is understood to include any possible combination of referenced items, including “any one of” the referenced items. The term “any of” is understood to include any possible combination of referenced claims of the appended claims, including “any one of” the referenced claims.

For consistency and convenience, directional adjectives might be employed throughout this detailed description corresponding to the illustrated examples. Ordinary skilled artisans will recognize that terms such as “above,” “below,” “upward,” “downward,” “top,” “bottom,” etc., may be used descriptively relative to the figures, without representing limitations on the scope of the invention, as defined by the claims.

The term “longitudinal,” as possibly used throughout this detailed description and in the claims, refers to a direction extending a length of a component. For example, a longitudinal direction of a shoe extends between a forefoot region and a heel region of the shoe. The term “forward” or “anterior” is used to refer to the general direction from a heel region toward a forefoot region, and the term “rearward” or “posterior” is used to refer to the opposite direction, i.e., the direction from the forefoot region toward the heel region. In some cases, a component may be identified with a longitudinal axis, as well as a forward and rearward longitudinal direction along that axis. The longitudinal direction or axis may also be referred to as an anterior-posterior direction or axis.

The term “transverse,” as possibly used throughout this detailed description and in the claims, refers to a direction extending a width of a component. For example, a transverse direction of a shoe extends between a lateral side and a medial side of the shoe. The transverse direction or axis may also be referred to as a lateral direction or axis or a medio-lateral direction or axis.

The term “vertical,” as possibly used throughout this detailed description and in the claims, refers to a direction generally perpendicular to both the lateral and longitudinal directions. For example, in cases where a sole is positioned flat on a ground surface, the vertical direction may extend from the ground surface upward. It will be understood that each of these directional adjectives may be applied to individual components of a sole. The term “upward” or “upwards” refers to the vertical direction pointing towards a top of the component, which may include an instep, a fastening region, and/or a throat of an upper. The term “downward” or “downwards” refers to the vertical direction pointing opposite the upwards direction, toward the bottom of a component, and may generally point towards the bottom of a sole structure of an article of footwear.

The “interior” of an article of footwear, such as a shoe, refers to portions at the space that is occupied by a wearer's foot when the shoe is worn. The interior can also be referred to as the foot-receiving cavity. The “inner side” of a component refers to the side or surface of the component that is (or will be) oriented toward the interior of the component or article of footwear in an assembled article of footwear. The “inner side” can also be referred to as the “inward-facing side” or “inward-facing surface.” The “outer side” or “exterior” of a component refers to the side or surface of the component that is (or will be) oriented away from the interior of the shoe in an assembled shoe. The “outer side” can also be referred to as the “outer-facing side” or “outer-facing surface, as well as the “exterior-facing side” or “exterior-facing surface.” In some cases, other components may be between the inner side of a component and the interior in the assembled article of footwear. Similarly, other components may be between an outer side of a component and the space external to the assembled article of footwear. Further, the terms “inward” and “inwardly” shall refer to the direction toward the interior of the component or article of footwear, such as a shoe, and the terms “outward” and “outwardly” shall refer to the direction toward the exterior of the component or article of footwear, such as a shoe. In addition, the term “proximal” refers to a direction that is nearer a center of a footwear component, or is closer toward a foot when the foot is inserted in the article of footwear as it is worn by a user. Likewise, the term “distal” refers to a relative position that is further away from a center of the footwear component or is further from a foot when the foot is inserted in the article of footwear as it is worn by a user. Thus, the terms proximal and distal may be understood to provide generally opposing terms to describe relative spatial positions.

Various examples are described below with reference to the drawings, and the structure, relationship, and/or functioning of examples can, in some instances, be better understood by reference to this detailed description. However, examples associated with the subject matter of this application are not limited to those illustrated in the drawings or explicitly described below. The drawings might not necessarily be to scale. In some instances, for clarity, brevity, and/or simplicity details might have been omitted, which does not preclude the inclusion of those details in association with examples of this disclosure.

Articles of Footwear

Reference is now made to FIGS. 1, 2, and 3 to describe elements of a footwear article 10. FIG. 1 depicts a lateral side of the footwear article 10, FIG. 2 depicts a top of the footwear article, and FIG. 3 depicts a partially deconstructed view. In an example, the footwear article can include a soccer/futbol boot. In other examples, the footwear article can include a variety of other types of footwear articles, such as other cleated or non-cleated footwear articles (e.g., for American football, golf, basketball, sportswear/leisure, tennis shoes, hiking boots/shoes, etc.). When describing the various figures mentioned in this disclosure, like reference numbers refer to like components throughout the views (although the components might not be the exact same).

The footwear article 10 includes at least two primary elements including a sole structure 12 and an upper 14. When the footwear article 10 is worn (as intended on a foot), the sole structure 12 is typically positioned near the foot plantar surface (i.e., the bottom of the foot). The sole structure 12 may protect the bottom of the foot, and in addition, may attenuate ground-reaction forces, absorb energy, provide traction, and control foot motion, such as pronation and supination. The upper 14 is coupled to the sole structure 12, and together with the sole structure 12, forms a foot-receiving cavity 16 (FIG. 2). That is, while the sole structure 12 typically encloses the bottom of the foot, the upper 14 extends over, and at least partially covers, a dorsal portion of the foot (i.e., the top of the foot or the instep) and secures the footwear article 10 to the foot. The upper 14 includes a foot-insertion opening 18, through which a foot is inserted when the footwear article 10 is put on as the foot is arranged into the foot-receiving cavity 16.

As indicated in FIG. 1 and FIG. 2, the footwear article 10 may include a forefoot region 20, a midfoot region 22, a heel region 24, and an ankle region 26. The forefoot region 20, the midfoot region 22, and the heel region 24 extend through the sole structure 12 and the upper 14. The ankle region 26 is located in a portion of the upper 14. The forefoot region 20 generally includes portions of the footwear article 10 corresponding with the toes and the joints connecting the metatarsals with the phalanges. The midfoot region 22 generally includes portions of the footwear article 10 corresponding with the arch area and instep of the foot. The heel region 24 corresponds with rear portions of the foot, including the calcaneus bone. The ankle region 26 corresponds with the ankle. The forefoot region 20, the midfoot region 22, the heel region 24, and the ankle region 26 are not intended to demarcate precise areas of the footwear article 10, and are instead intended to represent general areas of the footwear article 10 to aid in the understanding of various aspects of this specification. In addition, portions of a footwear article may be described in relative terms using these general zones. For example, a first structure may be described as being more heelward than a second structure, in which case the second structure would be more toeward and closer to the forefoot.

The footwear article 10 also has a medial side 28 (identified in FIG. 2 and obscured from view in FIG. 1) and a lateral side 30 (identified in FIG. 2 and viewable in FIG. 1). The medial side 28 and the lateral side 30 extend through each of the forefoot region 20, the midfoot region 22, the heel region 24, and the ankle region 26, and correspond with opposite sides of the footwear article 10, each falling on an opposite side of a longitudinal midline reference plane 29 of the footwear article 10, as is understood by those skilled in the art. For example, the longitudinal midline reference plane 29 may pass through the foremost point of the sole structure and the rearmost point of the sole structure. The medial side 28 is thus considered opposite to the lateral side 30. Typically, the lateral side corresponds with an outside area of the foot (i.e., the surface that faces away from the other foot), and the medial side corresponds with an inside area of the foot (i.e., the surface that faces toward the other foot). In another aspect, the footwear article includes an anterior portion (e.g., more forward) and a posterior portion (e.g., more rearward), falling on an opposite side of a latitudinal midline reference plane 31 of the footwear article 10. The latitudinal midline reference plane 31 extends perpendicular to the longitudinal midline reference plane 29 and to the ground-surface plane and is spaced evenly between the foremost point of the footwear article 10 and the rearmost point of the footwear article 10. In addition, these terms may also be used to describe relative positions of different structures. For example, a first structure that is closer to the inside portion of the footwear article might be described as medial to a second structure, which is closer to the outside area and is more lateral. In addition, a first structure that is closer to the forward end of the footwear article might be described as anterior to a second structure, which is closer to the rearward end that is more posterior.

In describing a footwear article, the relative terms “inferior” and “superior” may also be used. For example, the superior portion generally corresponds with a top portion that is oriented closer towards a person's head when the person's feet are positioned flat on a horizontal ground surface and the person is standing upright, whereas the inferior portion generally corresponds with a bottom portion oriented farther from a person's head and closer to the ground surface.

The sole structure 12 of the footwear article 10 can comprise a sole component such as one or more plates, midsoles, outsoles, insoles, and the like. In addition, as depicted in the reference view A-A in FIG. 1, at least a portion 110 of the upper 14 can be affixed to at least a portion 112 of the sole structure 14. In some examples, at least a portion of the surface of the upper 14 that is affixed to the sole structure 12 can comprise a synthetic leather material as described herein, optionally where the affixed surface of the upper 14 is at least partially defined by a polyolefin resin composition as described herein. In some examples, both the affixed surface of the upper 14, and the affixed surface of the sole structure 12, can comprise a polyolefin resin composition. The strength of bonds between two surfaces both formed of polyolefin compositions typically are stronger than the strength of bonds between a first surface formed of a polyolefin composition and a non-polyolefin polymeric composition, as the surface energy of polyolefins are typically different from other types of polymeric materials commonly used in footwear manufacturing. As the bond strength of a thermal bond formed between two polyolefin resin compositions is typically greater than an adhesive bond (e.g., a bond formed using a hot-melt adhesive or a cement), when both the surface of the upper and the surface of the sole structure are defined by a polyolefin resin composition, it is advantageous to affix the surfaces together using a thermal bond in which a polyolefin resin composition of the upper and/or of the sole structure is softened or melted and then re-solidified to form the bond.

As used in this disclosure, a “thermal bond” can include a bond between two components that is formed when at least one of the two components is heated to at least a softening point and is brought into contact with the other of the two components, such that upon cooling, the two components are bonded. In some examples, the two components are bonded by a chemical bond, by a mechanical bond, or by a combination of chemical bonds and mechanical bonds. For example, in some cases, a thermal bond can include chemical bonding based on van der Waals forces, dipole interactions, and/or dispersion forces, although covalent bonding of the components might not necessarily be modified or changed (e.g., neither created or destroyed). In at least some examples, a thermal bond can include a mechanical bond, such as where the softened material of the heated component flows around a portion of the other component and, upon cooling, is solidified to at least partially encapsulate the portion. In at least some examples, at least a small amount of material from a first component (e.g., sole structure 12) might mix with at least a small amount of material from the second component (e.g., the upper 14, including the portion of the upper that overlaps with the sole structure 12). An extent of mixing can depend on various factors, such as the extent to which one or both components are heated and/or the amount of time during which heat is applied.

In some examples, the materials of the upper and the sole can both be softened, at least partially mixed together, and then solidified to form the bond. The polyolefin resin composition of the synthetic leather material can be the same as the polyolefin resin composition of the sole structure. The polymeric component of the two polyolefin resin compositions (i.e., the portion of the composition consisting of all the polymers present in the polyolefin resin composition) can include the same types of polymers in the same concentrations, or can include the same types of polymers in different concentrations, or can include different types of polymers. The polyolefin component of the two polyolefin resin compositions (i.e., the portion of the composition consisting of all the polyolefins present in the polyolefin resin composition) can include the same types of polyolefins in the same concentrations, or can include the same types of polyolefins in different concentrations, or can include different types of polyolefins.

In some examples, the sole structure 12 can be constructed of various other materials and may include various elements (e.g., in addition to the polyolefin resin composition). For example, the sole structure 12 may include a compressible polymer foam element (e.g., a polyurethane or ethylvinylacetate (EVA) foam) that attenuates ground reaction forces (i.e., provides cushioning) when compressed between the foot and the ground during walking, running, or other ambulatory activities. In further aspects, the sole may incorporate fluid-filled chambers, plates, moderators, or other elements that further attenuate forces, enhance stability, or influence motions of the foot. The sole may be a single, one-piece sole, or could be multiple components integrated as a unit. In some aspects, the sole can include a midsole integrated with an outsole as a unisole. The outsole may be one-piece, or may be several outsole components, and may be formed from a wear-resistant rubber material that may be textured to impart traction and/or may include traction elements such as tread or cleats secured to a midsole. An outsole may extend either the entire length and width of the sole or only partially across the length and/or width.

As indicated, the upper 14 typically includes a portion that overlaps with, and is connected to, the sole structure 12. In examples, a biteline 116 is the junction of the terminal edge 114 of the sole structure 12 with the upper 14. In addition, the footwear article 10 can include a strobel 120 (or a lasting board or other lasting panel). The strobel 120 can function to provide structural integrity across the bottom of the upper 14, such as when the upper 14 is lasted and is being bonded to the sole structure 12. In some examples, the strobel 120 can also contribute to other properties in the footwear article 10, such as cushioning, motion control (e.g., of the wearer's foot relative to the footwear article 10), stiffness, etc. The strobel can, in some examples, be covered by an insole or other layer of material.

Examples of the present disclosure are related to the footwear article 10 associated with improved bonding (e.g., reduced likelihood of delamination) between the footwear upper 14 and the sole structure 12. In examples, the footwear upper 14 includes an outer-facing surface 122a (first zone), 122b (transition zone), and 122c (second zone) that faces away from the foot-receiving cavity 16. In addition, the outer-facing surface 122a-122c can include the first zone 122a that overlaps with, and is bonded to, the sole structure 12 (e.g., a plate or midsole or outsole or other sole component), and in the cross-sectional view in FIG. 1, an extent (e.g., length) of the first zone 122a is represented by a reference arrow 124a. In examples, the outer-facing surface 122a-122c can include the second zone 122c that does not overlap with the sole structure 12, and in the deconstructed view in FIG. 1, at least part of an extent (e.g., length) of the second zone 122c is represented by a reference arrow 124c. Examples of the present disclosure are directed to various features of the first zone 124a that improve bonding to the sole structure 12, such as bonding via thermal bonding, adhesive bonding, mechanical bonding, chemical bonding, and the like.

In examples, the footwear upper 14 can include a material (e.g., synthetic leather material) having properties (e.g., chemical composition) that are configured to bond with the sole structure 12. For example, the sole structure 12 can include a first thermoplastic composition and the footwear upper 14 (e.g., a textile of the footwear upper 14 and/or a coating or other material coupled to a surface of a textile) can include a second thermoplastic composition, which is configured to bond well with the first thermoplastic composition (e.g., via a thermal bond). Examples of the present disclosure can include the first zone 122a of the outer-facing surface (e.g., that overlaps with, and is bonded to, the sole structure 12) having different properties as compared to the second zone 122c of the outer-facing surface (e.g., that does not overlap with the sole structure). For example, the first zone 122a can include, on the outermost surface of the outer-facing surface, a first property (e.g., FIG. 6A with the outermost surface represented by the layer 620), and the first property is different from a second property, which is on the outermost surface of the outer-facing surface in the second zone 122c (e.g., FIG. 6B with the outermost surface represented by the layer 630, which could be a decorative layer or another layer). In FIG. 1, the second property of the second zone 122c is indicated by the stippled portions 129 and 128, which are absent from the first zone 122a.

The first property and the second property can include, among other things, a chemical composition (e.g., a surface chemistry or surface chemical composition), a surface texture, or a combination thereof, or any other surface property that might differ. In some examples, each of the first property and second property is a respective chemical composition, and the first property includes a thermoplastic polyolefin resin composition, which is different from the second property. For instance, the surface in the second zone 122c might not include any amount of the thermoplastic polyolefin resin composition, or might include less than some threshold amount (e.g., less than 5% percentage composition, such as by weight). In some examples, the second property can include a cleaning-solution composition, a more oxidized surface (as compared to the first zone), a primer composition, an ink composition (e.g., a polyurethane or other chemical composition that is different from the thermoplastic polyolefin resin composition), a surface texture, or any and all combinations thereof. The second zone 122c can have different properties in different regions of the upper 14. For example, the second zone 122c can have in some areas (e.g., 129 depicted with a first stipple pattern) an ink composition, and the second zone 122c can have in some other areas (e.g., 128 depicted with a second stipple pattern) different properties imparted by a different ink composition, corona treatment, cleaning solution, etc.). In examples, the first property can contribute to improved bond strength between the footwear upper and the sole structure.

Referring to FIG. 5A, an example is illustrated related to the second zone 122c having a surface texture (e.g., grooves or other debossed or impressed shapes or patterns) with one or more relief depths 510 and 512. A relief depth is a distance between an outermost surface of the second zone 122c and the base or bottom surface the relief portion. In at least some examples, the relief depth can be about zero. In at least some examples, the second property that is associated with the second zone 122c can include a larger relief depth (e.g., 510). In at least some examples, the relief depth can taper from a larger relief depth to a smaller relief depth as the outermost surface extends from a first position that is further away from the biteline to a second position that is closer to the biteline. In examples, the taper can be to a relief depth of almost zero. In at least some examples, the taper can decrease the likelihood that the surface texture might decrease a peel strength of a bond between the upper 14 and the sole structure 12. Stated differently, in at least some examples, if portions of the upper that overlap with the sole structure (e.g., for bonding) include a larger relief depth, there can be a higher likelihood that the part of the upper with the relief might contact the sole structure to a lesser extent (e.g., as compared to an upper with a lower relief), and as such, reducing the relief height can increase the likelihood that that part of the upper (with the relief) with have greater contact (e.g., over a greater surface area) and can form a stronger bond.

The first zone 122a can include a width (e.g., as represented by the arrow 124a) that extends from a terminal edge 126 of the upper 14 (e.g., the terminal edge that is wrapped beneath the footbed) to a position aligned with the biteline 116. In at least some examples, the width can vary depending on a position of the first zone 122a. For example, a first width of the first zone 122a along the midfoot can differ from a second width of the first zone in the forefoot. In some examples, the varied widths associated with the first zone 122a can contribute to balancing of various overall (and sometimes competing or conflicting) properties. For instance, at some positions, the first zone can include a larger width where increased bond strength is desired between the upper and other underfoot structures (e.g., the sole, lasting board, etc.), whereas in other positions the first zone can include a smaller width where sufficient bond strength can be achieved with less bonding surface area and the smaller width can contribute to less overall materials and a lower overall weight (of the footwear article).

In at least some examples, the outer-facing surface can include a transition zone 122b that is positioned spatially between the first zone 122a and the second zone 122c. In examples, the outermost surface of the transition zone 122b is not bonded to the sole structure 12. For example, the transition zone 122b can extend from a position that is aligned with the biteline 116 and to the second zone 122c. In addition, the transition zone can include properties (e.g., a chemical composition, a surface texture, or a combination thereof, or any other surface property) that are similar to the first zone 122a and that are different from the second zone 122c. In examples, the transition zone 122b can include a buffer zone that safeguards against properties of the second zone 122c being associated with a surface bonded to the sole structure, which could otherwise reduce the likelihood of bonding failure and delamination. In at least some instances, the transition zone 122b can extend around the entire periphery of the footwear article (e.g., along the entire biteline 116). In some instances, the transition zone 122b can extend around a portion of the periphery of the footwear article (e.g., along a portion of the biteline 116).

In some examples, a width of the transition zone (as represented by the reference arrow 124b) can vary depending on a position around the periphery. For example, a cross-reference B-B is identified in FIG. 2, and the dimension 124b of the transition zone 122b is labeled accordingly. In some examples, the width dimension 124b in the forefoot or toebox can be smaller than the corresponding width dimension 124b of the transition zone 122b in along other regions of the footwear article 10. Among other things, providing smaller transition zone can reduce a possible disruption in the surface coverage associated with the second zone 122c (e.g., ink or other print components; protective layer; abrasion resistant layer; etc.) in desired areas (e.g., areas that might be more visible), while still ensuring some buffer between the second zone 122c and the biteline 116.

In at least some examples, the strobel 120 (e.g., see also FIG. 5B) is affixed to a margin of the upper 14 that is at least partially wrapped underneath the footbed. The strobel 120 (or any portion of the strobel 120) can be affixed to the upper 14 in various manners, such as by stitching, adhering, chemical bonding, mechanical bonding, thermal bonding, and any combination thereof. In some examples an inner-facing surface 125 (e.g., FIG. 1 and FIG. 3) that faces towards the foot-receiving cavity 16 is adhered to the strobel 120. For example, a hotmelt glue (e.g., 127 in FIG. 5B) can bond the inner-facing surface 125 to the strobel 120. In some examples, a portion or segment of the upper can be adhesively bonded to the strobel 120, while another, different portion or segment of the upper can be stitched.

Referring to FIG. 3 a partially deconstructed view of a footwear article 10 is depicted, and unless otherwise expressly indicated, the footwear article 10 can include the same features as depicted and described with respect to FIG. 1 and FIG. 2. For example, the footwear article 10 includes the upper 14 that bonds to the sole structure 12, and a portion or zone 122a of the upper overlaps with and is bonded directly to the sole structure 12. In addition, the footwear article 10 can include the inner-facing surface 125 that is affixed to the strobel 120. Furthermore, the upper 14 can include the second zone 122c, which includes different properties as compared with the zone 122a, and for illustration purposes, a theoretical biteline 116 is identified.

In examples of this disclosure, the portion of the upper 14 that extends below the biteline 116 can be referred to as a bonding skirt (e.g., bonding selvage) and is identified by reference numeral 130 in FIG. 3 (see also Reference View A-A in FIG. 1). In at least some examples, the bonding skirt 130 includes the zone 122a of the outer-facing surface. In some examples, the bonding skirt 130 can include the inner-facing surface 125. In some examples of the present disclosure, the bonding skirt 130 can include a size dimension (e.g., width) as measured from the edge 126 to the biteline 116, and in Reference View A-A in FIG. 1, the width dimension of the bonding skirt 130 is identified by reference numeral 132.

In examples, the width 132 of the bonding skirt 130 as measured from the edge 126 to the biteline 116 can be consistent at two or more positions around the periphery of the footwear article 10. For example, the dimension of the bonding skirt 130 can be the same at two or more of the heel region, the midfoot region, the toebox region, the medial side, the lateral side, and any combinations thereof.

In some examples of the present disclosure, a dimension of the bonding skirt 130 (e.g., a width dimension) as measured from the edge 126 to the biteline 116 can vary as between two or more positions around the periphery of the footwear article 10. For example, the dimension of the bonding skirt 130 at a position associated with a toebox or forefoot can be greater than the dimension of the bonding skirt 130 at a more posterior portion of the footwear article. As an illustration, a cross-reference B-B is identified in FIG. 2, and the dimension 134 of the bonding skirt 130 is labeled accordingly. In some examples, the width dimension 134 can be larger than the width dimension 132. Among other things, providing a larger bounding skirt 130 with more surface area (e.g., on the outer-facing surface and on the inner-facing surface) can provide for stronger bonding to the sole structure 12 and/or to the strobel 120 in areas that can be subject to larger or more frequent forces (e.g., such as resulting from activity of the wearer).

A footwear article that includes the first zone 122a, the transition zone 122b, and the second zone 122c can be constructed or manufactured in various manners (e.g., illustrated operations in FIG. 4). In some examples, before the upper is bonded to the sole structure, the upper can include a first surface (e.g., 422 in FIG. 4), which is configured to operate or function as an outer-facing surface when the upper is bonded to the sole structure, and a second surface that is configured to operate as an inner-facing surface (e.g., facing towards the foot-receiving cavity). In at least some examples the first surface, which will eventually function as the outer facing surface, can include one or more properties (e.g., chemical composition, texture, etc.) that are conducive to bonding (e.g., thermal bonding) with the sole structure. For example, the first surface can include a thermoplastic composition (e.g., thermoplastic polyolefin resin composition) that is configured to form a strong bond with a thermoplastic composition (e.g., thermoplastic polyolefin resin composition) of the sole structure.

In some examples, a mask 450 is applied to the first surface (e.g., to a masked portion of the first surface) and along a peripheral margin of the upper. The mask (e.g., and the masked portion of the first surface) can extend from the terminal peripheral edge of the upper (e.g., from the edge 126 that will be wrapped underneath the footbed and in some instances attached to a lasting board or strobel) and inward to a position that extends beyond the portion of the first surface that will eventually align with the biteline when the upper is affixed to the sole. In addition, the mask can terminate at the position beyond the eventual biteline and leave a central portion of the first surface exposed. That is, the mask 450 can extend from the terminal peripheral edge of the upper and inward beyond the eventual biteline, and this portion inwardly beyond the eventual biteline (and to the central exposed portion) can operate as the transition or buffer zone. With the mask applied, the first surface can include a masked peripheral margin and an exposed central portion. In some examples, at least a portion of the upper that is covered by the mask will operate as the first zone 122a associated with the bonding skirt (e.g., 130). In some examples, at least a portion of the upper that is covered by the mask will include the transition zone 122b.

In some examples, with the mask applied to the first surface and along the peripheral margin, one or more operations are performed on the exposed central portion of the first surface, and the one or more operations can modify the surface properties of the exposed central portion. In examples, the mask reduces the likelihood of the operations modifying the surface properties of the masked peripheral margin (e.g., the thermoplastic composition of the masked peripheral margin can still include a state that is conducive to bond with the sole structure, despite properties of the exposed central portion being modified). In at least one example, the operation can include cleaning the first surface by applying a cleaning agent, and the application of the cleaning agent can modify the surface properties of the exposed central portion while the mask reduces the likelihood of changes to the masked peripheral margin. In at least one example, the operation can include subjecting the first surface to a corona treatment, and the corona treatment can modify the surface properties of the exposed central portion (e.g., by oxidizing the surface) while the mask reduces the likelihood of changes to the masked peripheral margin. In some examples, the operation can include applying a primer to the first surface, and the primer can modify the surface properties of the exposed central portion while the mask reduces the likelihood of changes to the masked peripheral margin. In some examples, the operation can include applying an ink to the first surface (e.g., by a screen printing or other ink-application process), and the ink (e.g., including at least some polymers other than a polyolefin) can modify the surface properties of the exposed central portion while the mask reduces the likelihood of changes to the masked peripheral margin. In some examples, the operation can include applying a surface texture the first surface (e.g., by depositing a material in a pattern having a relief and/or by impressing a surface texture into the surface), and the surface texture (e.g., including a relief having a depth) can modify the surface properties of the exposed central portion while the mask reduces the likelihood of changes to the masked peripheral margin.

In at least some examples, after the one or more operations that modify the surface properties of the exposed central portion, the mask can be removed to expose the peripheral margin of the first surface, which still includes the one or more properties (e.g., chemical composition, texture, etc.) that are conducive to bonding (e.g., thermal bonding) with the sole structure. As indicated above, the now uncovered peripheral margin can include the portions that will include the first zone 122a and the transition zone 122b.

The upper can be lasted using one or more various lasting techniques. In some examples, a strobel or lasting board is coupled (e.g., via stitching, adhesive, etc.) to the second surface of the upper (e.g., the surface on the opposite side of the upper as the first surface, and otherwise referred to herein as the inner-facing surface). For example, the peripheral margin of the upper (e.g., the bonding skirt 130) can be wrapped underneath the last (e.g., by stretching or pulling the peripheral margin) and attached to the strobel or lasting board. In some examples, the strobel is positioned on the underneath side of the last, and the bonding skirt 130 is pulled down underneath the last and affixed to the underneath side of the strobel. In some examples, a portion of the upper (a portion of the bonding skirt 130) can be pre-attached to the strobel prior to positioning on the last. For example, the pre-attachment can be via stitching, adhesive, or any other strobel attachment technique. In some examples, the pre-attachment can occur in the heel region.

In some examples, various portions of the bonding skirt 130 are stretched to varying degrees beneath the last when attach the bonding skirt 130 to the strobel (e.g., attaching the inner-facing surface of the bonding skirt 130 to the underneath side of the strobel). In some examples, added tension is desired to ensure as much of the outer-facing surface as possible is available for bonding to the sole structure. In some examples, added tension is desired to minimize a size of the transition zone. In some examples, less tension is applied to ensure sufficient buffer between the second zone 122c and the actual biteline (e.g., once the sole structure is attached). In some examples, the different tension applied at different regions of the bonding skirt 130 can contribute to the theoretical biteline and the transition zone 122b being pulled either further underneath the last or positioned higher up on the last. As such, once the sole structure is bonded to the upper (e.g., direct injection molded onto the upper with the upper on the last), the width (e.g., 124b) can vary at different positions around the periphery.

In examples, with the upper arranged on the last one or more additional operations can be executed to attach the upper to the strobel and/or to prepare the upper for bonding to the sole structure. For example, in some instances in which the upper (e.g., the inner facing surface of the upper) is adhesively bonded to the strobel or lasting board (e.g., via a hotmelt 127 along a bonding interface), the upper can be sanded or buffed (e.g., near 129 in FIG. 5B) to reduce the likelihood excess adhesive on the first surface of the upper, which can increase the likelihood of the peripheral margin of the first surface retaining the one or more properties (e.g., chemical composition, texture, etc.) that are conducive to bonding (e.g., thermal bonding) with the sole structure. Additional bonding and sanding/buffing can be performed, when needed, to sufficiently bond any portions of edges to the strobel or lasting board.

More specifically, in some examples, the strobel and the inner-facing side of the upper (e.g., the inner-facing side of the bonding skirt) can include a textile or a composite textile, including a knit textile, a woven textile, a nonwoven textile, a spacer textile, a foam layer, and any combinations thereof. In at least one example, at least the underneath side of the strobel 120 (e.g., the side that faces away from the foot-receiving cavity) and the inner-facing side 125 of the bonding skirt 130 can include a respective nonwoven textile. In addition, in some examples, the underneath side of the strobel 120 can be adhesively bonded (e.g., via 127) to the inner-facing surface 125 of the upper (e.g., along the bonding skirt 130) via a hotmelt film (e.g., a thermoplastic polyurethane (TPU) hotmelt film). As such, the bonding interface can include fibers of the strobel nonwoven textile and fibers of the inner-facing surface nonwoven textile adhesively bonded via the hotmelt film (e.g., the fibers are mechanically entrapped and/or encapsulated in the hotmelt film). In some examples, hotmelt film can extend to the terminal edge of the upper (e.g., the terminal edge along the portion that is pulled underneath the last and affixed to the strobel) and continuously along the edge (e.g., near 129). In this respect, the adhesive bond between the strobel and the upper can include a sealed edge (e.g., along 129) that operates as a barrier to other materials flowing or wedging into any gaps between the strobel and the bonding skirt and reducing the likelihood of delamination. For example, in a footwear article with this type of sealed edge or sealed bonding interface between the strobel and the inner-facing surface of the upper, the bond can be substantially free (e.g., equal to or less than 10%) of the sole-structure composition (e.g., a thermoplastic composition that is direct injected onto the strobel and upper under pressure and that, absent the sealed bonding interface, could enter gaps or spaces and cause delamination between the upper and strobel).

In addition, as indicated above, any excess hotmelt film (e.g., TPU hotmelt film) can be removed from the underneath side of the stobel that is not covered by the bonding skirt and from along the sealed edge (e.g., if any excess hotmelt has seeped out beyond the terminal edge). Among other things, removal of excess hotmelt (e.g., near 129) can reduce the likelihood that the thermoplastic composition of the hotmelt will soften and/or remelt and mix with the thermoplastic composition of the sole structure when the sole structure is bonded to the lasted upper (e.g., via direct injection molding).

In some examples, after the upper has been bonded (e.g., via 127 in FIG. 5B) to the strobel or lasting board, the upper can be bonded to the sole structure. For example, the sole structure can be bonded to the peripheral margin of the first surface (e.g., facing away from the last), which still includes the one or more properties (e.g., chemical composition, texture, etc.) that are conducive to bonding (e.g., thermal bonding) with the sole structure. In some examples, the sole structure can be directly injected (e.g., through an injection molding operation) onto the lasted upper, such that the sole structure bonds to the peripheral margin of the first surface. For example, a sole-structure mold can be positioned relative to the lasted upper and an edge of the mold can be positioned within the peripheral margin of the first surface (which includes the one or more properties), and the edge of the mold can be spaced apart from the portion having the modified properties (e.g., as a result of the cleaning, corona treatment, primer, ink, etc.). In examples, a thermoplastic composition of the sole structure can be deposited into the mold and can thermally bond to the peripheral margin of the first surface, thereby creating the first zone (e.g., with the first property and bonded to the sole structure), the transition zone (e.g., with the first property and not bonded to the sole structure), and the second zone (e.g., with the second property different from the first property and not bonded to the sole structure).

In some examples, the sole structure that is thermally bonded to the upper (e.g., to the bonding skirt) is substantially free of the thermoplastic composition comprising the hotmelt film used to attach the strobel to the upper. For example, where excess hotmelt is removed (e.g., via sanding or buffing) prior to directly injecting the sole structure onto the upper, the likelihood of the hotmelt thermoplastic composition mixing with the sole structure thermoplastic composition in minimized. As used herein, “substantially free of” in this context can include an amount of hotmelt thermoplastic composition equal to or less than 10% by weight of the sole structure in a sample unit (e.g., 5 mm cube). In examples, by minimizing the hotmelt thermoplastic composition mixed in the sole structure thermoplastic composition, the risk of fissures, cracks, weak points, breakage, and cracking is minimized.

The footwear upper 14 and the sole structure 12 can include various materials. As indicated above, the footwear upper can include a material (e.g., synthetic leather material) having properties (e.g., chemical composition) that are configured to bond with a sole structure (e.g., a plate, a midsole, an outsole, a lasting board, etc.). In some examples, the footwear-upper material, the sole structure, or both the footwear-upper material and the sole structure can include a polyolefin resin composition.

Polyolefin Resin Compositions

As disclosed herein, a polyolefin resin composition is a mixture or blend of one or more polyolefins, optionally with one or more additional ingredients chosen from a polymeric resin modifier, a clarifying agent, a coloring agent, a filler, a processing aid, a non-polyolefin polymer, or any combination thereof.

A variety of polyolefin resin compositions are provided having the abrasion resistance and flexural durability suitable for use in the articles and components described above. In some examples, a polyolefin resin composition is provided including a polyolefin copolymer, and an effective amount of a polymeric resin modifier. The effective amount of the resin modifier provides improved flexural durability while maintaining a suitable abrasion resistance. For example, in some examples the effective amount of the polymeric resin modifier is an amount effective to allow the resin composition to pass a flex test pursuant to the Cold Ross Flex Test using the Plaque Sampling Procedure. At the same time, the resin composition can still have a suitable abrasion loss when measured pursuant to the Abrasion Loss Test using the Neat Material Sampling Procedure. In some examples, the otherwise same resin composition except without the polymeric resin modifier does not pass the cold Ross flex test using the Neat Material Sampling Procedure.

The polymeric resin modifier can provide improved flexural strength, toughness, creep resistance, or flexural durability without a significant loss in the abrasion resistance. In some examples, a resin composition is provided including a polyolefin copolymer, and an effective amount of a polymeric resin modifier, where the effective amount of the polymeric resin modifier is an amount effective to allow the resin composition to pass a flex test pursuant to the Cold Ross Flex Test using the Plaque Sampling Procedure without a significant change in an abrasion loss as compared to an abrasion loss of a second resin composition identical to the resin composition except without the polymeric resin modifier when measured pursuant to the Abrasion Loss Test using the Neat Material Sampling Procedure. In other words, in some examples, the effective amount of the polymeric resin modifier is an amount which is sufficient to produce a resin composition that does not stress whiten or crack during 150,000 flex cycles of the Cold Ross Flex test, while the abrasion resistance of the resin composition has not been significantly degraded and thus is not significantly different than the abrasion resistance of a comparator resin composition which is otherwise identical to the resin composition except that it is free of the polymeric resin modifier.

In some examples, the polyolefin resin composition has an abrasion loss of about 0.05 cubic centimeters (cm³) to about 0.1 cubic centimeters (cm³), about 0.07 cubic centimeters (cm³) to about 0.1 cubic centimeters (cm³), about 0.08 cubic centimeters (cm³) to about 0.1 cubic centimeters (cm³), or about 0.08 cubic centimeters (cm³) to about 0.11 cubic centimeters (cm³) pursuant to the Abrasion Loss Test using the Neat Material Sampling Procedure. In some examples, the resin composition has no significant change in the abrasion loss as compared to an abrasion loss of a second resin composition identical to the resin composition except without the polymeric resin modifier when measured pursuant to the Abrasion Loss Test using the Neat Material Sampling Procedure. A change in abrasion loss, as used herein, is said to not be significant when the change is about 30 percent, about 25 percent, about 20 percent, about 15 percent, about 10 percent, or less when measured pursuant to the Abrasion Loss Test using the Neat Material Sampling Procedure.

The polyolefin resin compositions can include a variety of polyolefin copolymers. The copolymers can be alternating copolymers or random copolymers or block copolymers or graft copolymers. In some examples, the copolymers are random copolymers. In some examples, the copolymer includes a plurality of repeat units, with each of the plurality of repeat units individually derived from an alkene monomer having about 1 to about 6 carbon atoms. In other examples, the copolymer includes a plurality of repeat units, with each of the plurality of repeat units individually derived from a monomer selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-butene, 1-octene, and a combination thereof. In some examples, the polyolefin copolymer includes a plurality of repeat units each individually selected from Formula 1A-1D. In some examples, the polyolefin copolymer includes a first plurality of repeat units having a structure according to Formula 1A, and a second plurality of repeat units having a structure selected from Formula 1B-1D.

In some examples, the polyolefin copolymer includes a plurality of repeat units each individually having a structure according to Formula 2

where R¹ is a hydrogen or a substituted or unsubstituted, linear or branched, C₁-C₁₂ alkyl. C₁-C₆ alkyl, C₁-C₃ alkyl, C₁-C₁₂ heteroalkyl, C₁-C₆ heteroalkyl, or C₁-C₃ heteroalkyl. In some examples, each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A above, and each of the repeat units in the second plurality of repeat units has a structure according to Formula 2 above.

In some examples, the polyolefin copolymer is a random copolymer of a first plurality of repeat units and a second plurality of repeat units, and each repeat unit in the first plurality of repeat units is derived from ethylene and the each repeat unit in the second plurality of repeat units is derived from a second olefin. In some examples, the second olefin is an alkene monomer having about 1 to about 6 carbon atoms. In other examples, the second olefin includes propylene, 4-methyl-1-pentene, 1-butene, or other linear or branched terminal alkenes having about 3 to 12 carbon atoms. In some examples, the polyolefin copolymer contains about 80 percent to about 99 percent, about 85 percent to about 99 percent, about 90 percent to about 99 percent, or about 95 percent to about 99 percent polyolefin repeat units by weight based upon a total weight of the polyolefin copolymer. In some examples, the polyolefin copolymer consists essentially of polyolefin repeat units. In some examples, polymers in the resin composition consist essentially of polyolefin copolymers.

The polyolefin copolymer can include ethylene, i.e. can include repeat units derived from ethylene such as those in Formula 1A. In some examples, the polyolefin copolymer includes about 1 percent to about 5 percent, about 1 percent to about 3 percent, about 2 percent to about 3 percent, or about 2 percent to about 5 percent ethylene by weight based upon a total weight of the polyolefin copolymer.

The polyolefin resin compositions can be made without the need for polyurethanes and/or without the need for polyamides. For example, in some examples the polyolefin copolymer is substantially free of polyurethanes. In some examples, the polymer chains of the polyolefin copolymer are substantially free of urethane repeat units. In some examples, the resin composition is substantially free of polymer chains including urethane repeat units. In some examples, the polyolefin copolymer is substantially free of polyamide. In some examples, the polymer chains of the polyolefin copolymer are substantially free of amide repeat units. In some examples, the resin composition is substantially free of polymer chains including amide repeat units.

In some examples, the polyolefin copolymer includes polypropylene or is a polypropylene copolymer. In some examples, the polymeric component of the resin composition (i.e., the portion of the resin composition that is formed by all of the polymers present in the composition) consists essentially of polypropylene copolymers. In some examples the resin composition is provided including a polypropylene copolymer, and an effective amount of a polymeric resin modifier, wherein the resin composition has an abrasion loss as described above, and wherein the effective amount of the polymeric resin modifier is an amount effective to allow the resin composition to pass a flex test pursuant to the Cold Ross Flex Test using the Plaque Sampling Procedure. In some examples, the effective amount of the polymeric resin modifier is an amount effective to allow the resin composition to pass a flex test pursuant to the Cold Ross Flex Test using the Plaque Sampling Procedure without a significant change in an abrasion loss as compared to an abrasion loss of a second resin composition identical to the resin composition except without the polymeric resin modifier when measured pursuant to the Abrasion Loss Test using the Neat Material Sampling Procedure.

The polypropylene copolymer can include a random copolymer, e.g. a random copolymer of ethylene and propylene. The polypropylene copolymer can include about 80 percent to about 99 percent, about 85 percent to about 99 percent, about 90 percent to about 99 percent, or about 95 percent to about 99 percent propylene repeat units by weight based upon a total weight of the polypropylene copolymer.

In some examples, the polypropylene copolymer includes about 1 percent to about 5 percent, about 1 percent to about 3 percent, about 2 percent to about 3 percent, or about 2 percent to about 5 percent ethylene by weight based upon a total weight of the polypropylene copolymer. In some examples, the polypropylene copolymer is a random copolymer including about 2 percent to about 3 percent of a first plurality of repeat units by weight and about 80 percent to about 99 percent by weight of a second plurality of repeat units based upon a total weight of the polypropylene copolymer; wherein each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A above and each of the repeat units in the second plurality of repeat units has a structure according to Formula 1B above.

The combination of abrasion resistance and flexural durability can be related to the overall crystallinity of the resin composition. In some examples, the resin composition has a percent crystallization (% crystallization) of about 45 percent, about 40 percent, about 35 percent, about 30 percent, about 25 percent or less when measured according to the Crystallinity Test using the Neat Material Sampling Procedure. It has been found that adding the polymeric resin modifier to the resin composition in an amount which only slightly decreases the percent crystallinity of the resin composition as compared to an otherwise identical resin composition except without the polymeric resin modifier can result in resin compositions which are able to pass the Cold Ross Flex test while maintaining a relatively low abrasion loss. In some examples, the polymeric resin modifier leads to a decrease in the percent crystallinity (% crystallinity) of the resin composition. In some examples, the resin composition has a percent crystallization (% crystallization) that is at least 6, at least 5, at least 4, at least 3, or at least 2 percentage points less than a percent crystallization (% crystallization) of the otherwise same resin composition except without the polymeric resin modifier when measured according to the Crystallinity Test using the Neat Material Sampling Procedure.

In some examples, the effective amount of the polymeric resin modifier is about 5 percent to about 30 percent, about 5 percent to about 25 percent, about 5 percent to about 20 percent, about 5 percent to about 15 percent, about 5 percent to about 10 percent, about 10 percent to about 15 percent, about 10 percent to about 20 percent, about 10 percent to about 25 percent, or about 10 percent to about 30 percent by weight based upon a total weight of the resin composition. In some examples, the effective amount of the polymeric resin modifier is about 20 percent, about 15 percent, about 10 percent, about 5 percent, or less by weight based upon a total weight of the resin composition.

The polymeric resin modifier can include a variety of exemplary resin modifiers described herein. In some examples, the polymeric resin modifier is a metallocene catalyzed copolymer primarily composed of isotactic propylene repeat units with about 11 percent by weight-15 percent by weight of ethylene repeat units based on a total weight of metallocene catalyzed copolymer randomly distributed along the copolymer. In some examples, the polymeric resin modifier includes about 10 percent to about 15 percent ethylene repeat units by weight based upon a total weight of the polymeric resin modifier. In some examples, the polymeric resin modifier includes about 10 percent to about 15 percent repeat units according to Formula 1A above by weight based upon a total weight of the polymeric resin modifier. In some examples, the polymeric resin modifier is a copolymer of repeat units according to Formula 1B above, and the repeat units according to Formula 1B are arranged in an isotactic stereochemical configuration.

In some examples, the polymeric resin modifier is a copolymer containing isotactic propylene repeat units and ethylene repeat units. In some examples, the polymeric resin modifier is a copolymer including a first plurality of repeat units and a second plurality of repeat units; wherein each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A above and each of the repeat units in the second plurality of repeat units has a structure according to Formula 1B above, and wherein the repeat units in the second plurality of repeat units are arranged in an isotactic stereochemical configuration.

The term “externally facing” as used in “externally facing layer” refers to the position the element is intended to be in when the element is present in an article during normal use. If the article is footwear, the element is positioned toward the ground during normal use by a wearer when in a standing position, and thus can contact the ground including unpaved surfaces when the footwear is used in a conventional manner, such as standing, walking or running on an unpaved surface. In other words, even though the element may not necessarily be facing the ground during various steps of manufacturing or shipping, if the element is intended to face the ground during normal use by a wearer, the element is understood to be externally-facing or more specifically for an article of footwear, ground-facing. In some circumstances, due to the presence of elements such as traction elements, the externally facing (e.g., ground-facing) surface can be positioned toward the ground during conventional use but may not necessarily come into contact the ground. For example, on hard ground or paved surfaces, the terminal ends of traction elements on the outsole may directly contact the ground, while portions of the outsole located between the traction elements do not. As described in this example, the portions of the outsole located between the traction elements are considered to be externally facing (e.g., ground-facing) even though they may not directly contact the ground in all circumstances.

Synthetic Leather Materials

In various examples, disclosed herein are synthetic leather materials comprising a synthetic leather polymeric coating layer affixed to a synthetic leather textile layer; where the synthetic leather polymeric coating layer comprises a synthetic leather polymeric coating composition; and optionally where the synthetic leather textile layer comprises a fiber or a yarn comprising a synthetic leather fiber/yarn polymeric composition. In some examples, the disclosed synthetic leather materials can optionally further comprise a synthetic leather protective or decorative layer affixed to the polymeric coating layer.

The disclosed synthetic leather materials are believed to possess several advantages, particularly for use in the manufacture of articles, such as articles of footwear or articles of clothing. In some examples, the use of polyolefin resins makes it possible to create synthetic leather materials that are less susceptible to stress whitening. Additionally or alternatively, it is believe that the use of polyolefin resin compositions in the disclosed synthetic leather materials can promote better bonding between other components or materials used in articles, such as articles of footwear or articles of clothing or articles of sporting equipment. For example, in examples in which the disclosed synthetic leather materials, comprising polyolefin resin composition, are used in the manufacture of an upper, such an upper can show enhanced bonding to polyolefin components, such as a sole structure. Accordingly, use of the same or similar polymeric materials for the component and the synthetic leather material increases the ability to recycle both components in the same stream without having to separate them, reducing waste. Additionally or alternatively, use of polyolefin resin compositions in a disclosed synthetic leather provides materials having a lower density as compared to more traditional footwear materials such as TPU. Accordingly, use of a high percentage of these polyolefins in an article of footwear can result in a lighter article of footwear as compared to an article of footwear made using the same amount of a denser polymer such as TPU.

Referring to FIGS. 6A and 6B, FIGS. 6A-6B show cross-sectional view of a disclosed synthetic leather material. FIG. 6A is a cross-sectional view of a disclosed synthetic leather material 600 comprising a synthetic leather textile layer 610, to which is affixed a synthetic leather polymeric coating layer 620. In at least some examples, the cross-sectional view of FIG. 6A can represent a cross-sectional view of the upper 14 in at least the first zone 122a and in the transition zone 122b. FIG. 6B is a cross-sectional view of a disclosed synthetic leather material 600 comprising a synthetic leather textile layer 610, to which is affixed a synthetic leather polymeric coating layer 620, and further comprising a synthetic leather protective or decorative layer 630 affixed to the synthetic leather polymeric coating layer 620. In at least some examples, the cross-sectional view of FIG. 6B can represent a cross-sectional view of the upper 14 in second zone 122c.

FIG. 6A is a cross-sectional view of a disclosed synthetic leather material 600 comprising a synthetic leather textile layer 610, to which is affixed a synthetic leather polymeric coating layer 620, in which it is understood that the synthetic leather polymeric coating layer comprises a synthetic leather polymeric coating composition and the synthetic leather textile layer comprises a fiber or a yarn comprising a synthetic leather fiber/yarn polymeric composition. FIG. 6B is a cross-sectional view of a disclosed synthetic leather material 600 comprising a synthetic leather textile layer 610, to which is affixed a synthetic leather polymeric coating layer 620, and further comprising a synthetic leather protective or decorative layer 630 affixed to the synthetic leather polymeric coating layer 620. It is understood that the synthetic leather textile layer can be any suitable textile, including, but not limited to, a knit textile, a woven textile, a non-woven textile, a crocheted textile, and a braided textile. Knit textiles suitable for use in the disclosed synthetic leather materials include, but are not limited to, a flat knit textile, a circular knit textile, or a weft knit textile.

Referring to FIGS. 7A and 7B, FIGS. 7A-7B show cross-sectional view of a disclosed synthetic leather material. FIG. 7A is a cross-sectional view of a disclosed synthetic leather material 700 comprising a synthetic leather textile layer 710, to which is affixed a first synthetic leather polymeric coating layer 720 and a second synthetic leather polymeric coating composition 730 affixed to the first synthetic leather polymeric coating layer 720. In at least some examples, the cross-sectional view of FIG. 7A can represent a cross-sectional view of the upper 14 in the first zone 122a and in the transition zone 122b. FIG. 7B is a cross-sectional view of a disclosed synthetic leather material 700 comprising a synthetic leather textile layer 710, to which is affixed a first synthetic leather polymeric coating layer 720 and a second synthetic leather polymeric coating composition 730 affixed to the first synthetic leather polymeric coating layer 720, and further comprising a synthetic leather protective or decorative layer 740 affixed to the second synthetic leather polymeric coating layer 730. In at least some examples, the cross-sectional view of FIG. 7B can represent a cross-sectional view of the upper 14 in the second zone 122c.

The disclosed synthetic leather materials can comprise a plurality of synthetic leather polymeric coating layers, where plurality as used herein is two or more coating layers. FIG. 7A is a cross-sectional view of a disclosed synthetic leather material 700 comprising a synthetic leather textile layer 710, to which is affixed a first synthetic leather polymeric coating layer 720, and a second synthetic leather polymeric coating layer 730 affixed to the first synthetic leather polymeric coating layer 720, where it is understood that each of the plurality of the synthetic leather polymeric coating layers comprises a synthetic leather polymeric coating composition and the synthetic leather textile layer comprises a fiber or a yarn comprising a synthetic leather fiber/yarn polymeric composition. As illustrated in FIG. 7A, the synthetic leather textile layer 710 and the first synthetic leather polymeric coating layer 720 can be distinct layers. Alternatively, the combination of the synthetic textile and the first synthetic leather polymeric coating can form a single composite layer.

When a plurality of synthetic leather polymeric coating layers are used, the polymeric component of each polymeric coating (i.e., the portion of the coating material formed of all the polymers present in the material) can comprise the same or different types polymers. Examples of different types of polymers include polyolefins, polyesters, polyethers, polyamides, polyurethanes, and polyacrylates. For examples referring to FIG. 7A, the first synthetic leather polymeric coating composition 720 can be substantially free of the polyolefin resin composition described herein and is composed of one or more thermoplastic polymers such as, for example, polyesters, polyethers, polyamides, and polyurethanes, and the second synthetic leather polymeric coating composition 730 comprises a polyolefin resin composition as described herein.

Alternatively, the first synthetic leather polymeric coating composition 720 comprises a polyolefin resin composition as described herein and the second synthetic leather polymeric coating composition 730 is substantially free of the polyolefin resin composition described herein and is composed of one or more polymers such as, for example, polyesters, polyethers, polyamides, and polyurethanes as provided herein.

Alternatively, the first synthetic leather polymeric coating composition 720 and the second synthetic leather polymeric coating composition 730 are each a polyolefin resin composition as described herein, where the first synthetic leather polymeric coating composition and the second synthetic leather polymeric coating compositions comprise the same or different polyolefin resin compositions. For example, when the first and second polymeric coating compositions comprise different polyolefin resin compositions, the polymeric component of the different polyolefin resin compositions can comprise polyolefins having different chemical structures, or can comprise polyolefins having the same chemical structures but in different concentrations.

FIG. 7B is a cross-sectional view of a disclosed synthetic leather material 700 comprising a synthetic leather textile layer 710, to which is affixed a first synthetic leather polymeric coating layer 720, and a second synthetic leather polymeric coating layer 730 affixed to the first synthetic leather polymeric coating layer 720, and further comprising a synthetic leather protective or decorative layer 740 affixed to the synthetic leather polymeric coating layer 730. It is understood that the synthetic leather textile layer can be any suitable textile, including, but not limited to, a textile chosen from a knit textile, a woven textile, a non-woven textile, a crocheted textile, or a braided textile. Knit textiles suitable for use in the disclosed synthetic leather materials include, but are not limited to, a knit textile chosen from a flat knit textile, a circular knit textile, or a weft knit textile.

The thickness of the synthetic leather polymeric coating layer can modified as needed. In the case when two or more synthetic leather polymeric coating layers are used, the thickness of each layer can vary or can be modified. Referring to FIG. 7A, in one example, the thickness of the first synthetic leather polymeric coating composition 720 is less than thickness of the second synthetic leather polymeric coating composition 730, for example at least 5 percent less. In another example, the thickness of the first synthetic leather polymeric coating composition 720 is greater than thickness of the second synthetic leather polymeric coating composition 730, for example, at least 5 percent greater. In another example, the thickness of the first synthetic leather polymeric coating composition 720 is equal to the thickness of the second synthetic leather polymeric coating composition 730.

In one example, the synthetic leather polymeric coating layer can be a film that is affixed to the synthetic leather textile layer. For example, the polyolefin resin compositions described herein can be extruded into a film that is subsequently affixed to the synthetic leather textile layer. In other examples, two or more different films can be extruded and sequentially affixed to the synthetic leather textile layer. For example, the first and second synthetic leather polymeric coating compositions depicted in FIGS. 7A and 7B can each be films that have been affixed to the synthetic leather textile layer.

The disclosed synthetic leather materials can comprise a disclosed polyolefin resin composition in one or more of the synthetic leather textile layer, the synthetic leather polymeric coating, and/or the synthetic leather protective or decorative layer. As disclosed herein above, a disclosed polyolefin resin composition can comprise a polyolefin resin with a polymeric resin modified, and optionally with a clarifying agent), to form one or more layers of a synthetic leather material.

For example, the disclosed polyolefin resin compositions can be used to form one or more films that are combined with a non-woven textile to form an outer skin of the synthetic leather material. In other instances, the disclosed polyolefin resins can be used to form fibers or filaments, which in turn can be used to form a yarn, which can be used to form a non-woven textile portion of the synthetic leather material. In a further instance, the disclosed polyolefin resins can be used to form both the skin layer and the non-woven textile layer.

In some examples, the synthetic leather polymeric coating layer can be porous (e.g., foamed). Alternatively, or in combination with a porous synthetic leather polymer coating layer, a porous polymer layer can be positioned between the synthetic leather coating layer and the synthetic leather textile layer. Optionally, in various examples, a clear or colored protective or decorative coating may be applied or affixed to the outer surface of the polymeric layer.

In some examples, the clear or colored protective or decorative coating (e.g., 129 and 122c in FIGS. 1 through 3) can include different properties (e.g., different polymeric composition properties) as compared to the polyolefin resin composition in one or more of the synthetic leather textile layer and/or the synthetic leather polymeric coating. As such, it can be advantageous to include the bonding zone 122a, and optionally the transition zone 122b, which can be free of the clear or colored protective or decorative coating, to increase the likelihood of a stronger bond between the upper (e.g., in the bonding zone) and the sole (e.g., which can also include a polyolefin resin composition similar to the bonding zone).

Although polyester (PET) yarns or fibers can be used manufacture of a synthetic leather textile layer, e.g., used in a fiber or yarn used to make the textile layer, it is possible to use other types of synthetic fibers, natural fibers, or regenerated fibers. Moreover, the synthetic leather textile layer can utilize one or more fibers or yarns comprising a thermoplastic polymeric composition as disclosed herein. The use of microfibers in the synthetic leather textile layer can improve the hand (softness and flexibility) of the synthetic leather material.

In some instances, the synthetic leather polymeric coating layer can comprise a synthetic leather polymeric coating composition comprising a disclosed thermoplastic polymer composition. For example, a synthetic leather polymeric coating layer can comprise a synthetic leather polymeric coating composition comprising a polyurethane or a polyvinylchloride. It may be desirable to use a polyurethane-based synthetic leather materials in articles of footwear, and a polyvinylchloride-based synthetic leather materials are commonly used in sporting equipment. In other instances, the synthetic leather polymeric coating layer can comprise a synthetic leather polymeric coating composition comprising a disclosed polyolefin resin composition.

As described above, the synthetic leather material includes a synthetic leather textile layer including a textile (e.g., a first textile). The textile can be a nonwoven textile, a knit textile, or a woven textile. A “textile” may be defined as any material manufactured from fibers, filaments, or yarns characterized by flexibility, fineness, and a high ratio of length to thickness. Textiles generally fall into two categories. The first category includes textiles produced directly from webs of filaments or fibers by randomly interlocking to construct non-woven fabrics and felts. The second category includes textiles formed through a mechanical manipulation of yarn, thereby producing a woven fabric, a knitted fabric, a braided fabric, a crocheted fabric, and the like.

The terms “filament,” “fiber,” or “fibers” as used herein refer to materials that are in the form of discrete elongated pieces that are significantly longer than they are wide. The fiber can include natural, manmade or synthetic fibers. The fibers may be produced by conventional techniques, such as extrusion, electrospinning, interfacial polymerization, pulling, and the like. The fibers can include carbon fibers, boron fibers, silicon carbide fibers, titania fibers, alumina fibers, quartz fibers, glass fibers, such as E, A, C, ECR, R, S, D, and NE glasses and quartz, or the like. The fibers can be fibers formed from synthetic polymers capable of forming fibers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters, polyolefins (e.g., polyethylene, polypropylene), aromatic polyamides (e.g., an aramid polymer such as para-aramid fibers and meta-aramid fibers), aromatic polyimides, polybenzimidazoles, polyetherimides, polytetrafluoroethylene, acrylic, modacrylic, poly(vinyl alcohol), polyamides, polyurethanes, and copolymers such as polyether-polyurea copolymers, polyester-polyurethanes, polyether block amide copolymers, or the like. The fibers can be natural fibers (e.g., silk, wool, cashmere, vicuna, cotton, flax, hemp, jute, sisal). The fibers can be man-made fibers from regenerated natural polymers, such as rayon, lyocell, acetate, triacetate, rubber, and poly(lactic acid).

The fibers can have an indefinite length. For example, man-made and synthetic fibers are generally extruded in substantially continuous strands. Alternatively, the fibers can be staple fibers, such as, for example, cotton fibers or extruded synthetic polymer fibers can be cut to form staple fibers of relatively uniform length. The staple fiber can have a have a length of about 1 millimeter to 100 centimeters or more as well as any increment therein (e.g., 1 millimeter increments).

The fiber can have any of a variety of cross-sectional shapes. Natural fibers can have a natural cross-section, or can have a modified cross-sectional shape (e.g., with processes such as mercerization). Man-made or synthetic fibers can be extruded to provide a strand having a predetermined cross-sectional shape. The cross-sectional shape of a fiber can affect its properties, such as its softness, luster, and wicking ability. The fibers can have round or essentially round cross sections. Alternatively, the fibers can have non-round cross sections, such as flat, oval, octagonal, rectangular, wedge-shaped, triangular, dog-bone, multi-lobal, multi-channel, hollow, core-shell, or other shapes.

The fiber can be processed. For example, the properties of fibers can be affected, at least in part, by processes such as drawing (stretching) the fibers, annealing (hardening) the fibers, and/or crimping or texturizing the fibers.

The fiber can be a multi-component fiber, such as one comprising two or more co-extruded polymeric materials. The two or more co-extruded polymeric materials can be extruded in a core-sheath, islands-in-the-sea, segmented-pie, striped, or side-by-side configuration. A multi-component fiber can be processed in order to form a plurality of smaller fibers (e.g., microfibers) from a single fiber, for example, by remove a sacrificial material.

As used herein, the term “yarn” refers to an assembly formed of one or more fibers, wherein the strand has a substantial length and a relatively small cross-section, and is suitable for use in the production of textiles by hand or by machine, including textiles made using weaving, knitting, crocheting, braiding, sewing, embroidery, or ropemaking techniques. Thread is a type of yarn commonly used for sewing.

Yarns can be made using fibers formed of natural, man-made and synthetic materials. Synthetic fibers are most commonly used to make spun yarns from staple fibers, and filament yarns. Spun yarn is made by arranging and twisting staple fibers together to make a cohesive strand. The process of forming a yarn from staple fibers typically includes carding and drawing the fibers to form sliver, drawing out and twisting the sliver to form roving, and spinning the roving to form a strand. Multiple strands can be plied (twisted together) to make a thicker yarn. The twist direction of the staple fibers and of the plies can affect the final properties of the yarn. A filament yarn can be formed of a single long, substantially continuous filament, which is conventionally referred to as a “monofilament yarn,” or a plurality of individual filaments grouped together. A filament yarn can also be formed of two or more long, substantially continuous filaments which are grouped together by grouping the filaments together by twisting them or entangling them or both. As with staple yarns, multiple strands can be plied together to form a thicker yarn.

Once formed, the yarn can undergo further treatment such as texturizing, thermal or mechanical treating, or coating with a material such as a synthetic polymer. The fibers, yarns, or textiles, or any combination thereof, used in the disclosed articles can be sized. Sized fibers, yarns, and/or textiles are coated on at least part of their surface with a sizing composition selected to change the absorption or wear characteristics, or for compatibility with other materials. The sizing composition facilitates wet-out and wet-through of the coating or resin upon the surface and assists in attaining desired physical properties in the final article. An exemplary sizing composition can comprise, for example, epoxy polymers, urethane-modified epoxy polymers, polyester polymers, phenol polymers, polyamide polymers, polyurethane polymers, polycarbonate polymers, polyetherimide polymers, polyamideimide polymers, polystylylpyridine polymers, polyimide polymers bismaleimide polymers, polysulfone polymers, polyethersulfone polymers, epoxy-modified urethane polymers, polyvinyl alcohol polymers, polyvinyl pyrrolidone polymers, and mixtures thereof.

Two or more yarns can be combined, for example, to form composite yarns such as single- or double-covered yarns, and core-spun yarns. Accordingly, yarns may have a variety of configurations that generally conform to the descriptions provided herein.

The yarn can comprise at least one thermoplastic material (e.g., one or more of the fibers can be made of thermoplastic material). The yarn can be made of a thermoplastic material. The yarn can be coated with a layer of a material such as a thermoplastic material.

The linear mass density or weight per unit length of a yarn can be expressed using various units, including denier (D) and tex. Denier is the mass in grams of 9000 meters of yarn. The linear mass density of a single filament of a fiber can also be expressed using denier per filament (DPF). Tex is the mass in grams of a 1000 meters of yarn. Decitex is another measure of linear mass, and is the mass in grams for a 10,000 meters of yarn.

As used herein, tenacity is understood to refer to the amount of force (expressed in units of weight, for example: pounds, grams, centinewtons or other units) needed to break a yarn (i.e., the breaking force or breaking point of the yarn), divided by the linear mass density of the yarn expressed, for example, in (unstrained) denier, decitex, or some other measure of weight per unit length. The breaking force of the yarn is determined by subjecting a sample of the yarn to a known amount of force, for example, using a strain gauge load cell such as an INSTRON brand testing system (Norwood, MA, USA). Yarn tenacity and yarn breaking force are distinct from burst strength or bursting strength of a textile, which is a measure of how much pressure can be applied to the surface of a textile before the surface bursts.

Generally, in order for a yarn to withstand the forces applied in an industrial knitting machine, the minimum tenacity required is approximately 1.5 grams per Denier. Most yarns formed from commodity polymeric materials generally have tenacities in the range of about 1.5 grams per Denier to about 4 grams per Denier. For example, polyester yarns commonly used in the manufacture of knit uppers for footwear have tenacities in the range of about 2.5 to about 4 grams per Denier. Yarns formed from commodity polymeric materials which are considered to have high tenacities generally have tenacities in the range of about 5 grams per Denier to about 10 grams per Denier. For example, commercially available package dyed polyethylene terephthalate yarn from National Spinning (Washington, NC, USA) has a tenacity of about 6 grams per Denier, and commercially available solution dyed polyethylene terephthalate yarn from Far Eastern New Century (Taipei, Taiwan) has a tenacity of about 7 grams per Denier. Yarns formed from high performance polymeric materials generally have tenacities of about 11 grams per Denier or greater. For example, yarns formed of aramid fiber typically have tenacities of about 20 grams per Denier, and yarns formed of ultra-high molecular weight polyethylene (UHMWPE) having tenacities greater than 30 grams per Denier are available from Dyneema (Stanley, NC, USA) and Spectra (Honeywell-Spectra, Colonial Heights, VA, USA).

Various techniques exist for mechanically manipulating yarns to form a textile. Such techniques include, for example, interweaving, intertwining and twisting, and interlooping. Interweaving is the intersection of two yarns that cross and interweave at right angles to each other. The yarns utilized in interweaving are conventionally referred to as “warp” and “weft.” A woven textile includes include a warp yarn and a weft yarn. The warp yarn extends in a first direction, and the weft strand extends in a second direction that is substantially perpendicular to the first direction. Intertwining and twisting encompasses various procedures, such as braiding and knotting, where yarns intertwine with each other to form a textile. Interlooping involves the formation of a plurality of columns of intermeshed loops, with knitting being the most common method of interlooping. The textile may be primarily formed from one or more yarns that are mechanically-manipulated, for example, through interweaving, intertwining and twisting, and/or interlooping processes, as mentioned above.

The textile can be a nonwoven textile. Generally, a nonwoven textile or fabric is a sheet or web structure made from fibers and/or yarns that are bonded together. The bond can be a chemical and/or mechanical bond, and can be formed using heat, solvent, adhesive or a combination thereof. Exemplary nonwoven fabrics are flat or tufted porous sheets that are made directly from separate fibers, molten plastic and/or plastic film. They are not made by weaving or knitting and do not necessarily require converting the fibers to yarn, although yarns can be used as a source of the fibers. Nonwoven textiles are typically manufactured by putting small fibers together in the form of a sheet or web (similar to paper on a paper machine), and then binding them either mechanically (as in the case of felt, by interlocking them with serrated or barbed needles, or hydro-entanglement such that the inter-fiber friction results in a stronger fabric), with an adhesive, or thermally (by applying binder (in the form of powder, paste, or polymer melt) and melting the binder onto the web by increasing temperature). A nonwoven textile can be made from staple fibers (e.g., from wetlaid, airlaid, carding/crosslapping processes), or extruded fibers (e.g., from meltblown or spunbond processes, or a combination thereof), or a combination thereof. Bonding of the fibers in the nonwoven textile can be achieved with thermal bonding (with or without calendering), hydro-entanglement, ultrasonic bonding, needlepunching (needlefelting), chemical bonding (e.g., using binders such as latex emulsions or solution polymers or binder fibers or powders), meltblown bonding (e.g., fiber is bonded as air attenuated fibers intertangle during simultaneous fiber and web formation), spun-bond, non-woven, carded non-woven, and a melt-blown non-woven.

In some example, the synthetic leather textile layer can include fibers or filaments comprising or consisting essentially of a fiber/yarn polymeric composition. The fiber/yarn polymeric composition can be thermoplastic. The fiber/yarn polymeric composition can include a polyolefin, or a polyamide, or a polyurethane, or a polyester, or a polyether polymer, or any combination thereof. The polymeric component of the fiber/yarn polymeric composition can consist essentially of one or more polyesters. The polymeric component of the fiber/yarn polymeric composition can consist essentially of one or more polyolefins. The one or more polyolefins can include or consist essentially of one or more polypropylenes.

The synthetic leather material can have a thickness of about 0.8 millimeters to about 2.5 millimeters, or about 0.9 millimeters to about 2.2 millimeters, or about 1 millimeter to about 2 millimeters, or about 1.2 millimeters to about 1.4 millimeters, or about 1.3 millimeters to about 1.5 millimeters, or about 1.4 millimeters to about 1.6 millimeters. The synthetic leather material can have a weight of about 400 to about 1,000, or about 450 to about 900, or about 500 to about 700 grams per square meter. The synthetic leather material can have a Mullen burst score in the range of 15 to 25, or of 10 to 22, as determined according to the Mullen Burst Test, described herein.

Various methods can be used to manufacture a disclosed synthetic leather material. In general, these methods have a step of bringing together the synthetic leather textile layer with the synthetic leather polymeric coating layer and/or the synthetic leather polymeric coating composition. In one example, the synthetic leather polymeric coating can be applied to the synthetic leather textile layer as a liquid, followed by curing or drying. The particular approach to provide the liquid polymeric coating layer(s) can be any suitable method for application of a liquid polymer composition to a textile layer, including, but not limited to, spreading onto or spraying onto the textile layer. In some instances, depending on the properties of the liquid and the manufacturing process, the liquid polymeric coating layer may impregnate the textile layer. In another example, the polymeric coating can be initially formed into a film, and the film is then affixed to the textile layer, either using a separate adhesive layer, or by applying a solvent which softens the film and pressure, or by applying heat to soften the film and pressure. In some examples, affixing the synthetic leather textile layer to the synthetic leather polymeric coating layer comprises applying a liquid synthetic leather polymeric coating composition to the synthetic leather textile layer, and allowing the liquid synthetic leather polymeric coating composition to cure to a solid synthetic leather polymeric coating composition while in contact with the synthetic leather textile layer, thereby forming the synthetic leather polymeric coating layer and mechanically bonding the synthetic leather coating layer to the synthetic leather textile layer

In other examples, when a plurality of synthetic leather polymeric coating layers and/or synthetic leather polymeric coating compositions are to be applied to the synthetic leather textile layer, each polymeric coating layer or composition can be applied sequentially to the synthetic leather textile. In some examples, one or more layers of polymeric coating compositions or layers can be applied to the synthetic leather textile layer in the form of a film, including a single layer film or a multi-layer film. For example, the single layer film can be an extruded film, or the multi-layer film can be a co-extruded multi-layer film or a laminated multi-layer film. In other examples, one or more layers of polymeric coatings can be applied to the synthetic leather textile layer in the form of a liquid. The particular approach to provide the liquid polymeric coating layer(s) can be any suitable method for application of a liquid polymer composition to a substrate, including, but not limited to, spreading onto or spraying onto a polymeric coating layer that has been previously applied to the textile layer.

It is to be understood that the method of making a disclosed synthetic leather material can further include a step of texturizing the synthetic leather material. The texture can be applied during formation of the coating layer, or during adhesion of the coating layer and the textile layer to each other, or can be applied after affixing the textile layer and the coating layer to each other. The texture can be applied using a roller (e.g., a heated metal roller), or using a textured release paper.

In various examples, the disclosed synthetic leather material uses a composition comprising a disclosed polyolefin resin, e.g., a polyolefin copolymer and a polymeric resin modifier, optionally with a clarifying agent, as the coating layer of the synthetic leather material, or as a clear or colored protective or decorative coating applied to the outer surface of the polymeric layer, or both.

In various examples, the disclosed synthetic leather material uses fibers comprising a disclosed polyolefin resin, e.g., a polyolefin copolymer and a polymeric resin modifier, optionally with a clarifying agent, in the textile layer, optionally with the polyolefin-based coating or protective/decorative coating or both.

A polyolefin-based coating or protective/decorative layer can be formed by extruding a disclosed polyolefin resin composition into one or more films, which can be affixed to a textile layer.

In one example, a dispersion of a polyolefin resin composition, for example a water-borne dispersion, can be sprayed onto the textile layer, impregnating the textile layer and forming the synthetic leather material.

As noted above, it is believed that one advantage of using a disclosed polyolefin resin composition to form an outer surface of a disclosed synthetic leather material (i.e., the polymeric coating layer or the protective/decorative layer on the “top” or “front” side of the synthetic leather material) is that it provides an outer layer of the synthetic leather material which is easier to bond to other polyolefin-based polymers. For example, the bond score of a synthetic leather material having polyolefin-based solid resin components (e.g., a polypropylene-based plate) is improved as compared to PU-based or PVC-based synthetic leather materials.

In various further examples, it is believed that an advantage of using a disclosed polyolefin resin composition to form at least a portion of the fibers present in the synthetic leather textile layer of the synthetic leather (the “bottom” or “back” side of the synthetic leather material) is that it creates an outer layer of the synthetic leather material which is easier to bond to other polyolefin-based polymers. For example, the bond score with polyolefin-based solid resin components (such as a polypropylene-based plate) is improved as compared to PU-based or PVC-based synthetic leather materials.

Additionally or alternatively, when a synthetic leather material having a synthetic leather polymeric coating layer and/or a synthetic leather protective/decorative layer comprising a disclosed polyolefin resin composition, is that the fibers present in the textile layer of the synthetic leather material (the “bottom” or “back” side of the synthetic leather material) can be formed of other polymers, such as TPUs, polyesters or nylons, and can be substantially free of polyolefin-based fibers. In this instance, the “front” of the synthetic leather material can be easier to bond to other polyolefin-based polymers, while the “back” of the synthetic leather material is easier to bond to other polyester or nylon-based materials.

In some examples, the synthetic leather textile layer comprises lower-melting thermoplastic fibers or yarns (e.g., having a melting or softening temperature below about 150 degrees centigrade, or having a melting or softening temperature that is at least 20 degrees centigrade lower than the softening temperature of the polymeric coating layer and, if present, the protective/decorative layer). In such an instance, it is believed that an advantage of using lower-melting thermoplastic fibers or yarns in the synthetic leather textile layer is that it provides a synthetic leather material in which the “back” textile layer can be thermally bonded to another component, without affecting the appearance of the “front” of the synthetic leather material.

In has been previously observed that conventional materials comprising polyolefin resins that coloration of polyolefins can be more difficult than for other polymers. For example, unlike many synthetic, natural and regenerated fibers, it can be difficult to package dye polyolefin fibers. However, such issues can be obviated in the present disclosure by using package dyed fibers that are substantially free of polyolefins in the textile layer in combination with a clear or nearly clear polyolefin-based coating layer.

Polymeric Materials

In various examples, disclosed herein are compositions and materials, e.g., textiles, polymeric coating layers, and protective or decorative layers that comprise one or more polymeric materials, such as a thermoplastic polymeric material. The polymers utilized in preparation of the disclosed compositions and materials can include polymers of the same or different types of monomers (e.g., homopolymers and copolymers, including terpolymers). In certain examples, the polymers can include different monomers randomly distributed in the polymer (e.g., a random co-polymer). The term “polymer” refers to a polymerized molecule having one or more monomer species that can be the same or different. When the monomer species are the same, the polymer can be termed homopolymer and when the monomers are different, the polymer can be referred to as a copolymer. The term “copolymer” is a polymer having two or more types of monomer species, and includes terpolymers (i.e., copolymers having three monomer species). In an example, the “monomer” can include different functional groups or segments, but for simplicity is generally referred to as a monomer.

For example, the polymer can be a polymer having repeating polymeric units of the same chemical structure (segments) which are relatively harder (hard segments), and repeating polymeric segments which are relatively softer (soft segments). In various examples, the polymer has repeating hard segments and soft segments. Physical crosslinks can be present within the segments or between the segments or both within and between the segments. Particular examples of hard segments include isocyanate segments. Particular examples of soft segments include an alkoxy group such as polyether segments and polyester segments. As used herein, the polymeric segment can be referred to as being a particular type of polymeric segment such as, for example, an isocyanate segment (e.g., diisocyante segment), an alkoxy polyamide segment (e.g., a polyether segment, a polyester segment), and the like. It is understood that the chemical structure of the segment is derived from the described chemical structure. For example, an isocyanate segment is a polymerized unit including an isocyanate functional group. When referring to polymeric segments of a particular chemical structure, the polymer can contain up to 10 mole percent of segments of other chemical structures. For example, as used herein, a polyether segment is understood to include up to 10 mole percent of non-polyether segments.

In certain examples, the polymer can be a polyurethane or a thermoplastic polyurethane (also referred to as “TPU”). The polyurethane polymer can include hard and soft segments. In examples, the hard segments can comprise or consist of isocyanate segments (e.g., diisocyanate segments). In the same or alternative examples, the soft segments can comprise or consist of alkoxy segments (e.g., polyether segments, or polyester segments, or a combination of polyether segments and polyester segments). In a particular example, the thermoplastic material can comprise or consist essentially of an elastomeric thermoplastic polyurethane having repeating hard segments and repeating soft segments.

Polyamides

In various examples, the polymer can comprise a polyamide, including a thermoplastic polyamide. The polyamide can be a polyamide homopolymer having repeating polyamide segments of the same chemical structure. Alternatively, the polyamide can comprise a number of polyamide segments having different polyamide chemical structures (e.g., polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, etc.). The polyamide segments having different chemical structure can be arranged randomly, or can be arranged as repeating blocks.

The polyamide can be a co-polyamide (i.e., a co-polymer including polyamide segments and non-polyamide segments). The polyamide segments of the co-polyamide can comprise or consist of polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, or any combination thereof. The polyamide segments of the co-polyamide can be arranged randomly, or can be arranged as repeating segments. In a particular example, the polyamide segments can comprise or consist of polyamide 6 segments, or polyamide 12 segments, or both polyamide 6 segment and polyamide 12 segments. In the example where the polyamide segments of the co-polyamide include of polyamide 6 segments and polyamide 12 segments, the segments can be arranged randomly. The non-polyamide segments of the co-polyamide can comprise or consist of polyether segments, polyester segments, or both polyether segments and polyester segments. The co-polyamide can be a co-polyamide, or can be a random co-polyamide. The thermoplastic copolyamide can be formed from the polycodensation of a polyamide oligomer or prepolymer with a second oligomer prepolymer to form a copolyamide (i.e., a co-polymer including polyamide segments. Optionally, the second prepolymer can be a hydrophilic prepolymer.

In examples, the polyamide can be a block co-polyamide. For example, the block co-polyamide can have repeating hard segments, and repeating soft segments. The hard segments can comprise polyamide segments, and the soft segments can comprise non-polyamide segments. The polymer can be an elastomeric co-polyamide comprising or consisting of block co-polyamides having repeating hard segments and repeating soft segments. In block co-polymers, including block co-polymers having repeating hard segments and soft segments, physical crosslinks can be present within the segments or between the segments or both within and between the segments. In one example, the polyamide can be a poly(ether block amide) polymer.

Exemplary commercially available polyamide copolymers include, but are not limited to, those available under the tradenames of “VESTAMID” (Evonik Industries); “PLATAMID” (Arkema), e.g., product code H2694; “PEBAX” (Arkema), e.g., product code “PEBAX MH1657” and “PEBAX MV1074”; “PEBAX RNEW” (Arkema); “GRILAMID” (EMS-Chemie AG), or also to other similar materials produced by various other suppliers.

Polyesters

In examples, the polymers can comprise a polyester, including a thermoplastic polyester. The polyester can be formed by reaction of one or more carboxylic acids, or its ester-forming derivatives, with one or more bivalent or multivalent aliphatic, alicyclic, aromatic or araliphatic alcohols or a bisphenol. The polyester can be a polyester homopolymer having repeating polyester segments of the same chemical structure. Alternatively, the polyester can comprise a number of polyester segments having different polyester chemical structures (e.g., polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, etc.). The polyester segments having different chemical structure can be arranged randomly, or can be arranged as repeating blocks.

In some examples, the polyester is a polybutylene terephthalate (PBT), a polytrimethylene terephthalate, a polyhexamethylene terephthalate, a poly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate (PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), a polybutylene naphthalate (PBN), a liquid crystal polyester, or a blend or mixture of two or more of the foregoing.

The polyester can be a co-polyester (i.e., a co-polymer including polyester segments and non-polyester segments). The co-polyester can be an aliphatic co-polyester (i.e., a co-polyester in which both the polyester segments and the non-polyester segments are aliphatic). Alternatively, the co-polyester can include aromatic segments. The polyester segments of the co-polyester can comprise or consist of polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, or any combination thereof. The polyester segments of the co-polyester can be arranged randomly, or can be arranged as repeating blocks.

For example, the polyester can be a block co-polyester having repeating blocks of polymeric units of the same chemical structure (segments) which are relatively harder (hard segments), and repeating blocks of polymeric segments which are relatively softer (soft segments). In block co-polyesters, including block co-polyesters having repeating hard segments and soft segments, physical crosslinks can be present within the blocks or between the blocks or both within and between the blocks. In one example, material can comprise or consist essentially of an elastomeric thermoplastic co-polyester having repeating blocks of hard segments and repeating blocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consist of polyether segments, polyamide segments, or both polyether segments and polyamide segments. The co-polyester can be a block co-polyester, or can be a random co-polyester. The thermoplastic co-polyester can be formed from the polycodensation of a polyester oligomer or prepolymer with a second oligomer prepolymer to form a block copolyester. Optionally, the second prepolymer can be a hydrophilic prepolymer. For example, the co-polyester can be formed from the polycondensation of terephthalic acid or naphthalene dicarboxylic acid with ethylene glycol, 1,4-butanediol, or 1-3 propanediol. Examples of co-polyesters include polyethelene adipate, polybutylene succinate, poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene napthalate, and combinations thereof. In a particular example, the co-polyamide can comprise or consist of polyethylene terephthalate.

In some examples, the polyester is a block copolymer comprising segments of one or more of polybutylene terephthalate (PBT), a polytrimethylene terephthalate, a polyhexamethylene terephthalate, a poly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate (PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), a polybutylene naphthalate (PBN), and a liquid crystal polyester. For example, a suitable thermoplastic polyester that is a block copolymer can be a PET/PEI copolymer, a polybutylene terephthalate/tetraethylene glycol copolymer, a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, or a blend or mixture of any of the foregoing.

Polyolefins

In some examples, the polymers can comprise or consist essentially of a polyolefin, including a thermoplastic polyolefin. Exemplary polyolefins include, but are not limited to, polyethylene, polypropylene, and thermoplastic olefin elastomers (e.g., metallocene-catalyzed block copolymers of ethylene and α-olefins having 4 to about 8 carbon atoms). In a further example, the polyolefin is a polymer comprising a polyethylene, an ethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene, a poly-4-methylpent-1-ene, a polyisoprene, a polybutadiene, an ethylene-methacrylic acid copolymer, and an olefin elastomer such as a dynamically cross-linked polymer obtained from polypropylene (PP) and an ethylene-propylene rubber (EPDM), and blends or mixtures of the foregoing. Further exemplary polyolefins include polymers of cycloolefins such as cyclopentene or norbornene.

It is to be understood that polyethylene, which optionally can be crosslinked, is inclusive a variety of polyethylenes, including, but not limited to, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), and blends or mixtures of any the foregoing polyethylenes. A polyethylene can also be a polyethylene copolymer derived from monomers of monolefins and diolefins copolymerized with a vinyl, acrylic acid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinyl acetate. Polyolefin copolymers comprising vinyl acetate-derived units can be a high vinyl acetate content copolymer, e.g., greater than about 50 wt percent vinyl acetate-derived composition.

In some examples, the polyolefin can be formed through free radical, cationic, and/or anionic polymerization by methods well known to those skilled in the art (e.g., using a peroxide initiator, heat, and/or light). In a further example, the disclosed thermoplastic polyolefin can be prepared by radical polymerization under high pressure and at elevated temperature. Alternatively, the polyolefin can be prepared by catalytic polymerization using a catalyst that normally contains one or more metals from group IVb, Vb, VIb or VIII metals. The catalyst usually has one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that can be either p- or s-coordinated complexed with the group IVb, Vb, VIb or VIII metal. In various examples, the metal complexes can be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium (III) chloride, alumina, or silicon oxide. It is understood that the metal catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators can be used, typically a group 1a, 11a and/or Illa metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes. The activators can be modified conveniently with further ester, ether, amine or silyl ether groups.

Suitable polyolefins can be prepared by polymerization of monomers of monolefins and diolefins as described herein. Exemplary monomers that can be used to prepare disclosed thermoplastic polyolefin include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixtures thereof.

Suitable ethylene-α-olefin copolymers can be obtained by copolymerization of ethylene with an α-olefin such as propylene, butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like having carbon numbers of 3 to 12.

Suitable dynamically cross-linked polymers can be obtained by cross-linking a rubber component as a soft segment while at the same time physically dispersing a hard segment such as PP and a soft segment such as EPDM by using a kneading machine such as a Banbury mixer and a biaxial extruder.

In some examples, the polyolefin can be a mixture of polyolefins, such as a mixture of two or more polyolefins disclosed herein above. For example, a suitable mixture of polyolefins can be a mixture of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) or mixtures of different types of polyethylene (for example LDPE/HDPE).

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

In some examples, the polyolefin can be a polypropylene homopolymer, a polypropylene copolymers, a polypropylene random copolymer, a polypropylene block copolymer, a polyethylene homopolymer, a polyethylene random copolymer, a polyethylene block copolymer, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a medium density polyethylene, a high density polyethylene (HDPE), or blends or mixtures of one or more of the preceding polymers.

In some examples, the polyolefin is a polypropylene. The term “polypropylene,” as used herein, is intended to encompass any polymeric composition comprising propylene monomers, either alone or in mixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers (such as ethylene, butylene, and the like). Such a term also encompasses any different configuration and arrangement of the constituent monomers (such as atactic, syndiotactic, isotactic, and the like). Thus, the term as applied to fibers is intended to encompass actual long strands, tapes, threads, and the like, of drawn polymer. The polypropylene can be of any standard melt flow (by testing); however, standard fiber grade polypropylene resins possess ranges of Melt Flow Indices between about 1 and 1000.

In some examples, the polyolefin is a polyethylene. The term “polyethylene,” as used herein, is intended to encompass any polymeric composition comprising ethylene monomers, either alone or in mixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers (such as propylene, butylene, and the like). Such a term also encompasses any different configuration and arrangement of the constituent monomers (such as atactic, syndiotactic, isotactic, and the like). Thus, the term as applied to fibers is intended to encompass actual long strands, tapes, threads, and the like, of drawn polymer. The polyethylene can be of any standard melt flow (by testing); however, standard fiber grade polyethylene resins possess ranges of Melt Flow Indices between about 1 and 1000.

Methods of Making Resin Compositions

In various examples, this disclosure describes various polymeric compositions, including polyolefin resin compositions, synthetic leather polymeric coating compositions, and fiber/yarn polymeric compositions. The polymeric compositions can be made by dry blending, or by melt blending the various ingredients. Methods of blending polymers can include film blending in a press, blending in a mixer (e.g. mixers commercially available under the tradename “HAAKE” from Thermo Fisher Scientific, Waltham, MA), solution blending, hot melt blending, and extruder blending. In some examples, the polymeric resin modifier and polyolefin copolymer are miscible such that they can be readily mixed by the screw in the injection barrel during injection molding, e.g. without the need for a separate blending step.

The methods can further include extruding the polymeric composition to form an extruded polymeric composition. The methods of extruding the polymeric composition can include manufacturing long products of relatively constant cross-section (rods, sheets, pipes, films, wire insulation coating). The methods of extruding the polymeric composition can include conveying a softened polymeric composition through a die with an opening. The polymeric composition can be conveyed forward by a feeding screw and forced through the die. Heating elements, placed over the barrel, can soften and melt the polymeric composition. The temperature of the polymeric composition can be controlled by thermocouples. The polymeric composition going out of the die can be cooled by blown air or in a water bath to form the extruded polymeric composition. Alternatively, the polymeric composition going out of the die can be pelletized with little cooling as described below.

The method can further include injection molding the polymeric composition to form an article. The injection molding can include the use of a non-rotating, cold plunger to force the polymeric composition through a heated cylinder wherein the polymeric composition is heated by heat conducted from the walls of the cylinder to the polymeric composition. The injection molding can include the use of a rotating screw, disposed co-axially of a heated barrel, for conveying the polymeric composition toward a first end of the screw and to heat the polymeric composition by the conduction of heat from the heated barrel to the polymeric composition. As the polymeric composition is conveyed by the screw mechanism toward the first end, the screw is translated toward the second end so as to produce a reservoir space at the first end. When sufficient melted polymeric composition is collected in the reservoir space, the screw mechanism can be pushed toward the first end so as to inject the polymeric composition into a selected mold.

Now having described examples of the present disclosure generally, additional discussion regarding examples will be described in greater detail.

Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular examples described, and as such may, of course, vary. Other systems, methods, features, and advantages of resin compositions and articles and components thereof will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. It is also to be understood that the terminology used herein is for the purpose of describing particular examples only, and is not intended to be limiting. The skilled artisan will recognize many variants and adaptations of the examples described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein.

Methods of Making Components and Articles

The disclosure provides several methods for making components and articles described herein. The methods comprise affixing a synthetic leather material to a second element to form the component or article. The second element can include a textile or multilayer film. For example, the second element can include an upper. The second element can include one or both of polyolefin fibers and polyolefin yarns. The second element can comprise an injection molded element. The methods can further include injection molding a polymeric composition as described herein, including a polyolefin resin composition, to form the injection molded second element. The disclosure provides methods for manufacturing a component for an article of footwear, apparel or sporting equipment.

In some examples, a polyolefin resin composition defines a side or outer layer of the second element, and the method includes affixing together two sides or outer layers each of which is defined by a polyolefin resin composition. The second element can include a yarn, a textile, a film, or some other element. Affixing the component to the second element can include directly injecting a polymeric composition, such as a polyolefin resin composition, onto the second element. Affixing the component to the second element can include forming a mechanical bond between the polymeric composition and the second element. The mechanical bond can include a textile bonded at the interface between the component and the second element. Affixing the component to the second element can include (i) increasing a temperature of the polymeric composition to a first temperature above a melting or softening temperature (e.g., the Vicat softening temperature) of the polymeric composition, (ii) contacting the polymeric composition and the second element while the polymeric composition is at the first temperature, and (iii) keeping the polymeric composition and the second element in contact with each other while decreasing the temperature of the polymeric composition to a second temperature below the melting or softening temperature of the polymeric composition, forming a thermal bond between the polymeric composition and the second element.

The second element can comprise a second polymeric composition which is thermoplastic (e.g., a second thermoplastic composition), and affixing the component to the second element can include (i) increasing a temperature of the second thermoplastic composition to a first temperature above a melting or softening temperature of the second thermoplastic composition, (ii) contacting the polymeric composition and the second element with each other while the second thermoplastic composition is at the first temperature, and (iii) keeping the polymeric composition and the second element in contact with each other while decreasing the temperature of the second thermoplastic composition to a second temperature below the melting or softening temperature of the second thermoplastic composition, forming a thermal bond between the polymeric composition and the second element.

The polymeric composition can be a first thermoplastic composition, and the second element can include a second thermoplastic composition, and affixing the component to the second element can include (i) increasing a temperature of both the first thermoplastic composition and the second thermoplastic composition to a first temperature above both a melting or softening temperature of the first thermoplastic composition and a melting or softening temperature of the second thermoplastic composition, (ii) contacting the first thermoplastic composition and the second thermoplastic composition with each other while both the first thermoplastic composition and the second thermoplastic composition are at the first temperature, and (iii) keeping the first thermoplastic composition and the second thermoplastic composition in contact with each other while decreasing the temperature of both the first thermoplastic composition and the second thermoplastic composition to a second temperature below both the melting or softening temperature of the first thermoplastic composition and the melting or softening temperature of the second thermoplastic composition, forming a thermal bond between the first thermoplastic composition and the second thermoplastic composition in which polymer chains of the first thermoplastic composition and the second thermoplastic composition intermingle with each other.

In some examples, the article is an article of footwear and the method includes injection molding a plate directly onto the upper.

Property Analysis and Characterization Procedures

Cold Ross Flex Test Protocol

The cold Ross flex test is determined according the following test method. The purpose of this test is to evaluate the resistance to cracking of a sample under repeated flexing to 60 degrees in a cold environment. A thermoformed plaque of the material for testing is sized to fit inside the flex tester machine. Each material is tested as five separate samples. The flex tester machine is capable of flexing samples to 60 degrees at a rate of 100 plus or minus 5 cycles per minute. The mandrel diameter of the machine is 10 millimeters. Suitable machines for this test are the Emerson AR-6, the Satra STM141F, the Gotech GT-7006, and the Shin II Scientific SI-LTCO (DaeSung Scientific). The sample(s) are inserted into the machine according to the specific parameters of the flex machine used. The machine is placed in a freezer set to −6 degrees Celsius for the test. The motor is turned on to begin flexing with the flexing cycles counted until the sample cracks. Cracking of the sample means that the surface of the material is physically split. Visible creases of lines that do not actually penetrate the surface are not cracks. The sample is measured to a point where it has cracked but not yet broken in two.

Abrasion Loss Test Protocol ASTM D 5963-97a

Abrasion loss is tested on cylindrical test pieces with a diameter of 16 plus or minus 0.2 millimeter and a minimum thickness of 6 millimeters cut from sheets using a ASTM standard hole drill. The abrasion loss is measured using Method B of ASTM D 5963-97a on a Gotech GT-7012-D abrasion test machine. The tests are performed as 22 degrees Celsius with an abrasion path of 40 meters. The Standard Rubber #1 used in the tests has a density of 1.336 grams per cubic centimeter (g/cm³). The smaller the abrasion loss volume, the better the abrasion resistance.

Crystallinity Test Protocol

To determine percent crystallinity of a resin composition including a copolymer, or of the copolymer in neat resin form, and of a homopolymer of the main component of the copolymer (e.g., polypropylene homopolymer polypropylene), samples are analyzed by differential scanning calorimetry (DSC) over the temperature range from −80 degrees Celsius to 250 degrees Celsius. A heating rate of 10 degrees Celsius per minute is used. The melting endotherm is measured for each sample during heating. Universal Analysis software (TA Instruments, New Castle, DE, USA) is used to calculate percent crystallinity (% crystallinity) based upon the melting endotherm for the homopolymer (e.g., 207 Joules per gram for 100 percent crystalline polypropylene material). Specifically, the percent crystallinity (% crystallinity) is calculated by dividing the melting endotherm measured for the copolymer or for the resin composition by the 100 percent crystalline homopolymer melting endotherm.

Method to Determine the Vicat Softening Temperature Test Protocol

The Vicat softening temperature is be determined according to the test method detailed in ASTM T_m D1525-09 Standard Test Method for Vicat Softening Temperature of Plastics, preferably using Load A and Rate A. Briefly, the Vicat softening temperature is the temperature at which a flat-ended needle penetrates the specimen to the depth of 1 millimeter under a specific load. The temperature reflects the point of softening expected when a material is used in an elevated temperature application. It is taken as the temperature at which the specimen is penetrated to a depth of 1 millimeter by a flat-ended needle with a 1 square millimeter² circular or square cross-section. For the Vicat A test, a load of 10 Newtons (N) is used, whereas for the Vicat B test, the load is 50 Newtons. The test involves placing a test specimen in the testing apparatus so that the penetrating needle rests on its surface at least 1 millimeter from the edge. A load is applied to the specimen per the requirements of the Vicat A or Vicat B test. The specimen is then lowered into an oil bath at 23° C. degrees Celsius. The bath is raised at a rate of 50 degrees Celsius or 120 degrees Celsius per hour until the needle penetrates 1 millimeter. The test specimen must be between 3 and 6.5 millimeter thick and at least 10 millimeter in width and length. No more than three layers can be stacked to achieve minimum thickness.

Melting Temperature and Glass Transition Temperature Test Protocol

The melting temperature and glass transition temperature are determined using a commercially available Differential Scanning calorimeter (“DSC”) in accordance with ASTM D3418-97. Briefly, a 10-15 gram sample is placed into an aluminum DSC pan and then the lead was sealed with the crimper press. The DSC is configured to scan from −100 degrees Celsius to 225 degrees Celsius with a 20 degrees Celsius/minute heating rate, hold at 225 degrees Celsius for 2 minutes, and then cool down to 25 degrees Celsius at a rate of −10 degrees Celsius/minute. The DSC curve created from this scan is then analyzed using standard techniques to determine the glass transition temperature and the melting temperature.

Melt Flow Index Test Protocol.

The melt flow index is determined according to the test method detailed in ASTM D1238-13 Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer, using Procedure A described therein. Briefly, the melt flow index measures the rate of extrusion of thermoplastics through an orifice at a prescribed temperature and load. In the test method, approximately 7 grams of the material is loaded into the barrel of the melt flow apparatus, which has been heated to a temperature specified for the material. A weight specified for the material is applied to a plunger and the molten material is forced through the die. A timed extrudate is collected and weighed. Melt flow rate values are calculated in grams per 10 minutes. Alternatively, melt flow index can be determined using International Standard ISO1133 Determination of the Melt Mass-Flow Rate (MFR) and Melt Volume-Flow Rate (MVR) of Thermoplastics using Procedure A described therein, at 190 degrees Celsius and a load of 2.16 kilograms.

Durometer Hardness Test Protocol

The hardness of a material is determined according to the test method detailed in ASTM D-2240 Durometer Hardness, using a Shore A scale.

Flexural Modulus Test Protocol

The flexural modulus (modulus of elasticity) for a material is determined according to the test method detailed in ASTM D790. The modulus is calculated by taking the slope of the stress (megapascals) versus the strain in the steepest initial straight-line portion of the load-deflection curve.

Modulus Test Protocol (of plaque).

The (tensile) modulus for a thermoformed plaque of material is determined according to the test method detailed in ASTM D412-98 Standard Test Methods for Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers-Tension, with the following modifications. The sample dimension is the ASTM D412-98 Die C, and the sample thickness used is 2.0 millimeters plus or minus 0.5 millimeters. The grip type used is a pneumatic grip with a metal serrated grip face. The grip distance used is 75 millimeters. The loading rate used is 500 millimeters per minute. The modulus (initial) is calculated by taking the slope of the stress in megapascals (MPa) versus the strain in the initial linear region.

Modulus Test Protocol (of yarn).

The modulus for a yarn is determined according to the test method detailed in EN ISO 2062 (Textiles-Yarns from Packages)—Determination of Single-End Breaking Force and Elongation at Break Using Constant Rate of Extension (CRE) Tester, with the following modifications. The sample length used is 600 millimeters. The equipment used is an Instron and Gotech Fixture. The grip distance used is 250 millimeters. The pre-loading is set to 5 grams and the loading rate used is 250 millimeters per minute. The first meter of yarn is thrown away to avoid using damaged yarn. The modulus (initial) is calculated by taking the slope of the stress in megapascals (MPa) versus the strain in the initial linear region.

Tenacity and Elongation Test Protocol.

The tenacity and elongation of yarn can be determined according to the test method detailed in EN ISO 2062 Determination of single end breaking force and elongation at break using constant rate of extension tester with the pre-load set to 5 grams.

Mullen Burst Test Protocol

The Mullen burst of a web of material, such as textile or synthetic leather material, can be determined according to the test method detailed in ASTM D3786, Standard Test Method for Bursting Strength of Textile Fabrics.

Sampling Procedures

Using the Test Protocols described above, various properties of the materials disclosed herein and components and other articles formed therefrom can be characterized using samples prepared with the following sampling procedures:

Neat Material Sampling Procedure

A material sampling procedure can be used to obtain a neat sample of a polymer or a polymeric composition. The material is provided in media form, such as flakes, granules, powders, pellets, and the like. If a source of the polymer or polymeric composition is not available in a neat form, the sample can be cut from a film or plate or other component containing the polymeric composition, thereby isolating a sample of the material.

Plaque Sampling Procedure

A sample of a polymer or a polymeric composition is prepared. A portion of the polymer or polymeric composition is then molded into a film or plaque sized to fit inside the testing apparatus. For example, when using a Ross flexing tester, the film or plaque is sized to fit inside the Ross flexing tester used, the plaque having dimensions of about 15 centimeters (cm) by 2.5 centimeters (cm) and a thickness of about 1 millimeter (mm) to about 4 millimeters (mm) by thermoforming the polymer or polymeric composition in a mold, or extruding the polymer or polymeric composition into a film and cutting the film to size. A plaque sample is prepared by mixing the components of the polymer or polymeric composition together, melting the components, pouring or injecting the melted polymer or polymeric composition into the mold cavity, cooling the melted polymer or composition to solidify it in the mold cavity to form the plaque, and then removing the solid plaque from the mold cavity.

Component Sampling Procedure

This procedure can be used to obtain a sample of a polymer or polymeric composition from an article or component of an article, such as an article of footwear, apparel or sporting equipment. A sample including the polymer or polymeric composition in a non-wet state (e.g., at 25 degrees Celsius and 20 percent relative humidity) is cut from the article or component using a blade. If the polymer or polymeric composition is bonded to one or more additional materials, the procedure can include separating the additional materials from the polymer or polymeric composition to be tested. For example, to test a polymer or polymeric composition on a bottom surface of a sole structure, such as an outsole, the top surface can be skinned, abraded, scraped, or otherwise cleaned to remove any adhesives, yarns, fibers, foams, and the like which are affixed to the polymer or polymeric material to be tested. The resulting sample includes the polymer or polymeric composition and may include any additional materials bonded to it.

Definitions

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

All publications, patents, and patent applications cited in this specification are cited to disclose and describe the methods and/or materials in connection with which the publications are cited. All such publications, patents, and patent applications are herein incorporated by references as if each individual publication or patent were specifically and individually indicated to be incorporated by reference. Such incorporation by reference is expressly limited to the methods and/or materials described in the cited publications, patents, and patent applications and does not extend to any lexicographical definitions from the cited publications, patents, and patent applications. Any lexicographical definition in the publications, patents, and patent applications cited that is not also expressly repeated in the instant specification should not be treated as such and should not be read as defining any terms appearing in the accompanying claims.

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

It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’. The range can also be expressed as an upper limit, e.g. ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘less than x’, less than y′, and ‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y′, and ‘greater than z’. In addition, the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1% to 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.4%, 3.2%, and 4.4%) within the indicated range.

The term “providing,” as used herein and as recited in the claims, is not intended to require any particular delivery or receipt of the provided item. Rather, the term “providing” is merely used to recite items that will be referred to in subsequent elements of the claim(s), for purposes of clarity and ease of readability.

The terms and phrases used herein to refer to sampling procedures and testing protocols, for example, “Neat Material Sampling Procedure”, “Plaque Sampling Procedure”, “Cold Ross Flex Test”, “ASTM D 5963-97a”, “Crystallinity Test,” and the like, refer to the respective sampling procedures and test methodologies described in the Property Analysis and Characterization Procedure section. These sampling procedures and test methodologies characterize the properties of the recited materials, films, articles and components, and the like, and are not required to be performed as active steps in the claims.

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

PP9054 is a random copolymer of propylene with about 2.2 percent by weight (wt %) ethylene is commercially available under the tradename “PP9054” from ExxonMobil Chemical Company, Houston, TX. It has a MFR (ASTM-1238D, 2.16 kilograms, 230° C.) of about 12 grams/10 minutes and a density of 0.90 grams/cubic centimeter (g/cm³).

PP9074 is a random copolymer of propylene with about 2.8 weight by weight (wt %) ethylene and is commercially available under the tradename “PP9074” from ExxonMobil Chemical Company, Houston, TX. It has a MFR (ASTM-1238D, 2.16 kilograms, 230° C.) of about 24 grams/10 minutes and a density of 0.90 grams/cubic centimeter (g/cm³).

PP1024E4 is a propylene homopolymer commercially available under the tradename “PP1024E4” from ExxonMobil Chemical Company, Houston, TX. It has an MFR (ASTM-1238D, 2.16 kilograms, 230° C.) of about 13 grams/10 minutes and a density of 0.90 grams/cubic centimeter (g/cm³).

“VISTAMAXX 6202” is a copolymer primarily composed of isotactic propylene repeat units with about 15 percent by weight (wt %) of ethylene repeat units randomly distributed along the copolymer. It is a metallocene catalyzed copolymer available from ExxonMobil Chemical Company, Houston, TX and has an MFR (ASTM-1238D, 2.16 kilograms, 230° C.) of about 20 grams/10 minutes, a density of 0.862 grams/cubic centimeter (g/cm³), and a Durometer Hardness of about 64 (Shore A).

“VISTAMAXX 3000” is a copolymer primarily composed of isotactic propylene repeat units with about 11 percent by weight (wt %) of ethylene repeat units randomly distributed along the copolymer. It is a metallocene catalyzed copolymer available from ExxonMobil Chemical Company and has an MFR (ASTM-1238D, 2.16 kilograms, 230° C.) of about 8 grams/10 minutes, a density of 0.873 grams/cubic centimeter (g/cm³), and a Durometer Hardness of about 27 (Shore D).

“VISTAMAXX 6502” is a copolymer primarily composed of isotactic propylene repeat units with about 13 percent by weight of ethylene repeat units randomly distributed along the copolymer. It is a metallocene catalyzed copolymer available from ExxonMobil Chemical Company and has an MFR (ASTM-1238D, 2.16 kilograms, 230° C.) of about 45 grams/10 minutes, a density of 0.865 grams/cubic centimeter (g/cm³), and a Durometer Hardness of about 71 (Shore A).

Examples

Now having described the examples of the present disclosure, in general, the following Examples describe some additional examples of the present disclosure. While examples of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intent to limit examples of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure.

Materials

For the examples described below, the following base resins were used.

TABLE 1
Base Resins
Base Resin Description

Polyolefin Base Resin	Supplier	MFI	Description

PP9054	ExxonMobil	12	Propylene Random
			Copolymer
PP9074Med	ExxonMobil	24	Propylene Random
			Copolymer/High
			Clarity
PP1024E4	ExxonMobil	13	Propylene
			Homopolymer

The following polymeric resin modifiers were used in the examples.

TABLE 2
Polymeric Resin Modifiers
Modifier/Blend Description

Polymeric Resin				Ethylene
Modifiers	Supplier	MFI	Loading %	Percent

VISTAMAXX 6202	ExxonMobil	21	30	15
VISTAMAXX 3000	ExxonMobil	9.1	50	11
VISTAMAXX 6502	ExxonMobil	43	40	13

Polyolefin Resin Compositions

The polyolefin resin compositions including the polyolefin polymers (i.e., the base resins) and varying amounts of polymeric resin modifier were prepared and tested to determine the abrasion loss pursuant to the Abrasion Loss Test described herein and using the Neat Material Sampling Procedure; and by a flex test pursuant to the Cold Ross Flex Test using the Plaque Sampling Procedure. The results are presented in Table 3. The percent (%) crystallization was measured for sample resin compositions using according to the Crystallinity Test using the Neat Material Sampling Procedure. The results are reported in Table 4.

TABLE 3
Density, DIN Abrasion Loss, and Cold Ross Flex Summary of Resin
Compositions With Varying Amounts of Polymeric Resin Modifier

	Base	Polymeric	Resin	Cold Ross		DIN
Polyolefin	Resin	Resin	Modifier	Flex		Abrasion
Base Resin	wt %	Modifier	wt %	Summary	Density	Loss (cm3)

PP9054	100	n/a	0	Fail	0.896	0.089
PP9054	85	6202	15	Pass	0.891	0.085
PP9054	70	6202	30	*	0.891	0.095
PP9054	50	6202	50	*	0.883	0.158
PP9054	85	6502	15	*	0.896	0.084
PP9054	80	6502	20	Pass	*	*
PP9054	60	6502	40	*	*	*
PP9054	85	3000	15	*	0.897	0.078
PP9054	75	3000	25	Pass	*	*
PP9054	50	3000	50	*	*	*
PP9074Med	100	n/a	0	Fail	0.902	0.089
PP9074Med	85	6202	15	*	0.894	0.101
PP9074Med	70	6202	30	Pass	*	*
PP1024E4	100	n/a	0	Pass	0.903	0.083
PP1024E4	85	6202	15	*	0.899	0.162
PP1024E4	50	3000	50	Pass	*	*
* not determined

TABLE 4
Percent Crystallization of Representative Resin Compositions

	Base Resin	Blend	Blend Resin
Base Resin	wt %	Resin	wt %	% Crystallization

PP9054	100	n/a	0	38%
PP9054	85	6202	15	34%
PP9054	70	6202	30	30%
PP9054	80	6502	20	24%
PP9054	60	6502	40	24%
PP9054	75	3000	25	29%
PP9054	50	3000	50	23%
PP9074Med	100	n/a	0	45%
PP9074Med	70	6202	30	30%
PP1024E4	100	n/a	0	54%
PP1024E4	50	3000	50	30%

CLAUSES

Clause 1. A footwear article comprising: a sole structure comprising a first thermoplastic composition; a footwear upper comprising an outer-facing surface; the outer-facing surface comprising a first zone and a second zone; the first zone of the outer-facing surface overlapping with the sole structure and comprising a second thermoplastic composition, wherein the first zone is thermally bonded to the sole structure; and the second zone of the outer-facing surface comprising an outermost surface of the upper and comprising one or more properties that are different from the first zone.

Clause 2. The footwear article of clause 1, wherein the one or more properties comprises a composition.

Clause 3. The footwear article of clause 1 or clause 2, wherein the one or more properties comprises a cleaning solution composition.

Clause 4. The footwear article of any of clauses 1-3, wherein the one or more properties comprises a more oxidized state.

Clause 5. The footwear article of any of clauses 1-4, wherein the one or more properties comprises a primer composition.

Clause 6. The footwear article of any of clauses 1-5, wherein the one or more properties comprises an ink composition.

Clause 7. The footwear article of any of clauses 1-6, wherein the one or more properties comprises a surface texture.

Clause 8. The footwear article of clause 7, wherein the surface texture comprises, as compared to a second surface texture associated with the first zone, a deeper relief that extends further away from the upper material.

Clause 9. The footwear article of any of clauses 1-8, wherein, as compared to the second zone, the first zone comprises a lesser amount of at least one of the cleaning solution composition, the primer composition, and the ink composition.

Clause 10. The footwear article of clause 9, wherein the lesser amount comprises no detectable amount.

Clause 11. The footwear article of any of clauses 1-10 further comprising a biteline.

Clause 12. The footwear article of clause 11, wherein: the first zone extends to the biteline;

the outer-facing surface comprises a transition zone that is positioned between the first zone and the second zone and that comprises an outermost surface of the upper; and the transition zone, with respect to the one or more properties, is more similar to the first zone than to the second zone.

Clause 13. The footwear article of clause 12, wherein as compared to the second zone, the transition zone comprises a lesser amount of at least one of the cleaning solution composition, the primer composition, and the ink composition.

Clause 14. The footwear article of clause 13, wherein the lesser amount comprises no detectable amount.

Clause 15. The footwear article of any of clauses 12-14, wherein the transition zone comprises a width extending from the biteline to the second zone, and wherein the width is in a range of about 3 mm to about 7 mm.

Clause 16. The footwear article of clause 15, wherein the width is about 5 mm.

Clause 17. The footwear article of any of clauses 15 or 16, wherein the width comprises a first width at a first position around a periphery of the footwear article, wherein the transition zone comprises a second width extending from the biteline to the second zone and at a second position around the periphery of the footwear article, and wherein the second width is different from the first width.

Clause 18. The footwear article of clause 17, wherein the first position is in a forefoot region of the footwear article and the second position is in a midfoot region of the footwear article.

Clause 19. The footwear article of clause 18, wherein the first width is smaller than the second width.

Clause 20. The footwear article of any of clauses 11 to 19, wherein: the footwear upper comprises a bonding skirt that overlaps with the sole structure and that comprises the first zone of the outer-facing surface; and the bonding skirt comprising an inner-facing surface that faces towards a foot-receiving cavity of the footwear article.

Clause 21. The footwear article of clause 20, wherein the inner facing surface is coupled to a strobel.

Clause 22. The footwear article of clause 21, wherein the footwear upper comprise a terminal edge coupled to the stobel.

Clause 23. The footwear article of clause 22, wherein the terminal edge is coupled to the strobel by one or more of stitching and adhesive.

Clause 24. The footwear article of clause 23, wherein the terminal edge is coupled to the strobel by adhesive, and the strobel is adhesively bonded to the inner-facing surface of the bonding skirt.

Clause 25. The footwear article of clause 24, wherein the adhesive comprises a hotmelt adhesive.

Clause 26. The footwear article of clause 25, wherein the hotmelt adhesive comprises a thermoplastic polymer.

Clause 27. The footwear article of clause 26, wherein the thermoplastic polymer comprises a third thermoplastic composition that is different than the first thermoplastic composition of the sole structure.

Clause 28. The footwear article of clause 27, wherein the third thermoplastic composition comprises a thermoplastic polyurethane composition.

Clause 29. The footwear article of clause 27 or clause 28, wherein the sole structure is substantially free of the third thermoplastic composition.

Clause 30. The footwear article of any of clauses 24 to 29 further comprising a bonding interface between the strobel and the inner-facing surface of the upper, wherein the bonding interface comprises at least a portion of the strobel, a portion of the adhesive, and a portion of the inner-facing surface.

Clause 31. The footwear article of clause 30, wherein the bonding interface extends to the terminal edge of the footwear upper.

Clause 32. The footwear article of clause 31, wherein the bonding interface is substantially free of the first thermoplastic composition.

Clause 33. The footwear article of any of clauses 21 to clause 32, wherein the inner facing surface and the strobel comprise a nonwoven textile.

Clause 34. The footwear article of any of clauses 22-33, wherein the bonding skirt comprises a width extending from the biteline to the terminal edge.

Clause 35. The footwear article of clause 34, wherein the width comprises a first width at a first position around a periphery of the footwear article, wherein the bonding skirt comprises a second width extending from the biteline to the terminal edge and at a second position around the periphery of the footwear article, and wherein the second width is different from the first width.

Clause 36. The footwear article of clause 35, wherein the first position toeward relative to the second position.

Clause 37. The footwear article of clause 36, wherein the first width is larger than the second width.

Clause 38. The footwear article of clause 37, wherein the first position is in a forefoot region of the footwear article and the second position is in a midfoot region or a heel region.

Clause 39. The footwear article of any of clauses 1-38, wherein: the first thermoplastic composition comprises a first thermoplastic polyolefin composition; and the first zone of the outer-facing surface comprises a resin comprising the second thermoplastic composition; and the second thermoplastic composition comprises a second thermoplastic polyolefin composition.

Clause 40. The footwear article of clause 39, wherein footwear upper comprises the second thermoplastic polyolefin composition with one or more surface modifications in the second zone.

Clause 41. The footwear article of clause 40, wherein the one or more surface modifications comprise one or more of the cleaning solution composition, the more oxidized state, the primer composition, the ink composition, and the surface texture.

Clause 42. A footwear article comprising: a sole structure comprising a first thermoplastic composition; an upper comprising a first zone and a second zone; the first zone overlapping with the sole structure and thermally bonded to the sole structure; the second zone comprising a first portion of an outermost surface of the footwear article; and the first portion of the outermost surface comprising a surface chemical composition that is different from the first thermoplastic composition.

Clause 43. The footwear article of clause 42, wherein the first thermoplastic composition comprises a polyolefin resin composition.

Clause 44. The footwear article of clause 43, wherein the surface chemical composition comprises less than 5% of the polyolefin resin composition.

Clause 45. The footwear article of any of clauses 42 to clause 44, wherein the surface chemical composition comprises a polyurethane composition.

Clause 46. The footwear article of clause 45, wherein the first portion of the outermost surface comprises a polyurethane ink.

Clause 47. The footwear article of any of clauses 42 to 46 further comprising, a biteline.

Clause 48. The footwear article of clause 47, wherein the upper comprises a transition zone that is positioned between the biteline and the second zone and that comprises a second portion of the outermost surface of the footwear article.

Clause 49. The footwear article of clause 48, wherein the second portion of the outermost surface of the footwear article comprises a second thermoplastic composition.

Clause 50. The footwear article of clause 49, wherein the first thermoplastic composition and the second thermoplastic composition comprise a polyolefin resin composition.

Clause 51. The footwear article of clause 50, wherein the transition zone comprises a width extending from the biteline to the second zone, and wherein the width is in a range of about 3 mm to about 7 mm.

Clause 52. The footwear article of clause 50 or clause 51, wherein the width comprises a first width at a first position around a periphery of the footwear article, wherein the transition zone comprises a second width extending from the biteline to the second zone and at a second position around the periphery of the footwear article, and wherein the second width is different from the first width.

Clause 53. The footwear article of clause 52, wherein the first position is in a forefoot region of the footwear article and the second position is in a midfoot region of the footwear article.

Clause 54. The footwear article of clause 53, wherein the first width is smaller than the second width.

Clause 55. The footwear article of any of clauses 48 through 54, wherein the first portion of the outermost surface comprises a surface texture that, as compared to the second portion of the outermost surface, comprises larger relief depth.

Clause 56. A footwear article comprising: a sole structure comprising a first thermoplastic composition; an upper comprising a bonding skirt that overlaps with the sole structure and that is thermally bonded to the sole structure; the bonding skirt comprising an inner-facing surface that faces towards a foot-receiving cavity of the footwear article; and a strobel bonded, via a hotmelt adhesive, to the inner-facing surface.

Clause 57. The footwear article of clause 56, wherein the hotmelt adhesive comprises a second thermoplastic composition, which is different from the first thermoplastic composition.

Clause 58. The footwear article of clause 57, wherein the first thermoplastic composition comprises a polyolefin resin composition.

Clause 59. The footwear article of clause 58, wherein the second thermoplastic composition comprises a thermoplastic polyurethane composition.

Clause 60. The footwear article of 57, wherein the sole structure is substantially free of the second thermoplastic composition.

Clause 61. The footwear article of clause 56 wherein the inner-facing surface comprises a first nonwoven textile comprising first fibers and the strobel comprises a second nonwoven textile comprising second fibers, and wherein portions of the hotmelt adhesive at least partially encapsulates the first fibers and the second fibers.

Clause 62. A footwear article comprising: a sole structure; an upper comprising a first zone, a second zone, and a transition zone between the first zone and the second zone; the first zone overlapping with the sole structure at a biteline and thermally bonded to the sole structure; the transition zone extending from the biteline to the second zone; the transition zone comprising a first portion of an outermost surface of the footwear article, wherein the transition zone comprises a first surface texture that comprises a first relief depth; and the second zone comprising a second portion of the outermost surface of the footwear article, wherein the second zone comprises a second surface texture that comprises a second relief depth, which is larger than the first relief depth.

Clause 63. The footwear article of clause 62, wherein the transition zone comprises one or more widths extending from the biteline to the second zone.

Clause 64. The footwear article of clause 63, wherein the one or more widths are in a range of about 3 mm to about 7 mm.

Clause 65. The footwear article of clause 63 of clause 64, wherein the one or more widths comprise a first width at a first position around a periphery of the footwear article and a second width at a second position around the periphery of the footwear article, and wherein the second width is different from the first width.

Clause 66. The footwear article of clause 65, wherein the first position is in a forefoot region of the footwear article and the second position is in a midfoot region of the footwear article.

Clause 67. The footwear article of clause 66, wherein the first width is smaller than the second width.

Clause 68. The footwear article of clause 62, wherein the sole structure comprises a first thermoplastic composition, and wherein, in the second zone, the second portion of the outermost surface comprises a surface chemical composition that is different from the first thermoplastic composition.

Clause 69. The footwear article of clause 68, wherein the first thermoplastic composition comprises a polyolefin resin composition.

Clause 70. The footwear article of clause 69, wherein the surface chemical composition comprises a polyurethane composition.

Clause 71. The footwear article of any of clauses 68 through 70, wherein, in the first zone, the first portion of the outermost surface comprises the surface chemical composition that comprises a polyolefin resin composition.

As used herein, a recitation of “and/or” with respect to two or more elements should be interpreted to mean only one element, or a combination of elements. For example, “element A, element B, and/or element C” may include only element A, only element B, only element C, element A and element B, element A and element C, element B and element C, or elements A, B, and C. In addition, “at least one of element A or element B” may include at least one of element A, at least one of element B, or at least one of element A and at least one of element B. Further, “at least one of element A and element B” may include at least one of element A, at least one of element B, or at least one of element A and at least one of element B.

This detailed description is provided in order to meet statutory requirements. However, this description is not intended to limit the scope of the invention described herein. Rather, the claimed subject matter may be embodied in different ways, to include different steps, different combinations of steps, different elements, and/or different combinations of elements, similar or equivalent to those described in this disclosure, and in conjunction with other present or future technologies. The examples herein are intended in all respects to be illustrative rather than restrictive. In this sense, alternative examples or implementations can become apparent to those of ordinary skill in the art to which the present subject matter pertains without departing from the scope hereof.