Sole structure including a composite element and article of footwear formed therefrom

Abstract

Disclosed herein is a composite element including a textile and a hydrogel layer including a hydrogel material operably coupled to the textile, where a portion of the hydrogel layer extends through a first side of the textile and at least partially into a core of the textile, but does not extend onto a second side of the textile. Also disclosed are sole structures and articles of athletic footwear incorporating the composite elements, as well as methods of manufacturing such composite elements, sole structures, and articles of footwear.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 052,740, filed July 16, 2020, which is incorporated herein by reference in its entirety.

[0003] background

[0004] The design and manufacture of footwear and athletic equipment involves a multitude of factors, from aesthetics and comfort to performance and durability. While designs and fashion can change rapidly, the market's need for enhanced performance remains constant. Furthermore, the market has shifted towards demanding lower-cost and recyclable materials that still meet performance enhancement requirements. To balance these needs, footwear and athletic equipment designers are employing a variety of materials and designs across multiple components. Summary of the Invention

[0005] This public disclosure provides the following items:

[0006] 1. A sole structure for footwear articles, the sole structure comprising:

[0007] Composite components and sole parts;

[0008] The composite element comprises textiles and a hydrogel layer;

[0009] The textile comprises textile material and has a first side, a second side, and a core located between the first side and the second side;

[0010] The hydrogel layer comprises a hydrogel material and has a first side and a second side, the second side being operatively attached to the textile along the first side of the textile.

[0011] A portion of the hydrogel layer extends through the first side of the textile and at least partially into the core of the textile, but does not extend to the second side of the textile;

[0012] At least a portion of the first side of the hydrogel layer provides a first ground-facing surface of the sole structure; and

[0013] The sole component comprises a second polymer material and has a first side and a second side, wherein at least a portion of the first side of the sole component is operatively coupled to the second side of the textile.

[0014] 2. The sole structure according to Item 1, wherein the textile has a core thickness of about 0.1 mm to about 5 mm, measured between the first side and the second side of the textile, prior to operably attaching the textile to the hydrogel layer.

[0015] 3. The sole structure according to item 1 or 2, wherein the textile is a breathable textile prior to the first side of the textile being operatively bonded to the hydrogel layer.

[0016] 4. The sole structure according to any one of items 1 to 3, wherein the hydrogel material is a thermoplastic hydrogel material, and the textile material has a textile material melting temperature or textile material Vicat softening temperature that is at least 20 degrees Celsius greater than the melting temperature or Vicat softening temperature of the thermoplastic hydrogel material of the hydrogel layer.

[0017] 5. The sole structure according to any one of items 1 to 4, wherein the hydrogel layer permeates at least 10 percent of the core thickness of the textile.

[0018] 6. The sole structure according to any one of items 1 to 5, wherein the hydrogel layer permeates less than 90 percent of the core thickness of the textile.

[0019] 7. The sole structure according to any one of items 1 to 6, wherein the textile includes nonwoven textiles.

[0020] 8. The sole structure according to any one of items 1 to 7, wherein the textile has a basis weight of about 5 g / m² to about 500 g / m².

[0021] 9. The sole structure according to any one of items 1 to 8, wherein the hydrogel layer has a dry thickness in the range of 0.1 mm to 2 mm.

[0022] 10. The sole structure according to any one of items 1 to 9, wherein the hydrogel material is a thermoplastic hydrogel material, and the thermoplastic hydrogel material has a melt flow index from about 35 grams per 10 minutes to about 55 grams per 10 minutes according to the melt flow index test scheme.

[0023] 11. The sole structure according to any one of items 1 to 10, wherein the hydrogel material comprises polyurethane hydrogel.

[0024] 12. The sole structure according to any one of items 1 to 11, wherein the sole component includes one or more adhesion friction elements.

[0025] 13. The sole structure according to any one of items 1 to 12, wherein the second polymer material comprises a polyolefin.

[0026] 14. A footwear article comprising an upper operatively connected to the sole structure of any one of items 1 to 13.

[0027] 15. A method for manufacturing a sole structure for footwear articles, the method comprising:

[0028] A first composite element is operatively coupled to a second component; the first composite element includes a textile and a hydrogel layer; the textile comprises a textile material and has a first side, a second side, and a core located between the first side and the second side; the hydrogel layer comprises a hydrogel material and has a first side and a second side, the second side of the hydrogel layer being operatively coupled to the textile along the first side of the textile; wherein, in the sole structure, a portion of the hydrogel layer extends through the first side of the textile and at least partially extends into the core of the textile, but does not extend to the second side of the textile;

[0029] The operative connection includes forming a joint between the second side of the textile of the first composite element and the second component, such that the hydrogel layer of the first composite element defines at least a portion of the ground-facing surface of the sole structure.

[0030] 16. The method of claim 15, wherein the operably coupled step comprises placing the first composite element into a mold such that a portion of the first side surface of the hydrogel layer contacts a portion of the molded surface of the mold to form the prepared molded surface;

[0031] The second polymer material is loaded onto the prepared molding surface of the mold;

[0032] The loaded second polymer material is at least partially cured in the mold, thereby operably linking the first composite element and the at least partially cured second polymer material to form the sole structure including the hydrogel layer of the first composite element, the hydrogel layer defining at least a portion of the ground-facing surface of the sole structure; and

[0033] Remove the sole structure from the mold.

[0034] 17. The method of claim 16, wherein the method further comprises constraining the first composite element in the mold such that, while loading the second polymer material, at least a portion of the first side of the hydrogel layer contacts the molded surface.

[0035] 18. The method according to any one of items 15 to 17, wherein a) the textile has a core thickness of about 0.1 mm to about 5 mm, measured between the first side and the second side of the textile, prior to the first side of the textile being operably bonded to the hydrogel layer; or wherein b) the textile is a breathable textile prior to the first side of the textile being operably bonded to the hydrogel layer; or both a) and b).

[0036] 19. A sole structure manufactured according to any one of items 15 to 18.

[0037] 20. A method for manufacturing footwear, the method comprising:

[0038] An upper is attached to a sole structure, the sole structure including a hydrogel layer and a sole component, the hydrogel layer having a first side and a second side operatively connected to the first side of a textile, the sole component comprising a second polymer material operatively connected to the second side of the textile, such that the first side of the hydrogel layer of the sole structure defines the ground-facing surface of the footwear article. Brief description of the attached diagram

[0040] Further aspects of this disclosure will be readily understood when the detailed description described below is read in conjunction with the accompanying drawings.

[0041] Figure 1A This is a cross-sectional view of a textile product according to aspects of this disclosure.

[0042] Figure 1B This is a cross-sectional view of a composite element according to aspects of this disclosure.

[0043] Figures 2A-2I Exemplary athletic footwear items are depicted according to aspects of this disclosure. Figure 2A This is a perspective view of the exterior side of an exemplary athletic footwear item. Figure 2B This is a front view of the exterior of an exemplary athletic footwear item. Figure 2C This is a front view of the inside of an exemplary athletic footwear item. Figure 2D This is a top view of an exemplary athletic footwear item. Figure 2E This is a front view of an exemplary athletic footwear item. Figure 2F This is a rear view of an exemplary athletic footwear item. Figure 2G This is an exploded perspective view of an exemplary athletic footwear item. Figure 2H This is an exploded perspective view of the sole structure of an exemplary athletic footwear item. Figure 2I This is a cross-sectional view along 2-2 of an exemplary footwear item.

[0044] Figure 2J This is a cross-sectional view of a composite element combined with a plate according to aspects of this disclosure.

[0045] Figure 2K This is a bottom view of a plate having an adhesion traction element according to aspects of this disclosure.

[0046] Figure 3A This is a bottom side view of multiple components of a composite element and sole structure according to aspects of this disclosure.

[0047] Figure 3B This is a bottom side view of multiple components of a composite element and sole structure according to aspects of this disclosure.

[0048] Figure 3C This is a bottom side view of multiple components of a composite element and sole structure according to aspects of this disclosure.

[0049] Figure 4 This is a bottom view of some exemplary shoe outsoles decorated with printed and non-printed non-woven textiles according to aspects of this disclosure.

[0050] Detailed description

[0051] This disclosure generally relates to articles or components thereof having a surface-defining material capable of absorbing water. Certain polymeric hydrogels and hydrogel materials (i.e., compositions comprising at least one polymeric hydrogel), when applied to the outward-facing surface of an article, can effectively prevent or reduce the accumulation of dirt on that surface. However, the applicant has found that polymeric hydrogels and / or hydrogel materials can sometimes be separated or delaminated from other materials or components in the sole structure, including polyolefin-based materials or components.

[0052] This disclosure provides a composite element comprising a hydrogel layer containing a hydrogel material, wherein the hydrogel layer is operatively coupled to a textile, and a sole structure incorporated therein for footwear articles, as well as methods of forming and using the composite element and the sole structure. In the composite element, the hydrogel layer and the textile are operatively coupled such that the hydrogel layer permeates the textile structure, extending through a first side of the textile and at least partially into the core of the textile, but not extending continuously through the textile, for example, not extending to a second side of the textile. Without wishing to be bound by any particular theory, it is believed that providing a hydrogel layer coupled in this manner to a textile as part of the disclosed composite element can result in improved mechanical bonding between the textile and the hydrogel layer, and between the textile and the plate portion of the sole structure, thereby reducing or eliminating separation or delamination of the polymeric hydrogel and / or hydrogel material from the composite element and the plate when the composite element is used in a sole structure. In a particular aspect, the use of breathable textiles (i.e., textiles that are breathable prior to coupling with the hydrogel layer and / or plate) can result in further improvements in the level of mechanical bonding between the hydrogel layer and the textile, and between the textile and the plate.

[0053] In several aspects, this disclosure provides a sole structure including a composite element operatively coupled to a plate comprising a second polymer material. In one aspect, the hydrogel material of the hydrogel layer at least partially defines the outward-facing surface of the sole structure, including the ground-facing surface of the sole structure. Typically, the hydrogel material of the hydrogel layer will not be present on the outward-facing surface configured to contact the ground, such as the surface of an adhesive friction element configured to contact the ground during normal wear. The textile of the composite element facilitates the coupling of the hydrogel layer to the plate because the first side of the textile and the core of the textile increase the available surface area to which the hydrogel layer can mechanically bond compared to a substantially flat surface (e.g., in a membrane). This mechanically bonded structure of the composite element reduces or eliminates delamination of the hydrogel layer, which in turn improves the dirt-removing ability of the hydrogel layer. The textile of the composite element also facilitates the coupling of the composite element to the plate. Since the hydrogel layer does not extend to the second side of the textile, at least the second side of the textile, and in some aspects, a portion of the core, increases the available surface area to which the material (or adhesive layer) of the plate can mechanically bond to the composite element and thus to the hydrogel layer. When using polymeric materials with significantly different surface energies, such as relatively hydrophilic polymeric hydrogels (e.g., polyurethane hydrogels) in hydrogel layers and relatively hydrophobic materials (e.g., polyolefins) in sheets, it has been found that the increased bond strength provided by the presence of these mechanical bonds significantly improves the bond strength between these otherwise relatively incompatible materials. Conventional adhesives used in the footwear industry (e.g., polyurethane-based contact adhesives and / or hot melt adhesives) are used to complement these mechanical bonds; however, in many cases, the strength of these mechanical bonds, especially when they are thermal bonds formed by melting or softening the hydrogel and / or sheet materials, is large enough that the use of additional adhesives is unnecessary. Further aspects, geometries, and characteristics of this layered structure will be discussed in this paper.

[0054] As can be understood, preventing or reducing dirt buildup on items can offer numerous benefits. Preventing or reducing dirt buildup during use on unpaved, muddy, or wet surfaces can significantly affect the weight of dirt that adheres to the item during use. Preventing or reducing dirt buildup can help improve safety. Furthermore, preventing or reducing dirt buildup makes the item easier to clean after use.

[0055] This disclosure may be described according to the following numbered aspects, which should not be confused with the claims.

[0056] According to aspect 1, this disclosure relates to a composite element comprising:

[0057] A textile, the textile comprising textile material and having a first side, a second side, and a core located between the first side and the second side;

[0058] A hydrogel layer comprising a hydrogel material and having a first side and a second side, the second side being operatively attached to the textile along the first side of the textile.

[0059] A portion of the hydrogel layer extends through the first side of the textile and at least partially into the core of the textile, but does not extend to the second side of the textile.

[0060] According to aspect 2, this disclosure relates to a composite element of any one of aspects 1 to 20, wherein the textile has a core thickness of about 0.1 mm to about 5 mm, or about 0.2 mm to about 3 mm, or about 0.3 mm to about 2 mm, measured between the first and second sides of the textile, prior to the textile being operably coupled to the hydrogel layer.

[0061] According to aspect 3, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the textile is a breathable textile prior to its first side being operably bonded to the hydrogel layer, optionally wherein the textile has breathability from about 10 cubic centimeters per square centimeter per second to about 250 cubic centimeters per square centimeter per second, or from about 50 cubic centimeters per square centimeter per second to about 150 cubic centimeters per square centimeter per second, as determined using ASTM D737-4, prior to its first side being operably bonded to the hydrogel layer.

[0062] According to aspect 4, this disclosure relates to a composite element according to any one of aspects 1 to 20, wherein the textile material has a textile material melting temperature or textile material Vicat softening temperature that is at least 20 degrees Celsius, or at least 50 degrees Celsius, or at least 75 degrees Celsius, or at least 100 degrees Celsius greater than the melting temperature or Vicat softening temperature of the hydrogel material of the hydrogel layer.

[0063] According to aspect 5, this disclosure relates to a composite element of any one of aspects 1 to 20, wherein the hydrogel layer permeates at least 10 percent, or at least 20 percent, or at least 30 percent, or at least 40 percent, or at least 50 percent, or at least 60 percent of the core thickness of the textile.

[0064] According to aspect 6, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the hydrogel layer permeates less than 90 percent, or less than 80 percent, or less than 70 percent, or less than 60 percent, or less than 50 percent, or less than 40 percent, or less than 30 percent of the core thickness of the textile.

[0065] According to aspect 7, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the textile includes at least one textile selected from woven textiles, non-woven textiles, knitted textiles, braided textiles, crocheted textiles, or combinations thereof.

[0066] According to aspect 8, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the textile includes at least one nonwoven textile selected from carded materials, air-laid materials, wet-laid materials, spunbond materials, meltblown materials, or combinations thereof.

[0067] According to aspect 9, this disclosure relates to a composite element according to any one of aspects 1 to 20, wherein the textile comprises one or more natural fibers or yarns or synthetic fibers or yarns, optionally wherein the textile comprises one or more synthetic fibers, and the one or more synthetic fibers comprise a polymer material, said polymer material comprising polymers selected from polyesters, polyamides, polyolefins or combinations thereof.

[0068] According to aspect 10, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the textile comprises one or more recycled fibers.

[0069] According to aspect 11, this disclosure relates to a composite element according to any one of aspects 1 to 20, wherein the textile has a basis weight of about 5 g / m² to about 500 g / m², or wherein the hydrogel layer has a dry thickness in the range of 0.1 mm to 2 mm, or wherein the hydrogel material has a melt flow index of about 35 g / 10 min to about 55 g / 10 min according to the melt flow index test scheme, or any combination thereof.

[0070] According to aspect 12, this disclosure relates to a composite element according to any one of aspects 1 to 20, wherein the hydrogel material exhibits a wet glass transition temperature at 90 percent relative humidity equilibrium and a dry glass transition temperature at 0 percent relative humidity equilibrium, as characterized by a glass transition temperature testing scheme using a pure material sampling procedure.

[0071] The wet glass transition temperature is more than 6 degrees Celsius lower than the dry glass transition temperature.

[0072] According to aspect 13, this disclosure relates to a composite element according to any one of aspects 1 to 20, wherein the hydrogel material has a wet storage modulus at 90 percent relative humidity equilibrium and a dry storage modulus at 0 percent relative humidity equilibrium, characterized by a storage modulus testing scheme using a pure material sampling procedure.

[0073] The wet energy storage modulus is less than the dry energy storage modulus of hydrogel materials.

[0074] According to aspect 14, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the hydrogel material includes a thermoplastic hydrogel.

[0075] According to aspect 15, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the hydrogel material comprises one or more polymers selected from polyurethane, polyamide homopolymer, polyamide, and any combination thereof.

[0076] According to aspect 16, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the hydrogel material includes a polyurethane hydrogel.

[0077] According to aspect 17, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the hydrogel material comprises a polyamide block copolymer hydrogel.

[0078] According to aspect 18, this disclosure relates to a composite element as described in any one of aspects 1 to 20, wherein the hydrogel layer comprises a mixture or dispersion of a hydrogel material and an elastomer material.

[0079] According to aspect 19, this disclosure relates to a composite element according to any one of aspects 1 to 20, wherein the hydrogel layer comprises a first cured rubber and a mixture of hydrogel material from about 30% to about 70% by weight based on the total weight of the mixture, wherein the hydrogel material comprises a polyurethane hydrogel.

[0080] According to aspect 20, this disclosure relates to a composite element according to any one of aspects 1 to 20, wherein a hydrogel material is distributed throughout the hydrogel layer and embedded in a first polymer network comprising a first cured rubber.

[0081] According to aspect 21, this disclosure relates to an article comprising:

[0082] Composite element, the composite element comprising:

[0083] A first textile fabric comprising a first textile material and having a first side, a second side, and a core located between the first side and the second side;

[0084] A hydrogel layer comprising a hydrogel material and having a first side and a second side, the second side being operatively attached to the textile along the first side of the first textile.

[0085] A portion of the hydrogel layer extends through the first side of the first textile and at least partially into the core of the first textile, but does not extend to the second side of the first textile;

[0086] At least a portion of the first side of the hydrogel layer provides the first outward-facing surface of the article; and

[0087] The second element comprises a second polymer material and has a first side and a second side, wherein at least a portion of the first side of the second element is operatively connected to the second side of the first textile.

[0088] According to aspect 22, this disclosure relates to the articles described in aspect 21, wherein the articles are footwear articles, parts of footwear articles, clothing articles, parts of clothing articles, sports equipment articles, or parts of sports equipment articles.

[0089] According to aspect 23, this disclosure relates to the article described in aspect 21, wherein the composite element is the composite element according to any one of aspects 1 to 20.

[0090] According to aspect 24, this disclosure relates to a sole structure for footwear articles, said sole structure comprising:

[0091] Composite element, the composite element comprising:

[0092] A first textile fabric comprising a first textile material and having a first side, a second side, and a core located between the first side and the second side;

[0093] A hydrogel layer comprising a hydrogel material and having a first side and a second side, the second side being operatively attached to the textile along the first side of the first textile.

[0094] A portion of the hydrogel layer extends through the first side of the first textile and at least partially into the core of the first textile, but does not extend to the second side of the first textile;

[0095] At least a portion of the first side of the hydrogel layer provides the first ground-facing surface of the sole structure; and

[0096] A sole component comprising a second polymer material, the sole component having a first side and a second side, wherein at least a portion of the first side of the sole component is operatively connected to the second side of a first textile.

[0097] According to aspect 25, this disclosure relates to the sole structure described in aspect 24, wherein the sole component is a full plate or a partial plate, or wherein sole component b) includes one or more adhesive friction elements, or includes a pod containing more than one connected adhesive friction element, or wherein the sole component is a full plate or a partial plate including one or more adhesive friction elements.

[0098] According to aspect 26, this disclosure relates to the sole structure described in aspect 24, wherein the composite element includes the composite element according to any one of aspects 1 to 20.

[0099] According to aspect 27, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the sole structure further includes a second textile, the second textile comprising a second textile material and having a first side, a second side, and a core located between the first side and the second side, wherein the second side of the second textile is operatively connected to the second side of the sole component.

[0100] According to aspect 28, this disclosure relates to the sole structure described in aspect 27, wherein the second textile is a composite element according to any one of aspects 1 to 20.

[0101] According to aspect 29, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein the second polymer material comprises a thermoplastic polymer, optionally wherein the thermoplastic polymer is a thermoplastic polyolefin, optionally wherein the thermoplastic polyolefin is a thermoplastic polyolefin copolymer.

[0102] According to aspect 30, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein the second polymer material comprises a polyolefin.

[0103] According to aspect 31, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein the second polymer material comprises a copolymer.

[0104] According to aspect 32, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein the second polymer material comprises a polyolefin copolymer and optionally an effective amount of a polymer resin modifier, optionally wherein the effective amount of the polymer resin modifier is based on at least 5% by weight of the total weight of the second polymer material.

[0105] According to aspect 33, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein, according to the melt flow index test scheme, the second polymer material has a melt flow index from about 35 grams per 10 minutes to about 55 grams per 10 minutes.

[0106] According to aspect 34, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein a second polymer material has a density of approximately 0.05 cubic centimeters (cm³) using a pure material sampling procedure according to ASTM D 5963-97a. 3 From approximately 0.1 cubic centimeters (cm) 3 ), approximately 0.07 cubic centimeters (cm) 3 From approximately 0.1 cubic centimeters (cm) 3 ), approximately 0.08 cubic centimeters (cm) 3 From approximately 0.1 cubic centimeters (cm) 3 or approximately 0.08 cubic centimeters (cm) 3 From approximately 0.11 cubic centimeters (cm) 3 Wear and tear.

[0107] According to aspect 35, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the effective amount of the polymer resin modifier is such that it effectively allows the second polymer material to undergo a flexural test according to the Cold Sole Material Flexural Test Protocol using a substrate sampling procedure; optionally, the effective amount of the polymer resin modifier is such that it effectively allows the second polymer material to undergo a flexural test according to the Cold Sole Material Flexural Test Protocol using a substrate sampling procedure, and when measured using a pure material sampling procedure according to ASTM D 5963-97a, the abrasion loss is not significantly different compared to that of a similar polymer material identical to the second polymer material except without the polymer resin modifier.

[0108] According to aspect 36, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the abrasion loss of the second polymer material is from about 0.08 cubic centimeters to about 0.1 cubic centimeters.

[0109] According to aspect 37, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polyolefin copolymer is a random copolymer, optionally wherein the polyolefin copolymer comprises more than one repeating unit, wherein each of the more than one repeating unit is individually derived from an olefin monomer having about 1 to about 6 carbon atoms, optionally wherein the polyolefin copolymer is a random copolymer and comprises more than one repeating unit, wherein each of the more than one repeating unit is individually derived from an olefin monomer having about 1 to about 6 carbon atoms, optionally wherein the polyolefin copolymer comprises more than one repeating unit, wherein each of the more than one repeating unit is individually derived from a monomer selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-butene, and combinations thereof.

[0110] According to aspect 38, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polyolefin copolymer comprises more than one repeating unit, each repeating unit being individually selected from formula 1A to formula 1D.

[0111]

[0112] According to aspect 39, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polyolefin copolymer comprises more than one repeating unit, each repeating unit individually having a structure according to formula 2.

[0113]

[0114] Where R 1 It is hydrogen or a straight-chain or branched C1-C with or without substitution. 12 Alkyl or heteroalkyl.

[0115] According to aspect 40, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polymer in the second polymer material is substantially composed of a polyolefin copolymer.

[0116] According to aspect 41, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polyolefin copolymer is a random copolymer of a first repeating unit and a second repeating unit, and wherein each repeating unit in the first repeating unit is derived from ethylene, and each repeating unit in the second repeating unit is derived from a second olefin, optionally wherein the second olefin is selected from the group consisting of propylene, 4-methyl-1-pentene, 1-butene, and other terminal olefins having a straight chain or branched chain having about 3 to 12 carbon atoms.

[0117] According to aspect 42, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein each of the first more than one repeating unit has a structure according to formula 1A, and wherein each of the second more than one repeating unit has a structure selected from formulas 1B to 1D.

[0118]

[0119] Optionally, each of the first more than one repeating units has a structure according to Equation 1A, and each of the second more than one repeating units has a structure according to Equation 2.

[0120]

[0121] Where R 1It is hydrogen or a substituted or unsubstituted straight or branched C2-C chain. 12 Alkyl or heteroalkyl.

[0122] According to aspect 43, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polyolefin copolymer comprises 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 by weight based on the total weight of the polyolefin copolymer, optionally wherein the polyolefin copolymer comprises 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 by weight based on the total weight of the polyolefin copolymer.

[0123] According to aspect 44, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polyolefin copolymer is substantially free of polyurethane, or wherein the polymer chains of the polyolefin copolymer are substantially free of urethane repeating units, or wherein the second polymer material is substantially free of polymer chains comprising urethane repeating units, or any combination thereof.

[0124] According to aspect 45, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polyolefin copolymer is substantially free of polyamide, wherein the polymer chain of the polyolefin copolymer is substantially free of amide repeating units, or wherein the second polymer material is substantially free of polymer chains containing amide repeating units, or any combination thereof.

[0125] According to aspect 46, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein the polyolefin copolymer includes a polypropylene copolymer, optionally wherein the polypropylene copolymer comprises 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 by weight based on the total weight of the polypropylene copolymer, optionally wherein the polypropylene copolymer comprises 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 by weight based on the total weight of the polypropylene copolymer.

[0126] According to aspect 47, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polypropylene copolymer is a random copolymer comprising, by weight, a first more than one repeating unit of about 2% to about 3% and by weight, a second more than one repeating unit of about 80% to about 99%; wherein each repeating unit in the first more than one repeating unit has a structure according to formula 1A, and each repeating unit in the second more than one repeating unit has a structure according to formula 1B.

[0127]

[0128] According to aspect 48, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polymer in the second polymer material is substantially composed of repeating propylene units, optionally wherein the second polymer material is substantially composed of a polypropylene copolymer, optionally wherein the polypropylene copolymer is a random copolymer of ethylene and propylene, optionally wherein the second polymer material includes an elastomer material, optionally an olefin elastomer.

[0129] According to aspect 49, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein the second polymer material comprises polystyrene, polyethylene, ethylene-α-olefin copolymer, ethylene-propylene rubber (EPDM), polybutene, polyisobutylene, poly-4-methylpent-1-ene, polyisoprene, polybutadiene, ethylene-methacrylic acid copolymer, copolymers thereof, or blends or mixtures thereof; optionally, the second polymer material comprises repeating units of styrene, butene, isobutylene, isoprene, butadiene, or combinations thereof; optionally, the second polymer material comprises a block copolymer comprising polystyrene blocks; wherein the block copolymer comprises a copolymer of one or both of ethylene and butene with styrene; optionally, the second polymer material comprises ethylene-propylene-diene rubber (EPDM) dispersed in polypropylene.

[0130] According to aspect 50, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein the second polymer material includes polyurethane, polyamide, polyester, polyether, polyurea, or copolymers thereof, or combinations thereof.

[0131] According to aspect 51, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein, when measured using a pure material sampling procedure according to ASTM D 5963-97a, the abrasion loss of the second polymer material is within about 20 percent of the abrasion loss of a second polymer material that is otherwise identical except without a resin modifier; or wherein, when measured using a pure material sampling procedure according to a crystallinity test protocol, the second polymer material has a crystallinity percentage of about 35 percent, about 30 percent, about 25 percent, or lower; or wherein, when measured using a pure material sampling procedure according to a crystallinity test protocol, the second polymer material has a crystallinity percentage that is at least 4 percentage points lower than the crystallinity percentage of a second polymer material that is otherwise identical except without a polymer resin modifier.

[0132] According to aspect 52, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the effective amount of the polymeric resin modifier is about 5% to about 30%, about 5% to about 25%, about 5% to about 20%, about 5% to about 15%, about 5% to about 10%, about 10% to about 15%, about 10% to about 20%, about 10% to about 25%, or about 10% to about 30%, based on the total weight of the second polymeric material, or wherein the effective amount of the polymeric resin modifier is about 20%, about 15%, about 10%, about 5%, or less based on the total weight of the second polymeric material.

[0133] According to aspect 53, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polymer resin modifier comprises about 10 percent to about 15 percent by weight of ethylene repeating units based on the total weight of the polymer resin modifier; optionally, wherein the polymer resin modifier comprises about 10 percent to about 15 percent by weight of repeating units according to formula 1A based on the total weight of the polymer resin modifier.

[0134]

[0135] According to aspect 54, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the second polymer material has a total ethylene repeating unit content of about 3% to about 7% by weight based on the total weight of the second polymer material, or wherein the polymer resin modifier has a ethylene repeating unit content of about 10% to about 15% by weight based on the total weight of the polymer resin modifier.

[0136] According to aspect 55, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polymer resin modifier is a copolymer comprising isotactic repeating units derived from olefins, wherein the polymer resin modifier is a copolymer comprising repeating units according to formula 1B, and wherein the repeating units according to formula 1B are arranged in an isotactic stereochemical configuration.

[0137]

[0138] According to aspect 56, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein a cold sole material flexural test scheme and a pure material sampling procedure are used, and a second polymer material that is identical in all respects except for the absence of a polymer resin modifier fails the cold sole material flexural test.

[0139] According to aspect 57, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polymer resin modifier is a copolymer comprising isotactic propylene repeating units and ethylene repeating units, optionally wherein the polymer resin modifier is a copolymer comprising a first more than one repeating unit and a second more than one repeating unit; wherein each repeating unit in the first more than one repeating unit has a structure according to formula 1A, and each repeating unit in the second more than one repeating unit has a structure according to formula 1B, and wherein the repeating units in the second more than one repeating unit are arranged in an isotactic stereochemical configuration.

[0140]

[0141] According to aspect 58, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the polymer resin modifier is a metallocene-catalyzed polymer, optionally a metallocene-catalyzed copolymer, or optionally a metallocene-catalyzed propylene copolymer.

[0142] According to aspect 59, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the second polymer material further comprises a transparent agent, optionally wherein the transparent agent is present in an amount from about 0.5 percent to about 5 percent or from about 1.5 percent to about 2.5 percent by weight based on the total weight of the polyolefin resin, optionally wherein the transparent agent is selected from the group consisting of: substituted or unsubstituted dibenzyl sorbitol, 1,3-O-2,4-bis(3,4-dimethylbenzyl)sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene] and derivatives thereof.

[0143] According to aspect 60, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the transparent agent comprises an acetal compound, which is a condensation product of a polyol and an aromatic aldehyde, wherein the polyol is selected from the group consisting of: acyclic polyols such as xylitol and sorbitol, and acyclic deoxypolyols such as 1,2,3-trideoxynonitol or 1,2,3-trideoxynon-1-enitol, optionally wherein the aromatic aldehyde is selected from the group consisting of benzaldehyde and substituted benzaldehyde.

[0144] According to aspect 61, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein the first textile or the second textile or both include decorative elements, optionally wherein the decorative elements are printed elements, dyed elements, or structurally colored elements, or embroidered elements, or any combination thereof, optionally wherein the decorative elements are visible from the ground-facing side of the sole structure.

[0145] According to aspect 62, this disclosure relates to a sole structure of any one of aspects 24 to 78, wherein a first textile or a second textile or both include an adhesive layer, and the adhesive layer is on a first side or a second side of the first textile, or on a first side of the second textile, or on a second side of the second textile, or any combination thereof.

[0146] According to aspect 63, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the sole structure further includes a first adhesive layer operatively connecting a second side of a hydrogel layer to a first side of a first textile; a second adhesive layer operatively connecting a second side of the first textile to a first side of a sole component; or a third adhesive layer operatively connecting a second side of the second textile to a second side of a sole component; or a fourth adhesive layer positioned on a first side of the second textile; or any combination thereof.

[0147] According to aspect 64, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein a first adhesive layer, a second adhesive layer, or both penetrate at least a portion of the core thickness of a first textile; or a third adhesive layer or a fourth adhesive layer, or both penetrate at least a portion of the core thickness of a third textile; or any combination thereof.

[0148] According to aspect 65, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein a first adhesive layer, a second adhesive layer, or both penetrate at least 10 percent, or at least 20 percent, or at least 30 percent, or at least 40 percent of the core thickness of a first textile; or a third adhesive layer or a fourth adhesive layer, or both penetrate at least 10 percent, or at least 20 percent, or at least 30 percent, or at least 40 percent of the core thickness of a second textile; or any combination thereof.

[0149] According to aspect 66, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, or both penetrate the core thickness of the first textile by less than 80%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30%; or the third adhesive layer or the fourth adhesive layer, or both penetrate the core thickness of the second textile by less than 80%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30%; or any combination thereof.

[0150] According to aspect 67, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, the third adhesive layer, the fourth adhesive layer, or any combination thereof has a thickness from about 0.2 mm to about 2.0 mm.

[0151] According to aspect 68, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, the third adhesive layer, the fourth adhesive layer, or any combination thereof has a thickness from about 0.4 mm to about 1.5 mm.

[0152] According to aspect 69, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, the third adhesive layer, the fourth adhesive layer, or any combination thereof comprises a contact adhesive or a hot melt adhesive, optionally wherein the hot melt adhesive comprises polyurethane, optionally wherein the hot melt adhesive has a melt flow index from about 35 grams per 10 minutes to about 55 grams per 10 minutes according to the melt flow index test scheme.

[0153] According to aspect 70, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein a first ground-facing surface of the sole structure provides at least about 80 percent of the total ground-facing surface of the sole structure.

[0154] According to aspect 71, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein a first side of the sole component includes a second portion providing a second surface of the sole structure, and the second surface of the sole structure is configured to be a surface in contact with the ground.

[0155] According to aspect 72, this disclosure relates to a sole structure of any one of aspects 24 to 78, wherein the second surface includes one or more adhesion friction elements, optionally one or more adhesion friction elements being integrally formed with a sole component; or wherein the sole component includes one or more openings configured to receive removable adhesion friction elements; optionally one or more adhesion friction elements include lugs, anti-slip elements, studs, spikes, or combinations thereof.

[0156] According to aspect 73, this disclosure relates to a sole structure according to any one of aspects 24 to 78, wherein the hydrogel layer has an outer periphery, and one or more adhesive friction elements of the sole component are disposed outside the outer periphery of the hydrogel layer; optionally, wherein the hydrogel layer has a void at least partially defined by an inner periphery, and at least one of the one or more adhesive friction elements of the sole component occupies at least a portion of the void in the hydrogel layer.

[0157] According to aspect 74, this disclosure relates to a sole structure as described in any one of aspects 24 to 78, wherein the hydrogel layer has a dry thickness in the range of 0.1 mm to 2 mm.

[0158] According to aspect 75, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein the hydrogel material has a melt flow index from about 35 grams per 10 minutes to about 55 grams per 10 minutes according to the melt flow index test scheme.

[0159] According to aspect 76, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein the hydrogel layer has a water absorption capacity greater than 40 percent by weight at 1 hour, as characterized by a water absorption capacity test scheme using a component sampling procedure; or wherein the hydrogel layer has a water absorption rate greater than 20 g / m² / √min, as characterized by a water absorption rate test scheme using a component sampling procedure; or wherein the hydrogel layer has a swelling thickness increase greater than 20 percent at 1 hour, as characterized by a swelling capacity test scheme using a component sampling procedure; or wherein, using a component sampling procedure, at least a portion of the outer surface of the hydrogel layer exhibits one or more of a wet contact angle less than 80° as characterized by a contact angle test scheme and a wet coefficient of friction less than 0.8 as characterized by a coefficient of friction test scheme; or wherein the hydrogel material exhibits a wet glass transition temperature at 90 percent relative humidity equilibrium and a dry glass transition temperature at 0 percent relative humidity equilibrium, as characterized by a glass transition temperature test scheme using a pure material sampling procedure;

[0160] The wet glass transition temperature is more than 6 degrees Celsius lower than the dry glass transition temperature; or the hydrogel material has a wet storage modulus at 90 percent relative humidity equilibrium and a dry storage modulus at 0 percent relative humidity equilibrium, as characterized by a storage modulus testing scheme using a pure material sampling procedure.

[0161] The wet storage modulus is less than the dry storage modulus of the hydrogel material; or any combination thereof.

[0162] According to aspect 77, this disclosure relates to the sole structure of any one of aspects 24 to 78, wherein the hydrogel material comprises a thermoplastic hydrogel, optionally wherein the hydrogel material comprises one or more polymers selected from polyurethane, polyamide homopolymer, polyamide copolymer or any combination thereof; optionally wherein the hydrogel material comprises thermoplastic polyurethane, or wherein the hydrogel material comprises a polyamide block copolymer.

[0163] According to aspect 78, this disclosure relates to a sole structure of any one of aspects 24 to 78, wherein the hydrogel material comprises a mixture or dispersion of a polymeric hydrogel and an elastomeric material; optionally, wherein the hydrogel material comprises a first cured rubber and a mixture of polymeric hydrogel from about 30% to about 70% by weight based on the total weight of the mixture, wherein the polymeric hydrogel comprises a polyurethane hydrogel; optionally, wherein the polymeric hydrogel is distributed throughout the hydrogel material and is embedded in a first polymeric network comprising the first cured rubber.

[0164] According to aspect 79, this disclosure relates to a footwear article comprising an upper operatively connected to a sole structure as described in any one of aspects 24 to 78.

[0165] According to aspect 80, this disclosure relates to footwear articles according to any one of aspects 79 to 81, wherein the sole structure includes a sole component operatively attached to a second textile, the second textile including a fourth adhesive layer present on a first side of the second textile, and the fourth adhesive layer operatively attaching the upper to the sole structure.

[0166] According to aspect 81, this disclosure relates to footwear articles as described in any one of aspects 79 to 81, wherein the article includes a mechanical or adhesive joint between a second side of a sole component and an upper.

[0167] According to aspect 82, this disclosure relates to a method for manufacturing a composite element, the method comprising:

[0168] The hydrogel layer containing the hydrogel material is operatively attached to the first side of the textile.

[0169] A portion of the hydrogel layer extends through the first side of the textile and at least partially through the core of the textile, but does not extend to the second side of the textile.

[0170] According to aspect 83, this disclosure relates to a method according to any one of aspects 82-84, wherein the step of operatively attaching the hydrogel layer to a first side of the textile comprises spraying, dipping, brushing, or printing the hydrogel material onto the first side of the textile; or wherein the step of operatively attaching the hydrogel layer to the first side of the textile comprises extruding, casting, or injection molding the hydrogel material onto the first side of the textile; or wherein the step of operatively attaching the hydrogel layer to the first side of the textile comprises mechanically, chemically, and / or thermally bonding the hydrogel material to the first side of the textile; or wherein the step of operatively attaching the hydrogel layer to the first side of the textile comprises raising the temperature of the hydrogel material to an amount equal to or greater than the melting temperature or Vicat softening temperature of the hydrogel material, but lower than the Vicat softening temperature of the textile material. The first temperature; and contacting the softened hydrogel layer or the molten hydrogel layer with a first side of the textile, such that at least a portion of the hydrogel material permeates the first side of the textile; or wherein the step of operably linking the hydrogel layer includes melting both the hydrogel material and the textile material, contacting the molten hydrogel material with the molten textile material, and mixing the polymer chains of the molten hydrogel material and the polymer chains of the molten textile material; or wherein the step of operably linking the hydrogel layer with the first side of the textile further includes: after contacting the textile material with the molten hydrogel material or the softened hydrogel material, lowering the temperature of the hydrogel material to a second temperature below the melting temperature or Vicat softening temperature of the hydrogel material, thereby solidifying the molten hydrogel material or the softened hydrogel material.

[0171] According to aspect 84, this disclosure relates to the method of any one of aspects 82 to 84, wherein the textile material has a textile melting temperature or textile Vicat softening temperature that is at least 20 degrees Celsius, or at least 30 degrees Celsius, or at least 40 degrees Celsius, or at least 50 degrees Celsius, or at least 60 degrees Celsius, or at least 70 degrees Celsius, or at least 80 degrees Celsius, or at least 90 degrees Celsius, or at least 100 degrees Celsius greater than the melting temperature or Vicat softening temperature of the hydrogel material.

[0172] According to aspect 85, this disclosure relates to a method of manufacturing an article, the method comprising:

[0173] The first composite element is operatively coupled to the second component; the composite element includes a textile and a hydrogel layer; the textile comprises textile material and has a first side, a second side, and a core located between the first and second sides; the hydrogel layer comprises hydrogel material and has a first side and a second side, the second side of the hydrogel layer being operatively coupled to the textile along the first side of the textile; wherein, in the composite element, a portion of the hydrogel layer extends through the first side of the textile and at least partially extends into the core of the textile, but does not extend into the second side of the textile;

[0174] The operable connection includes forming a joint between a second side of the textile of the composite element and a second component, such that a hydrogel layer of the composite element defines at least a portion of the outward-facing surface of the second component.

[0175] According to aspect 86, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the operably coupled step includes forming a mechanical bond between a second side of the textile and a second polymer material.

[0176] According to aspect 87, this disclosure relates to the method of any one of aspects 85 to 114, wherein the article is a footwear article, a part of a footwear article, a clothing article, a part of a clothing article, a sports equipment article, or a part of a sports equipment article.

[0177] According to aspect 88, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the article is a sole structure of a footwear article, and optionally wherein the outward-facing surface is the ground-facing surface of the sole structure.

[0178] According to aspect 89, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the operably coupled step includes placing a first composite element into a mold such that a portion of a first side surface of the hydrogel layer contacts a portion of a molded surface of the mold to form the prepared molded surface.

[0179] The second polymer material is loaded onto the molding surface of the prepared mold;

[0180] The loaded second polymer material is at least partially cured in a mold, thereby operatively linking the composite element and the at least partially cured second polymer material to form a sole structure including a hydrogel layer of the composite element, the hydrogel layer defining at least a portion of the ground-facing surface of the sole structure; and

[0181] Remove the sole structure from the mold.

[0182] According to aspect 90, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the method further includes constraining the composite element in a mold such that, while loading the second polymer material, at least a portion of the first side of the hydrogel layer contacts the molded surface.

[0183] According to aspect 91, this disclosure relates to the method of any one of aspects 85 to 114, wherein the composite element is the composite element of any one of aspects 1 to 20.

[0184] According to aspect 92, this disclosure relates to the method of any one of aspects 85 to 114, wherein the sole structure is the sole structure of any one of aspects 26 to 78.

[0185] According to aspect 93, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the second polymer material is a thermosetting material, and the step of at least partially curing the loaded second material comprises at least partially curing the loaded second material into a thermosetting second material.

[0186] According to aspect 94, this disclosure relates to the method of any one of aspects 85 to 114, further comprising raising the temperature of the second polymer material to a molding temperature above the melting temperature or Vicat softening temperature of the second polymer material.

[0187] According to aspect 95, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the step of raising the temperature of the second polymer material to the molding temperature is performed before or during the step of loading the second polymer material.

[0188] According to aspect 96, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the step of raising the temperature of the second polymer material to the molding temperature is performed when the second polymer material comes into contact with the prepared molding surface.

[0189] According to aspect 97, this disclosure relates to a method according to any one of aspects 85 to 114, wherein after the temperature of the second polymer material is raised to the molding temperature, at least a portion of the second polymer material permeates the second side of the textile.

[0190] According to aspect 98, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the second polymer material is a thermoplastic material, and the step of curing the second polymer material includes lowering the temperature of the second polymer material to a second temperature below the melting temperature or Vicat softening temperature of the second polymer material.

[0191] According to aspect 99, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the first composite element further includes a hot melt adhesive layer on a second side of the textile, and the step of raising the temperature to the molding temperature includes raising the temperature of the hot melt adhesive to a temperature higher than the melting temperature of the hot melt adhesive, such that the adhesive bonds to the second polymer material.

[0192] According to aspect 100, this disclosure relates to the method of any one of aspects 85 to 114, and further includes a method for manufacturing a composite element according to any one of aspects 82 to 84.

[0193] According to aspect 101, this disclosure relates to the method of any one of aspects 85 to 114, further comprising raising the temperature of the second polymer material to a third temperature above the Vicat softening temperature of the second polymer material.

[0194] According to aspect 102, this disclosure relates to a method according to any one of aspects 85 to 114, wherein after the temperature of the second polymer material is raised to the molding temperature, at least a portion of the second polymer material permeates into the core of the textile.

[0195] According to aspect 103, this disclosure relates to a method according to any one of aspects 85 to 114, wherein curing the second polymer material includes lowering the temperature of the second polymer material to a temperature below the Vicat softening temperature of the second polymer material.

[0196] According to aspect 104, this disclosure relates to the method of any one of aspects 85 to 114, further comprising providing an adhesive layer on a first side of the textile, a second side of the textile, or both.

[0197] According to aspect 105, this disclosure relates to a method according to any one of aspects 85 to 114, wherein the step of loading a second polymer material into a mold includes closing the mold and injecting the second polymer material into the closed mold using an injection molding process.

[0198] According to aspect 106, this disclosure relates to a method according to any one of aspects 85 to 114, wherein loading a second polymer material into a mold includes loading the second polymer material into the mold, closing the mold before, during, or after loading, and applying compression to the closed mold.

[0199] According to aspect 107, this disclosure relates to the method of any one of aspects 85 to 114, wherein the step of constraining a portion of a first side of the hydrogel layer against a molded surface includes using a vacuum, using one or more retractable pins, or both using a vacuum and one or more retractable pins.

[0200] According to aspect 108, this disclosure relates to the method of any one of aspects 85 to 114, wherein the molded surface is in the predetermined shape of the sole component.

[0201] According to aspect 109, this disclosure relates to the method of any one of aspects 85 to 114, wherein at least a portion of the molded surface has a predetermined curvature.

[0202] According to aspect 110, this disclosure relates to a method according to any one of aspects 85 to 114, wherein placing the composite element in a mold and / or constraining a portion of a first side of the hydrogel layer against a molding surface includes bending or flexing the hydrogel layer to conform to the curvature of the molding surface while maintaining the hydrogel layer at a temperature in the range of about 10 degrees Celsius to about 80 degrees Celsius.

[0203] According to aspect 111, this disclosure relates to the method of any one of aspects 85 to 114, wherein one or more adhesive friction elements are integrally formed with the sole structure during the molding step; after the sole structure is removed from the mold, they are respectively added as snap-fit ​​parts or screw-in parts; or combinations thereof; wherein one or more adhesive friction elements are integrally formed with the sole structure using a second polymer material.

[0204] According to aspect 112, this disclosure relates to the method of any one of aspects 85 to 114, further comprising placing one or more pre-formed adhesion friction element tips into a mold before loading a second polymer material.

[0205] According to aspect 113, this disclosure relates to the method of any one of aspects 85 to 114, wherein the adhering friction element includes an adhering friction element material, and the adhering friction element material has a higher average hardness or a lower average wear loss, or both, compared to the second polymer material.

[0206] According to aspect 114, this disclosure relates to the method of any one of aspects 85 to 114, wherein the adhering friction element is a lug, anti-slip element, stud, shoe spike, or a combination thereof.

[0207] According to aspect 115, this disclosure relates to a method for manufacturing footwear articles, the method comprising:

[0208] The upper is attached to a sole structure, the sole structure including a hydrogel layer and a sole component, the hydrogel layer having a first side and a second side operatively connected to the first side of a textile, the sole component including a second polymer material operatively connected to the second side of the textile, such that the first side of the hydrogel layer of the sole structure defines the ground-facing surface of the footwear article.

[0209] According to aspect 116, this disclosure relates to a method according to any one of aspects 115 to 120, wherein the method further comprises:

[0210] Before attaching the sole structure to the upper, attach the sole interlayer to the sole structure and / or the upper, such that the sole interlayer is positioned between the sole structure and the upper.

[0211] According to aspect 117, this disclosure relates to the method of any one of aspects 115 to 120, wherein the upper comprises natural leather, thermosetting polymer, thermoplastic polymer or mixture thereof.

[0212] According to aspect 118, this disclosure relates to the method of any one of aspects 115 to 120, wherein the upper comprises a textile selected from knitted textiles, woven textiles, non-woven textiles, braided textiles, or combinations thereof; optionally wherein the textile comprises one or more natural fibers or yarns or synthetic fibers or yarns; optionally wherein the synthetic fibers or yarns comprise thermoplastic polyurethane (TPU), polyamide, polyester, polyolefin, or mixtures thereof.

[0213] According to aspect 119, this disclosure relates to a method according to any one of aspects 115 to 120, wherein attaching the sole structure to the upper includes using an adhesive, a primer, or a combination thereof.

[0214] According to aspect 120, this disclosure relates to footwear articles manufactured according to any one of aspects 115 to 120.

[0215] Before describing this disclosure in more detail, it should be understood that this disclosure is not limited to the specific aspects described, and therefore is naturally subject to variation. Other systems, methods, features, and advantages of polymeric hydrogels, composite elements, and articles and components formed therefrom will be apparent or will become apparent to those skilled in the art upon review of the accompanying drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within the description, within the scope of this disclosure, and protected by the appended claims. It should also be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Those skilled in the art will recognize many variations and modifications to the aspects described herein. These variations and modifications are intended to be included in the teachings of this disclosure and are covered by the claims herein.

[0216] Composite components

[0217] refer to Figures 1A to 1BIn one aspect, the composite element 110 has a textile 102 and a hydrogel layer 115. The textile 102 comprises a textile material and has a first side 106, a second side 104, and a core 105 between the first side 106 and the second side 104. The textile comprises one or more polymeric materials, wherein the polymeric materials include one or more polymers and optionally one or more non-polymeric components. The textile material comprises a polymeric component consisting of all polymeric components present in the textile material. Before being bonded to the hydrogel layer 115, the textile layer has a core thickness 108 measured between the first side 106 and the second side 104 of the textile. (Reference) Figure 1B The hydrogel layer 115 comprises a hydrogel material and has a first side 114 and a second side 112. The hydrogel layer comprises one or more hydrogel materials, wherein the hydrogel material includes one or more polymeric hydrogels and optionally one or more non-hydrogel polymeric components or one or more non-polymeric components or optionally both. The hydrogel material comprises a polymeric component consisting of all polymeric components present in the hydrogel material, including polymeric hydrogels and non-hydrogel polymers. Similarly, the hydrogel material comprises a hydrogel component consisting of all polymeric hydrogel components present in the hydrogel material. According to one aspect, the hydrogel layer 115 is operatively attached to the textile 102 along a first side 106 such that the hydrogel layer 115 extends through the first side 106 of the textile 102 and at least partially extends into the core 105 of the textile 102, but does not extend all the way through the textile 102. In some aspects, the hydrogel layer 115 extends through the first side 106 of the textile 102 and at least partially extends into the core 105 of the textile 102, but the second side 104 of the textile is substantially free of hydrogel material. In another aspect, the hydrogel layer 115 extends through the first side 106 of the textile 102, but does not extend onto or into the second side 104 of the textile 102. Due to the presence of fibers, filaments, or yarns in the textile, it will be understood that both the first and second sides of the textile have a certain level of surface texture, resulting in a surface area on the sides of the textile being larger than the surface area on the sides of a comparable flat (i.e., substantially untextured) film.

[0218] The presence of a core in the textile further increases the surface area available for forming mechanical joints. In some aspects, the hydrogel layer may permeate at least 10%, at least 20%, at least 30%, or at least 40% of the thickness of the textile core. In other aspects, the hydrogel layer may permeate less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, or less than 30% of the thickness of the textile core.

[0219] In some aspects, the hydrogel layer may have a dry thickness ranging from about 0.1 mm to about 2 mm, or from about 0.3 mm to about 1.5 mm, or from about 0.5 mm to about 1.0 mm.

[0220] The polymer hydrogel is present in the composite element in an amount from about 0.5% to about 85% by weight based on the total weight of the composite element. Alternatively, the polymer hydrogel is present in an amount from about 5% to about 80% by weight based on the total weight of the composite element; alternatively, it is present in an amount from about 10% to about 70% by weight, or from about 20% to about 70% by weight, or from about 30% to about 70% by weight, or from about 45% to about 70% by weight.

[0221] For the purposes of this disclosure, the term "weight" refers to a mass value, such as units having grams, kilograms, and similar units. Furthermore, descriptions of numerical ranges by endpoints include both the endpoints and all numbers within that range. For example, a concentration in the range of 40 percent by weight to 60 percent by weight includes concentrations of 40 percent by weight, 60 percent by weight, and all concentrations in between (e.g., 40.1 percent, 41 percent, 45 percent, 50 percent, 52.5 percent, 55 percent, 59 percent, etc.).

[0222] In one aspect, according to the melt flow index test scheme disclosed herein, the disclosed hydrogel material can have a melt flow index from about 35 g per 10 minutes to about 55 g per 10 minutes (at 190 degrees Celsius, 21.6 kg). In another aspect, the melt flow index can be about 35 g per 10 minutes, about 40 g per 10 minutes, about 45 g per 10 minutes, about 50 g per 10 minutes, or about 55 g per 10 minutes.

[0223] Shoe sole structure and footwear made from it

[0224] In some aspects, this disclosure relates to footwear articles including uppers and sole structures incorporating composite elements. As used herein, the terms "footwear article" and "footwear" are intended to be used interchangeably to refer to the same article. Generally, the term "footwear article" will be used first, and for ease of reading, the term "footwear" may subsequently be used to refer to the same article.

[0225] The sole structure has a plate operatively connected to a composite element, wherein a hydrogel material provides the ground-facing surface of the sole structure. A sole structure with a hydrogel material on the ground-facing surface can prevent or reduce dirt buildup on the ground-facing surface of an article during use on unpaved, muddy, or wet surfaces. However, the applicant has found that the hydrogel material in the hydrogel layer can sometimes separate or delaminate from other materials or components in the sole structure. Without wishing to be bound by any particular theory, it is believed that providing hydrogel material in the hydrogel layer as part of the disclosed composite element can result in improved bonding, reducing or eliminating separation or delamination of the polymer hydrogel, hydrogel material, and / or hydrogel layer from other materials or components.

[0226] The sole component may also include one or more adhesion friction elements or a pod comprising more than one adhesion friction element connected to each other. In one aspect, the sole structure also includes a second textile comprising a second textile material and having a first side, a second side, and a core located between the first and second sides, wherein the second side of the second textile is operatively coupled to the second side of the sole component.

[0227] As used herein with respect to certain structures, layers, or surfaces, the terms “outward-facing,” “ground-facing,” and “ground-contacting” refer to the position in which an element is intended to be when it is present in the article during normal use. As used herein, “outward-facing” refers to an element that forms the outermost surface of the article. If the article is footwear, “outward-facing” can refer to the outermost surface of an upper, sole structure, or both. If the article is footwear, “ground-contacting” refers to an element including the outermost surface that is configured to directly contact the ground and, during normal wear, directly contact the ground on a flat, paved surface. For example, the end of an attached friction element (i.e., the portion of the attached friction element that extends furthest from the bottom of the outsole) directly contacts the ground when used in a conventional manner, such as standing, walking, or running on a paved or unpaved surface. If the article is footwear, “ground-facing” refers to an element including the outermost surface that is positioned towards the ground during normal wear but does not directly contact the ground when the footwear article is in direct contact with a flat, paved surface. In some cases, such as when worn on soft surfaces, during normal wear, such as when worn on soft turf or in muddy conditions, the ground-facing surface may be in direct contact with the ground. During wear on soft surfaces, the ground-facing surface typically collects dirt and / or debris. Examples of ground-facing surfaces include the sides of the attached friction elements or the outsole area between the attached friction elements. In other words, even if an element may not necessarily face outwards or be ground-facing or in contact with the ground during multiple steps of manufacturing or shipping, if the element is expected to face outwards or be ground-facing or in contact with the ground during normal use by the wearer, then the element is understood to be outwards, and more specifically, may be "ground-facing" or "in contact with the ground."

[0228] Footwear can be designed for a variety of uses, such as sports, athletics, military, work-related, recreational, or leisure. Primarily, footwear is intended for outdoor use on unpaved surfaces (partially or entirely), such as on one or more of the following surfaces: grass, turf, gravel, sand, dust, clay, mud, pavement, and the like, whether as a sports performance surface or as a general outdoor surface. However, footwear can also be desirable for indoor applications, such as indoor sports involving dusty playing surfaces (e.g., an indoor baseball field with a dusty infield).

[0229] Footwear articles can be designed for indoor or outdoor sports activities such as football / soccer, golf, American football, rugby, baseball, running, athletics, cycling (e.g., road cycling and mountain biking), and similar sports. Footwear articles may optionally include adhesive friction elements (e.g., lugs, anti-slip elements, studs and cleats, and tread patterns) to provide adhesive friction on soft and smooth surfaces, wherein the articles of this disclosure may be used or applied between or among the adhesive friction elements, and optionally on the sides of the adhesive friction elements but on the surface in contact with the ground or surface. Anti-slip elements, studs, and cleats are commonly included in footwear designed for sports such as football / soccer, golf, American football, rugby, baseball, and similar sports, which are often played on unpaved surfaces. Lugs and / or reinforced tread patterns are commonly included in footwear, including boots, designed for use in harsh outdoor conditions such as cross-country running, hiking, and military applications.

[0230] refer to Figures 2A to 2K The sole structure and footwear articles will be described in more detail with reference to exemplary athletic footwear article 200 with anti-slip features, such as an English football boot / football boot. Footwear article 200 includes an upper 250 operatively coupled to a sole structure 213. The sole structure 213 includes a plate 216 and a composite element 210 disposed on at least a portion of the ground-facing side of the sole structure 213.

[0231] refer to Figure 2J The sole structure 213 is described in more detail below. As described herein, the composite element 210 includes a textile 202 and a hydrogel layer 215 operatively attached to a first side 206 of the textile 202. A second side 204 of the textile 202 is operatively attached to a first ground-facing side 2162 of the plate 216, resulting in the hydrogel layer 215 providing a first ground-facing surface 214 of the sole structure 213. (Reference) Figure 2K A more detailed bottom view of the plate is described below. As described herein, the plate includes a ground-facing surface 214 and a ground-contacting surface 2181.

[0232] The sole structure 213 can be secured to the upper 250. In some aspects, the lower surface of the upper 250 can be secured to the second upper surface 2160 of the plate 216 via an intermingled bond. In some aspects, the intermingled bond is formed by fusing or mixing the polymer in the upper 250 and the polymer resin of the plate 216. In some aspects, a mechanical bond is formed when material from the upper (e.g., any polymer material, hydrogel material, resin, yarn, or the like) penetrates to any distance in the second side 2160 of the plate 216. In some aspects, a mechanical bond is formed whenever there is entanglement between components of two or more elements (e.g., the upper and sole structures) such that they cannot be separated. In some aspects, the lower surface of the upper 250 can be adhesively bonded to the second upper surface 2160 of the plate 216 by providing an adhesive between the polymer resin of the upper 250 and the plate 216. In some aspects, when an adhesive is used, a mechanical bond is formed; that is, the adhesive forms a mechanical bond with both the upper and sole structures, respectively. In some aspects, when an adhesive is used, a chemical bond is formed. In one aspect, the adhesive can be applied to both the polymer resin of the upper 250 and the plate 216, and the two parts can be placed in contact with each other during the curing of the adhesive. In one aspect, this contact during curing results in the formation of a chemical bond. In at least one aspect, textiles are disposed between the plate 216 and the upper 250 to aid in bonding.

[0233] In some aspects, the second side 204 of the textile 202 can be bonded by mixing materials present with the first side 2162 of the plate 216. In some aspects, the second side 204 of the textile 202 can be mechanically bonded to the first side 2162 of the plate 216 by mixing a polymer in the textile 202 and a polymer resin in the plate 216. In some aspects, the second side 204 of the textile 202 can be adhesively bonded to the first side 2162 of the plate 216. In some aspects, bonding can include both mechanical bonding and adhesive bonding.

[0234] The plate 216 comprises a second polymer material. In some aspects, the second polymer material of the plate 216 extends through a second side 204 of the textile 202, forming a mechanical connection between the plate and the composite element. In some aspects, the second polymer material of the plate 216 also extends at least partially through the core 205 of the textile. In some aspects, the second polymer material of the plate may permeate at least 10%, at least 20%, at least 30%, or at least 40% of the core thickness 208 of the textile 202. In another aspect, the second polymer material of the plate 216 may permeate less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, or less than 30% of the core thickness 208 of the textile 202.

[0235] According to another aspect of this disclosure, the sole structure for footwear articles includes two or more composite elements, such as composite elements in the toe portion, heel portion, midfoot portion, or combinations thereof of the sole structure. Each composite element has a hydrogel layer operably bonded to a textile and is oriented such that the hydrogel material of the hydrogel layer defines the ground-facing surface of the sole structure. A second polymer material of a plate is operably bonded to a second side of the textile of the two or more composite elements. In some aspects, the second polymer material of the plate is also operably bonded to the entire outer periphery of each of the two or more composite elements.

[0236] As described herein, an article may include two or more composite elements of different types, wherein the hydrogel layer of each composite element has a different water absorption capacity, such that different physical properties are exhibited by the different types of composite elements.

[0237] refer to Figure 2A In some aspects, the sole structure 213 includes one or more adhesive friction elements, comprising a plurality of adhesive friction elements 218. When worn, the adhesive friction elements 218 provide adhesive friction to the wearer to enhance stability. One or more of the adhesive friction elements 218 may be integrally formed with the plate 216, such as... Figure 2AAs illustrated in the diagram, it may be removable. Optionally, one or more of the adhesion friction elements 218 may include an adhesion friction element tip (not shown) configured to contact the ground. The adhesion friction element tip may be integrally formed with the adhesion friction element 218. Optionally, the adhesion friction element tip may be formed of a material different from the rest of the adhesion friction element 218 (e.g., a metal or a polymeric material containing a harder or more wear-resistant polymeric material). Similarly, a portion (such as the tip) or the entire adhesion friction element may be formed of a material different from the second polymeric material of the plate (e.g., a metal or a polymeric material containing a harder or more wear-resistant polymeric material). Figure 2B This is a front view of the outer side of footwear 200. When footwear 200 is worn, the outer side of 200 is generally oriented on a side away from the center line of the wearer's body. Figure 2C This is a front view of the inner side of the footwear 200. When the footwear 200 is worn, the inner side generally faces the center line of the wearer's body. Figure 2D This is a top view of footwear article 200 (without an insole in place), without a last or other plate-like member 215, and also shows the upper 250. The upper 250 includes a padded collar 220. Optionally or additionally, the upper may include an area (not shown) configured to extend upwards to or cover the wearer's ankle. In at least one aspect, the upper 250 is tongueless, wherein the upper wraps around the inside of the wearer's foot, above the top of the foot, and below the outer portion of the upper, as shown... Figure 2D As illustrated in the diagram. Alternatively, footwear may include a tongue (not shown). Figures 2A-2G As illustrated, the shoelaces of footwear article 200 may optionally be located on the outer side of the article. In other instances, the footwear article may have an over-the-knee design or may include a closure system other than shoelaces (not shown). Figure 2E and Figure 2F These are the front and back views of footwear item 200.

[0238] Figure 2G This is an exploded perspective view of footwear article 200, showing the upper 250, plate 216, and composite element 210. (As shown) Figure 2D As seen in the image, the 250 upper includes the strobel 138. (For example...) Figure 2DAs illustrated, the Strambel 238 is generally shaped like the wearer's foot and closes the bottom of the upper 250. It is stitched to other components along the periphery of the Strambel 238 with stitches 285 to form the upper 250. A last or other plate-like member (not shown) may be located above or below the Strambel 238. In some aspects, a last or other plate-like member may replace the Strambel. The last or other plate-like member may extend substantially the entire length of the plate, or may be present in a portion of the plate's length, such as, for example, in the toe area, or in the midfoot area, or in the heel area. The upper 250, including the Strambel 238, is attached to the upper surface (not shown) of the sole structure 213. Figure 2H This is an exploded perspective view of an alternative embodiment of composite element 2101, which includes a toe portion 2021, a middle portion 2022 and a heel portion 2023 of a textile layer of the composite element, and a toe portion 2151, a middle portion 2152 and a heel portion 2153 of a hydrogel layer of the composite element.

[0239] In some aspects, footwear articles may have a strip operatively connected to the upper and sole construction. Generally, a strip is a component of the footwear article disposed on the outer surface of the footwear article. The strip may be disposed on the upper, the sole construction, or both. In some aspects, the strip may overlap with the bite line at the attachment point of the outsole and the upper, and may extend vertically above and / or below the bite line. The strip may be continuous around the footwear article, or it may be discontinuous or located only in selected areas. For example, the strip may extend around the entire outer perimeter of each of the forefoot portion, midfoot portion, and heel portion of the article. In other embodiments, the strip may be present only on the forefoot portion of the upper, or on both the forefoot and heel portions of the article. The strip may include any material that provides desired or desired properties and characteristics to that area of ​​the footwear article, such as, for example, additional bonding strength between the upper and sole construction, additional abrasion resistance, additional water resistance, or combinations thereof. In some respects, filaments can have a decorative appearance, such as through coloring or printing. In other respects, filaments can have a textured surface.

[0240] In some aspects, the upper of footwear article 200 may include a removable insole (not shown). As is known in the art, an insole conforms to and is lined on the inner sole surface of the shoe, and is a component that comes into contact with the sole of the wearer's foot (or the sole of a sock-wearing foot).

[0241] In one aspect, the hydrogel layer of the composite material provides at least about 50%, at least about 60%, at least about 70%, at least about 80%, and at least about 90% of the total ground-facing surface of the sole structure. In another aspect, a first side of the plate provides a second ground-facing surface of the sole structure.

[0242] According to another aspect of this disclosure, the sole structure also includes one or more adhesion friction elements, wherein one or more composite elements of the sole structure are configured to be fitted between or around the adhesion friction elements. The adhesion friction elements may have a surface in contact with the ground excluding the composite elements. The composite element may include a void having an inner periphery, and the adhesion friction element is present in the void or passes through the void of the composite element. When needed, the adhesion friction element may include a second polymer material operatively connected to the inner periphery of the composite element. The second polymer material may also define the ground-facing surface of the adhesion friction element (e.g., the side of the adhesion friction element), and / or one or more ground-contacting surfaces of the adhesion friction element (e.g., one or more tips of the adhesion friction element).

[0243] In one aspect, the composite element has an outer periphery, and one or more elements of the plate are disposed outside the outer periphery of the composite element. In another aspect, the composite element may have a void region at least partially defined by an inner periphery, and at least one of one or more adhesive friction elements is coupled to the plate in the void region of the composite element.

[0244] In some aspects, a portion of the composite element may be cut, stamped, or molded to form a shape similar to that of a composite element present in a shoe sole structure. In some aspects, the composite element is configured to be assembled between or around one or more adhesive friction elements; that is, the periphery of the composite element may be shaped to be disposed between or around the bases of the adhesive friction elements, or one or more internal portions of the membrane component may be cut away, for example, to form holes or voids, to be disposed between or around the bases of one or more adhesive friction elements, or both.

[0245] Now for reference Figures 3A-3B The composite element 300 is shown during manufacturing after cutting or molding. The cutting or molding step can be configured to provide one or more holes or gaps (e.g., 302, 308) around one or more adhesive friction elements, and to provide a substantially contiguous region of the composite element along at least a portion of the outsole of the footwear article. An exemplary outsole component 304 including an adhesive friction element 306, which can be attached to the composite element 300 during manufacturing, is also shown.

[0246] According to several aspects, at least a portion of the outer surface of the sole structure may include a pattern or texture. When desired, the pattern may represent a tread pattern. In some aspects, the outer surface of the outsole includes one or more adhesion friction elements, wherein the portions of said adhesion friction elements that contact the ground are substantially free of hydrogel materials and / or composite elements. In some aspects, the adhesion friction elements comprise a material that is harder than hydrogel materials and / or composite elements. In some aspects, one or more adhesion friction elements may have a conical or rectangular shape, as further described below. The adhesion friction elements can provide enhanced adhesion friction between the sole structure and the ground. The adhesion friction elements can also provide support or flexibility to the sole structure and / or provide aesthetic design or appearance for footwear articles.

[0247] According to several aspects, the adhesive friction elements can include, but are not limited to, protrusions of various shapes, such as anti-slip elements, studs, spikes, or similar elements, configured to enhance the adhesive friction between the sole structure and the ground for the wearer during sharp turns, steering, stopping, acceleration, and backward movement. According to some aspects, the adhesive friction elements can be arranged along the bottom surface of the sole structure in any necessary or desired pattern. For example, the adhesive friction elements can be distributed in groups or clusters along the sole structure (e.g., a cluster of 2-8 adhesive friction elements). In some aspects, the adhesive friction elements can be arranged symmetrically or asymmetrically along the outsole between the medial and lateral surfaces of the footwear article. In some aspects, one or more adhesive friction elements can be arranged along the centerline of the sole structure between the medial and lateral surfaces.

[0248] According to some aspects, the adhesive friction element comprises an adhesive friction element polymer material. In one aspect, the polymer components of the adhesive friction element polymer material and the second polymer material may comprise different types of polymers. In another aspect, the polymer components of the adhesive friction element polymer material and the second polymer material may comprise the same type of polymer in different proportions. In some aspects, one or more of the adhesive friction elements may comprise the same material as the second polymer material. In some aspects, one or more of the adhesive friction elements may be integrally formed with the sole structure during a molding step, as described in the methods for manufacturing shoe outsoles as defined herein. In yet another aspect, at least one of the adhesive friction elements may be substantially free of the second polymer material. In some aspects, one or more adhesive friction elements are made of a material harder than the second polymer material of the plate.

[0249] For example, in some aspects, the adhesive friction element may include one or more types of polymers. General types of polymers suitable for use in the composite elements, sole structures, and footwear articles described herein include thermoplastic polymers; thermoplastic elastomers; thermosetting polymers; elastomeric polymers; silicone polymers; natural and synthetic rubbers; composite elements, including polymers reinforced with carbon fibers and / or glass; natural leather; metals such as aluminum, steel, and the like; and combinations thereof. In some aspects, the adhesive friction element is integrally formed with the sole structure (e.g., molded together), and the adhesive friction element may include the same material as the component (e.g., a thermoplastic or thermosetting polymer). In some aspects, the adhesive friction element is provided separately (i.e., not molded with the outsole) and may otherwise be operatively coupled to the sole structure. For example, the sole structure may include certain fittings or receptacles or receiving holes to which the adhesive friction element may be coupled. In these respects, the adhesive friction element may include any suitable material (e.g., metals and polymers) that can be secured to the receiving holes of the sole structure as a snap-fit, screw-in, or similar means.

[0250] In some aspects, the adhesive friction elements can each independently have any necessary or desired dimensions (e.g., shape and size). Examples of shapes for adhesive friction elements include rectangles, hexagons, cylinders, cones, circles, squares, triangles, trapezoids, rhombuses, ovals, and other regular or irregular shapes (e.g., curves, C-shapes, etc.). In some aspects, adhesive friction elements can have the same or different heights, widths, and / or thicknesses. Further examples of suitable dimensions for adhesive friction elements and their arrangement along the sole structure include those provided in English / international football footwear, commercially available from Nike, Inc. of Beaverton, OR under the trade names “TIEMPO,” “HYPERVENOM,” “MAGISTA,” and “MERCURIAL.”

[0251] In several aspects, the adhesive friction element can be incorporated into the sole structure through any necessary or desired mechanism, such that the adhesive friction element extends from the bottom surface of the outsole. In some aspects, the adhesive friction element can be integrally formed with the sole structure through a molding process. In some aspects, the sole structure can be configured to receive a removable adhesive friction element, such as a screw-in or snap-in adhesive friction element. In these aspects, the sole structure may include receiving holes (e.g., threaded holes or snap-fit ​​holes) or fittings, and the adhesive friction element can be screwed or snapped into the receiving holes or fittings, or otherwise coupled to the receiving holes or fittings to secure the adhesive friction element to the sole structure.

[0252] In another aspect, the first portion of the adhesive friction element can be integrally formed with the sole structure, and the second portion of the adhesive friction element can be secured using a screw-in mechanism, a snap-in mechanism, or other similar mechanism. If desired, the adhesive friction element can also be configured as a short stud for use with artificial surface (AG) footwear. In some aspects, receiving holes or fittings can be raised or otherwise protruded from the overall plane of the outer surface of the sole structure. In some aspects, receiving holes can be flush with the outer surface. In some aspects, the sole structure can include a combination of these features and elements.

[0253] According to several aspects, one or more adhesive friction elements have a length greater than the thickness of the sole structure in its hydrated or saturated state (the dimension of which protrudes from the outward-facing surface of the sole structure). The material present in the sole structure and its corresponding dry and saturated thicknesses can be selected to ensure that the adhesive friction elements continue to provide adhesive friction against the ground during the use of the footwear, even when the hydrogel layer is in a fully swollen state. For example, the sole structure can be characterized by a “clearance,” which is the difference between the length of one or more adhesive friction elements and the thickness of the sole structure (in its dry, hydrated, or saturated state). In some aspects, the average clearance for the saturated state of the sole structure is desiccated to be at least 8 millimeters (mm). In some aspects, the average clearance of the sole structure in its saturated state can be at least 9 mm, at least 10 mm, or more.

[0254] Decorative features

[0255] In some aspects, this document discloses composite elements and / or sole structures including composite elements as described herein, wherein the textiles include decorative elements. Decorative elements can be printed elements, dyed elements, structurally colored elements, embroidered elements, or any combination thereof. In some aspects, the decorative elements are visible from the ground-facing side of the sole structure.

[0256] Figure 4 An exemplary sole structure according to one aspect of this disclosure is shown, wherein the ground-facing side of the sole structure is decorated with textiles. The textiles may be printed or decorated with patterns or images (left), or may be undecorated (middle, right).

[0257] Properties of composite components and sole structures

[0258] It has been found that composite elements and articles incorporated into composite elements (e.g., footwear) can prevent or reduce the accumulation of dirt on the outward-facing surfaces of composite elements during wear on unpaved surfaces. As used herein, the term "dirt" can include any of a variety of materials commonly present on ground or playing surfaces, and which may otherwise adhere to the outsole or exposed midsole of footwear articles. Dirt can include inorganic materials such as mud, sand, soil, and gravel; organic materials such as grass, turf, leaves, other vegetation, and excrement; and combinations of inorganic and organic materials such as clay. Additionally, dirt can include other materials such as pulverized rubber that may be present on or in unpaved surfaces.

[0259] As those skilled in the art will understand, preventing or reducing dirt buildup on footwear can provide numerous benefits. Preventing or reducing dirt buildup on the outsole of footwear during wear on unpaved surfaces can also significantly affect the weight of dirt adhering to the outsole during wear, thus reducing fatigue caused by the adhered dirt. Preventing or reducing dirt buildup on the outsole can help maintain adhesive friction during wear. For example, preventing or reducing dirt buildup on the outsole can improve or maintain the performance of the adhesive friction elements present on the ground-facing surface of the outsole during wear on unpaved surfaces. When worn during sports activities, preventing or reducing dirt buildup on the outsole can improve or maintain the wearer's ability to manipulate sports equipment such as balls with footwear. Furthermore, preventing or reducing dirt buildup on the outsole makes cleaning footwear easier after use.

[0260] Damage caused by dirt adhesion

[0261] While not wishing to be bound by theory, it is believed that the hydrogel layer of the composite element, and therefore the composite element itself as disclosed herein, can provide compressive flexibility and / or drainage of absorbed water when adequately wetted with water (including water containing dissolved, dispersed, or otherwise suspended materials). In particular, the compressive flexibility of the wet hydrogel layer, the drainage of liquid from the wet hydrogel material and / or composite element, changes in the morphology of the outward-facing surface, or combinations thereof, are considered to disrupt the adhesion of dirt to or on the outward-facing surface, or the adhesion of particles to each other on the outward-facing surface, or both adhesion and adhesion. This disruption of dirt adhesion and / or adhesion is considered a responsible mechanism for preventing (or otherwise reducing) the accumulation of dirt on the outward-facing surface (due to the presence of wet material).

[0262] This disruption of dirt adhesion and / or stickiness is considered a responsible mechanism for preventing (or otherwise reducing) the buildup of dirt on outward-facing surfaces (due to the presence of polymeric hydrogels in the hydrogel materials of this disclosure). It is understood that, in particular, preventing dirt buildup on articles, including footwear, clothing, or sports equipment articles, can improve the performance of adhesive friction elements present on the article (e.g., on shoe soles) during use or wear on unpaved surfaces, can prevent the article from gaining weight due to dirt buildup during use or wear, can maintain the performance of the article, and therefore can provide significant benefits to the user or wearer compared to articles without elastomeric materials.

[0263] Water absorption and swelling

[0264] The swelling of the polymer hydrogel in the hydrogel material present in the hydrogel layer of the composite element can be observed as an increase in the thickness of the polymer hydrogel itself (e.g., in its pure form), an increase in the thickness of the hydrogel material itself (e.g., in its pure form), an increase in the thickness of the hydrogel layer of the composite element, and / or an increase in the thickness of the composite element itself, from its dry thickness, through a series of intermediate thicknesses when additional water is absorbed, and finally reaching a saturated thickness, which is the average thickness of the polymer hydrogel, hydrogel material, hydrogel layer, and / or composite element when the polymer hydrogel, hydrogel material, hydrogel layer, and / or composite element are completely saturated with water. For example, the saturated thickness (or length and / or height) of a fully saturated polymeric hydrogel, hydrogel material, hydrogel layer, and / or composite element can be greater than 25%, greater than 50%, greater than 100%, greater than 150%, greater than 200%, greater than 250%, greater than 300%, greater than 350%, greater than 400%, or greater than 500% of the dry thickness of the same polymeric hydrogel, hydrogel material, hydrogel layer, and / or composite element, as characterized by a swelling capacity test. The saturated thickness (or length and / or height) of a fully saturated polymeric hydrogel, hydrogel material, hydrogel layer, and / or composite element can be approximately 150% to 500%, approximately 150% to 400%, approximately 150% to 300%, or approximately 200% to 300% of the dry thickness of the same polymeric hydrogel, hydrogel material, hydrogel layer, and / or composite element.

[0265] Polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements may have an increase in thickness (or length and / or height) of greater than 20%, 30%, 40%, or 50% at 1 hour, as characterized by a swelling capacity test. Polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements may have an increase in thickness (or length and / or height) of approximately 35% to 400%, approximately 50% to 300%, or approximately 100% to 200% at 1 hour, as characterized by a swelling capacity test. Polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements may have an increase in thickness (or length and / or height) of approximately 45% to 500%, approximately 100% to 400%, or approximately 150% to 300% at 24 hours. Accordingly, polymeric hydrogels, hydrogel materials, hydrogel layers and / or composite elements may have a volume increase of about 50% to 500%, about 75% to 400%, or about 100% to 300% over 1 hour.

[0266] Even though polymeric hydrogels, hydrogel materials, hydrogel layers, and / or composite elements can swell as they absorb water and transition between different material states with corresponding thicknesses, the saturated thickness of the composite element is preferably kept less than the length of the adhesive friction element. This selection of the composite element and its corresponding dry and saturated thickness ensures that the adhesive friction element can continue to provide adhesive friction to the ground during the use of the footwear, even when the composite element is in a fully swollen state. For example, the average gap difference between the length of the adhesive friction element and the saturated thickness of the composite element is desirablely at least 8 mm. For example, the average gap distance can be at least 9 mm, 10 mm, or greater.

[0267] Polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements can rapidly absorb water upon contact with them. For example, a composite element containing hydrogel material can absorb water from mud and wet grass, such as during warm-up phases before a competitive match. Optionally (or additionally), the hydrogel material can be pre-conditioned with water such that the hydrogel material or hydrogel layer of the composite element is partially or completely saturated, such as by spraying or soaking the structure with water prior to use.

[0268] Polymer hydrogels, hydrogel materials, and / or hydrogel layers can exhibit a total water absorption capacity of about 10% by weight to 225% by weight, as measured in a water absorption capacity test using a material sampling procedure, substrate sampling procedure, or component sampling procedure over a 24-hour immersion period, as will be defined below. The total water absorption capacity exhibited by the polymer hydrogel, hydrogel material, and / or hydrogel layer (over 24 hours) can range from about 10% by weight to about 225% by weight; about 30% by weight to about 200% by weight; about 50% by weight to about 150% by weight; or about 75% by weight to about 125% by weight. The water absorption capacity exhibited by the polymer hydrogel, hydrogel material, and / or hydrogel layer, as measured by a water absorption capacity test over 24 hours, can be about 20% by weight or more, about 40% by weight or more, about 60% by weight or more, about 80% by weight or more, or about 100% by weight or more. For the purposes of this disclosure, the term "total water absorption capacity" is used to express the amount of water absorbed by the polymer hydrogel, hydrogel material, and / or hydrogel layer as a percentage of the sample by weight when dry. The procedure for measuring total water absorption capacity includes measuring the "dry" weight of a sample of the polymer hydrogel, hydrogel material, and / or hydrogel layer, immersing the sample in water at ambient temperature (~23 degrees Celsius) for a predetermined amount of time, and then measuring the weight of the sample again when "wet". The procedure for measuring total water absorption capacity according to a water absorption capacity test is described below.

[0269] Samples of polymeric hydrogels or hydrogel materials in their pure form (e.g., polymeric hydrogels prior to being incorporated into hydrogel materials, and / or hydrogel materials prior to being formed into hydrogel layers); or hydrogel layers themselves (e.g., prior to being bonded to textiles) may exhibit a total water absorption capacity of about 10% by weight to 3000% by weight, as measured in a water absorption capacity test using a material sampling procedure, substrate sampling procedure, or component sampling procedure over a 24-hour immersion period, as defined below. The total water absorption capacity (over 24 hours) exhibited by the polymeric hydrogel, hydrogel material, and / or hydrogel layer may range from about 50% by weight to about 2500% by weight; from about 100% by weight to about 2000% by weight; from about 200% by weight to about 1500% by weight; or from about 300% by weight to about 1000% by weight. The water absorption capacity exhibited by a polymeric hydrogel, hydrogel material, or hydrogel layer, measured over 24 hours by a water absorption capacity test, can be about 20% by weight or more, about 40% by weight or more, about 60% by weight or more, about 80% by weight or more, or about 100% by weight or more. The water absorption capacity exhibited by a polymeric hydrogel, hydrogel material, and / or hydrogel layer, measured over 24 hours by a water absorption capacity test, can be about 100% by weight or more, about 200% by weight or more, about 300% by weight or more, about 400% by weight or more, or about 500% by weight or more. For the purposes of this disclosure, the term "total water absorption capacity" is used to express the amount of water absorbed by the polymeric hydrogel, hydrogel material, and / or hydrogel layer as a percentage of the sample by weight when dry. The procedure for measuring total water absorption capacity includes measuring the "dry" weight of the sample, immersing the sample in water at ambient temperature (~23 degrees Celsius) for a predetermined amount of time, and then measuring the weight of the sample again when "wet". The following describes the procedure for measuring total water absorption capacity using material sampling, substrate sampling, or component sampling procedures based on water absorption capacity testing.

[0270] Polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements may have a “time-value” equilibrium absorbance, where the time value corresponds to the duration of immersion or exposure to water (e.g., in the use of footwear exposed to water). For example, a “30-second equilibrium absorbance” corresponds to the absorbance during a 30-second immersion duration, a “2-minute equilibrium absorbance” corresponds to the absorbance during a 2-minute immersion duration, and so on for different immersion durations. A “0-second” duration refers to a dry state, and a 24-hour duration corresponds to a saturated state of the composite element after 24 hours. Further details are provided in the absorbance testing scheme described herein. In some aspects, polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements may have a 1-hour absorbance greater than 40 percent.

[0271] Polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements can also be characterized by their water absorption rate. The water absorption rate of polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements can be as high as 10 g / m³. 2 / √min to 120g / m 2 / √min, as measured using material sampling procedures, substrate sampling procedures, or component sampling procedures in water absorption rate testing. Water absorption rate is defined as per square meter (m²). 2 The weight (in grams) of water absorbed by the sample relative to the square root of the soaking time (√min). Alternatively, the water absorption rate can be from approximately 12 g / m³. 2 / √min to approximately 100g / m 2 Within the range of / √min; optionally, from approximately 20g / m 2 / √min to approximately 90g / m 2 Within the range of / √min; optionally, up to approximately 60g / m 2 / √min.

[0272] The total water absorption capacity and absorption rate can depend on the amount of polymeric hydrogel present in the hydrogel material, the volume of hydrogel material present in the composite element, and / or the thickness of the hydrogel layer in the composite element. The polymeric hydrogel and / or hydrogel material can be characterized by a water absorption capacity ranging from 50 wt% to 2500 wt%, as measured using a material sampling procedure, substrate sampling procedure, or component sampling procedure according to a water absorption capacity test. The water absorption capacity of the polymeric hydrogel is determined based on the amount of water absorbed by the polymeric hydrogel (in pure form) as a percentage of the dry polymeric hydrogel by weight. The water absorption capacity of the hydrogel material is determined based on the amount of water absorbed by the hydrogel material (in pure form) as a percentage of the dry hydrogel material by weight. Alternatively, the water absorption capacity exhibited by the polymeric hydrogel and / or hydrogel material can range from about 100 wt% to about 1500 wt%; or from about 300 wt% to about 1200 wt%.

[0273] Polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements may not exhibit significant weight loss during water cycling tests. As further defined below, a water cycling test involves comparing the initial weight of the sample with the weight of the composite element after immersion in a water bath for a predetermined amount of time, drying, and then weighing. Alternatively, composite elements, polymer hydrogels, hydrogel materials, hydrogel layers, and / or composite elements may exhibit a water cycling weight loss from 0% to approximately 15% of weight, as measured according to the water cycling test and using material sampling procedures, substrate sampling procedures, or component sampling procedures. Alternatively, the water cycling weight loss may be less than 15% of weight; alternatively, less than 10% of weight.

[0274] Hydrophilic properties of composite elements

[0275] The first side of the composite element (i.e., the side of the composite element comprising the hydrogel layer and configured to form the sole structure facing the ground) can also be characterized by the degree to which it exhibits a mud pull-out force of less than about 12 Newtons (N). Alternatively, the mud pull-out force is less than about 10 N; alternatively, it is in the range of about 1 N to about 8 N. The mud pull-out force is determined by mud pull-out testing using a component sampling procedure, as described below.

[0276] Individual hydrogel materials, or hydrogel materials present in hydrogel layers within composite elements, exhibit hydrophilic properties. These hydrophilic properties can be characterized by determining the static sessile droplet contact angle on the surface of the hydrogel material. Thus, in some instances, dry hydrogel materials have static sessile droplet contact angles (or dry contact angles) less than 105 degrees, or less than 95 degrees, or less than 85 degrees, as characterized by contact angle testing. Contact angle testing can be performed on samples obtained according to material sampling procedures, substrate sampling procedures, and / or component sampling procedures. In some other instances, dry hydrogel materials have static sessile droplet contact angles in the range of 60 to 100 degrees, 70 to 100 degrees, or 65 to 95 degrees.

[0277] In other aspects, the wet hydrogel material, either alone or in a hydrogel layer within a composite element, has a static fixation droplet contact angle (or wet contact angle) of less than 90 degrees, less than 80 degrees, less than 70 degrees, or less than 60 degrees. In some other aspects, the wet hydrogel material has a static fixation droplet contact angle in the range of 45 degrees to 75 degrees. In some cases, the dry static fixation droplet contact angle of the hydrogel material is at least 10 degrees, at least 15 degrees, or at least 20 degrees larger than the wet static fixation droplet contact angle, for example, from 10 degrees to 40 degrees, from 10 degrees to 30 degrees, or from 10 degrees to 20 degrees.

[0278] Hydrogel materials, whether alone or within a hydrogel layer of a composite element, can also exhibit low coefficients of friction when wet. Examples of suitable coefficients of friction (or dry-state coefficients of friction) for dry hydrogel materials are less than 1.5, for example, in the range of 0.3 to 1.3 or 0.3 to 0.7, as characterized by a coefficient of friction test. The coefficient of friction test can be performed on samples obtained according to a material sampling procedure, or a substrate sampling procedure, or a component sampling procedure. Examples of suitable coefficients of friction (or wet-state coefficients of friction) for wet hydrogel materials are less than 0.8 or less than 0.6, for example, in the range of 0.05 to 0.6, 0.1 to 0.6, or 0.3 to 0.5. Furthermore, hydrogel materials can exhibit a decrease in their coefficient of friction from their dry state to their wet state, such as a decrease in the range of 15% to 90% or 50% to 80%. In some cases, its dry friction coefficient is greater than its wet friction coefficient, for example, by at least 0.3 or 0.5 higher, such as 0.3 to 1.2 or 0.5 to 1.

[0279] Furthermore, the compliance of a standalone hydrogel material or a hydrogel material present in a composite element can be characterized based on its storage modulus in a dry state (when at 0% relative humidity (RH) equilibrium) and in a partially wet state (e.g., when at 50% RH or 90% RH equilibrium), as well as by the decrease in its storage modulus between the dry and wet states. Specifically, a hydrogel material can have a decrease in its storage modulus (ΔE') relative to its wet state from that of the dry state. With increasing water concentration in the hydrogel material, the decrease in storage modulus corresponds to an increase in compliance, as less stress is required for a given strain / deformation.

[0280] Compared to the storage modulus in the dry state and characterized by storage modulus testing using material sampling procedures, substrate sampling procedures, or component sampling procedures, polymeric hydrogels and / or hydrogel materials may exhibit a reduction in storage modulus by more than 20%, more than 40%, more than 60%, more than 75%, more than 90%, or more than 99% from their dry state to their wet state (50% RH).

[0281] In some other aspects, the dry storage modulus of the polymer hydrogel and / or hydrogel material is greater than its wet (50% RH) storage modulus by more than 25 MPa, more than 50 MPa, more than 100 MPa, more than 300 MPa, or more than 500 MPa, for example, in the range of 25 MPa to 800 MPa, 50 MPa to 800 MPa, 100 MPa to 800 MPa, 200 MPa to 800 MPa, 400 MPa to 800 MPa, 25 MPa to 200 MPa, 25 MPa to 100 MPa, or 50 MPa to 200 MPa. Additionally, the dry storage modulus can be in the range of 40 MPa to 800 MPa, 100 MPa to 600 MPa, or 200 MPa to 400 MPa, as characterized by storage modulus testing. In addition, the wet energy storage modulus can range from 0.003 MPa to 100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.

[0282] Compared to the storage modulus in the dry state and characterized by storage modulus testing using material sampling procedures, substrate sampling procedures, or component sampling procedures, polymeric hydrogels and / or hydrogel materials can exhibit a reduction in storage modulus by more than 20%, more than 40%, more than 60%, more than 75%, more than 90%, or more than 99% from their dry state to their wet state (90% RH). The dry-state storage modulus of polymer hydrogels or hydrogel materials can be greater than their wet-state (90% RH) storage modulus by more than 25 MPa, more than 50 MPa, more than 100 MPa, more than 300 MPa, or more than 500 MPa, for example, in the ranges from 25 MPa to 800 MPa, from 50 MPa to 800 MPa, from 100 MPa to 800 MPa, from 200 MPa to 800 MPa, from 400 MPa to 800 MPa, from 25 MPa to 200 MPa, from 25 MPa to 100 MPa, or from 50 MPa to 200 MPa. Additionally, the dry-state storage modulus can be in the ranges from 40 MPa to 800 MPa, from 100 MPa to 600 MPa, or from 200 MPa to 400 MPa, as characterized by storage modulus testing. In addition, the wet energy storage modulus can range from 0.003 MPa to 100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.

[0283] In addition to the reduction in storage modulus, the polymer hydrogel and / or hydrogel material of the hydrogel layer of the composite element can also exhibit a decrease in its glass transition temperature from the dry state (when at 0% relative humidity (RH) equilibrium) to the wet state (when at 90% RH equilibrium).

[0284] The polymeric hydrogel and / or hydrogel material of the hydrogel layer of the composite element can exhibit a decrease in glass transition temperature (ΔT) of more than 5 degrees Celsius, more than 6 degrees Celsius, more than 10 degrees Celsius, or more than 15 degrees Celsius from its dry (0% RH) glass transition temperature to its wet (90% RH) glass transition temperature. g (e.g., using material sampling procedures, substrate sampling procedures, or component sampling procedures characterized by glass transition temperature testing.) For example, a decrease in glass transition temperature can be in the range of more than 5 degrees Celsius to 40 degrees Celsius, more than 6 degrees Celsius to 50 degrees Celsius, more than 10 degrees Celsius to 30 degrees Celsius, more than 30 degrees Celsius to 45 degrees Celsius, or more than 15 degrees Celsius to 20 degrees Celsius. Polymer hydrogels and / or hydrogel materials can also exhibit dry glass transition temperatures in the range of -40 degrees Celsius to -80 degrees Celsius or -40 degrees Celsius to -60 degrees Celsius.

[0285] Optionally (or additionally), the reduction in glass transition temperature can be within the range of a difference of 5°C to 40°C, a difference of 10°C to 30°C, or a difference of 15°C to 20°C. Elastomer materials can also exhibit dry glass transition temperatures in the range of -40°C to -80°C or -40°C to -60°C.

[0286] The total amount of water that a polymer hydrogel, hydrogel material, hydrogel layer, and / or composite element can absorb depends on a variety of factors, such as the composition of the hydrogel material (e.g., the type and amount of components present in the hydrogel material besides the polymer hydrogel), the type of polymer hydrogel used (e.g., its hydrophilicity), the concentration of the polymer hydrogel present in the hydrogel material, the concentration of the hydrogel material in the hydrogel layer, the thickness of the hydrogel layer, and similar factors. The water absorption capacity and rate of absorption of a sample and / or component depend on the size and shape of its geometry and are generally based on the same factors. In contrast, the water absorption rate is instantaneous and can be defined kinetically. Three factors for the water absorption rate of a given sample and / or component with a given geometry include time, thickness, and the surface area of ​​the exposed region available for water absorption.

[0287] As mentioned above, in addition to swelling, the flexibility of polymeric hydrogels, hydrogel materials, and / or hydrogel layers can increase from relatively rigid (i.e., dry state) to increasingly stretchable, compressible, and extensible (i.e., wet state). Thus, increased flexibility can allow the hydrogel layer of the composite element to be easily compressed under applied pressure (e.g., during foot impact with the ground) and, in some instances, allow for the rapid expulsion of at least a portion of its retained water (depending on the degree of compression). While not wishing to be bound by theory, it is believed that such individual compressive flexibility, individual water expulsion, or a combination of both can disrupt dirt adhesion and / or stickiness, preventing or otherwise reducing dirt buildup on the surfaces of components including the composite element.

[0288] In addition to rapidly expelling water, in certain instances, the compressed composite element is capable of rapidly reabsorbing water when the compression is released (e.g., during a foot impact liftoff during normal use). Therefore, during use in wet or damp environments (e.g., muddy or wet surfaces), the composite element can dynamically expel and repeatedly absorb water with continuous foot impacts, particularly from wet surfaces. Thus, the composite element described herein can continue to prevent dirt buildup over extended periods, especially when surface water available for reabsorption is present (e.g., throughout a competitive sporting event).

[0289] As used herein, the terms “take up,” “taking up,” “uptake,” “uptaking,” and similar terms refer to the absorption of a liquid (e.g., water) from an external source into composite elements and hydrogels, such as by absorption, adsorption, or both. Furthermore, as briefly mentioned above, the term “water” refers to an aqueous liquid, which can be pure water or an aqueous carrier containing a small amount of dissolved, dispersed, or otherwise suspended material (e.g., particles, other liquids, and the like).

[0290] In addition to effectively preventing dirt buildup, composite elements have been found to be sufficiently durable for their intended use on the ground-facing surfaces of footwear. In several respects, the useful life of composite elements (and footwear incorporating composite elements) is at least 10, 20, 50, 100, 120, or 150 hours of wear.

[0291] textile

[0292] Several aspects have been described, providing further details regarding textiles. In one aspect, textiles can include any textile that allows permeation through a hydrogel layer. Generally, "textiles" can be defined as any article made from fibers, filaments, or yarns characterized by flexibility, fineness, and a high ratio of length to thickness, such as, for example, rolled pieces. Textiles typically fall into two categories. The first category includes textiles directly produced from webs of filaments or fibers through random interlocking of fibers or filaments to construct nonwoven textiles and felts. The second category includes textiles formed through the mechanical manipulation of yarns, thereby producing woven fabrics, knitted fabrics, braided fabrics, crocheted fabrics, and the like.

[0293] As used herein, the terms “filament,” “fiber,” or “fibers” refer to materials in the form of discrete elongated pieces that are significantly longer than their width. Fibers can include natural fibers, man-made fibers, or synthetic fibers. Fibers can be produced using conventional techniques such as extrusion, electrospinning, interfacial polymerization, stretching, and similar techniques. Fibers can include carbon fibers, boron fibers, silicon carbide fibers, titanium dioxide fibers, alumina fibers, quartz fibers, glass fibers, such as E, A, C, ECR, R, S, D, and NE glass and quartz or the like. The fiber can be formed from a synthetic polymer capable of forming fibers, such as poly(etherketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyester, polyolefin (e.g., polyethylene, polypropylene), aromatic polyamide (e.g., aromatic polyamide polymers, such as para-aromatic polyamide fibers and meta-aromatic polyamide fibers), aromatic polyimide, polybenzimidazole, polyetherimide, polytetrafluoroethylene, acrylics, modified acrylic fibers, poly(vinyl alcohol), polyamide, polyurethane, and copolymers such as polyether-polyurea copolymers, polyester-polyurethane, polyether block amide copolymers, or the like. The fiber can be a natural fiber (e.g., silk, wool, cashmere, vicuna, cotton, flax, hemp, jute, sisal). The fiber can be a man-made fiber derived from recycled natural polymers, such as rayon, lyocell, acetate, triacetate, rubber, and poly(lactic acid). The fiber can be made from commercially available synthetic polymer materials such as polyester or polyamide.

[0294] Fibers can have indefinite lengths. For example, man-made and synthetic fibers are typically extruded in substantially continuous lines. Alternatively, fibers can be short fibers, such as, for example, cotton fibers, or can be extruded synthetic polymer fibers that are cut to form short fibers of relatively uniform length. Short fibers can have lengths from about 1 mm to 100 cm or longer, and any increments therein (e.g., 1 mm increments).

[0295] Fibers can have any of a variety of cross-sectional shapes. Natural fibers can have a natural cross-section or a modified cross-sectional shape (e.g., through processes such as mercerizing). Man-made or synthetic fibers can be extruded to provide threads with a predetermined cross-sectional shape. The cross-sectional shape of a fiber can affect its properties, such as its softness, luster, and wicking capacity. Fibers can have a circular or substantially circular cross-section. Alternatively, fibers can have a non-circular cross-section, such as flat, elliptical, octagonal, rectangular, wedge-shaped, triangular, dogbone-shaped, multi-lobed, multi-channeled, hollow, core-shell, or other shapes.

[0296] Fibers can be processed. For example, the properties of fibers may be affected at least in part by processes such as drawing (stretching), annealing (hardening), and / or crimping or texturing the fibers.

[0297] In some cases, fibers can be multicomponent fibers, such as fibers comprising two or more polymeric materials. These two or more polymeric materials can exist in core-sheath configurations, island-in-the-sea configurations, segmented-pie configurations, strip configurations, or side-by-side configurations. Multicomponent fibers can be processed to form more than one smaller fiber (e.g., microfibers) from a single fiber, for example, by removing sacrificial material.

[0298] As used herein, the term "yarn" refers to an assembly formed of one or more fibers, wherein the thread has a considerably long length and a relatively small cross-section, and is suitable for use in the hand- or machine-made production of textiles, including textiles made using weaving, knitting, crocheting, braiding, sewing, embroidery, or rope-making techniques. Sewing thread is a type of yarn commonly used for sewing.

[0299] Yarn can be made from fibers formed from natural, man-made, and synthetic materials. Synthetic fibers are most commonly used in spinning from staple fibers and silk yarn. Spinning is done by arranging and twisting staple fibers together to create a cohesive strand. The process of forming yarn from staple fibers typically involves carding and drawing the fibers to form slivers, drawing and twisting the slivers to form rovings, and spinning the rovings to form yarn. Multiple yarns can be twisted together to create thicker yarns. The direction of twisting of the staple fibers and plies can affect the final properties of the yarn. Yarn can be formed from a single long, substantially continuous filament (commonly referred to as a "monofilament") or from more than one individual filament grouped together. Yarn can also be formed from two or more long, substantially continuous filaments grouped together by twisting or entanglement, or twisting and entanglement. Like staple yarns, multiple yarns can be twisted together to form thicker yarns.

[0300] Once formed, the yarn can undergo further processing, such as texturing, heat treatment, or mechanical treatment, or be coated with a material such as a synthetic polymer. The fibers, yarns, or textiles, or any combination thereof, used in the disclosed articles can be sizing. The sizing fibers, yarns, and / or textiles are coated with a sizing composition on at least a portion of their surface, which is selected to modify absorption or abrasion properties, or for compatibility with other materials. The sizing composition facilitates the impregnation and wetting of coatings or resins on the surface and contributes to achieving desired physical properties in the final article. Exemplary sizing compositions may include, for example, epoxy polymers, urethane-modified epoxy polymers, polyester polymers, phenolic polymers, polyamide polymers, polyurethane polymers, polycarbonate polymers, polyetherimide polymers, polyamideimide polymers, polystyrene-pyridine polymers, polyimide bismaleimide polymers, polysulfone polymers, polyethersulfone polymers, epoxy-modified urethane polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone polymers, and mixtures thereof.

[0301] For example, two or more types of yarn can be combined to form composite yarns, such as single-covered or double-covered yarns and core-spun yarns. Therefore, yarns can have a variety of configurations that generally conform to the descriptions provided herein.

[0302] The yarn may include at least one thermoplastic material (e.g., one or more fibers may be made of thermoplastic materials). The yarn may be made of thermoplastic materials. The yarn may be covered with a layer of material, such as a thermoplastic material.

[0303] The linear mass density or weight per unit length of yarn can be expressed using various units, including denier (D) and tex. Denier is the weight in grams of 9,000 meters of yarn. The linear mass density of a single filament of a fiber can also be expressed using denier per filament (DPF). Tetras is the weight in grams of 1,000 meters of yarn. Decitex is another measure of linear mass and is the weight in grams of 10,000 meters of yarn.

[0304] As used herein, toughness is understood to refer to the amount of force required to break a yarn (expressed in units of weight, such as pounds, grams, centinewtons, or other units) (i.e., the breaking force or point of break) divided by the yarn's linear mass density, which is expressed, for example, in denier (unstrained), deciter, or some other weight measure per unit length. The breaking force of a yarn is determined by subjecting a sample of yarn to a known amount of force, for example, using a strain gauge load cell, such as the INSTRON brand testing system (Norwood, MA, USA). Yarn toughness and yarn breaking force are distinct from burst strength or bursting strength of textiles, which is a measure of how much pressure can be applied to a textile surface before it breaks.

[0305] Typically, the minimum toughness required for yarn to withstand the forces applied in industrial knitting machines is about 1.5 g / denier. Most yarns made from commercial polymeric materials typically have a toughness in the range of about 1.5 g / denier to about 4 g / denier. For example, polyester yarns commonly used in the manufacture of knitted uppers for footwear have a toughness in the range of about 2.5 g / denier to about 4 g / denier. Yarns made from commercial polymeric materials considered to have high toughness typically have a toughness in the range of about 5 g / denier to about 10 g / denier. For example, commercially available packaged dyed polyethylene terephthalate yarn from National Spinning (Washington, NC, USA) has a toughness of about 6 g / denier, and commercially available solution dyed polyethylene terephthalate yarn from Far Eastern New Century (Taipei, Taiwan, China) has a toughness of about 7 g / denier. Yarns made from high-performance polymer materials typically have a toughness of about 11 g / denier or greater. For example, yarns made from aramid fibers typically have a toughness of about 20 g / denier, and yarns made from ultra-high molecular weight polyethylene (UHMWPE) with a toughness greater than 30 g / denier can be obtained from Dyneema (Stanley, NC, USA) and Spectra (Honeywell-Spectra, Colonial Heights, VA, USA).

[0306] There are various techniques for mechanically manipulating yarns to form textiles. Such techniques include, for example, interlacing, entanglement, and twisting, as well as interlocking. Interlacing is the crossing of two yarns that intersect and interweave with each other at a perpendicular angle. The yarns used for interlacing are conventionally referred to as “warp” and “weft”. Woven textiles consist of warp and weft yarns. The warp yarn extends in a first direction, and the weft strand extends in a second direction substantially perpendicular to the first direction. Entanglement and twisting encompass various procedures, such as braiding and knotting, in which yarns become entangled with each other to form textiles. Interlocking involves the formation of more than one column of interlocking loops, with knitting being the most common method of interlocking. Textiles can be formed primarily of one or more yarns that are mechanically manipulated, for example, through interlacing, entanglement, twisting, and / or interlocking processes, as mentioned above.

[0307] Textiles can be nonwoven textiles. Typically, nonwoven textiles or fabrics are sheet or mesh structures made of fibers and / or yarns bonded together. This bonding can be chemical and / or mechanical, and can be formed using heat, solvents, adhesives, or combinations thereof. Exemplary nonwoven fabrics are flat or clustered porous sheets made directly from separated fibers, molten plastic, and / or plastic films. They are not made by weaving or knitting, and do not necessarily require the fibers to be converted into yarns, although yarns can be used as a source of fibers. Nonwoven textiles are typically manufactured by placing small fibers together in the form of sheets or meshes (similar to paper on a paper machine) and then mechanically bonding them with adhesives or heat (by applying the adhesive (in the form of powder, paste, or polymer melt) and melting it onto the mesh by raising the temperature) (as in the case of felt, by interlocking them using serrated needles or barbed needles, or by hydro-entanglement, where friction between the fibers creates a stronger fabric). Nonwoven textiles can be made from short fibers (e.g., from wet-laid, air-laid, carding / crosslapping processes) or extruded fibers (e.g., from meltblown or spunbond processes or combinations thereof) or combinations thereof. The bonding of fibers in nonwoven textiles can be achieved using thermal bonding (with or without calendering), hydroentanglement, ultrasonic bonding, needle punching (needling), chemical bonding (e.g., using adhesives such as latex emulsions or solution polymers or adhesive fibers or powders), and meltblown bonding (e.g., fibers are bonded during simultaneous fiber formation and web formation as air decays and fibers intertwine). Nonwoven textiles may include textile materials comprising one or more polyurethanes, polyesters, polyethers, polyamides, or polyolefins. The polymeric component of the textile material may include polyurethane, or polyester, or polyamide, or polyolefin, or may consist substantially of polyurethane, or polyester, or polyamide, or polyolefin.

[0308] In any of these aspects, the textile may have a basis weight of from about 5 g / m² to about 500 g / m², or from about 5 g / m² to about 400 g / m², or from about 10 g / m² to about 300 g / m², or from about 20 g / m² to about 200 g / m².

[0309] In one aspect, prior to being operably coupled to the hydrogel layer, the textile may have a core thickness measuring between the first and second sides from about 0.5 mm to about 5 mm, or about 0.5 mm to about 3 mm, or about 0.5 mm to about 2 mm, or about 0.5 mm to about 1.5 mm, or about 0.75 mm to about 3 mm.

[0310] In one aspect, the textile is breathable prior to being operatively bonded to the hydrogel layer. Using a breathable textile (i.e., a textile that is breathable prior to being operatively bonded to the hydrogel layer in the composite element) can facilitate the penetration of the hydrogel layer through the first side of the textile and at least partially into the core of the textile. In one aspect, the textile may have a breathability from about 10 cubic centimeters per square centimeter per second to about 250 cubic centimeters per square centimeter per second, or from about 50 cubic centimeters per square centimeter per second to about 150 cubic centimeters per square centimeter per second, or from about 70 cubic centimeters per square centimeter per second to about 120 cubic centimeters per square centimeter per second, prior to operatively bonding the first side of the textile to the hydrogel layer. In some aspects, the breathability of the textile can vary across the textile.

[0311] In some aspects, the textile material, i.e., the chemical composition present in the textile, may have a textile material melting temperature or textile material Vicat softening temperature greater than the melting temperature or Vicat softening temperature of the polymer hydrogel, hydrogel material, and / or hydrogel layer. Using a textile material that will not melt or soften at or near the temperature at which the hydrogel material is applied to the textile to form the hydrogel layer can promote the penetration of the hydrogel material into the core of the textile without reducing the surface area of ​​the textile available for forming a mechanical bond with the hydrogel layer, which in turn can increase the bonding strength between the hydrogel layer and the textile in the composite element. The textile material melting temperature or textile material Vicat softening temperature may be at least 20°C, at least 30°C, at least 40°C, at least 50°C, at least 70°C, at least 80°C, at least 90°C, or at least 100°C greater than the melting temperature or Vicat softening temperature of the polymer hydrogel, hydrogel material, and / or hydrogel layer. In any of these aspects, using the material sampling procedures, substrate sampling procedures, and component sampling procedures described herein, the melting temperature can be expressed as melting temperature (T). mThe test protocol determines and the Vicat softening temperature can be determined using the Vicat softening temperature (T). vs The test plan is determined accordingly.

[0312] In one aspect, a textile comprises two or more textile layers, each layer comprising a textile material. Each layer may independently comprise a woven textile, a non-woven textile, a knitted textile, a braided textile, a crocheted textile, or a combination thereof. By way of example, a textile may comprise a first textile layer and a second textile layer, the first textile layer comprising a non-woven textile comprising a first textile material, and the second textile layer comprising a knitted textile comprising a second textile material; or a first layer and a second layer, the first layer comprising a first non-woven textile comprising a first textile material, and the second layer comprising a second non-woven textile comprising a second textile material. When a textile comprises two or more textile layers, the two or more layers may be operatively coupled. A layer of a multilayer textile may independently possess the textile properties described herein, or the entire multilayer textile may possess the properties described herein.

[0313] In some aspects, textiles may include one or more natural fibers or yarns or synthetic fibers or yarns containing polymeric materials. In aspects where textiles include one or more synthetic fibers, the synthetic fibers may be selected from polyesters, polyamides, polyolefins, or combinations thereof. In some aspects, textiles may include one or more recycled fibers. In one aspect, "recycled fiber" as used herein may refer to fibers recovered from pre-consumer waste. In another aspect, "recycled fiber" may refer to fibers recovered from post-consumer waste textiles. In yet another aspect, fibers may be recovered from pre-consumer waste and / or post-consumer waste, for example, by shredding or deconstructing textiles to produce loose fibers, by dissolving or melting existing textiles or fibers to form a recycled composition, and by reforming fibers from the recycled composition.

[0314] Polymer hydrogels, hydrogel materials and hydrogel layers

[0315] In one aspect, the hydrogel layer of the disclosed composite element may consist substantially of or may contain a hydrogel material. The hydrogel material includes one or more polymeric hydrogels. Therefore, the polymeric component of the hydrogel material may consist of a single polymeric hydrogel, or may consist of more than one polymeric hydrogel, or may consist of a mixture of one or more polymeric hydrogels and one or more non-hydrogelic polymers. One or more polymeric hydrogels may include thermoplastic hydrogels. In addition to one or more polymeric hydrogels, the hydrogel material may also include one or more additional components, such as, for example, non-hydrogelic polymeric materials, and / or one or more non-polymeric components, such as colorants, fillers, and processing aids. In another aspect, the hydrogel material or hydrogel layer, or both, may include one or more polymers or copolymers selected from polyurethane, polyamide, polyimide, or combinations thereof. For example, the hydrogel layer or hydrogel material, or both, may also include a tie material. The tie material may facilitate bonding between the hydrogel layer and textiles, or between the hydrogel layer and a second polymeric material present in a board. The connecting material can be a component of the hydrogel material (e.g., the connecting material can be mixed with the hydrogel material in a single hydrogel layer), or it can form a separate portion of the hydrogel layer (e.g., the hydrogel layer can be a multilayer structure comprising a first layer containing hydrogel material and a second layer containing the connecting material). In one aspect, the polymeric hydrogel of the hydrogel material or the polymeric component of the hydrogel material comprises a polyurethane hydrogel or is substantially composed of a polyurethane hydrogel. In another aspect, the polymeric hydrogel of the hydrogel material or the polymeric component of the hydrogel material comprises a polyamide block copolymer hydrogel or is substantially composed of a polyamide block copolymer hydrogel.

[0316] Hydrogel materials can be thermoplastic materials, including thermoplastic polymer hydrogels. In addition to thermoplastic polymer hydrogels, hydrogel materials may also contain at least one thermoplastic non-hydrogel polymer. Typically, thermoplastic materials soften or melt when heated and return to a solid state upon cooling. When the temperature of a thermoplastic material rises to a temperature at or above its Vicat softening temperature, the thermoplastic material transitions from a solid to a softened state, and when the temperature rises to a temperature at or above its melting temperature, the thermoplastic material transitions to a molten liquid state. Upon sufficient cooling, the thermoplastic material transitions from a softened or liquid state to a solid state. Therefore, thermoplastic materials can be softened or melted, molded, cooled, re-softened or re-melted, re-molded, and cooled again through multiple cycles. For amorphous thermoplastic polymers, the solid state is understood to be a “rubber” state above the polymer’s glass transition temperature. When measured according to ASTM D3418-97 as described below, thermoplastic materials can have a melting temperature from about 90°C to about 190°C. When measured according to ASTM D3418-97 as described below, thermoplastic materials may have a melting temperature from about 90°C to about 140°C, or about 90°C to about 100°C, or about 93°C to about 99°C. When measured according to ASTM D3418-97 as described below, thermoplastic materials may have a melting temperature from about 100°C to about 150°C, or about 100°C to about 130°C, or about 110°C to about 120°C, or about 112°C to about 118°C.

[0317] The glass transition temperature is the temperature at which an amorphous polymer transitions from a relatively brittle "glassy" state to a relatively flexible "rubbery" state. When measured according to ASTM D3418-97 as described below, thermoplastic materials can have a glass transition temperature ranging from about -20°C to about 30°C. When measured according to ASTM D3418-97 as described below, thermoplastic materials can have a glass transition temperature ranging from about -15°C to about -5°C, or from about -13°C to about -7°C. When measured according to ASTM D3418-97 as described below, thermoplastic materials can have a glass transition temperature ranging from about 15°C to about 25°C, or from about 17°C to about 23°C.

[0318] The polymer hydrogel can be an aliphatic or aromatic polyurethane hydrogel, including thermoplastic aliphatic or aromatic polyurethane hydrogels, comprising a combination of hard and soft segments, wherein the hard segments comprise one or more segments having isocyanate groups. The hard segments can comprise segments formed from hexamethylene diisocyanate (HDI) alone or in combination with 1,4-butanediol (1,4-BD) as a chain extender, as shown in formula (F-1A). Segments having isocyanate groups include segments having isocyanate groups directly bonded to segments formed from 1,4-BD. In one aspect, the soft segments can be formed from poly(ethylene oxide) (PEO), as shown in formula (F-1B). The reaction product (i.e., the polymer hydrogel) formed from both hard segments HS and soft segments SS can correspond to the formula shown in (F-1C), where SS and HS correspond to the formulas shown in (F-1D) and (F-1E), respectively. Such polymer hydrogels formed from soft and hard segments exhibit an average ratio (SS:HS) of the number of soft segments to the number of hard segments present in the polymer chain of the polymer hydrogel. The SS:HS ratio can range from about 6:1 to about 100:1; alternatively, from about 15:1 to about 99:1; alternatively, from about 30:1 to about 95:1; alternatively, from about 50:1 to about 90:1; alternatively, from 75:1 to 85:1. As the SS:HS ratio increases, more soft segments (e.g., PEO) are present in the structure of the polymer hydrogel. While not wishing to be bound by theory, it is believed that a higher SS:HS ratio results in a higher water absorption capacity of the polymer hydrogel. The chemical descriptions of formulas F-1A to F-1E are provided below.

[0319]

[0320] Polymer hydrogels can include polyurethane hydrogels, polyamide hydrogels, polyurea hydrogels, polyester hydrogels, polycarbonate hydrogels, polyetheramide hydrogels, hydrogels formed from addition polymers of olefinically unsaturated monomers, their copolymers (e.g., copolyesters, copolyethers, copolyamides, copolyurethanes, copolyolefins), and combinations thereof. Because hydrogel materials contain polymer hydrogels, they comprise a polymer component consisting of all the polymers present in the hydrogel material. Similarly, the hydrogel component of a hydrogel material consists of all the polymer hydrogels present in the hydrogel material. The polymer component of a hydrogel material can include or consist of: polyurethane hydrogels, polyamide hydrogels, polyurea hydrogels, polyester hydrogels, polycarbonate hydrogels, polyetheramide hydrogels, hydrogels formed from addition polymers of olefinically unsaturated monomers, their copolymers (e.g., copolyesters, copolyethers, copolyamides, copolyurethanes, copolyolefins), and combinations thereof. The polymer component of a hydrogel material may also include additional polymer components. Hydrogel materials may also include non-polymer components. Alternatively, hydrogel materials can consist substantially of polymeric components, meaning they can be substantially free of non-polymeric components. Similarly, hydrogel materials can consist substantially of hydrogelic components, meaning they can be substantially free of non-hydrogel polymers and non-polymeric components. Further details are provided herein.

[0321] As described herein, hydrogel materials include polymeric hydrogels. The hydrogel components of a hydrogel material may include one or more polyurethane hydrogels or consist substantially of one or more polyurethane hydrogels. Polyurethane hydrogels are prepared from one or more diisocyanates and one or more diols (including one or more hydrophilic diols), and thus may be said to include segments derived from diisocyanates and diols. Polymer hydrogels may also be prepared from hydrophilic and hydrophobic diols, wherein the hydrophobic diol is relatively more hydrophobic than the hydrophilic diol. Polymerization is typically carried out using approximately equivalent amounts of diols and diisocyanates. Examples of hydrophilic diols include polyethylene glycol and copolymers of ethylene glycol and propylene glycol. Diisocyanates may be selected from a variety of aliphatic or aromatic diisocyanates. The relative hydrophobicity of the resulting polymeric hydrogel is determined by the amount and type of hydrophilic diol, the type and amount of hydrophobic diol, and the type and amount of diisocyanate present in the polymer chains of the resulting polymeric hydrogel.

[0322] The hydrogel component of a polymer hydrogel and / or hydrogel mixture may include one or more polyurea hydrogels or consist substantially of one or more polyurea hydrogels. The polyurea hydrogel is prepared from one or more diisocyanates and one or more hydrophilic diamines. In addition to hydrophilic diamines, the polymer hydrogel may also include hydrophobic diamines. Polymerization is typically carried out using approximately equivalent amounts of diamines and diisocyanates. Typical hydrophilic diamines include amine-terminated polyethylene oxide and amine-terminated copolymers of polyethylene oxide / polypropylene. An example is JEFFAMINE diamine, sold by Huntsman (The Woodlands, TX, USA). The diisocyanate may be selected from a variety of aliphatic or aromatic diisocyanates. The relative hydrophobicity of the resulting polymer hydrogel is determined by the amount and type of hydrophilic diamine, the type and amount of hydrophobic diamine, and the type and amount of diisocyanate present in the polymer chain of the resulting polymer hydrogel.

[0323] The hydrogel component of polymer hydrogels and / or hydrogel mixtures may include one or more polyester hydrogels or consist substantially of one or more polyester hydrogels. The polyester hydrogel may be prepared from a dicarboxylic acid (or a dicarboxylic acid derivative) and a diol, wherein some or all of the diol is a hydrophilic diol. Examples of hydrophilic diols include polyethylene glycol and copolymers of ethylene glycol and propylene glycol. A second relatively hydrophobic diol may also be used to control the polarity of the polymer hydrogel. One or more diacids may be used, which may be aromatic or aliphatic. Of particular interest are block polyesters prepared from lactones of hydrophilic diols and hydroxy acids. The lactone is polymerized at each end of the hydrophilic diol to produce a triblock polymer. Furthermore, these triblock segments may be linked together to produce a multiblock polymer hydrogel through a reaction with a dicarboxylic acid.

[0324] The hydrogel component of a polymer hydrogel and / or hydrogel mixture may include one or more polycarbonate hydrogels or consist substantially of one or more polycarbonate hydrogels. Polycarbonates are typically prepared by reacting a glycol with phosgene or diester carbonate. When some or all of the glycol is hydrophilic, a hydrophilic polycarbonate is produced. Examples of hydrophilic glycols include hydroxyl-terminated polyethers of ethylene glycol and polyethers of ethylene glycol and propylene glycol. A second relatively hydrophobic glycol may also be included to control the polarity of the polymer hydrogel.

[0325] The hydrogel component of a polymer hydrogel and / or hydrogel mixture may include one or more polyetheramide hydrogels or consist substantially of one or more polyetheramide hydrogels. Polyetheramides are prepared from dicarboxylic acids (or dicarboxylic acid derivatives) and polyether diamines (polyethers with amino groups at each end). Hydrophilic amine-terminated polyethers produce polymer hydrogels. Relatively hydrophobic diamines can be used in combination with hydrophilic diamines to control the hydrophilicity of the polymer hydrogel. Furthermore, the type of dicarboxylic acid segment can be selected to control the polarity of the polymer and the physical properties of the polymer hydrogel. Typical hydrophilic diamines are amine-terminated polyethylene oxide and amine-terminated copolymers of polyethylene oxide / polypropylene. An example is JEFFAMINE diamine, sold by Huntsman (The Woodlands, TX, USA).

[0326] The hydrogel component of polymeric hydrogels and / or hydrogel mixtures may include one or more comb-shaped polymers. Addition polymers of olefinically unsaturated monomers are examples of comb-shaped polymers. Comb-shaped polymers are produced when one of the monomers is a macromonomer (an oligomer with an olefinically unsaturated group at one end). In one case, the main chain is hydrophilic, while the side chains are relatively hydrophobic. Alternatively, the comb-shaped main chain may be relatively hydrophobic, while the side chains are hydrophilic. An example is a polymeric hydrogel having a main chain of a hydrophobic monomer such as styrene and side chains including polyethylene glycol monomethacrylate.

[0327] The hydrogel component of a polymer hydrogel and / or hydrogel mixture may comprise one or more polymer hydrogels formed from addition polymers of olefinic unsaturated monomers, or substantially consist of said polymer hydrogels. The addition polymers of olefinic unsaturated monomers may be random polymers. The polymer hydrogel may be prepared by free radical polymerization of one or more hydrophilic olefinic unsaturated monomers and one or more hydrophobic olefinic unsaturated monomers. Examples of hydrophilic monomers include acrylic acid, methacrylic acid, 2-acryloylamino-2-methylpropanesulfonic acid, vinyl sulfonic acid, sodium p-styrene sulfonate, [3-(methacryloylamino)propyl]trimethylammonium chloride, 2-hydroxyethyl methacrylate, acrylamide, N,N-dimethylacrylamide, 2-vinylpyrrolidone, (meth)acrylates of polyethylene glycol, and (meth)acrylates of polyethylene glycol monomethyl ether. Examples of relatively hydrophobic monomers include (meth)acrylates of C1 to C4 alcohols, polystyrene, polystyrene methacrylate macromonomers, and mono(meth)acrylates of siloxanes. The water absorption and physical properties of polymer hydrogels can be tuned by selecting monomers and the amount of each monomer type used to prepare the polymer chains of the polymer hydrogel.

[0328] Addition polymers of olefinically unsaturated monomers can be block polymers. Block polymers of olefinically unsaturated monomers can be prepared by methods such as anionic polymerization or controlled radical polymerization. Polymer hydrogels are produced when the polymer chains of the resulting polymer hydrogel have both hydrophilic and relatively hydrophobic blocks. The polymer hydrogel can be a diblock polymer (AB), a triblock polymer (ABA), or a multiblock polymer. Triblock polymers with relatively hydrophobic terminal blocks and one or more hydrophilic central blocks can be used. Block polymers can also be prepared by other means. Partial hydrolysis of polyacrylonitrile polymers produces multiblock polymers with hydrophilic domains (e.g., hydrolyzed domains) separated by relatively hydrophobic domains (e.g., unhydrolyzed domains), such that the partially hydrolyzed polymer has hydrogel properties. Hydrolysis can convert acrylonitrile segments into hydrophilic acrylamide or acrylic segments in a multiblock configuration.

[0329] The hydrogel component of polymer hydrogels and / or hydrogel mixtures may include or consist substantially of the following: copolymer hydrogels, i.e., polymer hydrogels that include copolymers in their polymer chain structure. The copolymer combines two or more types of polymers within each polymer chain. Examples include polyurethane / polyurea copolymer hydrogels, polyurethane / polyester copolymer hydrogels, and polyester / polycarbonate copolymer hydrogels.

[0330] Hydrogel materials may include, or substantially consist of, one or more polymeric hydrogels combined with an elastomeric material such as rubber, including cured or uncured rubber. In some instances where the hydrogel material includes cured rubber, the hydrogel material may be an elastomeric hydrogel material, i.e., a hydrogel material having elastomeric properties. The rubber may be natural or synthetic rubber, such as, for example, butadiene rubber or isoprene rubber. In one aspect, the hydrogel material is a hydrogel coating on another material, such as a hydrogel coating on an elastomeric material. In another aspect, the hydrogel material is a mixture or dispersion of a polymeric hydrogel with or within an elastomeric material. In another aspect, the hydrogel material comprises a mixture of a first cured rubber and one or more polymeric hydrogels. In the hydrogel material, one or more polymeric hydrogels may be distributed throughout the hydrogel material and may be embedded in a polymeric network including the cured rubber. For example, the polymeric hydrogel may be physically entangled with the crosslinked network of the cured rubber and / or chemically crosslinked with the crosslinked network of the cured rubber. A polymer network comprising cured rubber can be formed by crosslinking a mixture of uncured rubber and hydrogel components. The hydrogel component may include or consist of one or more polyurethane hydrogels. The hydrogel material may contain a first concentration of hydrogel component from about 1% to about 70% by weight based on the total weight of the hydrogel material, or from about 5% to about 60% by weight, or from about 10% to about 50% by weight, or from about 20% to about 40% by weight based on the total weight of the hydrogel material.

[0331] plate

[0332] In some aspects, composite elements are present in a sole structure including a plate. In one aspect, the sole component may include a full plate extending from the toe region of a footwear article incorporated into the sole component through the midfoot region to the heel region. In another aspect, the sole component may include a partial plate covering a portion of the forefoot region, a portion of the heel region, a portion of the midfoot region, or a combination thereof. The plate comprises a second polymer material. The second polymer material of the plate comprises at least one polymer. The second polymer material may include a polymer component consisting of all polymers present in the second polymer material. In addition to at least one polymer, the second polymer material may also contain one or more additional materials, such as colorants, fillers, and resin modifiers. The second polymer material may contain one or more thermoplastic polymers and may be a thermoplastic second polymer material. Alternatively, the second polymer material may be a thermosetting material that is thermosetting upon curing. In such cases, the thermosetting second polymer material will contain one or more thermosetting polymers prior to curing. Upon curing, the thermosetting second polymer material will contain one or more thermosetting polymers.

[0333] In some aspects of the sole structure, a second polymer material of the plate extends through a first side of the textile of the composite element, thereby forming a mechanical bond between the composite element and the plate. To facilitate the formation of this mechanical bond by contacting the textile with the second polymer material in molten form, the second polymer material may have a melt flow index (at 190°C, 21.6 kg) from about 35 g / 10 min to about 55 g / 10 min, using the material sampling procedure, substrate sampling procedure, or component sampling procedure described herein, according to a melt flow index testing scheme. In one aspect, the melt flow index is about 35 g / 10 min, about 40 g / 10 min, about 45 g / 10 min, about 50 g / 10 min, or about 55 g / 10 min.

[0334] The second polymer material may include one or more polyolefin polymers or copolymers, including one or more thermoplastic polyolefin polymers or copolymers. The polymer component of the second polymer material may include one or more polyolefin polymers or copolymers, or be substantially composed of one or more polyolefin polymers or copolymers. One or more polyolefin polymers or copolymers may include, or be substantially composed of, the following: polypropylene, polystyrene, polyethylene, ethylene-α-olefin copolymers, ethylene-propylene rubber (EPDM), polybutene, polyisobutylene, poly-4-methylpent-1-ene, polyisoprene, polybutadiene, ethylene-methacrylic acid copolymers, any copolymers thereof, or mixtures thereof. The polymer component of the second polymer material may include, or be substantially composed of, polypropylene homopolymers, polypropylene copolymers, polyethylene homopolymers, polyethylene copolymers, or any combination thereof. The polymer component of the second polymer material may include, or be substantially composed of, a mixture of polyolefin homopolymers or copolymers and resin modifiers. For example, the polymer component may include or consist essentially of: a mixture of polypropylene homopolymer and polymer resin modifier, a mixture of polypropylene copolymer and polymer resin modifier, or a mixture of polypropylene homopolymer, polypropylene copolymer and polymer resin modifier.

[0335] In some aspects, at least one polyolefin or polymer component of the second polymer material may comprise ethylene-propylene rubber (EPDM) dispersed in polypropylene or consist substantially of ethylene-propylene rubber (EPDM) dispersed in polypropylene. In one aspect, at least one polyolefin or polymer component comprises a block copolymer containing polystyrene blocks or consists substantially of a block copolymer containing polystyrene blocks. In some aspects, the block copolymer comprises a copolymer of one or both of ethylene and butene with styrene.

[0336] In some aspects, one or more polymers of the second polymer material include non-polyolefin polymers. Similarly, the second polymer material may include a non-polyolefin polymer component consisting of all non-polyolefin polymers present in the second polymer material. For example, one or more non-polyolefin polymers or non-polyolefin polymer components may include or be substantially composed of polyurethane, polyamide, polyimide, polyester, polyether, polyurea, or any combination thereof. One or more non-polyolefin polymers or non-polyolefin polymer components may include polyurethane or be composed of polyurethane. The polyurethane may be thermoplastic polyurethane (TPU). The polyurethane may include polyether-polyurethane or polyester-polyurethane, or a mixture of both. One or more non-polyolefin polymers or non-polyolefin polymer components may include polyamide or be composed of polyamide, including thermoplastic polyamide. The polyamide may include polyamide homopolymers or polyamide copolymers, or a mixture of both, or be substantially composed of polyamide homopolymers or polyamide copolymers, or a mixture of both. The polyamide copolymer may include polyamide block copolymers, such as random polyamide block copolymers having polyamide segments and polyether segments.

[0337] One or more polymers of the second polymer material and / or the polymer components of the second polymer material may include one or more of a variety of polyolefin copolymers, or are substantially composed of one or more of a variety of polyolefin copolymers. One or more copolymers may include alternating copolymers, random copolymers, block copolymers, or graft copolymers. In some aspects, one or more copolymers include random copolymers. In some aspects, the copolymer comprises more than one repeating unit or segment, wherein each of the more than one repeating unit is individually derived from an olefin monomer having about one to about six carbon atoms. In other aspects, the copolymer comprises more than one repeating unit, wherein each of the more than one repeating unit is individually derived from a monomer selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-butene, 1-octene, and combinations thereof. In some aspects, the polyolefin copolymer comprises more than one repeating unit, each of which is individually selected from formula 1A to formula 1D. In some aspects, the polyolefin copolymer comprises a first more than one repeating unit having a structure according to formula 1A, and a second more than one repeating unit having a structure selected from formula 1B to formula 1D.

[0338]

[0339] In some respects, the polyolefin copolymer comprises more than one repeating unit, each of which individually has a structure according to Formula 2.

[0340]

[0341] Where R1 It is hydrogen or a straight-chain or branched C1-C with or without substitution. 12 Alkyl, C1-C6 alkyl, C1-C3 alkyl, C1-C 12 Heteroalkyl, C1-C6 heteroalkyl, or C1-C3 heteroalkyl. In some aspects, each repeating unit in the first more than one repeating unit has a structure according to Formula 1A above, and each repeating unit in the second more than one repeating unit has a structure according to Formula 2 above.

[0342] In some aspects, the polyolefin copolymer is a random copolymer of a first and a second repeating unit, wherein each of the first and a second repeating units is derived from ethylene, and each of the second and a second repeating units is derived from a second olefin. In some aspects, the second olefin is an olefin monomer having about 1 to about 6 carbon atoms. In other aspects, the second olefin includes propylene, 4-methyl-1-pentene, 1-butene, or other straight-chain or branched terminal olefins having about 3 to 12 carbon atoms. In some aspects, the polyolefin copolymer comprises about 80% to about 99%, about 85% to about 99%, about 90% to about 99%, or about 95% to about 99% polyolefin repeating units by weight based on the total weight of the polyolefin copolymer. In some aspects, the polyolefin copolymer consists essentially of polyolefin repeating units. In some aspects, the polymer in the polyolefin resin composition consists essentially of the polyolefin copolymer.

[0343] Polyolefin copolymers may include ethylene, i.e., may include repeating units derived from ethylene, such as those in Formula 1A. In some aspects, the polyolefin copolymer contains about 1% to about 5%, about 1% to about 3%, about 2% to about 3%, or about 2% to about 5% of ethylene by weight based on the total weight of the polyolefin copolymer.

[0344] The polymer component of the second polymer material may be substantially free of polyurethane and / or polyamide. For example, in some aspects, the polyolefin copolymer is substantially free of polyurethane. In some aspects, the polymer chain of the polyolefin copolymer is substantially free of urethane repeating units. In some aspects, the polymer component is substantially free of polymer chains containing urethane repeating units. In some aspects, the polyolefin copolymer is substantially free of polyamide. In some aspects, the polymer chain of the polyolefin copolymer is substantially free of amide repeating units. In some aspects, the second polymer material is substantially free of polymer chains containing amide repeating units.

[0345] In some aspects, the polyolefin copolymer includes polypropylene or a polypropylene copolymer. In some aspects, the polymer component of the resin composition includes or is substantially composed of a polypropylene copolymer. In some aspects, the second polymer material includes a polypropylene copolymer and a polymer resin modifier. In some aspects, the second polymer material has the abrasion loss as described above, and wherein the polymer resin modifier is present in an amount that effectively allows the second polymer material to be present in a flexural test according to a flexural test of cold shoe sole material using a substrate sampling procedure. In some aspects, the amount of polymer resin modifier is such that it effectively allows the resin composition to undergo a flexural test according to a flexural test of cold shoe sole material using a substrate sampling procedure, and when measured using a material sampling procedure according to ASTM D 5963-97a, the abrasion loss is not significantly different compared to the abrasion loss of the same polymer material as the second polymer material except without the polymer resin modifier.

[0346] The polypropylene copolymer and / or polymeric component may include or substantially consist of: a random copolymer, such as a random copolymer of ethylene and propylene. The polypropylene copolymer may contain about 80% to about 99%, about 85% to about 99%, about 90% to about 99%, or about 95% to about 99% of propylene repeating units by weight based on the total weight of the polypropylene copolymer. In some aspects, the polypropylene copolymer contains about 1% to about 5%, about 1% to about 3%, about 2% to about 3%, or about 2% to about 5% of ethylene by weight based on the total weight of the polypropylene copolymer. In some aspects, the polypropylene copolymer is a random copolymer containing about 2% to about 3% of a first more than one repeating unit and about 80% to about 99% of a second more than one repeating unit by weight based on the total weight of the polypropylene copolymer; wherein each repeating unit in the first more than one repeating unit has a structure according to Formula 1A above, and each repeating unit in the second more than one repeating unit has a structure according to Formula 1B above.

[0347] The polymeric components of the polypropylene copolymer and / or the second polymeric material may be substantially free of polyurethane and / or polyamide. For example, in some aspects, the polypropylene copolymer and / or polymeric components are substantially free of polyurethane. In some aspects, the polymer chains of the polypropylene copolymer are substantially free of urethane repeating units. In some aspects, the polypropylene copolymer is substantially free of polymer chains containing urethane repeating units. In some aspects, the polypropylene copolymer is substantially free of polyamide. In some aspects, the polymer chains of the polypropylene copolymer are substantially free of amide repeating units. In some aspects, the polypropylene copolymer is substantially free of polymer chains containing amide repeating units.

[0348] In one aspect, the polymer component of the second polymer material comprises a polypropylene homopolymer or a copolymer containing repeating propylene units, or both, or is substantially composed of a polypropylene homopolymer or a copolymer containing repeating propylene units, or both. In another aspect, the polymer component of the second polymer material comprises a polypropylene copolymer or is substantially composed of a polypropylene copolymer. In some aspects, the polypropylene copolymer may be a random copolymer of ethylene and propylene.

[0349] The combination of abrasion resistance and flexural durability can be related to the total crystallinity of the second polymer composition. In some aspects, when measured according to crystallinity testing using a material sampling procedure, the second polymer material has a crystallinity percentage (crystallinity%) of about 45%, about 40%, about 35%, about 30%, about 25%, or lower. It has been found that adding a polymer resin modifier to the second polymer material can produce a second polymer material capable of passing the flexural test of cold shoe sole materials while maintaining relatively low abrasion loss, with the amount of said polymer resin modifier only slightly reducing the crystallinity percentage of the second polymer material compared to a second polymer material that is otherwise identical except without the polymer resin modifier. In some aspects, the polymer resin modifier leads to a decrease in the crystallinity percentage (crystallinity%) of the second polymer material. In some aspects, when measured according to crystallinity testing using a material sampling procedure, the second polymer material has a crystallinity percentage (crystallinity%) that is at least 6%, at least 5%, at least 4%, at least 3%, or at least 2 percentage points lower than that of a second polymer material that is otherwise identical except without the polymer resin modifier.

[0350] In some aspects, the effective amount of the polymer resin modifier may be about 5% to about 30% by weight, about 5% to about 25% by weight, about 5% to about 20% by weight, about 5% to about 15% by weight, about 5% to about 10% by weight, about 10% to about 15% by weight, about 10% to about 20% by weight, about 10% to about 25% by weight, or about 10% to about 30% by weight.

[0351] In one aspect, one or more polymers of the second polymer material may have a total ethylene repeating unit content of from about 3% to about 7% by weight based on the total weight of the second polymer material. In another aspect, the polymer resin modifier may have an ethylene repeating unit content of from about 10% to about 15% by weight based on the total weight of the polymer resin modifier.

[0352] In some aspects, the polymer resin modifier comprises a copolymer containing isotactic repeating units derived from olefins or is substantially composed of copolymers containing isotactic repeating units derived from olefins. In some aspects, the polymer resin modifier comprises a copolymer containing repeating units according to Formula 1B above or is substantially composed of copolymers containing repeating units according to Formula 1B above, wherein the repeating units according to Formula 1B are arranged in an isotactic stereochemical configuration.

[0353] In some aspects, the polymer resin modifier comprises a copolymer containing isotactic propylene repeating units and ethylene repeating units, or is substantially composed of a copolymer containing isotactic propylene repeating units and ethylene repeating units. In one aspect, the polymer resin modifier is a copolymer containing a first and a second repeating unit. In this aspect, each repeating unit in the first and a second repeating unit has a structure according to Formula 1A above, and each repeating unit in the second and a second repeating unit has a structure according to Formula 1B above, and the repeating units in the second and a second repeating unit are arranged in an isotactic stereochemical configuration.

[0354] In this respect, a second polymer material containing a resin modifier as disclosed herein can pass the cold shoe sole material flex test using the cold shoe sole material flex test protocol and be sampled using the material sampling procedure, but a second polymer material without a polymer resin modifier but otherwise identical does not pass the cold shoe sole material flex test.

[0355] polymer materials

[0356] Having described aspects of hydrogel materials, textile materials, and second polymer materials for plates, further details are provided regarding polymer materials that may be included in hydrogel materials, textile materials, second polymer materials, or the first adhesive material disclosed herein, or the second adhesive material, or any combination thereof. As described herein, a polymer material may be a hydrogel material, a textile material, a second polymer material, or any combination thereof. Similarly, a polymer component of a polymer material (i.e., a portion of the polymer material consisting of all the polymers present in the polymer material) may be a polymer component of a hydrogel material, a hydrogel component of a hydrogel material, a polymer component of a textile material, a polymer component of a second polymer material, or any combination thereof. In some aspects, a polymer material may comprise polymers of the same or different types of monomers (e.g., homopolymers and copolymers, including terpolymers). In some aspects, a polymer material comprises a thermoplastic polymer. In other aspects, a polymer material comprises a thermosetting polymer. In some aspects, a polymer material comprises a polyolefin polymer. In some aspects, a polymer material may comprise one or more polymers having different monomer units randomly distributed in their polymer chains (e.g., random copolymers).

[0357] For example, a polymeric material can be or may include polymers of repeating polymeric units (i.e., segments) having the same chemical structure. Physical crosslinking can occur within or between segments, or both. Some polymers include relatively stiff repeating segments (hard segments) and relatively soft repeating polymeric segments (soft segments). In several respects, polymers have repeating hard and soft segments. Examples of hard segments include isocyanate segments. Examples of soft segments include alkoxy groups, such as polyether segments and polyester segments. As used herein, a polymeric segment may be referred to as a specific type of polymeric segment, such as, for example, isocyanate segments (e.g., diisocyanate segments), alkoxy polyamide segments (e.g., polyether segments, polyester segments), and similar segments. It should be understood that the chemical structure of a segment is derived from the described chemical structure. For example, an isocyanate segment is a unit of polymerization that includes isocyanate functional groups. When referring to a polymeric segment with a specific chemical structure, the polymer may contain segments with other chemical structures up to 10 molar percentages. For example, as used herein, polyether segments should be understood to include up to 10 molar percentages of non-polyether segments.

[0358] In some aspects, the polymeric material may include thermoplastic polyurethane (also referred to as "TPU"). In one aspect, the thermoplastic polyurethane may be a thermoplastic polyurethane polymer. In such an aspect, the thermoplastic polyurethane polymer may include hard segments and soft segments. In one aspect, the hard segments may include isocyanate segments (e.g., diisocyanate segments) or consist of isocyanate segments (e.g., diisocyanate segments). In the same or alternative aspects, the soft segments may include alkoxy segments (e.g., polyether segments, or polyester segments, or a combination of polyether and polyester segments) or consist of said alkoxy segments. In a particular aspect, the polymeric material may include an elastomeric thermoplastic polyurethane having repeating hard segments and repeating soft segments, or substantially composed of such an elastomeric thermoplastic polyurethane.

[0359] The hydrogel material, the second polymer material, or both may comprise one or more polymers, wherein the polymer chain structure includes at least a portion comprising a first hard segment and a first soft segment, wherein the hard segment is physically crosslinked to another hard segment in the same polymer chain or to a hard segment in another polymer, and the soft segment is covalently bonded to the first hard segment. For example, the hard segment and the soft segment may be covalently bonded via urethane bonds or ester bonds.

[0360] The hydrogel material, the second polymer material, or both may include one or more polymers, wherein the polymer chain structure includes a first segment, such as a hard segment, which forms crystalline or semi-crystalline regions of the polymer network by physical crosslinking with segments of the chain or with other polymer chains; and a second segment, such as a soft segment, covalently bonded to the first segment. In this example, the second segment may form amorphous regions of the polymer network.

[0361] Polyolefins

[0362] In some aspects, the polymer, polymeric components of the polymeric material, and / or the polymeric material may include or be substantially composed of thermoplastic polyolefins. Useful exemplary thermoplastic polyolefins may include, but are not limited to, polyethylene, polypropylene, and thermoplastic olefin elastomers (e.g., metallocene-catalyzed block copolymers of ethylene with α-olefins having 4 to about 8 carbon atoms). In other aspects, thermoplastic polyolefins include polymers comprising: polyethylene, ethylene-α-olefin copolymers, ethylene-propylene rubber (EPDM), polybutene, polyisobutylene, poly-4-methylpent-1-ene, polyisoprene, polybutadiene, ethylene-methacrylic acid copolymers, and olefin elastomers such as dynamically cross-linked polymers obtained from polypropylene (PP) and ethylene-propylene rubber (EPDM), as well as blends or mixtures thereof. Further exemplary thermoplastic polyolefins include cycloolefins, such as cyclopentene or norbornene.

[0363] It should be understood that optionally crosslinked polyethylene includes 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 ultra-high-molecular-weight polyethylene (HDPE-UHMW), and blends or mixtures of any of the aforementioned polyethylenes. Polyethylene can also be a polyethylene copolymer derived from monomers of monoolefins and dienes copolymerized with: vinyl, acrylic acid, methacrylic acid, ethyl acrylate, vinyl alcohol, and / or vinyl acetate. Polyolefin copolymers including vinyl acetate-derived units can be copolymers with a high vinyl acetate content, for example, a composition with more than about 50 percent vinyl acetate-derived by weight.

[0364] In some aspects, the thermoplastic polyolefins disclosed herein can be formed via free radical polymerization, cationic polymerization, and / or anionic polymerization using methods well known to those skilled in the art (e.g., using peroxide initiators, heat, and / or light). In other aspects, the disclosed thermoplastic polyolefins can be prepared by free radical polymerization under high pressure and at high temperature. Alternatively, the thermoplastic polyolefins can be prepared by catalytic polymerization using a catalyst, which typically comprises one or more metals from Group IVb, Vb, VIb, or VIII. The catalyst typically has one or more ligands complexed with the Group IVb, Vb, VIb, or VIII metal, typically oxides, halides, alcohols, esters, ethers, amines, alkyl groups, alkenyl groups, and / or aryl groups that can be para- or ortho-coordinated. In many aspects, the metal complex can be in free form or immobilized on a substrate, typically on activated magnesium chloride, titanium(III) chloride, alumina, or silica. It should be understood that metal catalysts may be soluble or insoluble in the polymerization medium. The catalyst can be used alone in the polymerization process, or it can be used with other activators, typically Group Ia, IIa, and / or IIIa metal alkyl groups, metal hydrides, metal alkyl halides, metal alkyl oxides, or metal alkyloxanes. The activator can be readily modified with additional ester, ether, amine, or silyl ether groups.

[0365] Suitable thermoplastic polyolefins can be prepared by polymerization of monomers of monoolefins and dienes as described herein. Exemplary monomers that can be used to prepare the disclosed thermoplastic polyolefins 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.

[0366] Suitable ethylene-α-olefin copolymers can be obtained by copolymerizing ethylene with α-olefins having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, or the like.

[0367] Suitable dynamic crosslinked polymers can be obtained by crosslinking the rubber component as a soft segment while simultaneously physically dispersing the hard segments, such as PP, and the soft segments, such as EPDM, using kneaders such as Banbury mixers and biaxial extruders.

[0368] In some respects, the thermoplastic polyolefin can be a mixture of thermoplastic polyolefins, such as a mixture of two or more polyolefins disclosed above. For example, a suitable thermoplastic polyolefin mixture can be a mixture of polypropylene and polyisobutylene, a mixture of polypropylene and polyethylene (e.g., PP / HDPE, PP / LDPE), or a mixture of different types of polyethylene (e.g., LDPE / HDPE).

[0369] In some aspects, the thermoplastic polyolefin can be a copolymer of a suitable monoolefin monomer or a copolymer of a suitable monoolefin monomer with a vinyl monomer. Exemplary thermoplastic polyolefin copolymers include, but are not limited to, ethylene / propylene copolymers, linear low-density polyethylene (LLDPE), and mixtures thereof with low-density polyethylene (LDPE), propylene / butene copolymers, propylene / isobutene copolymers, ethylene / butene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers, and their mixtures with monoxide Copolymers of carbon or ethylene / acrylic acid copolymers, and their salts (ionomers), and terpolymers of ethylene with propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with each other and with polymers mentioned in 1) above, such as 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 such as polyamides.

[0370] In some respects, the thermoplastic polyolefin can be a polypropylene homopolymer, a polypropylene copolymer, a polypropylene random copolymer, a polypropylene block copolymer, a polyethylene homopolymer, a polyethylene random copolymer, a polyethylene block copolymer, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene, high-density polyethylene (HDPE), or a blend or mixture of one or more of the aforementioned polymers.

[0371] In some respects, the polyolefin is polypropylene. As used herein, the term "polypropylene" is intended to cover any polymer composition comprising a propylene monomer, either alone or as a mixture or copolymer of other randomly selected and oriented polyolefins, dienes, or other monomers (such as ethylene, butene, and the like). Such a term also covers any different configurations and arrangements of the component monomers (such as atactic, syndiotactic, isotactic, etc.).

[0372] In some respects, the polyolefin is polyethylene. As used herein, the term "polyethylene" is intended to cover any polymer composition comprising ethylene monomer units, which are either alone or mixtures or copolymers of other randomly selected and oriented polyolefin, diene, or other monomer units (such as propylene, butene, and the like). Such a term also covers any different configurations and arrangements of the component monomer units (such as atactic, syndiotactic, isotactic, etc.).

[0373] polyurethane

[0374] The polymer, polymeric component of the polymeric material, polymeric material, or any combination thereof may include or be substantially composed of polyurethane. The polyurethane may be a thermoplastic polyurethane (also known as “TPU”). Alternatively, the polyurethane may be a thermosetting polyurethane. Furthermore, the polyurethane may be an elastomeric polyurethane, including elastomeric TPU or elastomeric thermosetting polyurethane. Elastomeric polyurethanes may include hard segments and soft segments. Hard segments may include urethane segments (e.g., isocyanate-derived segments) or be composed of urethane segments (e.g., isocyanate-derived segments). Soft segments may include alkoxy segments (e.g., polyol-derived segments comprising polyether segments, or polyester segments, or a combination of polyether and polyester segments) or be composed of such alkoxy segments. The polyurethane may include an elastomeric polyurethane having repeating hard segments and repeating soft segments or be substantially composed of such an elastomeric polyurethane.

[0375] In this regard, one or more thermoplastic polyurethanes can be produced by polymerizing one or more isocyanates with one or more polyols to generate polymer chains having urethane bonds (-N(CO)O-), wherein each isocyanate preferably comprises two or more isocyanate (-NCO) groups per molecule, such as two, three, or four isocyanate groups per molecule (although monofunctional isocyanates may optionally be included, for example, as chain-terminating units). Additionally, the isocyanates can be chain-extended with one or more chain extenders to bridge two or more isocyanates.

[0376] Each isocyanate-derived segment of polyurethane can independently include linear or branched C atoms. 3-30Segments. Depending on the specific isocyanate used to form the segment, the isocyanate segment can be aliphatic, aromatic, or a combination of aliphatic and aromatic moieties. The term "aliphatic" refers to a saturated or unsaturated organic molecule that does not include a cyclically conjugated ring system with delocalized π electrons. In contrast, the term "aromatic" refers to a cyclically conjugated ring system with delocalized π electrons, which exhibits greater stability than a hypothetical ring system with localized π electrons.

[0377] Each isocyanate-derived segment may be present in an amount of 5% to 85%, 5% to 70%, or 10% to 50% by weight, based on the total weight of the reactant monomers used to form the polyurethane.

[0378] In aliphatic embodiments (derived from aliphatic isocyanates), each isocyanate-derived segment may include a straight-chain aliphatic group, a branched aliphatic group, an alicyclic group, or a combination thereof. For example, each isocyanate-derived segment may include a straight-chain or branched C 3-20 alkylene segments (e.g., C10) 4-15 Alkylene or C 6-10 alkylene), one or more C 3-8 Cycloalkyl segments (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl) and combinations thereof.

[0379] Examples of suitable aliphatic diisocyanates for generating polyurethane polymer chains include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), diisocyanocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), diisocyanomethylcyclohexane, diisocyanomethyltricyclodecane, norbornane diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), diisocyanododecane, lysine diisocyanate, and combinations thereof.

[0380] In one aspect, the diisocyanate segments may include aliphatic diisocyanate segments. In one aspect, the majority of the diisocyanate segments include aliphatic diisocyanate segments. In one aspect, at least 90 percent of the diisocyanate segments are aliphatic diisocyanate segments. In one aspect, the diisocyanate segments are substantially composed of aliphatic diisocyanate segments. In one aspect, the aliphatic diisocyanate segments are substantially (e.g., about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more) linear aliphatic diisocyanate segments. In one aspect, at least 80 percent of the aliphatic diisocyanate segments are aliphatic diisocyanate segments without side chains. In one aspect, the aliphatic diisocyanate segments include C2-C 10 Straight-chain aliphatic diisocyanate segments.

[0381] In aromatic embodiments (from aromatic isocyanates), each segment R1 may include one or more aromatic groups, such as phenyl, naphthyl, tetrahydronaphthyl, phenanthryl, biphenylenyl, indanyl, indenyl, anthraceneyl, and fluorenyl. Unless otherwise indicated, the aromatic groups may be unsubstituted or substituted aromatic groups, and may also include heteroaromatic groups. “Hyperaromatic” refers to a monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ring system in which one to four ring atoms are selected from oxygen, nitrogen, or sulfur, and the remaining ring atoms are carbon, and wherein the ring system is connected to the rest of the molecule by any ring atoms. Examples of suitable heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyrroleyl, pyrazolyl, imidazoleyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, and benzothiazolyl.

[0382] Examples of suitable aromatic diisocyanates for generating polyurethane polymer chains include toluene diisocyanate (TDI), TDI adducts with trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene-1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3,3'-dimethyldiphenyl-4,4'-diisocyanate (DDDI), 4,4'-dibenzyl diisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate, and combinations thereof. In some embodiments, the polymer chain is substantially free of aromatic groups.

[0383] In certain aspects, the polyurethane polymer chain consists of HMDI, TDI, MDI, and H12 Diisocyanates of aliphatic compounds and combinations thereof are used to generate them. For example, the low-processing-temperature polymer compositions of this disclosure may include one or more polyurethane polymer chains generated from diisocyanates, such as HMDI, TDI, MDI, and H... 12 Aliphatic compounds and their combinations.

[0384] In some aspects, according to this disclosure, either crosslinked polyurethane chains (e.g., partially crosslinked polyurethane polymers that retain thermoplastic properties) or crosslinkable polyurethane chains can be used. It is possible to generate crosslinked or crosslinkable polyurethane polymer chains using polyfunctional isocyanates. Examples of suitable triisocyanates for generating polyurethane polymer chains include adducts of TDI, HDI, and IPDI with trimethylolpropane (TMP), uretdione (i.e., dimer isocyanates), polymeric MDI, and combinations thereof.

[0385] A portion of the isocyanate-derived chain segment may include straight-chain or branched C2-C segments. 10 The chain segment, depending on the specific chain extender used, can be, for example, aliphatic, aromatic, or polyether. Examples of suitable chain extenders for generating polyurethane polymer chains include ethylene glycol, lower oligomers of ethylene glycol (e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol), 1,2-propanediol, 1,3-propanediol, lower oligomers of propylene glycol (e.g., dipropylene glycol, tripropylene glycol, and tetrapropylene glycol), 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 2-ethyl-1,6-hexanediol, 1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylated aromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone and resorcinol, xylene-a,a-diol, bis(2-hydroxyethyl) ethers of xylene-a,a-diol, and combinations thereof).

[0386] The polyol-derived segments of polyurethane may include polyether groups, polyester groups, polycarbonate groups, aliphatic groups, or aromatic groups. Each polyol-derived segment may be present in an amount of 5% to 85%, 5% to 70%, or 10% to 50% by weight, based on the total weight of the reactant monomers used to form the polyurethane.

[0387] In some aspects, thermoplastic polyurethanes include polyether segments (i.e., segments having one or more ether groups). Suitable polyethers include, but are not limited to, polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof. As used herein, the term "alkyl" refers to a straight-chain and branched saturated hydrocarbon group containing one to thirty carbon atoms, for example, one to twenty carbon atoms or one to ten carbon atoms. Term C n This indicates that the alkyl group has "n" carbon atoms. For example, C4 alkyl refers to an alkyl group with 4 carbon atoms. 1-7 Alkyl refers to an alkyl group having a number of carbon atoms covering the entire range (i.e., 1 to 7 carbon atoms) and all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7 carbon atoms). Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), tert-butyl (1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unless otherwise indicated, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group.

[0388] In some aspects of thermoplastic polyurethanes, at least one polyol-derived segment includes a polyester segment. The polyester segment can be derived from the polyesterification of one or more dihydroxy alcohols (e.g., ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol, 1,5-diethylenediol, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanediol, and combinations thereof) with one or more dicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid, octanoic acid, methyl adipic acid, glutaric acid, pimelic acid, azelaic acid, thiodipropionic acid, and citralic acid, and combinations thereof). Polyesters can also be derived from polycarbonate prepolymers, such as poly(hexamethylene carbonate) glycol, poly(propylene carbonate) glycol, poly(tetramethylene carbonate) glycol, and poly(nonamethylene carbonate) glycol. Suitable polyesters may include, for example, polyethylene adipate (PEA), poly(1,4-butanediol adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), polycaprolactone, polyhexamethylene carbonate, poly(propylene carbonate), poly(tetramethylene carbonate), poly(nonamethylene carbonate), and combinations thereof.

[0389] In various thermoplastic polyurethanes, at least one polyol-derived segment includes a polycarbonate segment. The polycarbonate segment can be derived from the reaction of one or more dihydroxy alcohols (e.g., ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol, 1,5-diethylenediol, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanediol, and combinations thereof) with ethylene carbonate.

[0390] In many instances, the aliphatic group is straight-chain and may include, for example, C 1-20 alkylene chain or C 1-20 Alkenyl chains (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptadecylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, vinylene, propenylene, butenylene, pentenylene, hexenylene, heptadecylene, octylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). The term "alkylene" refers to a divalent hydrocarbon. The term C... n This means that the alkylene group has "n" carbon atoms. For example, C 1-6 Alkylene refers to an alkylene group having, for example, one, two, three, four, five, or six carbon atoms. The term "alkenylene" refers to a divalent hydrocarbon having at least one double bond.

[0391] In several aspects, aliphatic and aromatic groups may be substituted with one or more relatively hydrophilic and / or charged side groups. In some aspects, the hydrophilic side group comprises one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) hydroxyl groups. In several aspects, the hydrophilic side group comprises one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In some cases, the hydrophilic side group comprises one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) carboxylic acid ester groups. For example, the aliphatic group may comprise one or more polyacrylic acid groups. In some cases, the hydrophilic side group comprises one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, the hydrophilic side group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) phosphate ester groups. In some instances, the hydrophilic side group includes one or more ammonium groups (e.g., tertiary ammonium and / or quaternary ammonium). In other instances, the hydrophilic side group includes one or more zwitterionic groups (e.g., betaine, such as poly(carboxybetaine) (pCB) and phosphonate ammonium groups such as phosphatidylcholine groups).

[0392] Optionally, in some aspects, the polyurethane may comprise at least partially crosslinked polymer networks comprising polymer chains that are derivatives of the polyurethane. In such cases, the level of crosslinking may be such that the polyurethane retains its thermoplastic properties (i.e., the crosslinked thermoplastic polyurethane can soften or melt and re-cur under the processing conditions described herein). This crosslinked polymer network can be produced by polymerizing one or more isocyanates with one or more polyamine compounds, polysulfhydryl compounds, or combinations thereof.

[0393] As described herein, thermoplastic polyurethanes can be physically crosslinked, for example, through nonpolar or polar interactions between urethane groups or carbamate groups on the polymer. In these aspects, isocyanate-derived segments of the polymer chain are referred to as “hard segments,” and polyol-derived segments of the polymer chain are referred to as “soft segments.” In these aspects, soft segments are covalently bonded to hard segments within the polymer chain. In some aspects, hard segments within a single polymer chain can be physically crosslinked, or can be physically crosslinked with hard segments of other polymer chains. In some instances, thermoplastic polyurethanes with physically crosslinked hard segments can be hydrophilic thermoplastic polyurethanes (i.e., thermoplastic polyurethanes including hydrophilic groups as disclosed herein) and can be polyurethane hydrogels (i.e., polyurethanes capable of absorbing at least 10 percent of their weight in water).

[0394] polyamide

[0395] In several respects, a polymer, a polymeric component of a polymeric material, a polymeric material, or any combination thereof may include polyamides such as thermoplastic polyamides, or may consist substantially of polyamides such as thermoplastic polyamides. The polyamide may be a polyamide homopolymer having repeating polyamide segments having the same chemical structure. Alternatively, the polyamide may comprise a number of polyamide segments with different polyamide chemical structures (e.g., polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, etc.). The polyamide segments with different chemical structures may be arranged randomly or may be arranged as repeating blocks.

[0396] The polyamide can be a copolyamide (i.e., a copolymer comprising polyamide segments and non-polyamide segments). The polyamide segments of the copolyamide can include or consist of: polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, or any combination thereof. The polyamide segments of the copolyamide can be randomly arranged or can be arranged as repeating segments. In specific instances, the polyamide segments can include or consist of: polyamide 6 segments, or polyamide 12 segments, or both polyamide 6 and polyamide 12 segments. In instances where the polyamide segments of the copolyamide include polyamide 6 and polyamide 12 segments, the segments can be randomly arranged. The non-polyamide segments of the copolyamide can include or consist of: polyether segments, polyester segments, or both polyether and polyester segments. The copolyamide can be a copolyamide or a random copolyamide. The copolyamide can be formed by polycondensation of a polyamide oligomer or prepolymer with a second oligomer prepolymer to form a copolyamide (i.e., a copolymer containing polyamide segments). Optionally, the second prepolymer can be a hydrophilic prepolymer.

[0397] In this context, the copolyamide can be a block copolyamide. For example, a block copolyamide can have repeating hard segments and repeating soft segments. The hard segments can include polyamide segments, and the soft segments can include non-polyamide segments.

[0398] The copolyamide can be an elastomeric copolyamide, including thermoplastic copolyamides. Elastomeric copolyamides can include or consist of block copolyamides having repeating hard segments and repeating soft segments. In block copolymers comprising block copolymers having repeating hard segments and soft segments, physical crosslinking can exist within or between segments, or both.

[0399] In some respects, the polyamide itself or the polyamide segment of a thermoplastic copolyamide can be derived from the condensation of polyamide prepolymers such as lactams, amino acids, and / or diamino compounds with dicarboxylic acids or their activated forms. The resulting polyamide segment contains an amide bond (-(CO)NH-). The term "amino acid" refers to a molecule having at least one amino group and at least one carboxyl group. Each polyamide segment of a thermoplastic polyamide can be the same or different.

[0400] In several respects, polyamides are poly(ether-block amide) polymers. Poly(ether-block amide) polymers can be prepared by polycondensation of a polyamide block containing a reactive end and a polyether block containing a reactive end. Examples include, but are not limited to: 1) a polyamide block containing a diamine chain end and a polyoxyethylene block containing a carboxyl chain end; 2) a polyamide block containing a dicarboxyl chain end and a polyoxyethylene block containing a diamine chain end, wherein the polyoxyethylene block containing the diamine chain end is obtained by cyanoethylation and hydrogenation of an aliphatic dihydroxylated α-ω polyoxyethylene known as a polyether glycol; 3) a polyamide block containing a dicarboxyl chain end and a polyether glycol, in which case the product obtained is a polyether ester amide. The polyamide blocks of thermoplastic poly(ether-block-amide) can be derived from lactams, amino acids and / or diamino compounds and dicarboxylic acids, as previously described. The polyether block can be derived from one or more polyethers selected from the group consisting of: polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof.

[0401] Examples of poly(ether block amide) polymers include those comprising polyamide blocks ending in dicarboxylic acid chains, said dicarboxylic acid-ending polyamide blocks derived from the condensation of α,ω-aminocarboxylic acids, lactams, or dicarboxylic acids with diamines in the presence of chain-restricted dicarboxylic acids. In this type of poly(ether block amide) polymer, α,ω-aminocarboxylic acids such as aminoundecanoic acid can be used; lactams such as caprolactam or lauryl lactam can be used; dicarboxylic acids such as adipic acid, sebacic acid, or dodecanoic acid can be used; and diamines such as hexamethylenediamine; or any combination of the foregoing can be used. In several aspects, the copolymer comprises a polyamide block comprising polyamide 12 or polyamide 6. The poly(ether block amide) can have a melting point below 150 degrees Celsius, or between 90 degrees Celsius and 135 degrees Celsius.

[0402] In one aspect, the number-average molar mass of the polyamide block can be from about 300 g / mol to about 15,000 g / mol, from about 500 g / mol to about 10,000 g / mol, from about 500 g / mol to about 6,000 g / mol, from about 500 g / mol to 5,000 g / mol, and from about 600 g / mol to about 5,000 g / mol. In another aspect, the number-average molecular weight of the polyether block can be in the range from about 100 g / mol to about 6,000 g / mol, from about 400 g / mol to 3,000 g / mol, and from about 200 g / mol to about 3,000 g / mol. In yet another aspect, the polyether (PE) content (x) of the poly(ether block amide) polymer can be from about 0.05 to about 0.8 (i.e., from about 5 mol percent to about 80 mol percent). In another aspect, the polyether block may be present in amounts ranging from about 10 percent to about 50 percent by weight, from about 20 percent to about 40 percent by weight, and from about 30 percent to about 40 percent by weight. The polyamide block may be present in amounts ranging from about 50 percent to about 90 percent by weight, from about 60 percent to about 80 percent by weight, and from about 70 percent to about 90 percent by weight.

[0403] In this context, the polyether block can contain units different from the ethylene oxide unit, such as, for example, propylene oxide or polytetrahydrofuran (which results in a polytetramethylene glycol sequence). PEG blocks, i.e., blocks composed of ethylene oxide units; PPG blocks, i.e., blocks composed of propylene oxide units; and PT blocks can also be used simultaneously. m G-blocks are blocks composed of tetramethylene glycol units (also known as polytetrahydrofuran). PPG blocks or PT blocks are advantageously used. m G block. The amount of polyether block in these copolymers containing polyamide and polyether blocks can be from about 10 percent to about 50 percent by weight and from about 35 percent to about 50 percent by weight of the copolymer.

[0404] Exemplary commercially available copolyamides include, but are not limited to, copolyamides available under the following trade names: VESTAMID (Evonik Industries); PLATAMAID (Arkema), for example, product code H2694; PEBAX (Arkema), for example, product codes “PEBAX MH1657” and “PEBAX MV1074”; PEBAX RNEW (Arkema); GRILAMID (EMS-Chemie AG); or other similar materials produced by other suppliers.

[0405] In some instances, polyamides are physically crosslinked, for example, through nonpolar or polar interactions between the polyamide groups of the polymer. In instances where the polyamide is a copolyamide, the copolyamide can be physically crosslinked through interactions between the polyamide groups and optionally through interactions between the copolymer groups. When the copolyamide is physically crosslinked through interactions between the polyamide groups, polyamide segments can form portions of the polymer referred to as “hard segments,” and copolymer segments can form portions of the polymer referred to as “soft segments.” For example, when the copolyamide is a poly(ether-block-amide), the polyamide segments form the hard segment portions of the polymer, and the polyether segments can form the soft segment portions of the polymer. Thus, in some aspects, polymeric materials can include physically crosslinked polymer networks having one or more polymer chains with amide bonds.

[0406] In some aspects, the polyamide segment of the copolyamide includes polyamide-11 or polyamide-12, and the polyether segment is a segment selected from the group consisting of: polyethylene oxide segments, polypropylene oxide segments, and polytetramethylene oxide segments and combinations thereof.

[0407] Polyester

[0408] In this context, the polymer, polymeric component of the polymeric material, polymeric material, or any combination thereof may include polyesters such as thermoplastic polyesters, or may consist substantially of polyesters such as thermoplastic polyesters. Polyesters can be formed by reacting one or more carboxylic acids or their ester-forming derivatives with one or more divalent or polyvalent aliphatic alcohols, alicyclic alcohols, aromatic alcohols, or aliphatic alcohols or bisphenols. Polyesters may be polyester homopolymers of repeating polyester segments having the same chemical structure. Alternatively, polyesters may comprise a number of polyester segments with different polyester chemical structures (e.g., polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, etc.). Polyester segments with different chemical structures may be arranged randomly or may be arranged as repeating blocks.

[0409] Exemplary carboxylic acids that can be used to prepare polyesters include, but are not limited to, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, terephthalic acid, isophthalic acid, alkyl-substituted or halogenated terephthalic acid, alkyl-substituted or halogenated isophthalic acid, nitro-terephthalic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfide dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenylalkylene dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, and cyclohexane-1,3-dicarboxylic acid. Exemplary diols or phenols suitable for preparing thermoplastic polyesters include, but are not limited to, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, and bisphenol A.

[0410] In some respects, the polyester is polybutylene terephthalate (PBT), polypropylene terephthalate, polyhexamethylene terephthalate, poly(1,4-dimethylcyclohexane) terephthalate, polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, or blends or mixtures of two or more of the above.

[0411] The polyester can be a copolyester (i.e., a copolymer comprising polyester segments and non-polyester segments). The copolyester can be an aliphatic copolyester (i.e., a copolyester in which both polyester and non-polyester segments are aliphatic). Optionally, the copolyester may contain aromatic segments. The polyester segments of the copolyester may include or consist of the following: polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, or any combination thereof. The polyester segments of the copolyester may be arranged randomly or as repeating blocks.

[0412] For example, the polyester can be a block copolyester having repeating blocks (hard segments) of polymer units with relatively stiff, identical chemical structures (segments) and repeating blocks (soft segments) of relatively soft polymer segments. In block copolyesters comprising block copolyesters having repeating hard and soft segments, physical crosslinking can exist within or between blocks, or both. The polyester can comprise an elastomeric copolyester having repeating hard and soft segments, or is substantially composed of such an elastomeric copolyester.

[0413] The non-polyester segments of a copolyester may include or consist of polyether segments, polyamide segments, or both. The copolyester may be a block copolyester or a random copolyester. The copolyester may be formed by polycondensation of a polyester oligomer or prepolymer with a second oligomer prepolymer to form a block copolyester. Optionally, the second prepolymer may be a hydrophilic prepolymer. For example, the copolyester may be formed by polycondensation of terephthalic acid or naphthalene with ethylene glycol, 1,4-butanediol, or 1,3-propanediol. Examples of copolyesters include polyethylene adipate, polybutylene succinate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and combinations thereof. In certain instances, the copolyamide may comprise or consist of polyethylene terephthalate or polyethylene terephthalate.

[0414] In some aspects, thermoplastic polyesters are block copolymers comprising one or more segments of: polybutylene terephthalate (PBT), polypropylene terephthalate, polyhexamethylene terephthalate, poly(1,4-dimethylcyclohexane) terephthalate, polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylates (PAR), polybutylene naphthalate (PBN), and liquid crystal polyesters. For example, suitable thermoplastic polyesters as block copolymers may be PET / PEI copolymers, polybutylene terephthalate / tetraethylene glycol copolymers, polyoxyethylene diacid / polybutylene terephthalate copolymers, or blends or mixtures of any of the aforementioned copolymers.

[0415] In some respects, thermoplastic polyesters are biodegradable resins, such as copolyesters in which poly(α-hydroxy acids) such as polyglycolic acid or polylactic acid are included as the main repeating unit.

[0416] The disclosed polyester can be prepared by a variety of polycondensation methods known to those skilled in the art, such as solvent polymerization or melt polymerization.

[0417] Resin Modifier

[0418] The resin modifier can be a polymeric resin modifier (i.e., a resin modifier having a polymeric chain structure). In some aspects, the polymeric resin modifier is a metallocene-catalyzed polymer or a metallocene-catalyzed copolymer. In another aspect, the polymeric resin modifier may consist of isotactic propylene repeating units and ethylene repeating units, based on the total weight of the metallocene-catalyzed copolymer randomly distributed along the copolymer, at about 11% to 15% by weight. In some aspects, the polymeric resin modifier contains ethylene repeating units, based on about 10% to about 15% by weight of the total weight of the polymeric resin modifier. In some aspects, the polymeric resin modifier contains repeating units according to Formula 1A above, based on about 10% to about 15% by weight of the total weight of the polymeric resin modifier. In some aspects, the polymeric resin modifier is a copolymer of repeating units according to Formula 1B above, and the repeating units according to Formula 1B are arranged in an isotactic stereochemical configuration.

[0419] In some aspects, the polymer resin modifier is a copolymer comprising isotactic propylene repeating units and ethylene repeating units. In some aspects, the polymer resin modifier is a copolymer comprising a first repeating unit and a second repeating unit, wherein the repeating units in the second repeating unit are arranged in an isotactic stereochemical configuration.

[0420] In one aspect, the amount of polymer resin modifier is such that it effectively allows the polymer material to undergo flexural testing according to the flexural testing protocol for cold shoe sole materials using a substrate sampling procedure, as further described herein. In another aspect, when measured using a material sampling procedure according to ASTM D5963-97a, the amount of polymer resin modifier does not cause a significant change in abrasion loss compared to the abrasion loss of a similar polymer material that is otherwise identical to the disclosed polymer material, except without the polymer resin modifier. In one aspect, when measured using a material sampling procedure further described herein according to ASTM D 5963-97A, the abrasion loss of the polymer material is within approximately 20 percent of the abrasion loss of a polymer material that is otherwise identical, except without the resin modifier.

[0421] In one aspect, the effective amount of the polymer resin modifier can be from about 5% to about 30%, about 5% to about 25%, about 5% to about 20%, about 5% to about 15%, about 5% to about 10%, about 10% to about 15%, about 10% to about 20%, about 10% to about 25%, or about 10% to about 30% based on the total weight of the polymer material. In another aspect, the effective amount of the polymer resin modifier can be about 20%, about 15%, about 10%, about 5%, or less based on the total weight of the polymer material.

[0422] Transparent agent

[0423] In some aspects, it may be advantageous to include a clarifying agent in a polymeric material, which includes a second polymeric material present in the plate. The clarifying agent can allow clear visibility through the plate. For example, this can allow clear visibility of textiles bonded to the plate. The clarifying agent can be present in any suitable amount to provide sufficient optical transparency of the polymeric material. In some aspects, the clarifying agent is present in an amount from about 0.5 percent to about 5 percent by weight or from about 1.5 percent to about 2.5 percent by weight based on the total weight of the polymeric material. The clarifying agent may include those selected from the group consisting of substituted or unsubstituted dibenzyl sorbitol, 1,3-O-2,4-bis(3,4-dimethylbenzyl)sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene] and its derivatives. The clarifying agent may include an acetal compound, which is a condensation product of a polyol and an aromatic aldehyde. Polyols may include those selected from the group consisting of: acyclic polyols such as xylitol and sorbitol, and acyclic deoxypolyols such as 1,2,3-trideoxynonenose or 1,2,3-trideoxynon-1-enitol. Aromatic aldehydes may include those selected from the group consisting of benzaldehyde and substituted benzaldehyde.

[0424] Methods for preparing polymer materials

[0425] According to several aspects, this disclosure also provides a method for preparing polymeric materials such as one or more of the disclosed polymeric materials.

[0426] Generally, methods for preparing polymer materials involve blending polymers. Methods for blending polymers can include film blending in a press, blending in a mixer (e.g., a commercially available mixer from Thermo Fisher Scientific, Waltham, MA, under the trade name "HAAKE"), solution blending, hot melt blending, and extruder blending. In some aspects, the polymer and other components are miscible, allowing them to be easily mixed during injection molding via a screw in the injection barrel, thus eliminating the need for a separate blending step.

[0427] The method may also include extruding the blended polymer material to form an extruded polymer material. The method of extruding the blended polymer material may include manufacturing long products (rods, sheets, tubes, films, wire insulation coatings) with a relatively constant cross-section. The method of extruding the blended polymer material may include conveying a softened blended polymer material through a die having an opening. The blended polymer material may be conveyed forward by a feed screw and forced through the die. A heating element placed on the barrel may soften and melt the blended polymer material. The temperature of the material may be controlled by a thermocouple. The product exiting the die may be cooled by blown air or in a water bath to form the extruded polymer material. In one aspect, the polymer material may be a hydrogel material, and extruding a hydrogel material may include extruding all or part of a hydrogel layer. For example, the hydrogel material may be extruded into a film for forming all or part of a hydrogel layer. In another aspect, the polymer material may be a textile material, and the textile material may be extruded into fibers, which may then be drawn into yarns, or may be used to form nonwoven textiles. In another aspect, the polymer material can be a second polymer material and can be extruded onto a second side of the textile of the composite element. Alternatively, the product exiting the mold can be granulated with minimal cooling, as described below.

[0428] The method may also include granulating the extruded polymer material to form a granulated polymer material. Granulation methods may include melt granulation (thermal cutting), whereby melt from a die is cut into granules almost immediately, which are then conveyed and cooled by a liquid or gas. Granulation methods may include wire granulation (cold cutting), whereby melt from a die is converted into wire (extruded resin composition), which is then cut into granules after cooling and solidification.

[0429] The method may also include injection molding of polymer materials, such as granulated polymer materials, to form articles, such as shoe sole structures. Injection molding may include using a non-rotating cold plunger to force polymer material through a heated cylinder, wherein the polymer material is heated by heat conducted from the cylinder wall to the polymer material. Injection molding may include using a rotating screw arranged coaxially with the heated cylinder for delivering polymer material toward a first end of the screw and heating the polymer material by heat conduction from the heated cylinder to the polymer material. As the resin composition is delivered toward the first end through the screw mechanism, the screw translates toward a second end to create a reservoir space at the first end. When sufficient molten polymer material is collected in the reservoir space, the screw mechanism may be pushed toward the first end to inject the polymer material into a selected mold.

[0430] Other ingredients

[0431] Polymer materials may also include one or more additional components. These additional components may be polymeric or non-polymeric components. These additional components may be independently selected from, but are not limited to, the group consisting of: curing agents, initiators, plasticizers, release agents, lubricants, antioxidants, flame retardants, dyes, pigments, reinforcing and unreinforcing fillers, fiber reinforcements, and light stabilizers.

[0432] Adhesive materials

[0433] In some aspects, the composite element or sole structure, or both, further includes a first adhesive layer operatively connecting a second side of the hydrogel layer to a first side of the textile, a second adhesive layer operatively connecting a second side of the textile to a first side of the plate, or both of the first and second adhesive layers as described. In one aspect, the first adhesive layer, the second adhesive layer, or both permeate at least a portion of the thickness of the textile. In some aspects, the sole structure further includes a third adhesive layer that, when the second textile is included, operatively connects a second side of the second textile to a second side of the sole component; or, when the second textile is included, a fourth adhesive layer positioned on a first side of the second textile; or any combination thereof. In some aspects, the first adhesive layer, the second adhesive layer, the third adhesive layer, the fourth adhesive layer, or combinations thereof permeate at least 10%, at least 20%, at least 30%, or at least 40% of the thickness of the textile in contact with them. In another aspect, the first adhesive layer, the second adhesive layer, or both permeate less than about 80%, less than about 70%, less than about 60%, less than about 50%, less than about 40%, or less than about 30% of the core thickness of the textile. In some aspects, a fourth adhesive layer may be used to attach the sole structure to the upper of the shoe.

[0434] In one aspect, the first adhesive layer, the second adhesive layer, or both have a thickness from about 0.1 mm to about 2.0 mm, or from about 0.1 mm to about 1.5 mm, or from about 0.1 mm to 0.5 mm.

[0435] Contact adhesive: In one aspect, the first adhesive material of the first adhesive layer, the second adhesive material of the second adhesive layer, or both comprise a contact adhesive. The first adhesive material or the second adhesive material, or both, may comprise a thermosetting polymer material as described above. The adhesive material may comprise epoxy-based contact adhesives or binders, urethane-based contact adhesives or binders, acrylate-based contact adhesives or binders, including cyanoacrylate-based adhesives or binders, silicone-based contact adhesives or binders, or combinations thereof. The contact adhesive or binder may comprise a polyurethane-based contact adhesive, such as, for example, conventional polyurethane-based shoe adhesives.

[0436] Hot melt adhesive: In one aspect, the first adhesive material of the first adhesive layer, the second adhesive material of the second adhesive layer, or both comprise a hot melt adhesive. The first adhesive material or the second adhesive material or both may comprise a thermoplastic polymer material as described above. In some aspects, the hot melt adhesive comprises thermoplastic polyurethane. In another aspect, according to the melt flow index test scheme described herein, the hot melt adhesive may have a melt flow index from about 35 g per 10 minutes to about 55 g per 10 minutes (at 190 degrees Celsius, 21.6 kg), or about 35 g per 10 minutes, 40 g per 10 minutes, 45 g per 10 minutes, 50 g per 10 minutes, or about 55 g per 10 minutes.

[0437] Methods for manufacturing composite components

[0438] In this regard, a method for manufacturing a composite element is disclosed, the method comprising: operably attaching a hydrogel layer comprising a hydrogel material to a first side of a textile having the first side, a second side opposite to the first side, and a core located between the first side and the second side, wherein the hydrogel layer extends through the first side of the textile and at least partially extends into the core of the textile, but does not extend into the second side of the textile.

[0439] In one aspect, the step of operatively attaching the hydrogel layer to a first side of the textile includes spraying, brushing, or coating the hydrogel material onto the first side of the textile, or immersing the first side of the textile in the hydrogel material. In an alternative aspect, the step of operatively attaching the hydrogel layer to the first side of the textile includes injection molding or extruding the hydrogel material onto the first side of the textile.

[0440] In one aspect, the step of operatively linking a hydrogel layer to a first side of a textile includes forming a mechanical bond between the hydrogel layer and the first side of the textile. The process of forming the mechanical bond between the hydrogel layer and the textile may include softening or melting the hydrogel material, applying the softened or molten hydrogel material to the first side of the textile, allowing the softened or molten hydrogel material to permeate between and around the fibers of the textile, and permeating a portion of the thickness of the core of the textile, but not the entire thickness of the core and not permeating to the second side of the textile, and then solidifying the softened or molten hydrogel material. In other aspects, the process of forming a mechanical bond between the hydrogel layer and the textile can include softening or melting an adhesive material present in the hydrogel layer (the adhesive material may be a component of the hydrogel material or a capping layer of the hydrogel layer), applying the softened or molten adhesive material to a first side of the textile, allowing the softened or molten adhesive material to penetrate between and around the fibers of the textile, penetrating a portion of the thickness of the core of the textile, but not the entire thickness of the core and not penetrating to a second side of the textile, and then curing the softened or molten adhesive material. In one aspect, the process includes raising the temperature of the hydrogel material or adhesive material to a temperature at or above its Vicat softening temperature, or to a temperature at or above its melting temperature, before, during, or after the step of contacting the first side of the textile with the hydrogel layer, but before curing the hydrogel material or adhesive material. Pressure or heat, or both, may be applied during the process to increase the rate and extent of penetration of the hydrogel material or adhesive material into the textile core. In one aspect, the step of raising the temperature of the hydrogel material or adhesive material includes raising its temperature to a temperature at or above its Vicat softening temperature, but below the Vicat softening temperature of the textile material. In another aspect, the step of raising the temperature of the hydrogel material or adhesive material includes raising its temperature to a temperature at or above its melting temperature, but below the Vicat softening temperature of the textile material. By keeping the hydrogel material or adhesive material below the Vicat softening temperature of the textile material (e.g., at least 20°C lower, or at least 50°C lower, or at least 100°C lower), the texture of the first side of the textile and the complex structure of the textile core are allowed to remain intact, providing a large surface area (formed by the surface of the fibers and the area between the fibers) on which the softened or molten hydrogel material or adhesive material can flow and form a mechanical bond upon curing. Surprisingly, the strength of the mechanical bond formed in this way between the textile and the adhesive material of the hydrogel layer is sufficient to prevent delamination of the hydrogel material from the textile, even after repeated wet-dry cycles.

[0441] In other respects, it may be desirable to soften the textile material during the process of attaching the hydrogel layer and the textile. In such respects, the step of raising the temperature of the hydrogel material or adhesive material may include raising its temperature to a temperature at or above its Vicat softening temperature or its melting temperature, and also at or above the Vicat softening temperature of the textile material.

[0442] In other aspects, it may be desirable to form a thermal bond between the hydrogel material or adhesive material and the textile material, wherein polymer chains from the hydrogel material or adhesive material are mixed with polymer chains from the textile material. In such an aspect, the step of raising the temperature of the hydrogel material or adhesive material may include raising its temperature to a temperature above its melting temperature and also above the melting temperature of the textile material.

[0443] Methods for manufacturing shoe sole structure

[0444] In one aspect, this document provides a method of manufacturing an article, the method comprising operatively attaching a first composite element to a second component. In another aspect, the composite element comprises a textile and a hydrogel layer, wherein the textile comprises a textile material and has a first side, a second side, and a core located between the first and second sides. In yet another aspect, the hydrogel layer comprises a hydrogel material, has a first side and a second side, and the second side of the hydrogel layer is operatively attached to the textile along the first side of the textile. Furthermore, in the composite element, a portion of the hydrogel layer may extend through the first side of the textile and at least partially extend into the core of the textile, but not extend to the second side of the textile. In one aspect, operative attachment comprises forming a joint between the second side of the textile and the second component, such that the hydrogel layer of the composite element defines at least a portion of the outward-facing surface of the second component. In some aspects, operative attachment comprises forming a mechanical joint between the second side of the textile and the second polymer material. In one aspect, the article may be a footwear article, a component of a footwear article, a garment article, a component of a garment article, a sports equipment article, or a component of a sports equipment article. In some respects, the article is the sole structure of a footwear article, and optionally, the outward-facing surface is the ground-facing surface of the sole structure.

[0445] In one aspect, this document provides a method for manufacturing a sole structure for footwear articles, the method comprising (i) placing a first composite element into a mold, wherein the composite element comprises a textile having a first side, a core having a thickness, and a second side, and a hydrogel layer extending through the first side and into the core of the textile without contacting the second side, such that a portion of the first side of the hydrogel layer contacts a portion of a molding surface of the mold to form a prepared molding surface; (ii) loading a second polymer material onto the prepared molding surface of the mold; (iii) at least partially curing the loaded second polymer material in the mold and operatively joining the composite element and the at least partially cured second polymer material to form a sole structure having an outermost hydrogel layer; and (iv) removing the sole structure from the mold. The composite element and the sole structure can be any of those described herein.

[0446] In some aspects, a portion of the first side of the hydrogel layer may be constrained against a portion of the molding surface while a second polymer material is loaded onto the molding surface of the mold preparation.

[0447] In one aspect, the method further includes the step of raising the temperature of the second polymer material to a molding temperature higher than the melting temperature or Vicat softening temperature of the second polymer material. Furthermore, in this aspect, after the temperature of the second polymer material is raised to a first temperature, at least a portion of the second polymer material can permeate a second side of the textile. In another aspect, curing the second polymer material includes lowering the temperature of the second polymer material to a second temperature lower than the melting temperature or Vicat softening temperature of the second polymer material.

[0448] In some aspects, the first component further includes a hot melt adhesive layer on a second side of the textile, and the method further includes raising the temperature of the hot melt adhesive to a temperature above the melting temperature of the hot melt adhesive, such that the adhesive bonds to the second polymer material.

[0449] In some aspects, a mold with a molding surface is provided, and a composite element is placed in the mold such that a first side of the hydrogel layer contacts a portion of the molding surface of the mold to form the prepared molding surface.

[0450] In cases where the composite element is substantially planar and the molding surface is curved, the membrane component may be bent or flexed to fit into the mold and contact the molding surface. However, it should be understood that such bending or flexing will not include heating the membrane component to above 80 degrees Celsius (°C).

[0451] In some aspects, a portion of the first side of the hydrogel layer that contacts the molding surface is constrained against the molding surface while a second polymer material is loaded into the mold. Constraining the portion of the first layer against the molding surface reduces or eliminates the need for the thermoformed composite element and can prevent or reduce leakage of the second polymer material between the composite element and the molding surface during the loading step. In some aspects, the step of constraining the first side of the hydrogel layer against the molding surface may include applying a vacuum to the composite element, or applying a pin (e.g., a retractable pin) to the composite element, or both.

[0452] In some aspects, the loading step may include injecting or pouring a second polymer material into a mold. After the second polymer material has at least partially cured within the mold, the sole structure can be removed from the mold. Using the disclosed method avoids problems such as pulling and stretching the composite element during thermoforming, which could damage the composite element and generate scrap or waste. The use of this process also reduces the "thermal history" of the composite element by limiting the number of times the composite element is exposed to temperatures above 80°C during the manufacturing process, which could lead to degradation of the hydrogel material. The use of this process also reduces the amount of waste material compared to conventional thermoforming processes.

[0453] Methods of manufacturing parts and items

[0454] According to another aspect of this disclosure, a method of manufacturing footwear articles includes attaching an upper to a sole structure, the sole structure including a composite element comprising a hydrogel layer containing a hydrogel material as described herein, wherein the hydrogel material of the hydrogel layer of the composite element defines at least a portion of the ground-facing surface of the footwear article.

[0455] According to another aspect of this disclosure, a sole component for footwear articles includes one or more composite elements as described herein, wherein each composite element has an outer periphery and a hydrogel layer, such that the hydrogel material of each hydrogel layer defines a ground-facing surface of the sole component. A second polymeric material can operatively attach a second textile side of the composite element to the sole component, including attaching the entire outer periphery of each of the one or more composite elements to the sole component. The sole component may also include one or more adhesion friction elements, wherein one or more composite elements are configured to be fitted between or around the adhesion friction elements.

[0456] According to some aspects, one or more of the adhesion friction elements may include elements added separately after the sole component is removed from the mold, such as snap-fit ​​components, screw-on components, or combinations thereof. In these aspects, the separately added adhesion friction elements may be individually selected to comprise the same material as the second polymer material, or a material different from or substantially free of the second polymer material. The separately added adhesion friction elements may be permanently or removably coupled to the sole component and / or sole structure. When needed, one or more fittings may be used to removably couple the adhesion friction elements to the sole component and / or sole structure. For example, one or more adhesion friction elements may be placed in the mold before the addition of the second polymer material for molding together with the sole component and / or sole structure. These fittings are configured to couple with the separately added adhesion friction elements, such as snap-fit ​​components or screw-on components. According to certain aspects, the pre-formed attachment friction element tip, including the end of the attachment friction element, can be placed in a mold before the addition of the second polymer material for molding together with the sole structure or sole component. These pre-formed attachment friction elements can be individually selected to include a material that is the same as the second polymer material, a material that is different from the second polymer material (e.g., harder and / or more abrasion-resistant than the second polymer material), or a material that is substantially free of the second polymer material. For example, the polymer material at least at the end of the attachment friction element can contain a polymer component that is different from the polymer component of the second polymer material based on the presence of one or more types of polymers, the concentration of one or more types of polymers, or both.

[0457] This disclosure provides several methods for manufacturing the parts and articles described herein. These methods may include injection molding of the polymer material described herein. This disclosure provides a method for manufacturing parts for footwear articles by injection molding of the polymer material described herein.

[0458] In some aspects, the method includes forming a sole component, such as a plate. For example, a polymeric material can be injection molded to mold the sole component. In this aspect, a mold having a first mold portion having a first surface, a second surface, and an outer periphery can be provided. The polymeric material can be injected into the first portion of the mold. The resulting injection-molded component is an integral component comprising the sole component. In some aspects, a composite element can be placed in the mold prior to injection molding, and the injection molding step can form the sole component and a bond between the composite element and the sole component. The bond can be a thermal bond formed between polymeric materials present on a second side of the composite element and between the injection-molded polymeric material (such as a second polymeric material as described herein). The bond between the composite element and the sole component can be a mechanical bond formed between the textile second side of the composite element and the injected polymeric material.

[0459] In some aspects, composite elements and sole components, such as plates, are supplied separately and are attached, combined, or joined for operative engagement. For example, an adhesive may be provided between the composite element (e.g., between the second textile sides of the composite element) and the sole component to provide an adhesive bond between them. Any suitable adhesive compatible with both the composite element and the sole component can be used. For example, adhesives commonly used in the footwear industry, such as standalone polyurethane-based adhesive systems or polyurethane-based adhesive systems with a primer layer, can be used.

[0460] In other aspects, attaching a composite element to a sole component may include forming a mechanical bond between the sole component and the composite element. Optionally, pressure may be applied to the composite element, the sole component, or both during the formation of the mechanical bond. In some aspects, the mechanical bond may be a thermal bond, wherein a thermoplastic material is softened to facilitate deformation of the thermoplastic material against one or more surfaces to be bonded, and then the thermoplastic material is re-cured. In other aspects, the mechanical bond may be a thermally mixed bond, wherein a thermoplastic material is melted to facilitate mixing of the polymer chains of the thermoplastic material with another polymer material on one or more surfaces to be bonded, and then the thermoplastic material is re-cured. Attaching a sole component to a composite element may include (i) raising the temperature of the sole component, (ii) bringing the sole component into contact with the composite element, and (iii) maintaining contact between the sole component and the composite element while lowering the temperature of the sole component to a second temperature below the melting or softening point of the polymer material of the sole component, thereby forming a mechanical bond between the plate and the composite element.

[0461] In one aspect, this document discloses a method for manufacturing footwear articles, the method comprising securing a sole structure and an upper as disclosed herein to each other, such that a hydrogel layer of the sole structure defines the ground-facing surface of the footwear article. In some aspects, the method further includes attaching a sole interlayer to the sole structure and / or the upper prior to securing the sole structure to the upper, such that the sole interlayer is located between the sole structure and the upper.

[0462] The method may also include operatively attaching a composite element as described herein to a second element. The second element may include textiles or multilayer films or sole components for footwear articles, such as, for example, plates or adhesive friction elements. For example, the second element may additionally include an upper. In one aspect, the upper may include or further include natural leather, thermosetting polymers, thermoplastic polymers, or mixtures thereof. The second element may include polymeric materials comprising polyolefins. In some aspects, the second component may include textiles selected from knitted textiles, woven textiles, non-woven textiles, crocheted textiles, braided textiles, or combinations thereof. In one aspect, the textile includes one or more natural fibers or yarns or synthetic fibers or yarns. In some aspects, synthetic fibers and / or yarns include thermoplastic polyurethanes, polyamides, polyesters, polyolefins, or mixtures thereof. Securing the sole structure to the second component may include forming a mechanical connection, such as, for example, between a plate and a strut, between the sides of the sole structure and the second component. In another aspect, securing the sole structure to the second component may include using a separate adhesive or an adhesive in combination with a primer. Alternatively, securing the sole structure to the upper may include forming a thermal bond between thermoplastic materials present on the outer surface of the sole structure and between thermoplastic materials on the outer surface of the second component. Securing the sole structure to the second component may include forming a mechanical bond between textiles forming the outer surface of the sole structure and textiles such as Stellar forming the outer surface of the upper, at the interface between the outer surfaces of the sole structure and the upper, for example, using a hot melt adhesive.

[0463] As described herein, two elements can be operatively coupled to each other. For example, in a composite element, a hydrogel layer and a textile are operatively coupled. Similarly, in a sole structure, a composite element and a sole component are operatively coupled, and in footwear articles, a sole structure and an upper are operatively coupled. Two elements can be directly coupled or otherwise operatively coupled to each other using any suitable mechanism or method. As used herein, the term "operatively coupled," such as for a sole structure operatively attached to an upper, is collectively referred to as a direct connection, indirect connection, integrally formed portion, and combinations thereof. For example, for a sole structure operatively attached to an upper, the sole structure can be directly attached to the upper. A direct connection can be a mechanical bond. A mechanical bond can include a thermal bond formed by softening and then re-curing a thermoplastic material, or a thermal bond formed by melting and then re-curing two thermoplastic materials, such as a thermally mixed bond. Direct connections may include an adhesive layer present at the interface between two elements (e.g., directly adhered to it with an adhesive such as an adhesive (alone or with a base coat) or a hot melt adhesive), may be integrally formed with the upper (e.g., as a single component), and combinations thereof.

[0464] The upper of a footwear article has a body, which may be made of materials known in the art for manufacturing footwear articles and is configured to receive a user's foot. The upper of a shoe consists of all the parts of the shoe above the interlocking line (the interface between the bottom surface of the upper and the top surface of the sole structure). Different parts of the upper may include the toe; heel area, heel stabilizer; tongue; eyelets, medial side, lateral side, and forefoot panel, to name a few. These parts may be attached by stitching or by adhesive to become a single unit to which the sole structure is attached.

[0465] The upper or a component of the upper typically comprises a soft body made of one or more lightweight materials. The materials used in the upper provide stability, comfort, and a robust fit. For example, the upper may be made of or include one or more of the following components: natural or synthetic leather, thermoset polymers, thermoplastic polymers, or mixtures thereof. When desired, the upper may use one of these components as a textile comprising fibers made of polymer materials as described herein.

[0466] Textiles may include: knitted textiles, braided textiles, woven textiles, or non-woven textiles made wholly or partially of natural fibers; knitted textiles, braided textiles, woven textiles, or non-woven textiles made wholly or partially of synthetic polymers, films of synthetic polymers, etc.; and combinations thereof. Textiles may include one or more natural fibers or yarns or synthetic fibers or yarns. Synthetic yarns may include, consist of, or be substantially composed of: thermoplastic polyurethane (TPU), polyamide (e.g., "nylon"), polyester (e.g., polyethylene terephthalate or PET), polyolefins, or mixtures thereof.

[0467] Because the sole structure comprises the outermost portion of the sole, such as the part of the footwear that contacts the ground, it is directly exposed to abrasion and wear. In some aspects, different portions of the sole structure can be constructed with varying thicknesses and can exhibit different degrees of flexibility. The sole structure may include materials selected to provide necessary or desired properties, such as water resistance, durability, and / or a sufficiently high coefficient of friction to prevent slippage. In some cases, polymeric materials may be incorporated into the ground-contact portion of the sole structure to provide an abrasion-resistant surface. In some aspects, the ground-contact portion of the sole structure may be combined with a softer, more flexible midsole for greater comfort. For example, the midsole may include cushioning elements, such as air bladders or foam materials. In some aspects, the material of the cushioning element may include, but is not limited to, polymeric materials comprising one or more polyurethanes, or ethylene vinyl acetate, or copolyesters, or polyolefins, or combinations thereof.

[0468] According to another aspect of this disclosure, the use of a sole structure comprising at least a portion of a hydrogel material forming an outward-facing surface or a ground-facing surface is described. This use involves incorporating the sole structure as described herein as an outward-facing surface into finished footwear articles to prevent or reduce dirt buildup on the outward-facing or ground-facing surface of the sole structure. In some aspects, the sole structure or footwear article retains at least 5% or less dirt and / or debris by weight compared to conventional sole structures or footwear articles that are similar except that the outward-facing or ground-facing surface of the conventional sole structure or footwear article is substantially free of hydrogel material; alternatively, at least 10% or less dirt and / or debris by weight.

[0469] According to another aspect of this disclosure, the use of footwear articles comprising a hydrogel material on at least a portion of the outward-facing surface is described. This use involves incorporating a hydrogel layer, as a composite element as described herein, into the outward-facing surface of the finished footwear article to prevent or reduce dirt buildup on the sole structure and the outward-facing surface of the article. In some aspects, the footwear article retains at least 5% or less dirt by weight compared to conventional footwear articles that are similar except that the outward-facing surface of a conventional footwear article is substantially free of hydrogel material; alternatively, at least 10% or less dirt by weight.

[0470] Property analysis and characterization procedures

[0471] Cold shoe sole material flexural test plan

[0472] The flexural testing of cold-weather shoe sole materials is determined according to the following test method. The purpose of this test is to evaluate the crack resistance of samples when repeatedly flexed to 60 degrees in a cold environment. The substrate samples of the materials used for testing are prepared using a substrate sampling procedure and are sized for assembly inside the flexural testing machine. Each material is tested as five independent samples. The flexural testing machine is capable of flexing the samples to 60 degrees at a rate of 100 ± 5 cycles per minute. The machine's mandrel diameter is 10 mm. Suitable machines for this test are the Emerson AR-6 and Satra ST. m 141F, Gotech GT-7006, and ShinII Scientific SI-LTCO (DaeSung Scientific). The sample was inserted into the bending machine according to the specific parameters used. The machine was placed in a freezer set to -6 degrees Celsius for testing. The motor was turned on to begin bending, and the bending cycles were counted until the sample cracked. Cracking of the sample means that the surface of the material has physically separated. A visible crease that does not actually penetrate the surface is not a crack. The sample was measured until it had cracked but had not yet completely split in two.

[0473] Abrasion loss test protocol ASTM D 5963-97a

[0474] Abrasion loss was tested on cylindrical test specimens with a diameter of 16 ± 0.2 mm and a minimum thickness of 6 mm, cut from a sample. The specimens were prepared using a substrate sampling procedure and then cut to size using an ASTM standard drill. Abrasion loss was measured using Method B of ASTM D 5963-97a on a Gotech GT-7012-D abrasion testing machine. The test was conducted at 22 degrees Celsius with a 40-meter abrasion path. The No. 1 standard rubber used in the test had a strength of 1.336 g / cm³. 3The density of the material. The smaller the wear loss, the better the wear resistance.

[0475] Mud stripping test protocol

[0476] On a standard mechanical testing machine (e.g., an Instron tensile testing apparatus), a 2-inch diameter sample prepared using a substrate sampling procedure is cut and attached to the top plate of a set of parallel planar aluminum test plates. A 1-inch diameter mud sample, approximately 7 mm high, is loaded onto the bottom plate of the mechanical testing apparatus. The soil used to prepare the mud is commercially available from Timberline (a subsidiary of Old Castle, Inc., Atlanta, Ga.) under the trade name "TIMBERLINE TOP SOIL" model 50051562, and is sieved through a square mesh with 1.5 mm apertures on each side. The mud is pre-dried and then diluted with water to 22% by weight. The force sensor is normalized to zero force. The plates are then pressed together until a load of 445 Newtons is applied in the compression direction. The load is then immediately removed, and a small force hysteresis is measured at the detachment point, which is greater than zero in the tensile direction. The maximum force measured is the peel force of the mud adhering to the material substrate. The compression / separation cycle is repeated at least 10 times until a stable value is obtained.

[0477] Crystallinity testing scheme

[0478] To determine the percentage of crystallinity in polymeric materials containing copolymers, or homopolymers of copolymers and their major components (e.g., polypropylene homopolymers) prepared using a material sampling procedure, differential scanning calorimetry (DSC) was performed over a temperature range from -80°C to 250°C. A heating rate of 10°C per minute was used. The melting endotherm was measured for each sample during heating. General analytical software (TA Instruments, New Castle, DE, USA) was used to calculate the percentage of crystallinity based on the melting endotherm of the homopolymer (e.g., 207 joules / gram for 100% crystalline polypropylene material). Specifically, the percentage of crystallinity (crystallinity %) was calculated by dividing the melting endotherm measured for the copolymer or resin composition by the melting endotherm of 100% crystalline homopolymer.

[0479] Creep relaxation temperature T cr Test Plan

[0480] Creep relaxation temperature T cr The exemplary technique described in U.S. Patent No. 5,866,058 uses a sample prepared using a material sampling procedure to determine the creep relaxation temperature T.cr The stress relaxation modulus calculated for the tested material is the temperature at which the stress relaxation modulus of the tested material is 10 percent of the material's stress relaxation modulus at its curing temperature, which is measured according to ASTM E328-02. The curing temperature is defined as the temperature at which, approximately 300 seconds after stress is applied to the test material, there is little or no change in the stress relaxation modulus, or little or no creep. This can be observed by plotting the stress relaxation modulus (in Pa) as a function of temperature (in degrees Celsius).

[0481] Vicat softening temperature T vs Test Plan

[0482] Vicat softening temperature T vs The test method, described in detail in ASTM D1525-09 Standard Test Method for Vicat Softening Temperature of Plastics, is used with Load A and Rate A, and is determined using a sample prepared using a material sampling procedure. In short, the Vicat softening temperature is the temperature at which a flat-ended needle, under a specific load, penetrates a sample to a depth of 1 mm. The temperature reflects the expected softening point when the material is used in high-temperature applications. It is considered to be the temperature at which a sample is penetrated to a depth of 1 mm by a flat-ended needle having a circular or square cross-section of 1 square millimeter. For the Vicat A test, a load of 10 Newtons (N) is used, while for the Vicat B test, the load is 50 Newtons. The test involves placing the test sample in the test apparatus such that the penetrating needle is positioned on its surface at least 1 mm from the edge. The load is applied to the sample according to the requirements of the Vicat A or Vicat B test. The sample is then lowered into an oil bath at 23 degrees Celsius. The bath is heated at a rate of 50°C or 120°C per hour until the needle penetrates 1 mm. Test samples must be between 3 mm and 6.5 mm thick, and at least 10 mm wide and long. No more than three layers can be stacked to achieve the minimum thickness.

[0483] Heat distortion temperature T hd Test Plan

[0484] Heat distortion temperature T hdThe heat deflection temperature (HDT) is determined using a sample prepared with a material sampling procedure, according to the test method described in ASTM D648-16, the standard test method for determining the temperature of deformation of plastics under bending load at the edge location, with an applied stress of 0.455 MPa. In short, the heat deflection temperature is the temperature at which a polymer or plastic sample deforms under a specific load. This property of a given plastic material is applied in many aspects of product design, product engineering, and the manufacture of products using thermoplastic components. In the test method, a bar is placed under the deformation measuring device, and a load (0.455 MPa) is applied to each sample. The sample is then lowered into a siloxane oil bath, where the temperature is increased at 2 degrees Celsius per minute until the sample deforms 0.25 mm according to ASTM D648-16. ASTM uses a standard bar of 5” × 1 / 2” × 1 / 4”. ISO edge testing uses a bar of 120 mm × 10 mm × 4 mm. ISO flatwise testing uses a bar of 80 mm × 10 mm × 4 mm.

[0485] Test schemes for melting temperature, glass transition temperature and enthalpy of fusion

[0486] According to ASTM D3418-97, the melting temperature and glass transition temperature are determined using a commercially available differential scanning calorimeter (“DSC”) with samples prepared using a material sampling procedure. Briefly, 10–15 grams of sample are placed in an aluminum DSC pan, and the pan is then sealed with a tablet press. The DSC is configured to scan from -100°C to 225°C at a heating rate of 20°C / min, hold at 225°C for 2 minutes, and then cool to 25°C at a rate of -10°C / min. The DSC curves generated from this scan are then analyzed using standard techniques to determine the glass transition temperature and melting temperature. The enthalpy of fusion is calculated by integrating the area of ​​the endothermic melting peak and normalizing by the sample mass.

[0487] Melt Flow Index Test Protocol

[0488] The melt flow index is determined using a sample prepared with a material sampling procedure, according to the test method described in ASTM D1238-13, which specifies the melt flow rate of thermoplastics extruded through an extrusion plasticizer using procedure A described therein. In short, the melt flow index measures the rate at which thermoplastics are extruded through an orifice under a specified temperature and load. In the test method, approximately 7 grams of material are loaded into the cylinder of a melt flow apparatus that has been heated to a specified temperature for the material. A specified weight for the material is applied to the plunger, and the molten material is forced through the die. The extrudate is collected at timed intervals and weighed. The melt flow rate is calculated in grams per 10 minutes. Alternatively, the melt flow index can be determined using procedure A described therein at 190 degrees Celsius and a load of 2.16 kg, according to the international standard ISO 1133 for melt mass flow rate (MFR) and melt volumetric flow rate (MVR) of thermoplastics.

[0489] Hardness tester hardness testing scheme

[0490] The material hardness was determined using a Shore A grade according to the test method described in ASTM D-2240 hardness tester. Samples were prepared using material sampling procedures, substrate sampling procedures, or component sampling procedures.

[0491] Flexural modulus test scheme

[0492] The flexural modulus (elastic modulus) of a material is determined according to the test method described in detail in ASTM D790. Samples are prepared using a material sampling procedure, a substrate sampling procedure, or a component sampling procedure. The modulus is calculated by obtaining the slope of stress (MPa) relative to strain in the steepest initial linear portion of the load-deformation curve.

[0493] Modulus testing solution

[0494] Determine the (tensile) modulus of the material according to the test method described in detail in ASTM D412-98 Standard Test Method for Vulcanized Rubber and Thermoplastic Rubber and Thermoplastic Elastomers – Tensile Testing, with the following modifications. Prepare the sample using a material sampling procedure, substrate sampling procedure, or component sampling procedure. The sample size is ASTM D412-98 Die C, and the sample thickness is 2.0 mm ± 0.5 mm. The type of clamp used is a pneumatic clamp with a metalserrated grip face. The clamping distance used is 75 mm. The loading rate used is 500 mm / min. The initial modulus is calculated by obtaining the slope of stress (MPa) relative to strain in the initial linear region.

[0495] Water absorption capacity test plan

[0496] This test measures the water absorption capacity of a sample after a predetermined immersion duration. Samples are prepared using a material sampling procedure or a substrate sampling procedure. The samples are initially dried at 60°C until no weight change is observed for consecutive measurement intervals of at least 30 minutes (e.g., a 24-hour drying period at 60°C is typically a suitable duration). The total weight (Wt) of the dried sample is then measured. 干样品 Measured in grams. Allow the dried sample to cool to 25°C and fully immerse it in a deionized water bath maintained at 25°C. After the given immersion duration, remove the sample from the deionized water bath, blot dry with a cloth to remove surface water, and measure the total weight (Wt) of the immersed sample. 湿样品 It is measured in grams.

[0497] Any suitable soaking duration can be used, with a 24-hour soaking duration considered to simulate the saturation conditions of the material (i.e., the hydrophilic resin would be at its saturation point). Therefore, as used herein, the expression "having water absorption capacity at 5 minutes" refers to a 5-minute soaking duration, "having water absorption capacity at 1 hour" refers to a 1-hour soaking duration, "having water absorption capacity at 24 hours" refers to a 24-hour soaking duration, and so on. If no duration is indicated after the water absorption capacity value, the soaking duration corresponds to a 24-hour time period.

[0498] As can be understood, the total weight of the sample includes the weight of the dried or soaked material (Wt). 干样品 or Wt 湿样品 And the weight of the substrate (Wt) needs to be subtracted from the sample measurements. 基底 ).

[0499] The weight of the substrate (Wt) 基底 Use the sample surface area (e.g., 4.0 cm²). 2 The average measured thickness of the hydrogel material portion of the hydrogel layer and the average density of the hydrogel material are used to calculate the density. Alternatively, if the density of the substrate material is unknown or unavailable, the weight of the substrate (Wt) is used. 基底 The separation of the substrate was determined by obtaining a second sample using the same sampling procedure as the original sample and having the same dimensions (surface area and film / substrate thickness) as the original sample. The material of the second sample was then cut from the substrate of the second sample using a blade to provide a separated substrate. The separated substrate was then dried at 60°C for 24 hours, which could be done simultaneously with the drying of the original sample. The weight (Wt) of the separated substrate was then measured in grams. 基底 ).

[0500] Then the weight (Wt) of the dried and soaked original samples was calculated. 干样品 or Wt 湿样品 Subtract the obtained base weight (Wt) from ) 基底 ), to provide the weight (Wt) of the dried and soaked materials. 干部件 or Wt 湿部件 ), as described by Equations 1 and 2.

[0501] Wt 干部件 =Wt 干样品 -Wt 基底 (Equation 1)

[0502] Wt 湿部件 =Wt 湿样品 -Wt 基底 (Equation 2)

[0503] Then, the weight (Wt) of the soaked parts. 湿部件 Subtract the weight of the drying component (Wt) from the total weight. 干部件 The weight of the water absorbed by the component is provided, and then the weight of the water is divided by the weight of the drying component (Wt). 干部件 The absorbency is provided as a percentage for a given soaking duration, as described below by Equation 3.

[0504]

[0505] For example, a 50% water absorption capacity in 1 hour means that after soaking for 1 hour, the weight of the part is 1.5 times its dry weight. Similarly, a 500% water absorption capacity in 24 hours means that after soaking for 24 hours, the weight of the part is 5 times its dry weight.

[0506] Water absorption rate test plan

[0507] This test measures the water absorption rate of a material by modeling the weight gain as a function of immersion time using a one-dimensional diffusion model. Samples are prepared using either a material sampling procedure or a substrate sampling procedure. Samples are dried at 60°C until no weight change is observed for continuous measurement intervals of at least 30 minutes (a 24-hour drying period at 60°C is typically a suitable duration). The total weight of the dried sample (Wt) is then calculated. 干样品 The measurement is in grams. Additionally, the average thickness of the dried sample components is measured to calculate the water absorption rate, as explained below.

[0508] Allow the dried sample to cool to 25°C and then fully immerse it in a deionized water bath maintained at 25°C. Between immersion durations of 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, and 25 minutes, remove the sample from the deionized water bath, blot dry with a cloth to remove surface water, and measure the total weight (Wt) of the immersed sample. 湿样品 ), where “t” refers to a specific soaking duration data point (e.g., 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, or 25 minutes).

[0509] The exposed surface area of ​​the immersed samples was also measured using calipers to determine the specific weight gain, as explained below. The exposed surface area refers to the surface area in contact with deionized water when fully immersed in the bath. For samples obtained using footwear sampling procedures, the sample has only one exposed main surface. For convenience, the surface area of ​​the peripheral edges of the sample is ignored due to their relatively small size.

[0510] The sample is fully immersed back into the deionized water bath between measurements. The durations of 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, and 25 minutes refer to the cumulative immersion duration when the sample is fully immersed in the deionized water bath (i.e., after the first minute of immersion and the first measurement, the sample is returned to the bath for an additional minute of immersion before being measured in 2-minute increments).

[0511] As discussed above, in water absorption capacity testing, the total weight of the sample includes the weight of the dried or soaked material (Wt). 湿部件 or Wt 干部件 ) and the weight of the item or backing base (Wt) 基底 To determine the weight change of the material due to water absorption, the weight of the substrate (Wt) needs to be subtracted from the sample weight measurement. 基底 This can be accomplished using the same steps discussed above in the water absorption capacity test, in order to provide the obtained material weight Wt for each immersion duration measurement. 湿部件 and Wt 干 part.

[0512] Then the specific weight gain (Ws) of water absorbed from each soaked sample. t The weight (Wt) of the soaked sample is calculated. 湿部件 ) and the weight of the initially dried sample (Wt) 干部件 The difference between the two values ​​is then divided by the exposed surface area (A) of the soaked sample. t As described in Equation 4.

[0513]

[0514] Where t refers to a specific soaking duration data point (e.g., 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, or 25 minutes), as mentioned above.

[0515] Then, the water absorption rate of the material was determined as the specific weight gain (Ws). t The slope of the weight gain relative to the square root of time (in minutes), as determined by least-squares linear regression of the data points. For materials, the specific weight gain (Ws) t The curve representing the square root of time (in minutes) provides a substantially linear initial slope (to provide the water absorption rate via linear regression analysis). However, after a certain period of time, depending on the thickness of the component, the specific weight gain will slow down, indicating a decrease in the water absorption rate until saturation is reached. This is thought to be because as water absorption approaches saturation, water diffuses sufficiently throughout the material and will vary depending on the component thickness.

[0516] Therefore, for parts with an average thickness less than 0.3 mm (as measured above), only the specific weight gain data points at 1 minute, 2 minutes, 4 minutes, and 9 minutes are used in the linear regression analysis. In these cases, the data points at 16 minutes and 25 minutes may begin to deviate significantly from the linear slope due to water absorption approaching saturation and are omitted from the linear regression analysis. In contrast, for parts with an average dry thickness of 0.3 mm or greater (as measured above), the specific weight gain data points at 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, and 25 minutes are used in the linear regression analysis. The resulting slope, defining the water absorption rate of the sample, is expressed in units of weight / (surface area - square root of time), such as grams per (m²). 2 -minute 1 / 2 ) or g / m 2 / √min.

[0517] Furthermore, some surfaces can exhibit surface phenomena that rapidly attract and retain water molecules (e.g., via surface hydrogen bonding or capillary action) without actually drawing water molecules into the membrane or substrate. Therefore, for samples at 1 minute, and possibly 2 minutes, these membrane or substrate samples may show a rapid specific weight gain. However, after that, further weight gain is negligible. Therefore, linear regression analysis is only applicable if the specific weight gain at the 1-minute, 2-minute, and 4-minute data points continues to indicate an increase in water absorption. If not, the water absorption rate under this test method is considered to be approximately zero g / m³. 2 / √min.

[0518] Swelling capacity test scheme

[0519] This test measures the swelling capacity of a material based on the increase in thickness and volume of the sample after a given immersion duration. Samples are prepared using a material sampling procedure or a substrate sampling procedure. Samples are initially dried at 60°C until no weight change is observed over consecutive measurement intervals of at least 30 minutes (a 24-hour drying period is typically suitable). The dimensions of the dried samples are then measured (e.g., thickness, length, and width of rectangular samples; thickness and diameter of circular samples, etc.). The dried samples are then fully immersed in a deionized water bath maintained at 25°C. After the given immersion duration, the samples are removed from the deionized water bath, blotted dry with a cloth to remove surface water, and the same dimensions of the immersed samples are measured again.

[0520] Any suitable immersion duration can be used. Therefore, as used herein, the statement "with an increase in swelling thickness (or volume) at 5 minutes" refers to an immersion duration of 5 minutes, the statement "with an increase in swelling thickness (or volume) at 1 hour" refers to a test duration of 1 hour, the statement "with an increase in swelling thickness (or volume) at 24 hours" refers to a test duration of 24 hours, and so on.

[0521] The swelling of a component is determined by: (1) the increase in thickness between the dried component and the soaked component, (2) the increase in volume between the dried component and the soaked component, or (3) both. The increase in thickness between the dried component and the soaked component is calculated by subtracting the measured thickness of the initially dried component from the measured thickness of the soaked component. Similarly, the increase in volume between the dried component and the soaked component is calculated by subtracting the measured volume of the initially dried component from the measured volume of the soaked component. The increases in thickness and volume can also be expressed as a percentage increase relative to dry thickness or dry volume, respectively.

[0522] Contact Angle Testing Solution

[0523] This test measures the contact angle of a material based on the static contact angle of a fixed liquid droplet on the sample. Samples are prepared using material sampling procedures, substrate sampling procedures, or component sampling procedures. The contact angle refers to the angle at which a liquid interface meets a solid surface and is an indicator of the surface's hydrophilicity.

[0524] For the dry test (i.e., to determine the dry contact angle), the sample was initially held at 25°C and 20% humidity for 24 hours. For the wet test (i.e., to determine the wet contact angle), the sample was fully immersed in a deionized water bath maintained at 25°C for 24 hours. After this, the sample was removed from the bath and blotted dry with a cloth to remove surface water, and clamped on a glass slide if necessary to prevent curling.

[0525] The dry or wet sample is then placed on the movable stage of a contact angle goniometer, such as the commercially available RAME-HART F290 from Rame-Hart Instrument Co., Succasunna, NJ. A 10 μL droplet of deionized water is then placed onto the sample using a syringe and automatic pump. An image of the droplet is immediately taken (before the membrane can absorb the droplet), and the contact angles of the two edges of the droplet are measured from this image. The reduction in the contact angle between the dry and wet samples is calculated by subtracting the measured contact angle of the wet composite element from the measured contact angle of the dry composite element.

[0526] Friction coefficient test scheme

[0527] This test measures the coefficient of friction of the sample. Samples are prepared using material sampling, substrate sampling, or component sampling procedures. For dry testing (i.e., to determine the dry-state coefficient of friction), the sample is initially equilibrated at 25°C and 20% humidity for 24 hours. For wet testing (i.e., to determine the wet-state coefficient of friction), the sample is fully immersed in a deionized water bath maintained at 25°C for 24 hours. After this, the sample is removed from the bath and blotted dry with a cloth to remove surface water.

[0528] Measurements were performed using an aluminum sled mounted on an aluminum test track. This sled was used to perform a sliding friction test on the test sample against the aluminum surface of the test track. The test track measures 127 mm wide × 610 mm long. The aluminum sled measures 76.2 mm × 76.2 mm, with its leading edge cut to a radius of 9.5 mm. The contact area between the sled and the track is 76.2 mm × 66.6 mm, or 5,100 square millimeters.

[0529] Dry or wet samples are attached to the bottom of the skid using a room-temperature curing two-component epoxy adhesive, such as the commercially available epoxy adhesive from Henkel, Dusseldorf, Germany, under the trade name "LOCTITE 608". The adhesive is used to maintain the flatness of the wet sample, which can curl when saturated. A layer of polystyrene foam, approximately 25.4 mm thick, is attached to the top surface of the skid (opposite to the test sample) for structural support.

[0530] The sliding friction test was conducted using a screw-driven load frame. A tow cable, attached to a skid via a mount supported in a polystyrene foam structure, was wound around pulleys to drag the skid across an aluminum test track. Sliding force, or frictional force, was measured using a load transducer with a capacity of 2,000 Newtons. The normal force was controlled by placing a weight on top of the aluminum skid, supported by the polystyrene foam structure, with a total skid weight of 20.9 kg (205 Newtons). The crosshead of the test frame increased at a rate of 5 mm / s, and the total test displacement was 250 mm. The coefficient of friction was calculated based on the steady-state force parallel to the direction of motion required to pull the skid at a constant speed. The coefficient of friction itself was obtained by dividing the steady-state tension by the applied normal force. Any transient values ​​related to the static coefficient of friction at the start of the test were ignored.

[0531] Energy storage modulus testing scheme

[0532] This test measures the material's resistance to deformation (stress-to-strain ratio) when subjected to vibratory or oscillating force, and is a good indicator of film compliance in both dry and wet conditions. Samples are prepared using material sampling, substrate sampling, or component sampling procedures. For this test, a sample with a surface area of ​​5.35 mm wide and 10 mm long is provided. Sample thickness can range from 0.1 mm to 2 mm, and there is no particular limitation on the specific range, as the final modulus result is normalized according to the material thickness.

[0533] The storage modulus (E') of the sample, in megapascals (MPa), was determined by dynamic mechanical analysis (DMA) using a DMA analyzer, such as the commercially available analyzer from TA Instruments, New Castle, Del. under the trade name "Q800 DMAANALYZER," which is equipped with a relative humidity accessory to maintain the sample at a constant temperature and relative humidity during analysis.

[0534] Initially, the thickness of the test samples was measured using calipers (for use in modulus calculations). The test samples were then clamped into a DMA analyzer, which operated during analysis under the following stress / strain conditions: isothermal temperature of 25°C, frequency of 1 Hz, strain amplitude of 10 μm, preload of 1 N, and force track of 125%. DMA analyses were performed at a constant temperature of 25°C according to the following time / relative humidity (RH) profiles: (i) 0% RH for 300 minutes (representing the dry state for energy storage modulus determination), (ii) 50% RH for 600 minutes, (iii) 90% RH for 600 minutes (representing the wet state for energy storage modulus determination), and (iv) 0% RH for 600 minutes.

[0535] At the end of each time interval with a constant relative humidity value, the E' value (in megapascals) is determined from the DMA curve according to standard DMA techniques. That is, in the specified time / relative humidity profile, the E' value at 0 percent relative humidity (i.e., dry energy storage modulus) is the value at the end of step (i), the E' value at 50 percent relative humidity is the value at the end of step (ii), and the E' value at 90 percent relative humidity (i.e., wet energy storage modulus) is the value at the end of step (iii).

[0536] Materials can be characterized by a decrease in their dry storage modulus, their wet storage modulus, or a decrease in the storage modulus between the dry and wet states, wherein the wet storage modulus is less than the dry storage modulus. This decrease in storage modulus can be expressed as the difference between the dry and wet storage moduli, or as a percentage change relative to the dry storage modulus.

[0537] Sampling procedure

[0538] Using the test scheme described above, various properties of the materials disclosed herein and articles formed therefrom can be characterized using samples prepared with the following sampling procedure:

[0539] Material Sampling Procedure

[0540] Material sampling procedures can be used to obtain pure samples of polymeric materials or polymers, or in some cases, samples of materials used to form polymeric materials or polymers. The material is provided in the form of a medium, such as flakes, granules, powders, pellets, and the like. If the source of the polymeric material or polymer is not available in pure form, a sample of the material can be separated by cutting a sample from a part or component containing the polymeric material or polymer (such as a composite element or a shoe sole structure).

[0541] Substrate sampling procedure and film sampling procedure

[0542] Prepare a polymer material or a sample of polymer. Then, mold a portion of the polymer or polymer material into a film or substrate sized for assembly into a testing device. For example, when using a shoe sole material flexural tester, the polymer material is thermoformed in a mold, and the substrate is sized to fit inside the shoe sole material flexural tester, having dimensions of approximately 15 cm × 2.5 cm and a thickness of approximately 1 mm to approximately 4 mm. For a polymer substrate sample, the sample can be prepared by: melting the polymer, loading the molten polymer into a mold, recuring the polymer into the shape of the mold, and removing the cured molded sample from the mold. Alternatively, the polymer substrate sample can be melted and then extruded into a film cut to a specific size. For a polymer material substrate sample, the sample can be prepared by: mixing the components of the polymer material together, melting the thermoplastic components of the polymer material, loading the molten polymer into a mold, recuring the polymer material into the shape of the mold, and removing the cured molded sample from the mold. Alternatively, a substrate sample of the polymer material can be prepared by mixing and melting the components of the polymer material, and then the molten polymer material can be extruded into a film cut to a certain size. For the polymer film sample, the film is extruded into a mesh or sheet having a substantially constant film thickness (within ±10 percent of the average film thickness), and cooled to solidify the resulting mesh or sheet. A sample of the film with a surface area of ​​4 square centimeters is then cut from the resulting mesh or sheet. Alternatively, if the source of the film material is not available in its pure form, the film can be cut from a substrate of the footwear component, or from a backing substrate of a co-extruded sheet or mesh, thereby separating the film. In either case, a sample of the film with a surface area of ​​4 square centimeters is then cut from the resulting separated film.

[0543] Component sampling procedure

[0544] This procedure can be used to obtain samples of material from components of footwear articles, apparel articles, sports equipment articles, or sports equipment articles. A blade is used to cut a sample from the article or component containing material in a non-wet state (e.g., at 25 degrees Celsius and 20% relative humidity). If the material is bonded to one or more other materials, the procedure may include separating the other materials from the material being tested. For example, to test material on the ground-facing surface of a shoe sole structure, the opposing surface may be peeled, polished, scraped, or otherwise cleaned to remove any adhesives, yarns, fibers, foams, and the like attached to the material being tested. The resulting sample includes the material and may include any other materials bonded to it.

[0545] This procedure can be used to obtain samples of the hydrogel material when it is incorporated as a composite element or layer of the sole structure of footwear articles (e.g., a material bonded to a second polymer material and / or other materials). The resulting component sample includes the hydrogel material and any substrate bonded to it, maintaining the interfacial bonding between the hydrogel material and the textile of the finished article and optionally other related materials. Therefore, any test using the component sampling procedure can simulate how the hydrogel material w...

Claims

1. A sole structure for footwear articles, the sole structure comprising: Composite components and sole parts; The composite element comprises textiles and a hydrogel layer; The textile comprises textile material and has a first side, a second side, and a core located between the first side and the second side; The hydrogel layer comprises a hydrogel material and has a first side and a second side, the second side being operatively attached to the textile along the first side of the textile. A portion of the hydrogel layer extends through the first side of the textile and at least partially into the core of the textile, but does not extend to the second side of the textile; At least a portion of the first side of the hydrogel layer provides a first ground-facing surface of the sole structure; and The sole component comprises a second polymer material and has a first side and a second side, wherein at least a portion of the first side of the sole component is operatively coupled to the second side of the textile. "Operationally coupled" refers to a connection made by means of mechanical bonding, chemical bonding and / or thermal bonding.

2. The sole structure of claim 1, wherein the textile has a core thickness of 0.1 mm to 5 mm, measured between the first and second sides of the textile, prior to operably attaching the textile to the hydrogel layer.

3. The sole structure according to claim 1 or 2, wherein the textile is a breathable textile prior to the first side of the textile being operably bonded to the hydrogel layer.

4. The sole structure according to any one of claims 1 to 3, wherein the hydrogel material is a thermoplastic hydrogel material, and the textile material has a textile material melting temperature or textile material Vicat softening temperature that is at least 20 degrees Celsius greater than the melting temperature or Vicat softening temperature of the thermoplastic hydrogel material of the hydrogel layer.

5. The sole structure according to any one of claims 1 to 4, wherein the hydrogel layer permeates at least 10 percent of the core thickness of the textile.

6. The sole structure according to any one of claims 1 to 5, wherein the hydrogel layer permeates less than 90 percent of the core thickness of the textile.

7. The sole structure according to any one of claims 1 to 6, wherein the textile comprises a nonwoven textile.

8. The sole structure according to any one of claims 1 to 7, wherein the textile has a basis weight of 5 g / m² to 500 g / m².

9. The sole structure according to any one of claims 1 to 8, wherein the hydrogel layer has a dry thickness in the range of 0.1 mm to 2 mm.

10. The sole structure according to any one of claims 1 to 9, wherein the hydrogel material is a thermoplastic hydrogel material, and the thermoplastic hydrogel material has a melt flow index from 35 g per 10 minutes to 55 g per 10 minutes according to the melt flow index test scheme.

11. The sole structure according to any one of claims 1 to 10, wherein the hydrogel material comprises polyurethane hydrogel.

12. The sole structure according to any one of claims 1 to 11, wherein the sole component comprises one or more adhesion friction elements.

13. The sole structure according to any one of claims 1 to 12, wherein the second polymer material comprises a polyolefin.

14. A footwear article comprising an upper operatively connected to the sole structure of any one of claims 1 to 13.

15. A method for manufacturing a sole structure for footwear articles, the method comprising: The first composite element is operatively coupled to the second component; the first composite element includes a textile and a hydrogel layer; The textile comprises textile material and has a first side, a second side, and a core located between the first side and the second side; the hydrogel layer comprises hydrogel material and has a first side and a second side, the second side of the hydrogel layer being operatively attached to the textile along the first side of the textile; wherein, in the sole structure, a portion of the hydrogel layer extends through the first side of the textile and at least partially extends into the core of the textile, but does not extend to the second side of the textile; The first composite element is operatively coupled to the second component by forming a joint between the second side of the textile of the first composite element and the second component, such that the hydrogel layer of the first composite element defines at least a portion of the ground-facing surface of the sole structure. "Operationally coupled" refers to a connection made by means of mechanical bonding, chemical bonding and / or thermal bonding.

16. The method of claim 15, wherein the second component comprises a second polymer material, and wherein operably coupling the first composite element to the second component further comprises placing the first composite element into a mold such that a portion of the first side surface of the hydrogel layer contacts a portion of the molding surface of the mold to form the prepared molding surface; The second polymer material is loaded onto the prepared molding surface of the mold; The loaded second polymer material is at least partially cured in the mold, thereby operably linking the first composite element and the at least partially cured second polymer material to form the sole structure including the hydrogel layer of the first composite element, the hydrogel layer defining at least a portion of the ground-facing surface of the sole structure; as well as Remove the sole structure from the mold.

17. The method of claim 16, wherein the method further comprises constraining the first composite element in the mold such that, while loading the second polymer material, at least a portion of the first side of the hydrogel layer contacts the molded surface.

18. The method according to any one of claims 15 to 17, wherein a) the textile has a core thickness of 0.1 mm to 5 mm measured between the first side and the second side of the textile before the first side of the textile is operably bonded to the hydrogel layer; or wherein b) the textile is a breathable textile before the first side of the textile is operably bonded to the hydrogel layer; or both a) and b).

19. A sole structure manufactured by the method according to any one of claims 15 to 18.

20. A method for manufacturing footwear, the method comprising: An upper is attached to a sole structure, the sole structure including a hydrogel layer and a sole component, the hydrogel layer having a first side and a second side operably coupled to the first side of a textile, the sole component comprising a second polymer material operably coupled to the second side of the textile, such that the first side of the hydrogel layer of the sole structure defines the ground-facing surface of the footwear article, wherein "operably coupled" means coupled by mechanical bonding, chemical bonding and / or thermal bonding.

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