Stratified materials, methods of manufacture and use, and articles incorporating the stratified materials

Abstract

This application relates to a layered material, method of manufacture and use, and articles incorporating the layered material. The present disclosure generally provides a layered material that can be incorporated into textiles (e.g., footwear, apparel, sports equipment, or components of each). In aspects, the layered material includes an outer-facing layer and a thermoplastic hot melt adhesive layer, and optionally one or more inner layers between the outer-facing layer and the thermoplastic hot melt adhesive layer. The present disclosure provides articles including the layered material, such as footwear, apparel, sports equipment, components of sports equipment articles, components of apparel articles, or components of footwear articles, including an outsole structure for footwear.

Description

[0001] This application is a divisional application of the application with the filing date of April 19, 2019, application number 201980041721.8, and invention name "Layered Materials, Methods of Making, Methods of Use, and Articles Incorporating the Layered Materials (the changed name is "Footwear Articles and Methods of Manufacturing Thereof").

[0002] Cross - Reference to Related Applications

[0003] This application claims the priority of the co - pending U.S. patent application titled "LAYERED MATERIALS, METHODS OF MAKING, METHODS OF USE, AND ARTICLES INCORPORATION THE LAYERED MATERIALS" filed on May 3, 2018 and assigned application number 62 / 666,248, which is incorporated herein by reference in its entirety. Background

[0004] Multiple types of clothing articles and sports equipment articles are often used for multiple activities, including outdoor, military use, and / or competitive sports. During the use of these articles, the outward - facing surface of the article can often come into contact with the ground and / or be exposed to dirt. As a result, ground matter or dirt can accumulate on the outward - facing surface. Such ground matter or dirt typically includes inorganic materials such as mud, dust, and gravel; organic materials such as grass, sod, and excrement; or combinations thereof. Brief Description of the Drawings

[0005] Figures 1A - 1D A cross - sectional view of the layered material of the present disclosure is illustrated.

[0006] Figure 2 Is a side view of an example of footwear.

[0007] Figure 3 Is a bottom view of an example of footwear.

[0008] Figure 4 Is a side view of an example of footwear.

[0009] Figure 5 Is a bottom view of an example of footwear.

[0010] Description

[0011] The present disclosure generally provides a layered material that can be incorporated into textiles (e.g., footwear, apparel, sports equipment, or components of each). Specifically, the layered material can be included in footwear having attachment friction elements such as anti-slip members, where the layered material can be positioned among the attachment friction elements and / or between the toe region and the heel region of the outsole component of the footwear (e.g., the midfoot region). The layered material includes an outer-facing layer and a second layer (e.g., a thermoplastic hot melt adhesive layer) and optionally one or more inner layers between the outer-facing layer and the second layer. The outer-facing layer can absorb fluid (e.g., water), and when sufficiently wetted, can provide compressive compliance and / or expulsion of the absorbed water and / or an outer-facing surface having a high concentration of water. In particular, it is believed that the compressive compliance of the wet layered material, the expulsion of water from the wet layered material, the presence of a water layer on the outer-facing layer, or any combination of these mechanisms, can disrupt the adhesion of dirt to or at the outsole component of the footwear, or the sticking of particles to each other, or can disrupt both adhesion and sticking. This disruption of dirt adhesion and / or sticking is believed to be the mechanism responsible for preventing (or otherwise reducing) the accumulation of dirt on the outsole component of the footwear (due to the presence of the wet material). As can be appreciated, preventing dirt from accumulating on the bottom of the footwear can improve the performance of the attachment friction elements present on the outsole component during use on an unpaved surface, can prevent the footwear from gaining weight due to dirt accumulated during use, can maintain the ball control performance of the footwear, and thus can provide significant benefits to the wearer compared to footwear items that do not have such material on the outsole component. The thermoplastic hot melt adhesive layer allows attachment of the layered material including the hydrogel layer to be fixed to an article (e.g., footwear).

[0012] As stated above, the layered material can include one or more inner layers, such as a tie layer, an elastic layer, or a regrind layer. In some instances, including a tie layer can improve the adhesion of the hydrogel layer to the thermoplastic hot melt adhesive layer. In other instances, including an elastic layer can improve the ability of the layered material to conform to a curved surface. In other instances, including a regrind layer in the layered material can provide a core layer that is less costly and reduces waste in the manufacturing process. Including regrind hydrogel material in the regrind layer can also provide additional water absorption capacity while serving as a tie layer.

[0013] The hydrogel material may include a polyurethane hydrogel. The thermoplastic hot melt adhesive material may include one or more thermoplastic polymers such as polyesters, polyethers, polyamides, polyurethanes, and polyolefins, any copolymers thereof, and combinations thereof. The elastic layer may include an elastomeric material such as a thermoplastic polymer. The connecting material may include a thermoplastic polymer. The thermoplastic polymer may be a polyester, polyether, polyamide, polyurethane, polyolefin, any copolymer thereof, and any combination thereof. The regrind layer may include a regrind material, which may be waste such as from unused hydrogel material, thermoplastic hot melt adhesive material, elastic material, and / or connecting material, or waste from other areas in the manufacture of the article or waste from other sources, and optionally may also include no waste.

[0014] The present disclosure provides a footwear article that includes: an outsole component on a side of the footwear article configured to face the ground, the outsole component including a layered material having an outward-facing layer and a second layer opposite the outward-facing layer, the outward-facing layer including at least a portion of an outer surface of the footwear article, the outward-facing layer including a hydrogel material, and the second layer including a thermoplastic hot melt adhesive material, and wherein the footwear article includes one or more attachment friction elements on the side of the footwear article configured to face the ground.

[0015] The present disclosure provides a method of manufacturing a footwear article, the method including: attaching an outsole component and a layered material to each other to form an article, the layered material including an outward-facing layer and a second layer opposite the outward-facing layer, the outward-facing layer including a hydrogel material, and the second layer including a thermoplastic hot melt adhesive material, and wherein the footwear article includes one or more attachment friction elements on the side of the footwear article configured to face the ground.

[0016] The present disclosure provides a layered material that includes: an outward-facing layer of a first material that includes a hydrogel material and a second material that includes a thermoplastic hot melt adhesive. Additionally, a structure may include the layered material as described herein.

[0017] The present disclosure provides a method of manufacturing an article, the method including: attaching a first component and a layered material as described herein to each other to form an article. In aspects, the article includes the product of the method described above.

[0018] The present disclosure provides a process for manufacturing an article, the process comprising: placing a first element on a molding surface; placing a thermoplastic hot melt adhesive layer as described herein in contact with at least a portion of the first element on the molding surface; raising the temperature of the thermoplastic hot melt adhesive layer to a temperature at or above the activation temperature of the thermoplastic hot melt adhesive when the thermoplastic hot melt adhesive layer is in contact with the component on the molding surface; and after raising the temperature of the thermoplastic hot melt adhesive, lowering the temperature of the thermoplastic hot melt adhesive to a temperature below the melting temperature T m of the thermoplastic hot melt adhesive while the thermoplastic hot melt adhesive layer remains in contact with the component on the molding surface; and thereby bonding the layered material to the component to form a bonded component. The structure may include an article formed by the process described above.

[0019] The present disclosure provides a component comprising: a layered material as described herein, the layered material comprising an outermost layer of a first material comprising a hydrogel material and a second material comprising a thermoplastic hot melt adhesive, the layered material having an outer perimeter, wherein the outermost layer of the layered material is present on at least a portion of the side of the component; and a second polymeric material attached to the thermoplastic hot melt adhesive layer and the outer perimeter of the layered material.

[0020] The present disclosure provides a method of manufacturing a component, the method comprising: placing a layered material as described herein comprising an outer perimeter, an outermost layer comprising a hydrogel material, and a second material comprising a thermoplastic hot melt adhesive into a mold such that a portion of the outermost layer contacts a portion of the molding surface; constraining the portion of the outermost layer against the portion of the molding surface when a second polymeric material is flowed into the mold; curing the second polymeric material in the mold to thereby bond the second polymeric material to the thermoplastic hot melt adhesive layer and the outer perimeter of the layered material, producing a component, wherein the portion of the outermost layer of the layered material forms the outermost layer of the component; and removing the component from the mold.

[0021] The present disclosure is not limited to the particular aspects described and may, of course, vary. The terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting, as the scope of the present disclosure will be limited only by the appended claims.

[0022] When a range of values is provided, every intermediate value between the upper and lower limits of that range (in increments of one-tenth of the lower limit unit, unless the context clearly indicates otherwise) as well as any other stated value or intermediate value in the stated range is included in the present disclosure. The upper and lower limits of these smaller ranges may be independently included in the smaller ranges and are also included in the present disclosure, subject to any specific excluded limits in the stated range. When the stated range includes one or both of the limits, ranges excluding any one or both of the included limits are also included in the present disclosure.

[0023] It will be apparent to those skilled in the art upon reading the present disclosure that each of the various aspects described and illustrated herein has discrete components and features that can be readily separated or combined with the features of any one of several other aspects without departing from the scope or spirit of the present disclosure. Any recited method may be performed in the recited order of events or in any other order that is logically possible.

[0024] Unless otherwise indicated, the present disclosure may employ techniques within the skill of the art in materials science, chemistry, textiles, polymer chemistry, textile chemistry, and the like. Such techniques are well explained in the literature.

[0025] Unless otherwise indicated, any functional group or compound described herein may be substituted or unsubstituted. A "substituted" group or compound, such as an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxy, ester, ether, or carboxylate ester, refers to an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heteroaryl group, alkoxy group, ester group, ether group, or carboxylate ester group having at least one hydrogen group substituted by a non-hydrogen group (i.e., a substituent). Examples of non-hydrogen groups (or substituents) include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ether, aryl, heteroaryl, heterocycloalkyl, hydroxy, oxo (or keto), alkoxy, ester, thioester, acyl, carboxyl, cyano, nitro, amino, amido, sulfur, and halogen. When a substituted alkyl group contains more than one non-hydrogen group, the substituents may be attached to the same carbon atom or two or more different carbon atoms.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the fields of microbiology, molecular biology, medicinal chemistry, and / or organic chemistry. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described herein.

[0027] As used in the specification and the appended claims, the singular forms "a", "an", and "the" may include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a support" includes more than one support. In this specification and the appended claims, a number of terms will be referred to that shall be defined to have the following meanings unless the contrary intention is apparent.

[0028] As used herein, the term "weight" refers to a mass value, such as units having grams, kilograms, and like units. Further, the recitation of a numerical range by endpoints includes the endpoints and all numbers within that numerical range. For example, a concentration within the range from 40 percent by weight to 60 percent by weight includes 40 percent by weight, 60 percent by weight, and all concentrations between 40 percent by weight and 60 percent by weight (e.g., 40.1 percent, 41 percent, 45 percent, 50 percent, 52.5 percent, 55 percent, 59 percent, etc.).

[0029] As used herein, the term "provide", such as for "provide a layered material", when recited in a claim, is not intended to require any particular delivery or receipt of the item being provided. Rather, for purposes of clarity and ease of reading, the term "provide" is used only to recite the item that will be referred to in subsequent elements of the claim.

[0030] As used herein, the terms "at least one" element and "one or more" elements may be used interchangeably and have the same meaning including a single element and more than one element, and may also be indicated by the suffix "(s)" at the end of the element. For example, "at least one polyurethane", "one or more polyurethanes", and "polyurethane(s)" may be used interchangeably and have the same meaning.

[0031] The present disclosure has been generally described, and additional details are provided. The present disclosure includes a layered material that can be incorporated into textiles such as footwear or components thereof, apparel or components thereof, or sports equipment or components thereof. Specifically, the layered material can be included in a footwear article having an attachment friction element disposed on an outsole component of the shoe. The layered material can be disposed between or within the attachment friction elements and / or along a vertical surface of an axis of the attachment friction element. The layered material is not on a surface of the attachment friction element, where such a location could cause the footwear article to slip or slide during use. The layered material can optionally be positioned between attachment friction elements that are located on a toe region (e.g., a top plate) and a heel region (e.g., a heel plate) of the outsole component of the shoe. In other words, the layered material can be positioned in a midfoot region of the outsole component between the toe region and the heel region of the outsole component of the shoe.

[0032] The layered material includes an outermost layer and a second layer including a thermoplastic hot melt adhesive layer and optionally one or more inner layers between the outermost layer and the thermoplastic hot melt adhesive layer. Each of the outermost layer, the second layer, and (when present) the inner layers (individually) can independently have a thickness of from about 0.1 millimeters to 10 millimeters, from about 0.1 millimeters to 5 millimeters, from about 0.1 millimeters to 2 millimeters, from about 0.25 millimeters to 2 millimeters, or from about 0.5 millimeters to 1 millimeter, where the width and length can vary according to a particular application (e.g., the article to be incorporated).

[0033] The hydrogel material can include a polyurethane hydrogel. The hydrogel material can include a polyamide hydrogel, a polyurea hydrogel, a polyester hydrogel, a polycarbonate hydrogel, a polyetheramide hydrogel, a hydrogel formed from an addition polymer of an ethylenically unsaturated monomer, a copolymer thereof (e.g., a copolyester, a copolyether, a copolyamide, a copolyurethane, a copolymerized olefin), and combinations thereof. Additional details are provided herein.

[0034] The material of the second layer (e.g., the thermoplastic hot melt adhesive layer) can include one or more thermoplastic polymers such as polyesters, polyethers, polyamides, polyurethanes, and polyolefins, copolymers thereof (e.g., copolyesters, copolyethers, copolyamides, copolyurethanes, copolymerized olefins), and combinations thereof. In aspects, the thermoplastic hot melt adhesive material can include a low processing temperature polymer composition. Additional details are provided herein.

[0035] The optional inner layer can be one or more types of layers, such as a bonding layer, an elastic layer, or a regrind layer. The layered material can include one type of inner layer, two types of inner layers, or three types of inner layers. Any type of inner layer can be adjacent to the out-facing layer (e.g., in contact with the out-facing layer). Additionally, any type of inner layer can be adjacent to the thermoplastic hot melt adhesive layer. Any type of inner layer can be adjacent to each other.

[0036] The elastic layer can include an elastomeric material such as a thermoplastic polymer. The thermoplastic polymer can include one or more polyesters, polyethers, polyamides, polyurethanes, polyolefins, including any copolymers thereof (e.g., copolyesters, copolyethers, copolyamides, copolyurethanes, copolyolefins) and any combinations thereof. Additional details are provided herein.

[0037] The bonding material can include a thermoplastic polymer. The thermoplastic polymer can include one or more polyesters, polyethers, polyamides, polyurethanes, polyolefins, any copolymers thereof (e.g., copolyesters, copolyethers, copolyamides, copolyurethanes, copolyolefins) and any combinations thereof. Additional details are provided herein.

[0038] The regrind layer can include a regrind material, which can be waste from other areas in the manufacture of the article or from other sources. The regrind material can include two or more of the following: a hydrogel material, a thermoplastic hot melt adhesive material, an elastomeric material, and a bonding material. Additional details are provided herein.

[0039] Figures 1A to 1D FIG. shows a cross-sectional view of the layered materials 10a, 10b, 10c, and 10d. Figure 1A FIG. shows the layered material 10a having an out-facing layer 12 and a second layer (e.g., a thermoplastic hot melt adhesive layer and hereinafter referred to as the thermoplastic hot melt adhesive layer in Figures 1A - 1D ). Figure 1B FIG. shows the layered material 10b having an out-facing layer 12 and a thermoplastic hot melt adhesive layer 16, with an inner layer 14a disposed therebetween. The inner layer 14a can be any one of a bonding layer, an elastic layer, or a regrind layer.

[0040] Figure 1C FIG. shows the layered material 10c having an out-facing layer 12 and a thermoplastic hot melt adhesive layer 16, with two inner layers 14a and 14b therebetween. The inner layers 14a and 14b can each be one of a bonding layer, an elastic layer, or a regrind layer, and any type of inner layer can be adjacent to the out-facing layer 12 or the thermoplastic hot melt adhesive layer 16. Alternatively, each of 14a and 14b can be two different types of bonding layers (or elastic layers or regrind layers).

[0041] Figure 1D The figure shows a laminated material 10d having an outer-facing layer 12 and a thermoplastic hot melt adhesive layer 16, with three inner layers 14a, 14b, and 14c therebetween. The inner layers 14a, 14b, and 14c can each be one of a tie layer, an elastic layer, or a regrind layer, and any type of inner layer can be adjacent to the outer-facing layer 12 or the thermoplastic hot melt adhesive layer 16. Optionally, two or three of 14a, 14b, and 14c can be two or three different types of tie layers (or elastic layers or regrind layers).

[0042] The laminated material can be incorporated into articles such as textiles. For example, textiles can include footwear or components thereof, apparel (e.g., shirts, sweaters, pants, shorts, gloves, eyewear, socks, billed caps, beanies, jackets, undergarments) or components thereof, containers (e.g., backpacks, bags), and decorative items for furniture (e.g., chairs, sofas, vehicle seats), bedding (e.g., sheets, blankets), tablecloths, towels, flags, tents, sails, and parachutes. Additionally, the laminated material can be used in the production of articles or other products disposed on articles, where the articles can be striking devices (e.g., baseball bats, rackets, clubs, sticks, golf clubs, paddles, etc.), sports equipment (e.g., golf bags, baseball and football gloves, soccer restraint structures), protective equipment (e.g., pads, helmets, protectors, visors, face masks, goggles, etc.), locomotive equipment (e.g., bicycles, motorcycles, skateboards, cars, trucks, boats, surfboards, sleds, snowboards, etc.), balls or pucks for various sports, fishing or hunting equipment, furniture, electronic equipment, building materials, eye protection, watches, jewelry, and the like.

[0043] The footwear article of the present disclosure can be designed for a variety of uses, such as sports use, athletic use, military use, work-related use, recreational use, or leisure use. Primarily, the footwear article is intended for outdoor use on an unpaved surface (partially or fully), such as on a ground including one or more of grass, turf, gravel, sand, dirt, clay, mud, and the like, whether as a sports performance surface or as a general outdoor surface. However, the footwear article can also be desirable for indoor applications, such as for example indoor sports including a dirt playing surface (e.g., an indoor baseball field with a dirt infield).

[0044] Footwear articles can be designed for outdoor sports activities such as international football / soccer, golf, American football, rugby, baseball, running, track and field, cycling (e.g., road bikes and mountain bikes), and similar outdoor sports activities. The footwear article can optionally include attachment friction elements (e.g., lugs, cleats, studs, and spikes, as well as tread patterns) to provide attachment friction on soft and smooth surfaces, where the layered material can be between or within the attachment friction elements and optionally on the sides of the attachment friction elements, rather than on the surface of the attachment friction element that contacts the ground or surface. Cleats, studs, and spikes are typically included in footwear designed for sports such as international football / soccer, golf, American football, rugby, baseball, and similar sports that are often played on unpaved surfaces. Lugs and / or enhanced tread patterns are typically included in footwear that includes boots designed for use in harsh outdoor conditions such as cross-country running, hiking, and military use.

[0045] The attachment friction elements can each include any suitable cleats, studs, spikes, or similar elements that are configured to enhance attachment friction for the wearer during sharp turns, pivots, stops, accelerations, and backward movements. The attachment friction elements can be arranged in any suitable pattern along the bottom surface of the footwear. For example, the attachment friction elements can be grouped or clustered along the outsole component of the footwear (e.g., clusters of 2 - 8 attachment friction elements). The attachment friction elements can be grouped into one cluster in the front (toe) region of the shoe, one cluster in the midfoot region of the shoe, and one cluster in the heel region of the shoe. In an example, six of the attachment friction elements are generally aligned along the medial side of the outsole component of the shoe, while the other six attachment friction elements are generally aligned along the lateral side of the outsole component of the shoe.

[0046] Optionally, the attachment friction elements can be arranged symmetrically or asymmetrically between the medial and lateral sides along the outsole component of the footwear as needed. Additionally, one or more of the attachment friction elements, such as blades, can be arranged between the medial and lateral sides along the centerline of the outsole component of the footwear to enhance or otherwise modify performance.

[0047] Optionally (or alternatively), the attachment friction elements may also include one or more front edge attachment friction elements that are fixed to the backing plate (e.g., formed integrally with the backing plate) at the front edge region between the front of the shoe and the cluster, such as one or more blades, one or more fins, and / or one or more anti-slip members (not shown). In this application, the outward-facing portion of the layered material may optionally extend across the bottom surface at the front edge region while maintaining good attachment friction performance.

[0048] In addition, the attachment friction elements may each independently have any suitable dimensions (e.g., shape and size). For example, in some designs, each attachment friction element within a given cluster (e.g., the cluster) may have the same or substantially the same dimensions, and / or each attachment friction element across the entire outsole component of the shoe may have the same or substantially the same dimensions. Optionally, the attachment friction elements within each cluster may have different dimensions, and / or each attachment friction element across the entire outsole component of the shoe may have different dimensions.

[0049] Examples of suitable shapes for the attachment 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.). The attachment friction elements may also have the same or different heights, widths, and / or thicknesses from each other, as discussed further below. Additional examples of suitable dimensions for the attachment friction elements and their arrangement along the plate include those provided in soccer / football footwear that is commercially available under the trade names "TIEMPO", "HYPERVENOM", "MAGISTA", and "MERCURIAL" from Nike, Inc. of Beaverton, OR.

[0050] The attachment friction element can be incorporated into the outsole component, including an optional backing plate, by any suitable mechanism such that the attachment friction element preferably extends from the bottom surface. The attachment friction element can be disposed in a different zone (e.g., in the toe region, the heel region, or both) than the layered material (e.g., in the midfoot region). As discussed below, the attachment friction element can be integrally formed with the backing plate by a molding process (e.g., for footwear for firm ground (FG)). Alternatively, the outsole component or the optional backing plate can be configured to receive a removable attachment friction element, such as a screw-in or snap-in attachment friction element. The backing plate can include receiving holes (e.g., threaded or snap-fit holes, not shown), and the attachment friction element can be screwed or snapped into the receiving holes to secure the attachment friction element to the backing plate (e.g., for footwear for soft ground (SG)).

[0051] In another example, a first portion of the attachment friction element can be integrally formed with the outsole component or the optional backing plate, and a second portion of the attachment friction element can be fixed using a screw-in, snap-in, or other similar mechanism (e.g., for SG professional footwear). If desired, the attachment friction element can also be configured as short studs for use with footwear for artificial ground (AG). In some applications, the receiving holes can be raised or otherwise protrude from the general plane of the bottom surface of the backing plate. Alternatively, the receiving holes can be flush with the bottom surface.

[0052] The attachment friction element can be made of any suitable material for use with the outsole component. For example, the attachment friction element can include one or more of the following polymer materials: thermoplastic elastomers; thermosetting polymers; elastic polymers; silicone polymers; natural and synthetic rubbers; composite materials comprising polymers reinforced with carbon fibers and / or glass; natural leather; metals such as aluminum, steel, and the like; and combinations thereof. In aspects where the attachment friction element is integrally formed (e.g., molded together) with the backing plate, the attachment friction element preferably includes the same material as the outsole component or the backing plate (e.g., a thermoplastic material). Alternatively, in aspects where the attachment friction element is separate and insertable into the receiving holes of the backing plate, the attachment friction element can include any suitable material that can be fixed in the receiving holes of the backing plate (e.g., metals and thermoplastic materials).

[0053] As mentioned above, the attachment friction element can have any suitable size and shape, where the shaft (and outer surface) can accordingly have a rectangular, hexagonal, cylindrical, conical, circular, square, triangular, trapezoidal, rhomboidal, oval, and other regular or irregular shapes (e.g., curved, C-shaped, etc.). Similarly, the end edges can have dimensions and sizes corresponding to the dimensions and sizes of the outer surface and can be generally flat, inclined, rounded, and the like. Additionally, the end edges can be generally parallel to the bottom surface and / or the layered material.

[0054] Examples of suitable average lengths of each shaft relative to the bottom surface are in the range from 1 millimeter to 20 millimeters, from 3 millimeters to 15 millimeters, or from 5 millimeters to 10 millimeters, where, as mentioned above, each attachment friction element can have different sizes and dimensions (i.e., the shafts of multiple attachment friction elements can have different lengths).

[0055] The layered material can be used as one or more components in a footwear item (e.g., typically on the outsole component that contacts the ground or surface). Figure 2 and Figure 3 FIG. shows a footwear item 100 including an upper 120 and an outsole component 130, where the upper 120 is secured to the outsole component 130. The outsole component 130 can include a toe plate 132 (e.g., the toe region), a midplate 134 (e.g., the midfoot region), and a heel plate 136 (e.g., the heel region) as well as attachment friction elements 138 and a layered material 110, where the outermost layer is on the outer surface so as to be able to contact the ground or surface during normal use. Optionally, the layered material 110 can be the outermost layer of the upper 120 in the region adjacent to the outsole component 130. In other aspects not depicted, the outsole component 130 can incorporate fluid-filled chambers, plates, regulators, or other elements that further attenuate forces, enhance stability, or influence foot movement.

[0056] The upper 120 of the footwear 100 has a body that can be made of materials known in the art for manufacturing footwear articles and is configured to receive a user's foot. For example, the upper 120 can be made of or include one or more components made of one or more of the following: natural leather; knitted textiles, braided textiles, woven textiles, or non-woven textiles made entirely or in part of natural fibers; knitted textiles, braided textiles, woven textiles, or non-woven textiles made entirely or in part of synthetic polymers, membranes of synthetic polymers, etc.; and combinations thereof. The upper 120 and the components of the upper 120 can be manufactured according to conventional techniques (e.g., molding, extrusion, thermoforming, stitching, knitting, etc.). The upper 120 can optionally have any desired aesthetic design, functional design, brand designator, and the like.

[0057] The outsole component 130 can be directly or otherwise fixed to the upper 120 using any suitable mechanism or method. As used herein, the term "fixed to", such as for an outsole fixed to an upper, e.g., an outsole operatively fixed to an upper, collectively refers to direct connection, indirect connection, integrally formed, and combinations thereof. For example, for the outsole component 130 fixed to the upper 120, the outsole component 130 can be directly connected to the upper 120 using a thermoplastic hot melt adhesive layer and optionally includes an outsole component 130 indirectly connected to the upper (e.g., employing an intermediate midsole), can be integrally formed with the upper (e.g., as a one-piece component), and combinations thereof.

[0058] Figure 4 and Figure 5 FIG. illustrates a footwear article 200 including an upper 220 and an outsole component 230, wherein the upper 220 is fixed to the outsole component 230. The outsole component 230 can include a toe plate 232 (e.g., the toe region), a mid-plate 234 (e.g., the midfoot region), and a heel plate 236 (e.g., the heel region) and attachment friction elements 238 that are in the toe plate 232 and the heel plate 236 but not in the mid-plate 234. The footwear 200 is similar to the footwear 100, except that a layered material 210 is positioned between the toe plate 232 and the heel plate 236. The mid-plate 234 includes the layered material 210, with the outermost layer on the outer surface so as to be able to contact the ground or surface during normal use. The components or elements 110, 120, 130, 132, 136, and 138 are similar to the components or elements 210, 220, 230, 232, 236, and 238. In other aspects not depicted, the outsole component 230 can incorporate fluid-filled chambers, plates, regulators, or other elements that further attenuate forces, enhance stability, or affect foot movement.

[0059] For example, the present disclosure provides an article of footwear having an outsole component on a side of the article of footwear. The side is configured to face the ground. The outsole component includes a layered material having an outward-facing layer and a second layer opposite the outward-facing layer. The outward-facing layer includes at least a portion of the outer surface of the article of footwear. The outward-facing layer includes a hydrogel material, and the second layer includes a thermoplastic hot melt adhesive material. The article of footwear includes one or more attachment friction elements on a side of the article of footwear configured to face the ground. The attachment friction elements may be in the toe region, the heel region, or both, when the layered material is in the midfoot region.

[0060] As used in the "outward-facing layer", the term "outward-facing" refers to the position where the element is expected to be when the element is present in the article during normal use. If the article is footwear, the element is positioned towards the ground during normal use by a wearer when in a standing position, and thus when the footwear is used in a conventional manner, such as standing, walking, or running on an unpaved surface, the element can contact the ground including the unpaved surface. In other words, even if the element may not have to face the ground during multiple steps of manufacturing or transportation, if the element is expected to face the ground during normal use by the wearer, the element is understood to be outward-facing or more specifically, for an article of footwear, ground-facing. In some cases, due to the presence of elements such as attachment friction elements, the outward-facing (e.g., ground-facing) surface may be positioned towards the ground during normal use, but may not have to contact the ground. For example, on a hard or paved surface, the ends of the attachment friction elements on the outsole of the footwear may directly contact the ground, while the portion of the outsole located between the attachment friction elements does not contact the ground. As described in this example, the portion of the outsole located between the attachment friction elements is considered to be outward-facing (e.g., ground-facing), even if they may not directly contact the ground in all cases.

[0061] It has been found that the layered material and articles incorporating the layered material (e.g., footwear) can prevent or reduce the accumulation of dirt on the outward-facing layer of the layered material during wear on an unpaved surface. As used herein, the term "dirt" may include any of a variety of materials commonly present on the ground or playing surface and that may otherwise adhere to the outsole or exposed midsole of an article of footwear. Dirt may include inorganic materials such as mud, sand, dust, and gravel; organic materials such as grass, turf, leaves, other plants, and excrement; and combinations of inorganic and organic materials such as clay. Additionally, dirt may include other materials such as pulverized rubber that may be present on or in an unpaved surface.

[0062] While not wishing to be bound by theory, it is believed that a layered material according to the present disclosure (e.g., a hydrogel material in an outermost layer), when sufficiently wetted with water (including water containing dissolved, dispersed, or otherwise suspended materials), can provide compressive compliance and / or expulsion of absorbed water. In particular, it is believed that the compressive compliance of the wet layered material, the expulsion of liquid from the wet layered material, or a combination of both, can disrupt the adhesion of dirt to or at the shoe outsole, or the adhesion of particles to each other, or can disrupt both the adhesion and the adhesion. This disruption of the adhesion and / or adhesion of dirt is believed to be the mechanism responsible for preventing (or otherwise reducing) the accumulation of dirt on the shoe outsole component (due to the presence of the wet material).

[0063] This disruption of the adhesion and / or adhesion of dirt is believed to be the mechanism responsible for preventing (or otherwise reducing) the accumulation of dirt on the shoe outsole component (due to the presence of the layered material). As can be appreciated, preventing the accumulation of dirt on the bottom of the footwear can improve the performance of the traction elements present on the shoe outsole component during wear on an unpaved surface, can prevent the footwear from gaining weight due to dirt accumulated during wear, can maintain the ball control performance of the footwear, and thus can provide significant benefits to the wearer compared to a footwear item in which the material is not present on the shoe outsole component.

[0064] In the case where the layered material (e.g., a hydrogel material in an outermost layer) swells, the swelling of the layered material can be observed as an increase in the material thickness, starting from the dry thickness of the layered material, through a series of intermediate thicknesses as additional water is absorbed, and ultimately reaching the saturated state thickness of the layered material, which is the average thickness of the layered material when completely saturated with water. For example, the saturated state thickness of a completely saturated layered material can be greater than 150 percent, greater than 200 percent, greater than 250 percent, greater than 300 percent, greater than 350 percent, greater than 400 percent, or greater than 500 percent of the dry thickness of the same layered material (e.g., a hydrogel material), as characterized by a swelling capacity test. The saturated state thickness of a completely saturated layered material can be from about 150 percent to 500 percent, from about 150 percent to 400 percent, from about 150 percent to 300 percent, or from about 200 percent to 300 percent of the dry thickness of the same layered material. Examples of suitable average thicknesses (referred to as the saturated state thickness) of the layered material in the wet state can be from about 0.2 millimeters to 10 millimeters, from about 0.2 millimeters to 5 millimeters, from about 0.2 millimeters to 2 millimeters, from about 0.25 millimeters to 2 millimeters, or from about 0.5 millimeters to 1 millimeter.

[0065] The layered material in pure form (e.g., the hydrogel material in the outermost layer) can have an increase in thickness of about 35% to 400%, about 50% to 300%, or about 100% to 200% at 1 hour, as characterized by the swelling ability test. In some additional embodiments, the layered material in pure form can have an increase in thickness of about 45% to 500%, about 100% to 400%, or about 150% to 300% at 24 hours. Accordingly, the outsole component film in pure form can have an increase in film volume of about 50% to 500%, about 75% to 400%, or about 100% to 300% at 1 hour.

[0066] The layered material (e.g., the hydrogel material in the outermost layer) can rapidly absorb water in contact with the layered material. For example, the layered material can absorb water from mud and wet grass, such as during a warm-up period before a competitive event. Alternatively (or additionally), the layered material can be pre-conditioned with water so that the layered material is partially or fully saturated, such as by spraying or soaking the layered material with water before use.

[0067] The layered material (e.g., the hydrogel material in the outermost layer) can exhibit a total water absorption capacity of about 25% to 225% as measured over a 24-hour soak time using the component sampling procedure in the water absorption capacity test, as defined below. Alternatively, the total water absorption capacity exhibited by the layered material is in the range of about 30% to about 200%; alternatively, in the range of about 50% to about 150%; alternatively, in the range of about 75% to about 125%. For the purposes of this disclosure, the term "total water absorption capacity" is used to express the weight percentage of the amount of water absorbed by the layered material as a percentage of the weight of the dry layered material. The procedure for measuring the total water absorption capacity includes measuring the "dry" weight of the layered material, immersing the layered material in water at ambient temperature (~23 °C) for a predetermined amount of time, and then re-measuring the weight of the layered material when "wet". The procedure for measuring the total water absorption capacity according to the water absorption capacity test using the component sampling procedure is described below.

[0068] A layered material (e.g., a hydrogel material in an outermost layer) can also be characterized by a water absorption rate of from 10 grams per square meter per square root minute to 120 grams per square meter per square root minute, as measured, for example, using a material sampling procedure in a water absorption rate test. The water absorption rate is defined as the weight (in grams) of water absorbed by the elastic material per square meter per square root of the immersion time (square root minute). Optionally, the water absorption rate is in the range from about 12 grams per square meter per square root minute to about 100 grams per square meter per square root minute; optionally, in the range from about 25 grams per square meter per square root minute to about 90 grams per square meter per square root minute; optionally, up to about 60 grams per square meter per square root minute.

[0069] The total water absorption capacity and the water absorption rate can depend on the amount of the hydrogel material present in the layered material. The hydrogel material can be characterized by a water absorption capacity of from 50 percent to 2000 percent, as measured, for example, using a material sampling procedure in a water absorption capacity test. In this case, the water absorption capacity of the hydrogel material is determined based on the weight percentage of the water absorbed by the hydrogel material as a percentage of the weight of the dry hydrogel material. Optionally, the water absorption capacity exhibited by the hydrogel material is in the range from about 100 percent to about 1500 percent; optionally, in the range from about 300 percent to about 1200 percent.

[0070] Also as discussed above, in some aspects, the surface of the layered material (e.g., the hydrogel material in the outermost layer) preferably exhibits a hydrophilic property. The hydrophilic property of the surface of the layered material can be characterized by determining the static sessile drop contact angle of the surface of the layered material. Thus, in some instances, the surface of the layered material in the dry state has a static sessile drop contact angle (or dry contact angle) of less than 105 degrees, or less than 95 degrees, less than 85 degrees, as characterized by a contact angle test. The contact angle test can be performed on a sample obtained according to an article sampling procedure or a coextruded film sampling procedure. In some additional instances, the layered material in the dry state has a static sessile drop contact angle in the range from 60 degrees to 100 degrees, from 70 degrees to 100 degrees, or from 65 degrees to 95 degrees.

[0071] In other instances, the surface of a layered material in a wet state (e.g., a hydrogel material in an outermost layer) has a static sessile drop 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 additional instances, the wet surface has a static sessile drop contact angle in the range from 45 degrees to 75 degrees. In some cases, the dry-state static sessile drop contact angle of the surface is at least 10 degrees, at least 15 degrees, or at least 20 degrees greater than the wet-state static sessile drop contact angle of the surface, such as from 10 degrees to 40 degrees, from 10 degrees to 30 degrees, or from 10 degrees to 20 degrees.

[0072] The surface of a layered material (e.g., a hydrogel material in an outermost layer), including the surface of an article, can also exhibit a low coefficient of friction when the material is wet. Examples of suitable coefficients of friction (or dry coefficients of friction) for the layered material in a dry state are less than 1.5, such as in the range from 0.3 to 1.3 or from 0.3 to 0.7, as characterized by a coefficient of friction test. The coefficient of friction test can be performed on a sample obtained according to an article sampling procedure or a coextruded film sampling procedure. Examples of suitable coefficients of friction (or wet coefficients of friction) for the layered material in a wet state are less than 0.8 or less than 0.6, such as in the range from 0.05 to 0.6, from 0.1 to 0.6, or from 0.3 to 0.5. Additionally, the layered material can exhibit a decrease in its coefficient of friction from its dry state to its wet state, such as a decrease in the range from 15 percent to 90 percent or from 50 percent to 80 percent. In some cases, the dry coefficient of friction of the material is greater than the wet coefficient of friction, such as a value that is at least 0.3 or 0.5 higher, such as from 0.3 to 1.2 or from 0.5 to 1.

[0073] Furthermore, the compliance of a layered material (e.g., a hydrogel material in an outermost layer), including the compliance of an article containing the material, can be characterized based on the storage modulus of the layered material in a dry state (when equilibrated at 0% relative humidity (RH)) and in a partially wet state (e.g., when equilibrated at 50% RH or at 90% RH), as well as by the decrease in the storage modulus between its dry and wet states. In particular, the layered material can have a decrease in the storage modulus from the dry state storage modulus (ΔE’) relative to the wet state storage modulus. As the water concentration in the hydrogel-containing material increases, the decrease in the storage modulus corresponds to an increase in compliance because a given strain / deformation requires less stress.

[0074] The layered material (e.g., the hydrogel material in the outermost layer), relative to the dry-state storage modulus and as characterized by storage modulus testing using a pure film sampling process, exhibits a reduction in storage modulus of more than 20 percent, more than 40 percent, more than 60 percent, more than 75 percent, more than 90 percent, or more than 99 percent from its dry state to its wet state (50% RH).

[0075] In some additional aspects, the dry-state storage modulus of the layered material (e.g., the hydrogel material in the outermost layer) is greater than its wet-state (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, e.g., in the range 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 range 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. Additionally, the wet-state storage modulus can be in the range from 0.003 MPa to 100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.

[0076] The layered material (e.g., the hydrogel material in the outermost layer), relative to the dry-state storage modulus and as characterized by storage modulus testing using a pure film sampling process, can exhibit a reduction in storage modulus of more than 20 percent, more than 40 percent, more than 60 percent, more than 75 percent, more than 90 percent, or more than 99 percent from its dry state to its wet state (90% RH). The dry-state storage modulus of the layered material can be greater than its 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, e.g., in the range 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 range 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. Additionally, the wet-state storage modulus can be in the range from 0.003 MPa to 100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.

[0077] In addition to the reduction in storage modulus, a layered material (e.g., a hydrogel material in an out-facing layer) can also exhibit a decrease in its glass transition temperature from its dry state (when equilibrated at 0% relative humidity (RH)) to its wet state (when equilibrated at 90% RH). Without wishing to be bound by theory, it is believed that the water absorbed by the layered material plasticizes the layered material, which reduces its storage modulus and its glass transition temperature, rendering the layered material more compliant (e.g., compressible, expandable, and stretchable).

[0078] A layered material (e.g., a hydrogel material in an out-facing layer) can exhibit a decrease in glass transition temperature (ΔT g ) 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 state (0% RH) glass transition temperature to its wet state (90% RH) glass transition temperature, as characterized by glass transition temperature testing using a pure film sampling process or a pure material sampling process. For example, the decrease in glass transition temperature (ΔT g ) can be in the range from more than 5 degrees Celsius difference to 40 degrees Celsius difference, from more than 6 degrees Celsius to 50 degrees Celsius difference, from more than 10 degrees Celsius difference to 30 degrees Celsius difference, from more than 30 degrees Celsius difference to 45 degrees Celsius difference, or from 15 degrees Celsius difference to 20 degrees Celsius difference. The layered material can also exhibit a dry state glass transition temperature in the range from -40 degrees Celsius to -80 degrees Celsius or from -40 degrees Celsius to -60 degrees Celsius.

[0079] Optionally (or additionally), the decrease in glass transition temperature (ΔT g ) can be in the range from 5 degrees Celsius difference to 40 degrees Celsius difference, from 10 degrees Celsius difference to 30 degrees Celsius difference, or from 15 degrees Celsius difference to 20 degrees Celsius difference. The layered material can also exhibit a dry state glass transition temperature in the range from -40 degrees Celsius to -80 degrees Celsius or from -40 degrees Celsius to -60 degrees Celsius.

[0080] The total amount of water that a layered material (e.g., a hydrogel material in an out-facing layer) can absorb depends on a variety of factors, such as its composition (e.g., its hydrophilicity), its crosslink density, its thickness, and the like. The water absorption capacity and water absorption rate of the layered material depend on the size and shape of its geometric structure and are generally based on the same factors. In contrast, the water absorption rate is instantaneous and can be defined kinetically. The three main factors for the water absorption rate of the layered material present in a given part geometry include time, thickness, and the exposed surface area available for absorbing water.

[0081] Even though the layered material (e.g., a hydrogel material in an outermost layer) can swell as it absorbs water and transitions between different material states having corresponding thicknesses, the saturated state thickness of the layered material is preferably maintained less than the length of the attachment friction element. This selection of the layered material and its corresponding dry thickness and saturated thickness ensures that the attachment friction element can continue to provide ground-engaging attachment friction during use of the footwear, even when the layered material is in a fully swollen state. For example, the average gap difference between the length of the attachment friction element and the saturated state thickness of the layered material is desirably at least 8 millimeters. For example, the average gap distance can be at least 9 millimeters, 10 millimeters, or greater.

[0082] Also as mentioned above, in addition to swelling, the compliance of the layered material (e.g., a hydrogel material in an outermost layer) can increase from relatively rigid (i.e., dry state) to progressively stretchable, compressible, and extensible (i.e., wet state). Thus, the increased compliance can allow the layered material to be easily compressed under an applied pressure (e.g., during foot strike on the ground), and in some aspects, allow at least a portion of its retained water to be quickly expelled (depending on the degree of compression). While not wishing to be bound by theory, it is believed that this separate compression compliance, separate water expulsion, or a combination of both can disrupt the adhesion and / or sticking of dirt, which prevents or otherwise reduces the accumulation of dirt.

[0083] In addition to quickly expelling water, in certain instances, when the compression is released (e.g., during liftoff from a foot strike during normal use), the compressed layered material is capable of quickly reabsorbing water. Thus, during use in a wet or moist environment (e.g., muddy or wet ground), the layered material can dynamically expel and repeatedly absorb water during successive foot strikes, particularly from a wet surface. Accordingly, the layered material can continue to prevent dirt accumulation (e.g., throughout a competitive event) over an extended period of time, particularly when there is ground water available for reabsorption.

[0084] In addition to effectively preventing dirt accumulation, it has also been found that the layered material (e.g., a hydrogel material in an outermost layer) is also durable enough for its intended use on the ground-engaging side of a footwear item. The useful life of the layered material (and the footwear incorporating the layered material) is at least 10 hours, 20 hours, 50 hours, 100 hours, 120 hours, or 150 hours of wear.

[0085] As used herein, the terms "take up", "taking up", "uptake", "uptaking" and like terms refer to the drawing of a liquid (e.g., water) from an external source into a layered material (e.g., a hydrogel material in an out-facing layer), such as by absorption, adsorption or both. Further, as briefly mentioned above, the term "water" refers to an aqueous liquid, which can be pure water or can be an aqueous carrier having a lesser amount of dissolved, dispersed or otherwise suspended materials (e.g., particles, other liquids and the like).

[0086] Aspects of the present disclosure have been generally described above, and additional details of the hydrogel material, thermoplastic hot melt adhesive material, elastic material, joining material and regrind material will be provided.

[0087] As described herein, the out-facing layer includes a first material. The first material includes a hydrogel material. The hydrogel material can include a polymer hydrogel. The polymer hydrogel can include a polyurethane hydrogel or consist essentially of a polyurethane hydrogel. The polyurethane hydrogel is prepared from one or more diisocyanates and one or more hydrophilic diols. In addition to the hydrophilic diols, the polymer can also include hydrophobic diols. Polymerization is typically carried out using approximately equal amounts of diol and diisocyanate. Examples of hydrophilic diols are polyethylene glycol or copolymers of ethylene glycol and propylene glycol. The diisocyanate can be selected from a variety of aliphatic diisocyanates or aromatic diisocyanates. The hydrophobicity of the resulting polymer is determined by the amount and type of hydrophilic diol, the type and amount of hydrophobic diol, and the type and amount of diisocyanate. Additional details regarding polyurethanes are provided herein.

[0088] The polymer hydrogel can include a polyurea hydrogel or consist essentially of a polyurea hydrogel. The polyurea hydrogel is prepared from one or more diisocyanates and one or more hydrophilic diamines. In addition to the hydrophilic diamines, the polymer can also include hydrophobic diamines. Polymerization is typically carried out using approximately equal amounts of diamine and diisocyanate. Typical hydrophilic diamines are amine-terminated polyethylene oxide and amine-terminated copolymers of polyethylene oxide / polypropylene. Examples are the diamines sold by Huntsman (The Woodlands, TX, USA). The diisocyanate can be selected from a variety of aliphatic diisocyanates or aromatic diisocyanates. The hydrophobicity of the resulting polymer is determined by the amount and type of hydrophilic diamine, the type and amount of hydrophobic diamine, and the type and amount of diisocyanate. Additional details regarding polyureas are provided herein.

[0089] Polymer hydrogels can include polyester hydrogels or consist essentially of polyester hydrogels. Polyester hydrogels can be prepared from dicarboxylic acids (or dicarboxylic acid derivatives) and diols, where some or all of the diols are hydrophilic diols. Examples of hydrophilic diols are polyethylene glycol or copolymers of ethylene glycol and propylene glycol. A second hydrophobic diol can also be used to control the polarity of the final polymer. One or more diacids that can be aromatic or aliphatic can be used. Of particular interest are block polyesters prepared from hydrophilic diols and lactones of hydroxy acids. The lactone is polymerized at each end of the hydrophilic diol to produce a triblock polymer. Additionally, these triblock segments can be linked together to produce a multiblock polymer by reaction with a dicarboxylic acid. Additional details regarding polyesters are provided herein.

[0090] Polymer hydrogels can include polycarbonate hydrogels or consist essentially of polycarbonate hydrogels. Polycarbonates are typically prepared by reacting diols with phosgene or a carbonate diester. When some or all of the diols are hydrophilic diols, hydrophilic polycarbonates are produced. Examples of hydrophilic diols are hydroxy-terminated polyethers of ethylene glycol or polyethers of ethylene glycol and propylene glycol. A second hydrophobic diol can also be included to control the polarity of the final polymer. Additional details regarding polycarbonates are provided herein.

[0091] In an embodiment, polymer hydrogels can include polyetheramide hydrogels or consist essentially of polyetheramide hydrogels. Polyetheramides are prepared from dicarboxylic acids (or dicarboxylic acid derivatives) and polyether diamines (polyethers terminated with amino groups at each end). Hydrophilic amine-terminated polyethers produce hydrophilic polymers that will be swollen by water. Hydrophobic diamines can be used in combination with hydrophilic diamines to control the hydrophilicity of the final polymer. Additionally, the type of dicarboxylic acid segment can be selected to control the polarity and physical properties of the polymer. Typical hydrophilic diamines are amine-terminated polyethylene oxide and amine-terminated copolymers of polyethylene oxide / polypropylene. An example is the diamine sold by Huntsman (The Woodlands, TX, USA). Additional details regarding polyetheramides are provided herein.

[0092] A polymeric hydrogel can comprise or consist essentially of: a hydrogel formed from an addition polymer of ethylenically unsaturated monomers. The addition polymer of ethylenically unsaturated monomers can be a random polymer. The polymer is prepared by free radical polymerization of one or more hydrophilic ethylenically unsaturated monomers and one or more hydrophobic ethylenically unsaturated monomers. Examples of hydrophilic monomers are acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, sodium p-styrenesulfonate, [3-(methacryloylamino)propyl]trimethylammonium chloride, 2-hydroxyethyl methacrylate, acrylamide, N,N-dimethylacrylamide, 2-vinylpyrrolidone, (meth)acrylates of polyethylene glycol and (meth)acrylates of monomethyl ethers of polyethylene glycol. Examples of hydrophobic monomers are (meth)acrylates of C1 to C4 alcohols, polystyrene, polystyrene methacrylate macromonomers and mono(meth)acrylates of siloxanes. The water absorption and physical properties are adjusted by selecting the monomers and the amounts of each monomer type. Additional details regarding ethylenically unsaturated monomers are provided herein.

[0093] The addition polymer of ethylenically unsaturated monomers can be a comb polymer. A comb polymer is produced when one of the monomers is a macromonomer (an oligomer having an ethylenically unsaturated group at one end). In one case, the main chain is hydrophilic while the side chains are hydrophobic. Alternatively, the comb main chain can be hydrophobic while the side chains are hydrophilic. An example is a main chain of a hydrophobic monomer such as styrene with a methacrylate monoester of polyethylene glycol.

[0094] The addition polymer of ethylenically unsaturated monomers can be a block polymer. Block polymers of ethylenically unsaturated monomers can be prepared by methods such as anionic polymerization or controlled free radical polymerization. A hydrogel is produced when the polymer has both hydrophilic and hydrophobic blocks. The polymer can be a diblock polymer (A-B), a triblock polymer (A-B-A) or a multiblock polymer. A triblock polymer having hydrophobic end blocks and a hydrophilic central block is most useful for such applications. Block polymers can also be prepared by other means. Partial hydrolysis of a polyacrylonitrile polymer produces a multiblock polymer having hydrophilic domains (hydrolyzed) separated by hydrophobic domains (unhydrolyzed), such that the partially hydrolyzed polymer acts as a hydrogel. Hydrolysis converts acrylonitrile units to hydrophilic acrylamide units or acrylic acid units in a multiblock pattern.

[0095] A polymeric hydrogel can comprise or consist essentially of: a hydrogel formed from a copolymer. Copolymers combine two or more types of polymers within each polymer chain to achieve a desired set of properties. Of particular interest are polyurethane / polyurea copolymers, polyurethane / polyester copolymers, polyester / polycarbonate copolymers.

[0096] As described herein, the layered material includes a second material or layer that includes a thermoplastic hot melt adhesive layer. The thermoplastic hot melt adhesive can be a polymer composition that can include one or more thermoplastic polymers. The thermoplastic polymers can include one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and polyolefins, as well as copolymers or combinations thereof of each polymer, such as those described herein. The thermoplastic polymers can include one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and combinations thereof. Additional details regarding the thermoplastic polymers are provided herein.

[0097] The thermoplastic hot melt adhesive can be a low processing temperature polymer composition that includes one or more polyesters. The low processing temperature polymer composition can include one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and polyolefins, as well as copolymers or combinations thereof of each polymer, such as those described herein having a low processing temperature. The thermoplastic polymers can include one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and combinations thereof, as well as copolymers or combinations thereof of each polymer, such as those described herein having a low processing temperature. Additional details regarding the thermoplastic polymers are provided herein.

[0098] The low processing temperature polymer composition can include one or more thermoplastic polymers and can exhibit a heat distortion temperature T hd , Vicat softening temperature T vs , creep relaxation temperature T cr or melting temperature T m that is at least one of the melting temperatures T m (or melting point) of the polymer hydrogel. In the same or alternative aspects, the low processing temperature polymer composition can exhibit a heat distortion temperature T hd , Vicat softening temperature T vs , creep relaxation temperature T cr or melting temperature T m that is one or more of the melting temperatures T m , heat distortion temperature T hd , Vicat softening temperature T vs and creep relaxation temperature T cr of the polymer hydrogel. As used herein, "creep relaxation temperature T cr ", "Vicat softening temperature T vs ", "heat distortion temperature T hd " and "melting temperature T m " refer to the corresponding test methods described below in the section on property analysis and characterization procedures.

[0099] The low processing temperature polymer composition can exhibit a melting temperature T of about 135 °C or lower m (or melting point). The low processing temperature polymer composition can exhibit a melting temperature T of about 125 °C or lower m . In another aspect, the low processing temperature polymer composition can exhibit a melting temperature T of about 120 °C or lower m . The low processing temperature polymer composition can exhibit a melting temperature T ranging from about 80 °C to about 135 °C m . The low processing temperature polymer composition can exhibit a melting temperature T ranging from about 90 °C to about 120 °C m . The low processing temperature polymer composition can exhibit a melting temperature T ranging from about 100 °C to about 120 °C m .

[0100] The low processing temperature polymer composition can exhibit a glass transition temperature T of about 50 °C or lower g . The low processing temperature polymer composition can exhibit a glass transition temperature T of about 25 °C or lower g . The low processing temperature polymer composition can exhibit a glass transition temperature T of about 0 °C or lower g . In various aspects, the low processing temperature polymer composition can exhibit a glass transition temperature T ranging from about -55 °C to about 55 °C g . The low processing temperature polymer composition can exhibit a glass transition temperature T ranging from about -50 °C to about 0 °C g . The low processing temperature polymer composition can exhibit a glass transition temperature T ranging from about -30 °C to about -5 °C g . As used herein, the term "glass transition temperature T g " refers to the corresponding test method described below in the section on property analysis and characterization procedures.

[0101] Using a 2.16 kg test weight, the low processing temperature polymer composition can exhibit a melt flow index ranging from about 0.1 g / 10 minutes (min) to about 60 g / 10 min. In certain aspects, using a 2.16 kg test weight, the low processing temperature polymer composition can exhibit a melt flow index ranging from about 2 g / 10 min to about 50 g / 10 min. Using a 2.16 kg test weight, the low processing temperature polymer composition can exhibit a melt flow index ranging from about 5 g / 10 min to about 40 g / 10 min. Using a 2.16 kg test weight, the low processing temperature polymer composition can exhibit a melt flow index of about 25 g / 10 min. As used herein, the term "melt flow index" refers to the corresponding test method described below in the section on property analysis and characterization procedures.

[0102] The low processing temperature polymer composition can exhibit a melting enthalpy of at least 5 J / g or from about 8 J / g to about 45 J / g. The low processing temperature polymer composition can exhibit a melting enthalpy from about 10 J / g to about 30 J / g. The low processing temperature polymer composition can exhibit a melting enthalpy from about 15 J / g to about 25 J / g. As used herein, the term "melting enthalpy" refers to the corresponding test method described below in the section on property analysis and characterization procedures.

[0103] The layered material or article comprising the low processing temperature polymer composition can exhibit a modulus from about 1 megapascal to about 500 megapascals. The layered material or article comprising the low processing temperature polymer composition can exhibit a modulus from about 5 MPa to about 150 megapascals. The layered material or article comprising the low processing temperature polymer composition can exhibit a modulus from about 20 MPa to about 130 megapascals. The layered material or article comprising the low processing temperature polymer composition can exhibit a modulus from about 30 megapascals to about 120 megapascals. The layered material or article comprising the low processing temperature polymer composition can exhibit a modulus from about 40 megapascals to about 110 megapascals. As used herein, the term "modulus" refers to the corresponding test method described below in the section on property analysis and characterization procedures.

[0104] When the layered material or article comprising the low processing temperature polymer composition is brought to a temperature above the melting temperature T m of the low processing temperature polymer composition and then to a temperature below the melting temperature T m of the low processing temperature polymer composition, when tested at about 20 degrees Celsius and 1 A T m pressure, the resulting thermoformed material can exhibit a modulus from about 1 megapascal to about 500 megapascals. When the layered material or article comprising the low processing temperature polymer composition is brought to a temperature above the melting temperature T m of the low processing temperature polymer composition and then to a temperature below the melting temperature T m of the low processing temperature polymer composition, when tested at about 20 degrees Celsius and 1 A T m pressure, the resulting thermoformed material can exhibit a modulus from about 5 megapascals to about 150 megapascals. When the layered material or article comprising the low processing temperature polymer composition is brought to a temperature above the melting temperature T m of the low processing temperature polymer composition and then to a temperature below the melting temperature T m of the low processing temperature polymer composition, when at about 20 degrees Celsius and 1 A T mDuring the pressure test, the thermoformed material obtained can exhibit a modulus ranging from about 20 MPa to about 130 MPa. Heating a laminated material or article comprising a low processing temperature polymer composition to a temperature above the melting temperature T m and then to a temperature below the melting temperature T m of the low processing temperature polymer composition, when at about 20 degrees Celsius and a pressure test of 1 A T m the thermoformed material obtained can exhibit a modulus ranging from about 30 MPa to about 120 MPa. Heating a laminated material comprising a low processing temperature polymer composition to a temperature above the melting temperature T m and then to a temperature below the melting temperature T m of the low processing temperature polymer composition, when at about 20 degrees Celsius and a pressure test of 1 A T m the thermoformed material obtained can exhibit a modulus ranging from about 40 MPa to about 110 MPa.

[0105] When a laminated material or article comprising a low processing temperature polymer composition is present in a textile and has been heated to a temperature above the melting temperature T m of the low processing temperature polymer composition and then to a temperature below the melting temperature T m of the low processing temperature polymer composition, when at about 20 degrees Celsius and a pressure test of 1 A T m the thermoformed material obtained exhibits cold sole material flexing from about 5,000 cycles to about 500,000 cycles. When a laminated material or article comprising a low processing temperature polymer composition is present in a textile and has been heated to a temperature above the melting temperature T m of the low processing temperature polymer composition and then to a temperature below the melting temperature T m of the low processing temperature polymer composition, when at about 20 degrees Celsius and a pressure test of 1 A T m the thermoformed material obtained exhibits cold sole material flexing from about 10,000 cycles to about 300,000 cycles. When a laminated material or article comprising a low processing temperature polymer composition is present in a textile and has been heated to a temperature above the melting temperature T m of the low processing temperature polymer composition and then to a temperature below the melting temperature T m of the low processing temperature polymer composition, when at about 20 degrees Celsius and a pressure test of 1 A T m the thermoformed material obtained exhibits cold sole material flexing of at least about 150,000 cycles. As used herein, the term "cold sole material flexing" refers to the corresponding test method described below in the section on property analysis and characterization procedures.

[0106] As described herein, the layered material can optionally include one or more inner layers, and one type of inner layer is a connecting layer. The connecting layer can include a connecting material that includes at least one thermoplastic material. When present in the layered material, the connecting layer joins together different layers that can be different from each other. The connecting layer can be formed by extrusion, coextrusion, solvent casting, granulation, injection molding, lamination, spraying, and similar processes. Based on the corresponding chemical structure of the polymer, the corresponding concentration of the polymer, the corresponding number average molecular weight of the polymer, the corresponding average degree of crosslinking of the polymer, the corresponding melting point of the polymer, and similar properties, including any combination thereof, the materials of the layers joined by the connecting layer can be different from each other. The connecting layer can include materials present in one or both of the layers joined by the connecting material.

[0107] In some cases, the joined layers without a connecting layer can delaminate from each other. It has been found that the presence of a connecting layer reduces delamination in cases where delamination is a concern. The connecting layer can be a layer that helps to fix or bond two or more layers to each other. In aspects, the connecting layer can be made of one or more layers and can provide good interfacial bonding with the layers to which it is joined, as discussed below.

[0108] The connecting material can include one or more polymeric materials, such as thermoplastic elastomers; thermosetting polymers; elastic polymers; silicone polymers; natural and synthetic rubbers; composite materials comprising polymers reinforced with carbon fibers and / or glass; natural leather; metals such as aluminum, steel, and the like; and combinations thereof.

[0109] The connecting material can be a thermoplastic polymer composition that can include one or more thermoplastic polymers. The thermoplastic polymers can include one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and polyolefins, as well as copolymers or combinations of each polymer, such as those described herein. The thermoplastic polymers can include one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and combinations thereof. Additional details regarding the thermoplastic polymers are provided herein. The connecting material includes aliphatic thermoplastic polyurethane (TPU) or consists essentially of aliphatic thermoplastic polyurethane (TPU), such as those described herein. An example of such TPU is available under the trade names "Bio TPU" and "Pearlthane ECO TPU", such as Pearlthane TM ECO D12T80, Pearlthane TM ECOD12T80E, Pearlthane TM ECO D12T85, Pearlthane TMECO D12T90, Pearlthane TM ECO D12T90E, Pearlthane TM ECO 12T95 and Pearlthane TM ECO D12T55D (Lubrizol, Countryside IL) is commercially available. The tie material can also include ethylene vinyl alcohol copolymer (EVOH).

[0110] As described herein, the layered material can optionally include one or more inner layers, one type of inner layer being an elastomeric layer. The elastomeric layer can include an elastomeric material. The elastomeric material can be a thermoplastic polymer composition that can include one or more thermoplastic polymers. The thermoplastic polymers can include one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and polyolefins, and copolymers or combinations thereof of each polymer, such as those described herein. The thermoplastic polymers can include one or more polymers selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, and combinations thereof. Additional details regarding the thermoplastic polymers are provided herein.

[0111] As described herein, the layered material can optionally include one or more inner layers, one type of inner layer being a regrind layer. The regrind layer can be formed by obtaining recycled, ground, or regrind scrap from one or more of the outermost layer, the thermoplastic hot melt adhesive layer, the tie layer, or the elastomeric layer, and scrap from other polymer sources such as scrap obtained from other parts of fabricated articles (e.g., shoes, clothing, sports equipment, and the like).

[0112] The scrap can be pelletized to form a pelletized material and used to form the regrind layer. This pelletizing step can be carried out under conditions that minimize water absorption of the material. For example, it has been found that a pelletizer under the trade name "EREMA" (EREMA, Engineering Recycling Maschinen und Anlagen Ges.m.b.H., Unterfeldstraβe 3, 4052 Ansfelden, Austria) minimizes water absorption during the pelletizing process. The pelletizing can be carried out under conditions such that the pelletized material absorbs less than about 50 percent by weight of water, as characterized by a water absorption test using the article sampling procedure discussed below. After pelletizing, the pelletized material can be extruded or coextruded to form the regrind layer or to form a coextruded structure that includes one or more of the outermost layer, the thermoplastic hot melt adhesive layer, the tie layer, or the elastomeric layer.

[0113] The regrind layer can be formed by grinding a composition comprising a polymer hydrogel under conditions such that the polymer hydrogel is maintained at a grinding temperature below its melting point to form a ground material. Additionally or alternatively, the polymer hydrogel can be maintained at a grinding temperature below the softening point of the polymer hydrogel.

[0114] Aspects of the hydrogel material, elastomeric material, thermoplastic hot melt adhesive, and tie layer have now been described, and additional details regarding the thermoplastic polymer are provided. The thermoplastic polymer can include polymers of the same or different types of monomers (e.g., homopolymers and copolymers, including terpolymers). The thermoplastic polymer can include different monomers randomly distributed in the polymer (e.g., random copolymers). The term "polymer" refers to a polymeric molecule having one or more monomeric species that can be the same or different. When the monomeric species are the same, the polymer can be referred to as a homopolymer, and when the monomers are different, the polymer can be referred to as a copolymer. The term "copolymer" is a polymer having two or more types of monomeric species and includes terpolymers (i.e., copolymers having three monomeric species). A "monomer" can include different functional groups or segments, but for simplicity, it is generally referred to as a monomer.

[0115] For example, the thermoplastic polymer can be a polymer having repeating polymer units (hard segments) of a relatively hard, same chemical structure (segment) and repeating polymer segments (soft segments) that are relatively soft. The polymer has repeating hard and soft segments, and physical crosslinks can be present within the segments or between the segments, or both within and between the segments. Specific examples of hard segments include isocyanate segments. Specific examples of soft segments include alkoxy groups such as polyether segments and polyester segments. As used herein, a polymer segment can be referred to as a particular type of polymer segment, such as, for example, an isocyanate segment (e.g., a diisocyanate segment), an alkoxy polyamide segment (e.g., a polyether segment, a polyester segment), and the like. It should be understood that the chemical structure of the segment is derived from the described chemical structure. For example, an isocyanate segment is a polymeric unit that includes an isocyanate functional group. When referring to a polymer segment of a specific chemical structure, the polymer can contain up to 10 mol% of segments of other chemical structures. For example, as used herein, a polyether segment should be understood to include up to 10 mol% of non-polyether segments.

[0116] The thermoplastic polymer can be thermoplastic polyurethane (also known as "TPU"). The thermoplastic polyurethane can be a thermoplastic polyurethane polymer. The thermoplastic polyurethane polymer can include hard segments and soft segments. The hard segments can include isocyanate segments (such as diisocyanate segments) or consist of isocyanate segments (such as diisocyanate segments). In the same or alternative aspects, the soft segments can include alkoxy segments (such as, polyether segments, or polyester segments, or a combination of polyether segments and polyester segments) or consist of alkoxy segments. The thermoplastic material can include an elastomeric thermoplastic polyurethane having repeating hard segments and repeating soft segments or consist essentially of such an elastomeric thermoplastic polyurethane.

[0117] Thermoplastic polyurethane

[0118] One or more of the thermoplastic polyurethanes can be produced by polymerizing one or more isocyanates with one or more polyols to produce polymer chains having urethane bonds (-N(CO)O-), as shown below in Formula 1, where the isocyanates each preferably contain two or more isocyanate (-NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups per molecule (although monofunctional isocyanates can also optionally be included, for example as chain terminating units).

[0119]

[0120] In these embodiments, each R 1 and R 2 is independently an aliphatic segment or an aromatic segment. Optionally, each R 2 can be a hydrophilic segment.

[0121] Additionally, the isocyanate can also be chain extended with one or more chain extenders to bridge two or more isocyanates. This can produce a polyurethane polymer chain as shown below in Formula 2, where R 3 includes the chain extender. As with each R 1 and R 2 each R 3 is independently an aliphatic segment or an aromatic segment.

[0122]

[0123] Each segment R 1 in Formula 1 and Formula 2 or the first segment can independently include a straight-chain or branched C 3-30a segment and can be aliphatic, aromatic, or include 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 having delocalized π electrons. In contrast, the term "aromatic" refers to a cyclically conjugated ring system having delocalized π electrons that exhibits greater stability than a hypothetical ring system having localized π electrons.

[0124] Based on the total weight of the reactant monomers, each segment R 1 can be present in an amount of from 5 percent to 85 percent by weight, from 5 percent to 70 percent by weight, or from 10 percent to 50 percent by weight.

[0125] In an aliphatic embodiment (from an aliphatic isocyanate), each segment R 1 can include a straight-chain aliphatic group, a branched-chain aliphatic group, an alicyclic group, or a combination thereof. For example, each segment R 1 can include a straight-chain or branched-chain C 3-20 alkylene segment (e.g., C 4-15 alkylene or C 6-10 alkylene), one or more C 3-8 subcycloalkylene segments (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinations thereof.

[0126] Examples of suitable aliphatic diisocyanates for producing polyurethane polymer chains include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), dicyclohexylmethane diisocyanate (HMDI), 2,2,4-trimethylhexamethylene diisocyanate (T m DI), dicyclohexylmethane diisocyanate, dicyclohexylmethyl tricyclodecane diisocyanate, norbornane diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), dodecane diisocyanate, lysine diisocyanate, and combinations thereof.

[0127] The diisocyanate segments can include aliphatic diisocyanate segments. Most of the diisocyanate segments include aliphatic diisocyanate segments. At least 90 percent of the diisocyanate segments are aliphatic diisocyanate segments. The diisocyanate segments consist essentially of aliphatic diisocyanate segments. 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) straight-chain aliphatic diisocyanate segments. At least 80 percent of the aliphatic diisocyanate segments are aliphatic diisocyanate segments without side chains. The aliphatic diisocyanate segments include C 2 -C 10 straight-chain aliphatic diisocyanate segments.

[0128] In aromatic embodiments (from aromatic isocyanates), each segment R 1 can include one or more aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl, phenanthryl, biphenylenyl, indanyl, indenyl, anthryl, and fluorenyl. Unless otherwise indicated, the aromatic groups can be unsubstituted aromatic groups or substituted aromatic groups and can also include heteroaromatic groups. "Heteroaromatic" refers to a monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ring system in which one to four ring atoms are selected from oxygen, nitrogen, or sulfur and the remaining ring atoms are carbon, and in which the ring system is attached to the remainder of the molecule through any ring atom. Examples of suitable heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, furyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, and benzothiazolyl.

[0129] Examples of suitable aromatic diisocyanates for producing polyurethane polymer chains include toluene diisocyanate (TDI), the TDI adduct with trimethylolpropane (T m P), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (T m XDI), hydrogenated xylene diisocyanate (HXDI), naphthalene-1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3,3'-dimethyl diphenyl-4,4'-diisocyanate (DDDI), 4,4'-dibenzyl diisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate, and combinations thereof. In some embodiments, the polymer chains are substantially free of aromatic groups.

[0130] Polyurethane polymer chains can be produced from diisocyanates including HMDI, TDI, MDI, H 12 aliphatic compounds, and combinations thereof. For example, the low processing temperature polymer compositions of the present disclosure can include one or more polyurethane polymer chains produced from diisocyanates including HMDI, TDI, MDI, H 12 aliphatic compounds, and combinations thereof.

[0131] According to the present disclosure, crosslinked polyurethane chains (e.g., partially crosslinked polyurethane polymers retaining thermoplastic properties) or polyurethane chains that can be crosslinked can be used. It is possible to produce crosslinked or crosslinkable polyurethane polymer chains using polyfunctional isocyanates. Examples of suitable triisocyanates for producing polyurethane polymer chains include TDI, HDI, and IPDI adducts with trimethylolpropane (T m P), uretdione (i.e., dimerized isocyanate), polymeric MDI, and combinations thereof.

[0132] The segment R in Formula 2 3 can include straight-chain or branched C 2 -C 10 segments based on the specific chain extender polyol used and can be, for example, aliphatic, aromatic, or polyether. Examples of suitable chain extender polyols for producing 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-cyclohexanedimethanol, 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) ether of xylene-a,a-diol, and combinations thereof.

[0133] The segment R in Formula 1 and Formula 2 2 can include polyether groups, polyester groups, polycarbonate groups, aliphatic groups, or aromatic groups. Based on the total weight of the reactant monomers, each segment R 2 can be present in an amount of 5 percent to 85 percent by weight, 5 percent to 70 percent by weight, or 10 percent to 50 percent by weight.

[0134] In some instances, at least one R of the thermoplastic polyurethane 2The segment includes a polyether segment (i.e., a segment having one or more ether groups). Suitable polyethers include, but are not limited to, polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF), polytetramethylene oxide (PT m O), and combinations thereof. As used herein, the term "alkyl" refers to straight-chain and branched-chain saturated hydrocarbon groups containing from one to thirty carbon atoms, such as from one to twenty carbon atoms or from one to ten carbon atoms. The term C n means that the alkyl group has "n" carbon atoms. For example, C 4 alkyl refers to an alkyl group having 4 carbon atoms. C 1-7 alkyl refers to an alkyl group having a carbon atom number covering the entire range (i.e., from 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, the alkyl group can be an unsubstituted alkyl group or a substituted alkyl group.

[0135] In some examples of the thermoplastic polyurethane, the at least one R 2 segment includes a polyester segment. The polyester segment can be derived from the poly-esterification of one or more dihydroxy alcohols (such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol, 1,5-diethylene glycol, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with one or more dicarboxylic acids (such as adipic acid, succinic acid, sebacic acid, suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, thiodipropionic acid, and citraconic acid, and combinations thereof). The polyester can also be derived from polycarbonate prepolymers, such as poly(hexamethylene carbonate) glycol, poly(propylene carbonate) glycol, poly(tetramethylene carbonate) glycol, and poly(nonanemethylene carbonate) glycol. Suitable polyesters can include, for example, polyethylene adipate (PEA), poly(1,4-butylene adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), polycaprolactone, polyhexamethylene carbonate, poly(propylene carbonate), poly(tetramethylene carbonate), poly(nonanemethylene carbonate), and combinations thereof.

[0136] In a plurality of thermoplastic polyurethanes, at least one R 2 segment comprises a polycarbonate segment. The polycarbonate segment can be derived from the reaction of one or more dihydroxy alcohols (such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol, 1,5-diethylene glycol, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with ethylene carbonate.

[0137] In a number of instances, the aliphatic group is straight-chain and can include, for example, C 1-20 alkylene chain or C 1-20 alkenylene chain (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, vinylidene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). The term "alkylene" refers to a divalent hydrocarbon. The term C n means that the alkylene group has "n" carbon atoms. For example, C 1-6 alkylene refers to an alkylene group having, for example, 1, 2, 3, 4, 5, or 6 carbon atoms. The term "alkenylene" refers to a divalent hydrocarbon having at least one double bond.

[0138] Aliphatic and aromatic groups can be substituted by one or more relatively hydrophilic and / or charged side groups. Hydrophilic side groups include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) hydroxyl groups. Hydrophilic side groups include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In some cases, hydrophilic side groups include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, an aliphatic group can include one or more polyacrylic acid groups. In some cases, hydrophilic side groups include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, hydrophilic side groups include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) phosphate groups. In some instances, hydrophilic side groups include one or more ammonium groups (e.g., tertiary ammonium and / or quaternary ammonium). In other instances, hydrophilic side groups include one or more zwitterionic groups (e.g., betaines such as poly(carboxybetaine) (pCB) and phosphonium ammonium groups such as phosphatidylcholine groups).

[0139] R 2 The segment can include charged groups capable of binding counterions to ionically crosslink the thermoplastic polymer and form an ionomer. For example, R 2 is an aliphatic or aromatic group having an amino side group, a carboxylate side group, a sulfonate side group, a phosphate side group, an ammonium side group or a zwitterionic side group or a combination thereof.

[0140] In various cases, when a hydrophilic side group is present, the "hydrophilic" side group is at least one polyether group, such as two polyether groups. In other cases, the hydrophilic side group is at least one polyester. In various cases, the hydrophilic side group is a polylactone group (e.g., polyvinylpyrrolidone). Each carbon atom in the hydrophilic side group can optionally be substituted by, for example, C 1-6 alkyl groups. Aliphatic and aromatic groups can be graft polymer groups, where the side groups are homopolymer groups (e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

[0141] The hydrophilic side group is a polyether group (e.g., a polyethylene oxide group, a polyethylene glycol group), a polyvinylpyrrolidone group, a polyacrylic acid group or a combination thereof.

[0142] The hydrophilic side group can be attached to the aliphatic or aromatic group via a linker. The linker can be any bifunctional small molecule capable of attaching the hydrophilic side group to the aliphatic or aromatic group (e.g., C1-20 )。For example, the linking group can include a diisocyanate group as previously described herein, which forms a urethane bond when linked to a hydrophilic side group and to an aliphatic or aromatic group. The linking group can be 4,4'-diphenylmethane diisocyanate (MDI), as shown below.

[0143]

[0144] In some exemplary aspects, the hydrophilic side group is a poly(ethylene oxide) group, and the linking group is MDI, as shown below.

[0145]

[0146] In some cases, the hydrophilic side group is functionalized to enable it to optionally bind to an aliphatic or aromatic group through a linking group. For example, when the hydrophilic side group includes an olefin group, the olefin group can undergo a Michael addition with a thiol-containing bifunctional molecule (i.e., a molecule having a second reactive group such as a hydroxyl group or an amino group) to produce a hydrophilic group that can react with the polymer backbone using the second reactive group, optionally through a linking group. For example, when the hydrophilic side group is a polyvinylpyrrolidone group, it can react with the thiol group on mercaptoethanol to produce a hydroxyl-functionalized polyvinylpyrrolidone, as shown below.

[0147]

[0148] At least one R 2 segment can include a poly(tetramethylene oxide) group. At least one R 2 segment can include an aliphatic polyol group functionalized with a poly(ethylene oxide) group or a polyvinylpyrrolidone group, such as the polyols described in European Patent No. 2462908. For example, the R 2 segment can be derived from the reaction product of a polyol (e.g., pentaerythritol or 2,2,3-trihydroxypropanol) with MDI-derived methoxypolyethylene glycol (to obtain a compound as shown in Formula 6 or Formula 7) or with MDI-derived polyvinylpyrrolidone (to obtain a compound as shown in Formula 8 or Formula 9), where the MDI-derived methoxypolyethylene glycol and MDI-derived polyvinylpyrrolidone have previously reacted with mercaptoethanol, as shown below.

[0149]

[0150] In a variety of cases, at least one R 2 is a polysiloxane. In these cases, R 2It can be derived from a siloxane monomer of Formula 10, such as the siloxane monomers disclosed in U.S. Patent No. 5,969,076, which is hereby incorporated by reference:

[0151]

[0152] wherein: a is from 1 to 10 or greater (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10); each R 4 is independently hydrogen, C 1-18 alkyl, C 2-18 alkenyl, aryl, or polyether; and each R 5 is independently C 1-10 alkylene, polyether, or polyurethane.

[0153] Each R 4 can independently be H, C 1-10 alkyl, C 2-10 alkenyl, C 1-6 aryl, polyethylene, polypropylene, or polybutene group. For example, each R 4 can independently be selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, vinyl, propenyl, phenyl, and polyethylene group.

[0154] Each R 5 can independently include a C 1-10 alkylene group (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, or decylene group). In other cases, each R 5 is a polyether group (e.g., polyethylene, polypropylene, or polybutene group). In various cases, each R 5 is a polyurethane group.

[0155] Optionally, in some aspects, the polyurethane can contain at least partially crosslinked polymer network, which contains polymer chains as derivatives of polyurethane. In such a case, it should be understood that the crosslinking level is such that the polyurethane retains thermoplastic properties (i.e., the crosslinked thermoplastic polyurethane can be softened or melted and re-cured under the processing conditions described herein). As shown in Formula 11 and Formula 12 below, the crosslinked polymer network can be produced by polymerizing one or more isocyanates with one or more polyamino compounds, polysulfhydryl compounds, or combinations thereof:

[0156]

[0157] The variables are as described above. Additionally, the isocyanate can also be chain extended with one or more polyamine or polythiol chain extenders to bridge two or more isocyanates, such as those described previously for the polyurethanes of Formula 2.

[0158] As described herein, thermoplastic polyurethanes can be physically crosslinked by, for example, nonpolar or polar interactions between urethane or carbamate groups (hard segments) on the polymer. Component R in Formula 1 1 and component R in Formula 2 1 and R 3 can form a polymer portion commonly referred to as the "hard segment", and component R 2 forms a polymer portion commonly referred to as the "soft segment". The soft segment can be covalently bonded to the hard segment. In some instances, a thermoplastic polyurethane having physically crosslinked hard and soft segments can be a hydrophilic thermoplastic polyurethane (i.e., a thermoplastic polyurethane comprising hydrophilic groups as disclosed herein).

[0159] Thermoplastic polyamide

[0160] The thermoplastic polymer can include a thermoplastic polyamide. The thermoplastic polyamide can be a polyamide homopolymer having repeating polyamide chain segments of the same chemical structure. Alternatively, the polyamide can include a number of polyamide chain segments having different polyamide chemical structures (e.g., polyamide 6 chain segments, polyamide 11 chain segments, polyamide 12 chain segments, polyamide 66 chain segments, etc.). The polyamide chain segments having different chemical structures can be arranged randomly or can be arranged as repeating blocks.

[0161] The thermoplastic polymer can be a block copolymer polyamide. For example, the block copolymer polyamide can have repeating hard segments and repeating soft segments. The hard segments can include polyamide chain segments, and the soft segments can include non-polyamide chain segments. The thermoplastic polymer can be an elastomeric thermoplastic copolymer polyamide that comprises or consists of a block copolymer polyamide having repeating hard segments and repeating soft segments. In a block copolymer comprising a block copolymer having repeating hard and soft segments, physical crosslinking can be present within the segments or between the segments, or both within and between the segments.

[0162] The thermoplastic polyamide can be a copolyamide (i.e., a copolymer comprising polyamide segments and non-polyamide segments). The polyamide segments of the copolyamide can comprise or consist of the following: polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, or any combination thereof. The polyamide segments of the copolyamide can be arranged randomly or can be arranged as repeating segments. In certain instances, the polyamide segments can comprise or consist of the following: polyamide 6 segments, or polyamide 12 segments, or both polyamide 6 segments and polyamide 12 segments. In instances where the polyamide segments of the copolyamide comprise polyamide 6 segments and polyamide 12 segments, the segments can be arranged randomly. The non-polyamide segments of the copolyamide can comprise or consist of the following: polyether segments, polyester segments, or both polyether segments and polyester segments. The copolyamide can be a copolyamide or can be a random copolyamide. The thermoplastic copolyamide can be formed by the polycondensation of a polyamide oligomer or prepolymer with a second oligomer prepolymer to form a copolyamide (i.e., a copolymer comprising polyamide segments). Optionally, the second prepolymer can be a hydrophilic prepolymer.

[0163] The polyamide segments of the thermoplastic polyamide per se or of the 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 segments contain amide bonds (-(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 the thermoplastic polyamide can be the same or different.

[0164] The polyamide segments of the thermoplastic polyamide or thermoplastic copolyamide are derived from the polycondensation of lactams and / or amino acids and include amide segments having the structure shown in Formula 13, wherein R 6 is a polyamide segment derived from a lactam or an amino acid.

[0165]

[0166] R 6 can be derived from a lactam. In some cases, R 6 is derived from C 3-20 lactam, or C 4-15 lactam or C 6-12 lactam. For example, R 6 can be derived from caprolactam or laurolactam. In some cases, R 6 is derived from one or more amino acids. In various cases, R 6 is derived from C 4-25 amino acid, or C 5-20 amino acid or C 8-15 amino acid. For example, R 6It may be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

[0167] Optionally, in order to increase the relative hydrophilicity degree of the thermoplastic copolyamide, Formula 13 may include a polyamide-polyether block copolymer segment, as shown below:

[0168]

[0169] where m is from 3 to 20, and n is from 1 to 8. In some exemplary aspects, m is from 4 to 15 or from 6 to 12 (e.g., 6, 7, 8, 9, 10, 11 or 12), and n is 1, 2 or 3. For example, m may be 11 or 12, and n may be 1 or 3. The polyamide segment of the thermoplastic polyamide or thermoplastic copolyamide is derived from the condensation of a diamino compound with a dicarboxylic acid or its activated form, and includes an amide segment having the structure shown in Formula 15 below, where R 7 is a polyamide segment derived from a diamino compound, and R 8 is a segment derived from a dicarboxylic acid compound:

[0170]

[0171] R 7 may be derived from a diamino compound, which includes an aliphatic group having C 4-15 carbon atoms, or C 5-10 carbon atoms, or C 6-9 carbon atoms. The diamino compound may include an aromatic group, such as phenyl, naphthyl, xylenyl and tolyl. R 7 The suitable diamino compounds from which it may be derived include, but are not limited to, hexamethylenediamine (HMD), tetramethylenediamine, trimethylhexamethylenediamine (T m MD), meta-xylenediamine (MXD) and 1,5-pentamine diamine. R 8 may be derived from a dicarboxylic acid or its activated form, including an aliphatic group having C 4-15 carbon atoms, or C 5-12 carbon atoms, or C 6-10 carbon atoms. In some cases, the dicarboxylic acid or its activated form from which R 8 may be derived includes an aromatic group, such as phenyl, naphthyl, xylenyl and tolyl groups. R 8 The suitable carboxylic acids or their activated forms from which it may be derived include, but are not limited to, adipic acid, sebacic acid, terephthalic acid and isophthalic acid. The polymer chain is substantially free of aromatic groups.

[0172] Each polyamide segment of the thermoplastic polyamide (including thermoplastic copolyamide) can be independently derived from a polyamide prepolymer selected from the group consisting of 12-aminolauric acid, caprolactam, hexamethylenediamine, and adipic acid.

[0173] The thermoplastic polyamide includes or consists of a thermoplastic poly(ether-block-amide). The thermoplastic poly(ether-block-amide) can be formed by polycondensation of a carboxylic acid-terminated polyamide prepolymer and a hydroxyl-terminated polyether prepolymer to form a thermoplastic poly(ether-block-amide), as shown in Formula 16:

[0174]

[0175] The disclosed poly(ether-block-amide) polymers are prepared by polycondensation of a polyamide block having reactive ends and a polyether block having reactive ends. Examples include but are not limited to: 1) a polyamide block having diamine chain ends and a polyoxyalkylene block having carboxyl chain ends; 2) a polyamide block having dicarboxyl chain ends and a polyoxyalkylene block having diamine chain ends, the polyoxyalkylene block having diamine chain ends being obtained by cyanoethylation and hydrogenation of an α,ω-polyoxyalkylene known as a polyether diol; 3) a polyamide block having dicarboxyl chain ends and a polyether diol, and in this particular case, the product obtained is a polyether ester amide. The polyamide block of the 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 ether (PTMO), and combinations thereof.

[0176] The disclosed poly(ether-block-amide) polymers include those polymers comprising a polyamide block having dicarboxyl chain ends, the polyamide block having dicarboxyl chain ends being derived from the condensation of an α,ω-aminocarboxylic acid, a lactam, or a dicarboxylic acid and a diamine in the presence of a chain-limiting dicarboxylic acid. In this type of poly(ether-block-amide) polymer, an α,ω-aminocarboxylic acid such as aminoundecanoic acid can be used; a lactam such as caprolactam or lauryl lactam can be used; a dicarboxylic acid such as adipic acid, sebacic acid, or dodecanedioic acid can be used; and a diamine such as hexamethylenediamine can be used; or various combinations of any of the foregoing. The copolymer can comprise a polyamide block that includes polyamide 12 or polyamide 6.

[0177] The disclosed poly(ether-block-amide) polymers include those polymers comprising a polyamide block and are of low mass, i.e., they have an M from 400 to 1000 n, the polyamide block-containing polymer is derived from the condensation of one or more α,ω-amino carboxylic acids and / or one or more lactams containing from 6 to 12 carbon atoms in the presence of a dicarboxylic acid containing from 4 to 12 carbon atoms. In this type of poly(ether block amide) polymer, α,ω-amino carboxylic acids such as undecanoic acid or dodecanoic acid can be used; dicarboxylic acids such as adipic acid, sebacic acid, isophthalic acid, succinic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, sodium or lithium salts of sulfoisophthalic acid, dimer fatty acids (these dimer fatty acids have a dimer content of at least 98 percent and are preferably hydrogenated), and dodecanedioic acid HOOC—(CH 2 ) 10 —COOH can be used; and lactams such as caprolactam and lauryllactam can be used; or any combination of the foregoing. The copolymer includes a polyamide block obtained by condensing lauryllactam in the presence of adipic acid or dodecanedioic acid, and wherein the M of 750 n has a melting point of 127 °C - 130 °C. The various components of the polyamide block and their proportions can be selected so as to obtain a melting point of less than 150 °C and advantageously between 90 °C and 135 °C.

[0178] The disclosed poly(ether block amide) polymers include those polymers containing a polyamide block, said polyamide block-containing polymer being derived from the condensation of at least one α,ω-amino carboxylic acid (or lactam), at least one diamine, and at least one dicarboxylic acid. In this type of copolymer, the α,ω-amino carboxylic acid, lactam, and dicarboxylic acid can be selected from those described above, and diamines such as aliphatic diamines containing from 6 to 12 atoms, and can be acyclic and / or saturated cyclic, such as but not limited to hexamethylenediamine, piperazine, 1-aminoethylpiperazine, diaminopropylpiperazine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyol, isophoronediamine (IPD), methylpentamethylenediamine (MPDM), bis(aminocyclohexyl)methane (BACM), and bis(3-methyl-4-aminocyclohexyl)methane (BMACM) can be used.

[0179] The components of the polyamide block and their proportions can be selected so as to obtain a melting point of less than 150 °C and advantageously between 90 °C and 135 °C. The various components of the polyamide block and their proportions can be selected so as to obtain a melting point of less than 150 °C and advantageously between 90 °C and 135 °C.

[0180] 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. 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 3000 g / mol, and from about 200 g / mol to about 3,000 g / mol. 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% to about 80 mol%). The polyether block can be present in an amount from about 10 wt% to about 50 wt%, from about 20 wt% to about 40 wt%, and from about 30 wt% to about 40 wt%. The polyamide block can be present in an amount from about 50 wt% to about 90 wt%, from about 60 wt% to about 80 wt%, and from about 70 wt% to about 90 wt%.

[0181] The polyether block can contain units different from ethylene oxide units, such as, for example, propylene oxide or polytetrahydrofuran (which results in polybutylene glycol sequences). PEG blocks, i.e., blocks consisting of ethylene oxide units; PPG blocks, i.e., blocks consisting of propylene oxide units; and PT m G blocks, i.e., blocks consisting of tetramethylene glycol units (also known as polytetrahydrofuran) can also be used simultaneously. PPG blocks or P T m G blocks are advantageously used. The amount of the polyether block in these copolymers containing polyamide blocks and polyether blocks can be from about 10 wt% to about 50 wt% and from about 35 wt% to about 50 wt% of the copolymer.

[0182] Copolymers containing polyamide blocks and polyether blocks can be prepared by any means for attaching polyamide blocks and polyether blocks. In practice, essentially two processes are used, one is a two-step process, and the other is a one-step process.

[0183] In a two-step process, first a polyamide block with dicarboxylic acid chain ends is prepared, and then in a second step, these polyamide blocks are linked to a polyether block. The polyamide block with dicarboxylic acid chain ends is derived from the condensation of a polyamide precursor in the presence of a chain terminator dicarboxylic acid. If the polyamide precursor is only a lactam or an α,ω-aminocarboxylic acid, a dicarboxylic acid is added. If the precursor already includes a dicarboxylic acid, this is used in excess relative to the stoichiometry of the diamine. The reaction typically occurs between 180 degrees Celsius and 300 degrees Celsius, preferably between 200 degrees Celsius and 290 degrees Celsius, and the pressure in the reactor is set between 5 bar and 30 bar and maintained for about 2 hours to 3 hours. The pressure in the reactor is slowly reduced to atmospheric pressure, and then the excess water is distilled off, for example for one hour or two hours.

[0184] After the polyamide with carboxylic acid end groups has been prepared, then a polyether, a polyol and a catalyst are added. The total amount of polyether can be divided into one or more portions and added in one or more portions, and the same can be done for the catalyst. First, the polyether is added, and the reaction of the OH end groups of the polyether and the polyol with the COOH end groups of the polyamide begins, where ester bonds are formed and water is eliminated. As much water as possible is removed from the reaction mixture by distillation, and then the catalyst is introduced to complete the linking of the polyamide block with the polyether block. This second step occurs under stirring, preferably under a vacuum of at least 50 mbar (5000 Pa), at a temperature at which the reactants and the copolymer obtained are in a molten state. By way of example, this temperature can be between 100 degrees Celsius and 400 degrees Celsius, and typically between 200 degrees Celsius and 250 degrees Celsius. The reaction is monitored by measuring the torque exerted by the polymer melt on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the torque or the target power. The catalyst is defined as any product that promotes the linking of the polyamide block with the polyether block by esterification. Advantageously, the catalyst is a derivative of a metal (M) selected from the group formed by titanium, zirconium and hafnium. The derivative can be prepared from a tetraalkoxide conforming to the general formula M(OR) 4 where M represents titanium, zirconium or hafnium, and R, which can be the same or different, represents a straight-chain or branched alkyl group having from 1 to 24 carbon atoms.

[0185] The catalyst may comprise a salt of a metal (M), in particular a salt of (M) with an organic acid, and a complex salt of an oxide and / or hydroxide of (M) with an organic acid. The organic acid may be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, and crotonic acid. Acetic acid and propionic acid are particularly preferred. M may be zirconium, and such salts are referred to as zirconyl salts, for example, commercially available products sold under the name zirconyl acetate.

[0186] The weight ratio of the catalyst varies from about 0.01 percent to about 5 percent of the weight of the mixture of the dicarboxylic acid polyamide, the polyether diol, and the polyol. The weight ratio of the catalyst varies from about 0.05 percent to about 2 percent of the weight of the mixture of the dicarboxylic acid polyamide, the polyether diol, and the polyol.

[0187] In a one-step process, the polyamide precursor, the chain terminator, and the polyether are blended together; then what is obtained is a polymer having polyether blocks and polyamide blocks of substantially very variable lengths, but also a variety of reactants that have reacted randomly and are randomly distributed along the polymer chain. They are the same reactants and the same catalyst as in the two-step process described above. If the polyamide precursor is only lactam, it is advantageous to add a small amount of water. The copolymer substantially has the same polyether blocks and the same polyamide blocks, but also a small fraction of a variety of reactants that have reacted randomly and are randomly distributed along the polymer chain. As in the first step of the two-step process described above, the reactor is closed and heated with stirring. The determined pressure is between 5 bar and 30 bar. When the pressure no longer changes, the reactor is placed under reduced pressure while still maintaining vigorous stirring of the molten reactants. The reaction is monitored as previously in the case of the two-step process.

[0188] An appropriate ratio of polyamide blocks to polyether blocks can be found in a single poly(ether block amide), or blends of two or more poly(ether block amides) of different compositions can be used with an appropriate average composition. It may be useful to blend a block copolymer with a high level of polyamide groups with a block copolymer with a higher level of polyether blocks to produce a blend having an average polyether block level of from about 20 wt% to 40 wt%, and preferably from about 30 wt% to 35 wt%, of the total blend of poly(amide-block-ether) copolymer. The copolymer comprises a blend of two different poly(ether-block-amides), the blend comprising at least one block copolymer having a polyether block level of less than about 35 wt% and a second poly(ether-block-amide) having a polyether block level of at least about 45 wt%.

[0189] The thermoplastic polymer is a polyamide or a poly(ether-block-amide) which, when determined according to ASTM D3418-97 as described below, has a melting temperature (T m ) of from about 90 degrees Celsius to about 120 degrees Celsius. The thermoplastic polymer is a polyamide or a poly(ether-block-amide) which, when determined according to ASTM D3418-97 as described below, has a melting temperature (T m ) of from about 93 degrees Celsius to about 99 degrees Celsius. The thermoplastic polymer can be a polyamide or a poly(ether-block-amide) which, when determined according to ASTM D3418-97 as described below, has a melting temperature (T m ) of from about 112 degrees Celsius to about 118 degrees Celsius. The thermoplastic polymer can be a polyamide or a poly(ether-block-amide) which, when determined according to ASTM D3418-97 as described below, has a melting temperature of about 90 degrees Celsius, about 91 degrees Celsius, about 92 degrees Celsius, about 93 degrees Celsius, about 94 degrees Celsius, about 95 degrees Celsius, about 96 degrees Celsius, about 97 degrees Celsius, about 98 degrees Celsius, about 99 degrees Celsius, about 100 degrees Celsius, about 101 degrees Celsius, about 102 degrees Celsius, about 103 degrees Celsius, about 104 degrees Celsius, about 105 degrees Celsius, about 106 degrees Celsius, about 107 degrees Celsius, about 108 degrees Celsius, about 109 degrees Celsius, about 110 degrees Celsius, about 111 degrees Celsius, about 112 degrees Celsius, about 113 degrees Celsius, about 114 degrees Celsius, about 115 degrees Celsius, about 116 degrees Celsius, about 117 degrees Celsius, about 118 degrees Celsius, about 119 degrees Celsius, about 120 degrees Celsius, any range of melting temperature (T m ) values covered by any of the foregoing values, or any combination of the foregoing melting temperature (T m ) values. m ) The thermoplastic polymer can be a polyamide or a poly(ether-block-amide) which, when determined according to ASTM D3418-97 as described below, has a melting temperature (T m ) of from about 112 degrees Celsius to about 118 degrees Celsius. The thermoplastic polymer can be a polyamide or a poly(ether-block-amide) which, when determined according to ASTM D3418-97 as described below, has a melting temperature of about 90 degrees Celsius, about 91 degrees Celsius, about 92 degrees Celsius, about 93 degrees Celsius, about 94 degrees Celsius, about 95 degrees Celsius, about 96 degrees Celsius, about 97 degrees Celsius, about 98 degrees Celsius, about 99 degrees Celsius, about 100 degrees Celsius, about 101 degrees Celsius, about 102 degrees Celsius, about 103 degrees Celsius, about 104 degrees Celsius, about 105 degrees Celsius, about 106 degrees Celsius, about 107 degrees Celsius, about 108 degrees Celsius, about 109 degrees Celsius, about 110 degrees Celsius, about 111 degrees Celsius, about 112 degrees Celsius, about 113 degrees Celsius, about 114 degrees Celsius, about 115 degrees Celsius, about 116 degrees Celsius, about 117 degrees Celsius, about 118 degrees Celsius, about 119 degrees Celsius, about 120 degrees Celsius, any range of melting temperature (T m ) values covered by any of the foregoing values, or any combination of the foregoing melting temperature (T m ) values.

[0190] The thermoplastic polymer is a polyamide or poly(ether-block-amide) when prepared according to the AS T as described below. m It has a glass transition temperature (T) from about -20 degrees Celsius to about 30 degrees Celsius when measured with D3418-97. g ). The thermoplastic polymer is a polyamide or a poly(ether-block-amide), when the thermoplastic polymer is a polyamide or a poly(ether-block-amide) according to the AS T as described below. m It has a glass transition temperature (T) from about -13 degrees Celsius to about -7 degrees Celsius when measured with D3418-97. g ). The thermoplastic polymer is a polyamide or a poly(ether-block-amide), when the thermoplastic polymer is a polyamide or a poly(ether-block-amide) according to the AS T as described below. m It has a glass transition temperature (T) from about 17 degrees Celsius to about 23 degrees Celsius when measured with D3418-97. g ). The thermoplastic polymer may be a polyamide or a poly(ether-block-amide) when prepared according to AST as described below. m D3418-97, which has a temperature of about -20 degrees Celsius, about -19 degrees Celsius, about -18 degrees Celsius, about -17 degrees Celsius, about -16 degrees Celsius, about -15 degrees Celsius, about -14 degrees Celsius, about -13 degrees Celsius, about -12 degrees Celsius, about -10 degrees Celsius, about -9 degrees Celsius, about -8 degrees Celsius, about -7 degrees Celsius, about -6 degrees Celsius, about -5 degrees Celsius, about -4 degrees Celsius, about -3 degrees Celsius, about -2 degrees Celsius, about The glass transition temperatures (T) of about 10°C, about 0°C, about 1°C, about 2°C, about 3°C, about 4°C, about 5°C, about 6°C, about 7°C, about 8°C, about 9°C, about 10°C, about 11°C, about 12°C, about 13°C, about 14°C, about 15°C, about 16°C, about 17°C, about 18°C, about 19°C, about 20°C. g ), any range of glass transition temperature values ​​encompassed by any of the preceding values, or any combination of the preceding glass transition temperature values.

[0191] The thermoplastic polymer may be a polyamide or a poly(ether-block-amide) when prepared according to the AS T as described below. m D1238-13 has a melt flow index of from about 10 cubic centimeters per 10 minutes to about 30 cubic centimeters per 10 minutes when tested at 160 degrees Celsius using a 2.16 kg weight. The thermoplastic polymer may be a polyamide or a poly(ether-block-amide) when subjected to an AS T as described below. mWhen tested at 160 °C using a 2.16 kg weight, D1238-13 has a melt flow index of from about 22 cm³ / 10 min to about 28 cm³ / 10 min. The thermoplastic polymer is a polyamide or a poly(ether-block-amide), when according to AST as described below m When determined at 160 °C using a 2.16 kg weight, D1238-13 has a melt flow index of about 10 cm³ / 10 min, about 11 cm³ / 10 min, about 12 cm³ / 10 min, about 13 cm³ / 10 min, about 14 cm³ / 10 min, about 15 cm³ / 10 min, about 16 cm³ / 10 min, about 17 cm³ / 10 min, about 18 cm³ / 10 min, about 19 cm³ / 10 min, about 20 cm³ / 10 min, about 21 cm³ / 10 min, about 22 cm³ / 10 min, about 23 cm³ / 10 min, about 24 cm³ / 10 min, about 25 cm³ / 10 min, about 26 cm³ / 10 min, about 27 cm³ / 10 min, about 28 cm³ / 10 min, about 29 cm³ / 10 min, about 30 cm³ / 10 min, any range of melt flow index values covered by any of the foregoing values, or any combination of the foregoing melt flow index values.

[0192] The thermoplastic polymer is a polyamide or a poly(ether-block-amide) that has a cold sole material flex test result of from about 120,000 to about 180,000 when tested on a thermoformed substrate of the polyamide or poly(ether-block-amide) according to the cold sole material flex test described hereinafter. The thermoplastic polymer is a polyamide or a poly(ether-block-amide) that has a cold sole material flex test result of from about 140,000 to about 160,000 when tested on a thermoformed substrate of the polyamide or poly(ether-block-amide) according to the cold sole material flex test described hereinafter. The thermoplastic polymer is a polyamide or a poly(ether-block-amide) that has a cold sole material flex test result of from about 130,000 to about 170,000 when tested on a thermoformed substrate of the polyamide or poly(ether-block-amide) according to the cold sole material flex test described hereinafter. The thermoplastic polymer is a polyamide or a poly(ether-block-amide) that has a cold sole material flex test result of about 120,000, about 125,000, about 130,000, about 135,000, about 140,000, about 145,000, about 150,000, about 155,000, about 160,000, about 165,000, about 170,000, about 175,000, about 180,000 when tested on a thermoformed substrate of the polyamide or poly(ether-block-amide) according to the cold sole material flex test described hereinafter, any range of cold sole material flex test values covered by any of the foregoing values, or any combination of the foregoing cold sole material flex test values.

[0193] The thermoplastic polymer is a polyamide or a poly(ether-block-amide) that has a modulus of from about 5 megapascals to about 100 megapascals when determined on a thermoformed substrate under the modified conditions described hereinafter according to the ASTM m D412-98 standard test method for Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers-Tension. The thermoplastic polymer is a polyamide or a poly(ether-block-amide) that has a modulus of from about 20 megapascals to about 80 megapascals when determined on a thermoformed substrate under the modified conditions described hereinafter according to the ASTM m D412-98 standard test method for Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers-Tension. The thermoplastic polymer is a polyamide or a poly(ether-block-amide) that has a modulus of from about 20 megapascals to about 80 megapascals when determined on a thermoformed substrate under the modified conditions described hereinafter according to the ASTM mWhen tested on a thermoformed substrate of polyamide or poly(ether-block-amide) according to the D412-98 standard test method, it has a modulus of about 5 MPa, about 10 MPa, about 15 MPa, about 20 MPa, about 25 MPa, about 30 MPa, about 35 MPa, about 40 MPa, about 45 MPa, about 50 MPa, about 55 MPa, about 60 MPa, about 65 MPa, about 70 MPa, about 75 MPa, about 80 MPa, about 85 MPa, about 90 MPa, about 95 MPa, about 100 MPa, any range of modulus values covered by any of the foregoing values, or any combination of the foregoing modulus values.

[0194] The thermoplastic polymer is polyamide or poly(ether-block-amide), and when determined according to ASTM m D3418-97 as described below, it has a melting temperature (T m ) of about 115 °C; when determined according to ASTM m D3418-97 as described below, it has a glass transition temperature (T g ) of about -10 °C; when tested according to the cold sole material flexure test described below on a thermoformed substrate, it has a cold sole material flexure test result of about 150,000; and when determined on a thermoformed substrate according to the ASTM m D1238-13 using a 2.16 kg weight at 160 °C, it has a melt flow index of about 25 cm³ / 10 min; and when determined on a thermoformed substrate according to the modified ASTM m D412-98 standard test method for vulcanized rubber and thermoplastic rubber and thermoplastic elastomers - tension, it has a modulus ranging from about 25 MPa to about 70 MPa.

[0195] The thermoplastic polymer is polyamide or poly(ether-block-amide), and when determined according to ASTM m D3418-97 as described below, it has a melting temperature (T m ) of about 96 °C; when determined according to ASTM m D3418-97 as described below, it has a glass transition temperature (T g ) of about 20 °C; when tested according to the cold sole material flexure test described below on a thermoformed substrate, it has a cold sole material flexure test result of about 150,000; and when determined on a thermoformed substrate according to the modified ASTM m D412-98 standard test method for vulcanized rubber and thermoplastic rubber and thermoplastic elastomers - tension, it has a modulus less than or equal to about 10 MPa.

[0196] The thermoplastic polymer is a polyamide or a poly(ether-block-amide), a mixture of a first polyamide or poly(ether-block-amide) and a second polyamide or poly(ether-block-amide), the first polyamide or poly(ether-block-amide) having a melting temperature (T m ) of about 115 degrees Celsius when determined according to ASTM m D3418-97; a glass transition temperature (T m ) of about -10 degrees Celsius when determined according to ASTM g D3418-97; a melt flow index of about 25 cubic centimeters / 10 min when tested according to ASTM m D1238-13 at 160 degrees Celsius using a 2.16 kg weight; a cold sole material flex test result of about 150,000 when tested on a thermoformed substrate according to the cold sole material flex test described below; and a modulus of from about 25 megapascals to about 70 megapascals when determined on a thermoformed substrate according to the ASTM m D412-98 standard test method for vulcanized rubber and thermoplastic rubber and thermoplastic elastomers - tension, in the modified case described below; the second polyamide or poly(ether-block-amide) having a melting temperature (T m ) of about 96 degrees Celsius when determined according to ASTM m D3418-97; a glass transition temperature (T m ) of about 20 degrees Celsius when determined according to ASTM g D3418-97; a cold sole material flex test result of about 150,000 when tested on a thermoformed substrate according to the cold sole material flex test described below; and a modulus of less than or equal to about 10 megapascals when determined on a thermoformed substrate according to the ASTM m D412-98 standard test method for vulcanized rubber and thermoplastic rubber and thermoplastic elastomers - tension, in the modified case described below.

[0197] Exemplary commercially available copolymers include, but are not limited to, copolymers available under the following trade names or other similar materials produced by other various suppliers: (Evonik Industries); (Arkema), for example, product code H2694; (Arkema), for example product codes "PEBAX MH1657" and "PEBAX MV1074"; RNEW (Arkema); (EMS-Chemie AG).

[0198] In some instances, the thermoplastic polyamide is physically crosslinked by, for example, non-polar or polar interactions between the polyamide groups of the polymer. In instances where the thermoplastic polyamide is a thermoplastic copolyamide, the thermoplastic copolyamide can be physically crosslinked by interactions between the polyamide groups and optionally by interactions between the copolymer groups. When the thermoplastic copolyamide is physically crosslinked by interactions between the polyamide groups, the polyamide segments can form a polymer portion referred to as a "hard segment", and the copolymer segments can form a polymer portion referred to as a "soft segment". For example, when the thermoplastic copolyamide is a thermoplastic poly(ether-block-amide), the polyamide segments form the hard segment portion of the polymer, and the polyether segments can form the soft segment portion of the polymer. Thus, in some instances, the thermoplastic polymer can include a physically crosslinked polymer network having one or more polymer chains with amide bonds.

[0199] The polyamide segments of the thermoplastic copolyamide include polyamide-11 or polyamide-12, and the polyether segments are segments selected from the group consisting of polyethylene oxide segments, polypropylene oxide segments, and polytetramethylene oxide segments and combinations thereof.

[0200] Optionally, the thermoplastic polyamide can be partially covalently crosslinked as previously described herein. In such a case, it should be understood that the degree of crosslinking present in the thermoplastic polyamide is such that, when it is thermally processed in the form of a yarn or fiber to form the footwear articles of the present disclosure, the partially covalently crosslinked thermoplastic polyamide retains sufficient thermoplastic characteristics such that the partially covalently crosslinked thermoplastic polyamide softens or melts and re-cures during processing.

[0201] Thermoplastic polyester

[0202] The thermoplastic polymer may include a thermoplastic polyester. The thermoplastic polyester may be formed by the reaction of one or more carboxylic acids or their ester-forming derivatives with one or more divalent or polyvalent aliphatic alcohols, cycloaliphatic alcohols, aromatic alcohols, or araliphatic alcohols or bisphenols. The thermoplastic polyester may be a polyester homopolymer having repeating polyester segments of the same chemical structure. Alternatively, the polyester may include a number of polyester segments having different polyester chemical structures (such as polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, etc.). The polyester segments having different chemical structures may be arranged randomly or may be arranged as repeating blocks.

[0203] Exemplary carboxylic acids that can be used to prepare the thermoplastic polyester include, but are not limited to, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decane dicarboxylic acid, undecane dicarboxylic acid, terephthalic acid, isophthalic acid, alkyl-substituted or halogenated terephthalic acid, alkyl-substituted or halogenated isophthalic acid, nitro-terephthalic acid, 4,4'-diphenylether dicarboxylic acid, 4,4'-diphenylsulfide dicarboxylic acid, 4,4'-diphenylsulfone-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 the thermoplastic polyester 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-xylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and bisphenol A.

[0204] The thermoplastic polyester is polybutylene terephthalate (PBT), polytrimethylene terephthalate, polyhexamethylene terephthalate, poly(1,4-dimethylcyclohexane terephthalate), polyethylene terephthalate (PET), poly(ethylene isophthalate) (PEI), polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, or a blend or mixture of two or more of the foregoing.

[0205] The thermoplastic 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 the polyester segments and the non-polyester segments are aliphatic). Alternatively, the copolyester can contain aromatic segments. The polyester segments of the copolyester can include or consist of: polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, or any combination thereof. The polyester segments of the copolyester can be arranged randomly or can be arranged as repeating blocks.

[0206] For example, the thermoplastic polyester can be a block copolyester having repeating blocks (hard segments) of polymer units that are relatively hard and of the same chemical structure (segments) and repeating blocks (soft segments) of polymer segments that are relatively soft. In a block copolyester comprising a block copolyester having repeating hard segments and soft segments, physical crosslinking can be present within the blocks or between the blocks, or both within and between the blocks. In certain instances, the thermoplastic material can comprise or consist essentially of an elastomeric thermoplastic copolyester having repeating blocks of hard segments and repeating blocks of soft segments.

[0207] The non-polyester segments of the copolyester can include or consist of: polyether segments, polyamide segments, or both polyether segments and polyamide segments. The copolyester can be a block copolyester or can be a random copolyester. The thermoplastic copolyester can be formed by the polycondensation of a polyester oligomer or prepolymer with a second oligomer prepolymer to form a block copolyester. Optionally, the second prepolymer can be a hydrophilic prepolymer. For example, the copolyester can be formed by the polycondensation of terephthalic acid or naphthalenedicarboxylic acid 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 copolyester can include or consist of polyethylene terephthalate.

[0208] The thermoplastic polyester is a block copolymer including segments of one or more of the following: polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene terephthalate hexamethylene ester, poly(1,4-dimethylcyclohexane terephthalate), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylate (PAR), polybutylene naphthalate (PBN), and liquid crystal polyester. For example, suitable thermoplastic polyesters as block copolymers can be PET / PEI copolymers, polybutylene terephthalate / tetraethylene glycol copolymers, poly(oxyalkylene diimide diacid) / polybutylene terephthalate copolymers, or blends or mixtures of any of the foregoing copolymers.

[0209] The thermoplastic polyester is a biodegradable resin, such as a copolyester in which poly(α-hydroxy acids) such as polyglycolic acid or polylactic acid are included as main repeating units.

[0210] The disclosed thermoplastic polyester can be prepared by various polycondensation methods known to those skilled in the art, such as solution polymerization processes or melt polymerization processes.

[0211] Thermoplastic polyolefin

[0212] The thermoplastic polymer can include a thermoplastic polyolefin or consist essentially of a thermoplastic polyolefin. Useful exemplary thermoplastic polyolefins can include, but are not limited to, polyethylene, polypropylene, and thermoplastic olefin elastomers (e.g., metallocene-catalyzed block copolymers of ethylene and α-olefins having 4 to about 8 carbon atoms). Thermoplastic polyolefins are polymers including the following: polyethylene, ethylene-α-olefin copolymers, ethylene-propylene rubber (EPDM), polybutene, polyisobutene, poly-4-methylpent-1-ene, polyisoprene, polybutadiene, ethylene-methacrylic acid copolymers, and olefin elastomers, such as dynamically cross-linked polymers obtained from polypropylene (PP) and ethylene-propylene rubber (EPDM), and blends or mixtures of the foregoing. Additional exemplary thermoplastic polyolefins useful in the disclosed compositions, yarns, and fibers are polymers of cycloolefins such as cyclopentene or norbornene.

[0213] It should be understood that the optionally crosslinkable polyethylene includes various 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 foregoing polyethylenes. The polyethylene may also be a polyethylene copolymer derived from monomers of monoolefins and diolefins copolymerized with the following substances: vinyl, acrylic acid, methacrylic acid, ethyl acrylate, vinyl alcohol and / or vinyl acetate. The polyolefin copolymer including vinyl acetate-derived units may be a copolymer with a high vinyl acetate content, for example, a composition with more than about 50 wt% of vinyl acetate-derived units.

[0214] The thermoplastic polyolefins disclosed herein can be formed via free radical polymerization, cationic polymerization, and / or anionic polymerization by methods well known to those skilled in the art (e.g., using peroxide initiators, heat, and / or light). The disclosed thermoplastic polyolefins can be prepared by free radical polymerization under high pressure and at elevated temperatures. Alternatively, the thermoplastic polyolefins can be prepared by catalytic polymerization using a catalyst that typically contains one or more metals from Group IVb, Vb, VIb, or VIII of the periodic table. The catalyst typically has one or more ligands that can coordinate para or ortho to the Group IVb, Vb, VIb, or VIII metal, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls, and / or aryls. 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 the metal catalyst can be soluble or insoluble in the polymerization medium. The catalyst can be used alone for polymerization, or additional activators can be used, typically metal alkyls of Group Ia, IIa, and / or IIIa of the periodic table, metal hydrides, metal alkyl halides, metal alkoxides, or metal alkyloxanes. The activator can be conveniently modified with additional ester groups, ether groups, amine groups, or silyl ether groups.

[0215] Suitable thermoplastic polyolefins can be prepared by polymerization of monomers of monoolefins and diolefins 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.

[0216] Suitable ethylene-α-olefin copolymers can be obtained by copolymerizing ethylene with an α-olefin having 3 to 12 carbon atoms such as propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene or the like.

[0217] Suitable dynamically crosslinked polymers can be obtained by crosslinking a rubber component as a soft segment while physically dispersing a hard segment such as PP and a soft segment such as EPDM by using a kneading machine such as a Banbury mixer and a twin-screw extruder.

[0218] 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).

[0219] The thermoplastic polyolefin can be a copolymer of a suitable monoolefin monomer or a copolymer of a suitable monoolefin monomer and 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 / but-1-ene copolymers, propylene / isobutene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers, and copolymers of them with carbon monoxide or ethylene / acrylic acid copolymers, and salts (ionomers) thereof, and terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with each other and with the polymers mentioned in 1) above, such as polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA, and alternating or random polyalkylene / carbon monoxide copolymer and mixtures thereof with other polymers such as polyamides.

[0220] 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 foregoing polymers.

[0221] The polyolefin can be polypropylene. As used herein, the term "polypropylene" is intended to encompass any polymer composition comprising propylene monomers, either alone or as a mixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers (such as ethylene, butene, and the like). Such term also encompasses any different configurations and arrangements of the component monomers (such as atactic, syndiotactic, isotactic, etc.). Thus, as applied to fibers, the term is intended to encompass the actual long strands, tapes, sutures, and the like of the drawn polymer. Polypropylene can have any standard melt flow (by testing); however, standard fiber-grade polypropylene resins have a melt flow index range between about 1 and 1000.

[0222] The polyolefin can be polyethylene. As used herein, the term "polyethylene" is intended to encompass any polymer composition comprising ethylene monomers, either alone or as a mixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers (such as propylene, butene, and the like). Such term also encompasses any different configurations and arrangements of the component monomers (such as atactic, syndiotactic, isotactic, etc.). Thus, as applied to fibers, the term is intended to encompass the actual long strands, tapes, sutures, and the like of the drawn polymer. Polyethylene can have any standard melt flow (by testing); however, standard fiber-grade polyethylene resins have a melt flow index range between about 1 and 1000.

[0223] The hydrogel material, thermoplastic hot melt adhesive, joining material, elastic material, and / or regrind material can also comprise, consist of, or consist essentially of one or more processing aids. These processing aids can be independently selected from the group consisting of, but not limited to, curing agents, initiators, plasticizers, mold release agents, lubricants, antioxidants, flame retardants, dyes, pigments, reinforcing fillers and non-reinforcing fillers, fiber reinforcements, and light stabilizers.

[0224] Now that various aspects of the present disclosure have been described, additional details regarding methods of manufacturing and using the layered material are provided. A method of manufacturing an article (e.g., a footwear article, a clothing article, or a sports equipment article or a component of each) can include attaching a first component and the layered material as described herein to each other to form the article.

[0225] Regarding a footwear item, the first component can be an upper component for the footwear item and / or an outsole component for the footwear item. For example, the attaching step can include attaching an outsole component and a layered material such that an outward-facing layer of the layered material forms at least a portion of a side of the outsole component configured to face the ground. The footwear can include attachment friction elements, where the layered material is positioned between or within the attachment friction elements and optionally on sides of the attachment friction elements, but not on the side contacting the ground or surface. Additionally, the layered material can be positioned in a midfoot region (e.g., a midfoot plate) between attachment friction elements located in a toe region (e.g., a toe plate) and a heel region (e.g., a heel plate). Optionally, the layered material can be positioned in a midfoot region (e.g., a midfoot plate) between a toe region (e.g., a toe plate) and a heel region (e.g., a heel plate), where the attachment friction elements are positioned in the toe region, the heel region, or both.

[0226] A process for manufacturing an item can include placing a first element on a molding surface and then placing a thermoplastic hot melt adhesive layer in contact with at least a portion of the first element on the molding surface. When the thermoplastic hot melt adhesive layer contacts the component on the molding surface, the temperature of the thermoplastic hot melt adhesive layer is raised to a temperature at or above the activation temperature of the thermoplastic hot melt adhesive. After raising the temperature of the thermoplastic hot melt adhesive, while the thermoplastic hot melt adhesive layer remains in contact with the component on the molding surface, the temperature of the thermoplastic hot melt adhesive is lowered to a temperature below the melting temperature T m of the temperature. Accordingly, the layered material is bonded to the component, forming a bonded component.

[0227] The first element can be a first formed component, a first film, a first textile, a first yarn, and a first fiber. The first element includes a first element material. Raising the temperature of the thermoplastic hot melt adhesive to a temperature at or above its activation temperature includes raising the temperature of the first element to a temperature above the melting temperature T m of the temperature.

[0228] The activation temperature of the thermoplastic hot melt adhesive can be a temperature at or above the Vicat softening temperature T vs or the melting temperature T m of the temperature. The activation temperature of the thermoplastic hot melt adhesive can be a temperature lower than at least one of 1) the creep relaxation temperature T cr ; 2) the heat distortion temperature T hd ; or 3) the Vicat softening temperature T vs of the hydrogel material of the layered material.

[0229] The method can include manufacturing a component (e.g., a footwear item, a component of a footwear item, a clothing item, a component of a clothing item, a sports equipment item, or a component of a sports equipment item) by placing a layered material including an outer perimeter into a mold such that a portion of the layered material (e.g., the outermost layer) contacts a portion of the molding surface. The portion of the outermost layer can be constrained against the portion of the molding surface while flowing a second polymeric material into the mold. During the flowing, the temperature of the second polymeric material is at or above the activation temperature of the thermoplastic hot melt adhesive of the layered material. During the constraining, the temperature of the thermoplastic hot melt adhesive of the layered material is at or above the activation temperature of the thermoplastic hot melt adhesive. During the constraining and flowing, the temperature of the layered material is maintained below 1) the creep relaxation temperature T cr ; 2) the heat distortion temperature T hd ; or 3) the Vicat softening temperature T vs of at least one of the hydrogel materials of the layered material.

[0230] The layered material can be constrained or held against the molding surface using a holding mechanism, which can include but is not limited to a vacuum, one or more retractable pins, or a combination thereof. The constraining of the layered material against the mold can cause the portion of the layered material to assume the shape of the mold. The constraining can be applied to the outer perimeter of the layered material.

[0231] Next, the second polymeric material in the mold is cured, thereby bonding the second polymeric material to the thermoplastic hot melt adhesive layer and the outer perimeter of the layered material, thereby producing a component having a portion of the layered material that forms the outermost layer of the component. Subsequently, the component can be removed from the mold.

[0232] The activation temperature of the thermoplastic hot melt adhesive can be a temperature at or above the Vicat softening temperature T vs or the melting temperature T m of the thermoplastic hot melt adhesive.

[0233] The activation temperature of the thermoplastic hot melt adhesive is below 1) the creep relaxation temperature T cr ; 2) the heat distortion temperature T hd ; or 3) the Vicat softening temperature T vs of at least one of the hydrogel materials of the layered material.

[0234] A component (e.g., footwear) can include a layered material having an outer perimeter, wherein an outermost layer of the layered material is present on at least a portion of the side of the component, and a second polymeric material is attached to the thermoplastic hot melt adhesive layer and the outer perimeter of the layered material.

[0235] In one aspect, a method of manufacturing a footwear item can include attaching a shoe outsole component and a layered material to each other to form the item. The layered material includes an out-facing layer and a second layer opposite the out-facing layer. The out-facing layer includes a hydrogel material, and the second layer includes a thermoplastic hot melt adhesive material. The footwear item includes one or more attachment friction elements on a side of the footwear item configured to face the ground. The attaching step includes attaching the shoe outsole component and the layered material to each other such that the out-facing layer forms at least a portion of the side of the shoe outsole component configured to face the ground.

[0236] Property analysis and characterization procedures

[0237] The evaluation of the various properties and characteristics of the components and support materials described herein is carried out by the various test procedures described below.

[0238] Method for measuring creep relaxation temperature T cr ​

[0239] Creep relaxation temperature T cr Determined according to the exemplary technique described in U.S. Patent No. 5,866,058. Creep relaxation temperature T cr Is calculated as the temperature at which the stress relaxation modulus of the tested material is 10 percent of the stress relaxation modulus of the tested material at the curing temperature of the material, where the stress relaxation modulus is measured according to AS T m E328-02. The curing temperature is defined as the temperature at which, about 300 seconds after applying stress to the test material, the stress relaxation modulus shows little or no change or little or no creep, which can be observed by plotting the stress relaxation modulus (in Pa) as a function of temperature (in degrees Celsius).

[0240] Method for measuring the Vicat softening temperature T vs ​

[0241] Vicat softening temperature T vs According to AS T for the Vicat softening temperature of plastics mDetermined by the test methods described in detail in the D1525-09 standard test method, preferably using Load A and Rate A. Briefly, the Vicat softening temperature is the temperature at which a flat-ended needle penetrates a specimen to a depth of 1 mm under a specific load. This temperature reflects the softening point expected when the material is used in elevated temperature applications. It is considered to be the temperature at which the specimen is penetrated to a depth of 1 mm by a flat-ended needle with a circular or square cross-section of 1 square millimeter. For the Vicat A test, a load of 10 N is used, while for the Vicat B test, the load is 50 N. The test involves placing the test specimen in the test equipment such that the penetrating needle rests on a surface at least 1 mm from the edge. The load is applied to the specimen according to the requirements of the Vicat A test or Vicat B test. Then the specimen is lowered into an oil bath at 23 degrees Celsius. The bath is heated at a rate of 50 degrees Celsius per hour or 120 degrees Celsius per hour until the needle penetrates 1 mm. The thickness of the test specimen must be between 3 mm and 6.5 mm, and the width and length must be at least 10 mm. Up to three layers can be stacked to achieve the minimum thickness.

[0242] Method for measuring the heat distortion temperature T hd ​

[0243] The stress applied at 0.455 megapascals, according to ASTM for the deflection temperature of plastics under flexural load in the edgewise position m Determined by the test methods described in detail in the D648-16 standard test method for the heat deflection temperature T hd . Briefly, the heat deflection temperature is the temperature at which a polymer or plastic specimen deforms under a specific load. This property of a given plastic material is applied in many aspects of product design, product engineering, and manufacturing products using thermoplastic components. In the test method, a bar is placed under a deflection measuring device, and a load (0.455 megapascals) is placed on each specimen. According to ASTM m D648-16, then the specimen is lowered into a silicone oil bath, where the temperature is increased at a rate of 2 degrees Celsius per minute until the specimen deflects 0.25 mm. ASTM m Using a standard bar 5" x " x ”. The ISO edgewise test uses a bar 120 mm × 10 mm × 4 mm. The ISO flatwise testing uses a bar 80 mm × 10 mm × 4 mm.

[0244] Method for measuring melting temperature T m and glass transition temperature T g .

[0245] According to ASTM m D3418-97, the melting temperature T is determined using a commercially available differential scanning calorimeter (“DSC”)m and the glass transition temperature T g . Briefly, 10 - 15 grams of the sample are placed in an aluminum DSC pan, and then the lid is sealed with a press. The DSC is configured to scan from -100 °C to 225 °C at a heating rate of 20 °C per minute, hold at 225 °C for 2 minutes, and then cool to 25 °C at a rate of -10 °C per minute. The DSC curve generated by this scan is then analyzed using standard techniques to determine the glass transition temperature T g and the melting temperature T m .

[0246] Method for determining the melt flow index.

[0247] The melt flow index is determined using Procedure A described in the test method for the melt flow rate of thermoplastics by an extrusion plastometer as detailed in the ASTM m D1238 - 13 standard test method. Briefly, the melt flow index measures the rate at which a thermoplastic extrudes through an orifice at a specified temperature and load. In the test method, approximately 7 grams of the material are loaded into the barrel of the melt flow device, which has been heated to the temperature specified for the material. The weight specified for the material is applied to the plunger, and the molten material is forced through the die. The timed extrudate is collected and weighed. The melt flow value is calculated in g / 10 min.

[0248] Method for determining the flexure of cold sole materials.

[0249] The cold sole material flex test is determined according to the following test method. The purpose of this test is to evaluate the crack resistance of the sample when repeatedly flexed to 60 degrees in a cold environment. The thermoformed substrate of the material used for the test is sized to fit inside the flex test machine. Each material is tested as five separate samples. The flex test machine is capable of flexing the sample to 60 degrees at a rate of 100 + / - 5 cycles per minute. The mandrel diameter of the machine is 10 mm. Machines suitable for this test are Emerson AR - 6, Satra ST m 141F, Gotech GT - 7006, and Shin II Scientific SI - LTCO (DaeSung Scientific). The sample is inserted into the machine according to the specific parameters of the flex machine used. The machine is placed in a freezer set at -6 °C for the test. The motor is turned on to start flexing, and the flex cycles are counted until the sample cracks. Cracking of the sample means that the surface of the material is physically separated. A visible crease without a line actually penetrating the surface is not a crack. The sample is measured to the extent that it has cracked but not split in two.

[0250] Method for determining the modulus (substrate).

[0251] Determine the modulus of the thermoformed substrate of the material according to the test method detailed in the ASTM D412-98 Standard Test Method for Vulcanized Rubber and Thermoplastic Elastomers - Tension, with the following modifications. The sample size is ASTM D412-98 Die C, and the sample thickness used is 2.0 mm + / - 0.5 mm. The type of fixture used is a pneumatic fixture with a metal serrated grip face. The fixture distance used is 75 mm. The loading rate used is 500 mm / min. The modulus (initial) is calculated by obtaining the slope of the stress (MPa) versus strain in the initial linear region. m D412-98 Standard Test Method for Vulcanized Rubber and Thermoplastic Elastomers - Tension, with the following modifications. The sample size is ASTM D412-98 Die C, and the sample thickness used is 2.0 mm + / - 0.5 mm. The type of fixture used is a pneumatic fixture with a metal serrated grip face. The fixture distance used is 75 mm. The loading rate used is 500 mm / min. The modulus (initial) is calculated by obtaining the slope of the stress (MPa) versus strain in the initial linear region. m D412-98 Die C, and the sample thickness used is 2.0 mm + / - 0.5 mm. The type of fixture used is a pneumatic fixture with a metal serrated grip face. The fixture distance used is 75 mm. The loading rate used is 500 mm / min. The modulus (initial) is calculated by obtaining the slope of the stress (MPa) versus strain in the initial linear region.

[0252] Method for determining the modulus (yarn).

[0253] Determine the modulus of the yarn according to the test method detailed in EN ISO 2062 (Textiles - Yarns from packages) - Determination of the single-end breaking force and elongation at break using a constant rate of extension (CRE) tester, with the following modifications. The sample length used is 600 mm. The equipment used is Instron and Gotech fixtures. The fixture distance used is 250 mm. The preload is set to 5 g, and the loading rate used is 250 mm / min. The first meter of the yarn is discarded to avoid using damaged yarn. The modulus (initial) is calculated by obtaining the slope of the stress (MPa) versus strain in the initial linear region.

[0254] Method for determining toughness and elongation.

[0255] The tenacity and elongation of the yarn can be determined according to the test method detailed in EN ISO 2062, using a constant rate of extension tester with a preload set to 5 g to determine the single-end breaking force and elongation at break.

[0256] Method for determining the shrinkage rate.

[0257] The free shrinkage rate of the fiber and / or yarn can be determined by the following method. Cut the sample fiber or yarn into lengths of approximately 30 mm with minimal tension at approximately room temperature (e.g., 20 degrees Celsius). Place the cut samples in an oven at 50 degrees Celsius or 70 degrees Celsius for 90 seconds. Remove the samples from the oven and measure. Using the pre-oven and post-oven measurements of the samples, calculate the shrinkage percentage by dividing the post-oven measurement by the pre-oven measurement and multiplying by 100.

[0258] Method for determining the melting enthalpy.

[0259] The enthalpy of fusion is determined as follows. A 5 mg - 10 mg sample of the fiber or yarn is weighed to determine the sample mass, placed in an aluminum DSC pan, and then the lid of the DSC pan is sealed using a press. The DSC is configured to scan from -100 °C to 225 °C at a heating rate of 20 °C per minute, hold at 225 °C for 2 minutes, and then cool to room temperature (e.g., 25 °C) at a rate of -10 °C per minute. The enthalpy of fusion is calculated by integrating the area of the melting endothermic peak and normalizing by the sample mass.

[0260] Water absorption capacity test scheme

[0261] This test measures the water absorption capacity of the delaminated material of a sample (e.g., obtained using the footwear sampling procedure discussed above) after a predetermined soak duration. The sample is initially dried at 60 °C until there is no weight change for at least 30 - minute intervals of consecutive measurement periods (e.g., a 24 - hour drying period at 60 °C is typically a suitable duration). Then, the total weight (Wt, 干样品 ) of the dried sample is measured in grams. The dried sample is allowed to cool to 25 °C and is completely immersed in a deionized water bath maintained at 25 °C. After a given soak duration, the sample is removed from the deionized water bath, blotted dry with a cloth to remove surface water, and the total weight (Wt, 湿样品 ) of the soaked sample is measured in grams.

[0262] Any suitable soak duration can be used, where a 24 - hour soak duration is considered to simulate the saturation condition of the delaminated material of the present disclosure (i.e., the hydrophilic resin will be in its saturated state). Thus, as used herein, the expression "having a water absorption capacity at 5 minutes" refers to a 5 - minute soak duration, the expression "having a water absorption capacity at 1 hour" refers to a 1 - hour soak duration, the expression "having a water absorption capacity at 24 hours" refers to a 24 - hour soak duration, and the like. If no duration is indicated after the water absorption capacity value, the soak duration corresponds to a 24 - hour period.

[0263] As can be understood, the total weight of a sample obtained in accordance with the footwear sampling procedure includes the weight of the dry or soaked material (Wt, 干样品 or Wt, 湿样品 ), and the weight of the substrate (Wt, 基底 ) needs to be subtracted from the sample measurement.

[0264] The weight of the substrate (Wt, 基底) It is calculated using the surface area of the sample (e.g., 4.0 square centimeters), the average measured thickness of the layered material, and the average density of the layered material. Optionally, if the density of the material of the substrate is unknown or unavailable, the weight of the substrate (Wt, 基底 ) is determined by obtaining a second sample using the same sampling procedure as used for the original sample and having the same dimensions (surface area and film thickness / substrate thickness) as the original sample. Then, the material of the second sample is cut from the substrate of the second sample using a blade to provide a separated substrate. Then, the separated substrate is dried at 60 degrees Celsius for 24 hours, which can be done simultaneously with the drying of the original sample. Then, the weight of the separated substrate is measured in grams (Wt, 基底 ).

[0265] Then, the obtained substrate weight (Wt, 干样品 or Wt, 湿样品 ) is subtracted from the weights of the dried original sample and the soaked original sample (Wt, 基底 ) to provide the weights of the dried material and the soaked material (Wt, 干部件 or Wt, 湿部件 ), as depicted by Equation 1 and Equation 2.

[0266] Wt. 干部件 = Wt, 干样品 - Wt, 基底 (Equation 1)

[0267] Wt 湿部件 = Wt, 湿样品 - Wt, 基底 (Equation 2)

[0268] Then, the weight of the water absorbed by the component is provided by subtracting the weight of the dried component (Wt. 湿部件 ) from the weight of the soaked component (Wt 干部件 ), and then the weight of the water is divided by the weight of the dried component (Wt. 干部件 ) to provide the water absorption capacity at a given soaking duration in percentage, as depicted by Equation 3 below.

[0269]

[0270] For example, a water absorption capacity of 50% in 1 hour means that the weight of the soaked component after 1 hour of soaking is 1.5 times its dry weight. Similarly, a water absorption capacity of 500% in 24 hours means that the weight of the soaked component after 24 hours of soaking is 5 times more than its dry weight.

[0271] Water absorption rate test scheme

[0272] This test measures the water absorption rate of the delaminated material by modeling the weight gain over time of the sample using a one-dimensional diffusion model. The sample can be obtained using any of the sampling procedures including the footwear sampling procedure discussed above. The sample is dried at 60 degrees Celsius until there is no weight change for consecutive measurement intervals of at least 30 minutes (a 24-hour drying period at 60 degrees Celsius is typically a suitable duration). Then the total weight (Wt, 干样品 ) of the dried sample is measured in grams. Additionally, the average thickness of the components of the dried sample is measured for calculating the water absorption rate, as explained below.

[0273] The dried sample is allowed to cool to 25 degrees Celsius and is completely immersed in a deionized water bath maintained at 25 degrees Celsius. Between immersion durations of 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, and 25 minutes, the sample is removed from the deionized water bath, blotted dry with a cloth to remove surface water, and the total weight (Wt, 湿样品 ) of the immersed sample is measured, where "t" refers to a specific immersion duration data point (e.g., 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, or 25 minutes).

[0274] The exposed surface area of the immersed sample is also measured using calipers for determining the specific weight gain, as explained below. The exposed surface area refers to the surface area in contact with the deionized water when completely immersed in the bath. For samples obtained using the footwear sampling procedure, the sample has only one exposed major surface. For convenience, the surface area of the peripheral edges of the sample is ignored due to its relatively small size.

[0275] The measured sample is completely 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 completely 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 another minute of immersion before being measured at the 2-minute mark).

[0276] As discussed above, in the water absorption capacity test, the total weight of a sample obtained according to the footwear sampling procedure includes the weight of the dry or immersed material (Wt 湿部件 or Wt. 干部件 ) and the weight of the article or backing substrate (Wt, 基底 ). To determine the weight change of the material due to water absorption, the weight of the substrate (Wt, 基底 ) needs to be subtracted from the sample weight measurements. This can be done using the same procedure discussed above in the water absorption capacity test to provide the resulting material weight Wt for each immersion duration measurement.湿部件 and Wt. 干部件 .

[0277] Then, the specific weight gain (Ws t ) of water absorption from each soaked sample is calculated as the difference between the weight of the soaked sample (Wt 湿部件 ) and the weight of the initial dry sample (Wt. 干部件 ), where the resulting difference is then divided by the exposed surface area (A t ) of the soaked sample, as depicted in Equation 4.

[0278]

[0279] where t refers to a specific soak duration data point (e.g., 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, or 25 minutes), as mentioned above.

[0280] Then, the water absorption rate of the elastomeric material is determined as the slope of the specific weight gain (Ws t ) relative to the square root of time (in minutes), as determined by the least squares linear regression of the data points. For the elastomeric materials of the present disclosure, the curve of the specific weight gain (Ws t ) relative to the square root of time (in minutes) provides a generally linear initial slope (to provide the water absorption rate through linear regression analysis). However, after a certain period of time depending on the thickness of the part, the specific weight gain will slow down, indicating a decrease in the water absorption rate until a saturation state is reached. This is thought to be due to the fact that as water absorption approaches saturation, water diffuses sufficiently throughout the elastomeric material and will vary depending on the part thickness.

[0281] Accordingly, for parts having an average thickness of 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 start 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 having 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 has units of weight / (surface area - square root of time), such as grams / (m 2 - minute 1 / 2 ) or grams per square meter per √minute.

[0282] In addition, some component surfaces can exhibit surface phenomena that rapidly attract and retain water molecules (e.g., via surface hydrogen bonding or capillary action) without actually absorbing the water molecules into the membrane or substrate. Thus, for a 1-minute sample, and possibly for a 2-minute sample, samples of these membranes or substrates can show rapid specific weight gain. However, after that, further weight gain is negligible. Therefore, linear regression analysis is applicable only when the specific weight gain at the data points of 1 minute, 2 minutes, and 4 minutes continues to show an increase in water absorption. If not, the water absorption rate under this test method is considered to be approximately zero grams per square meter per √minute.

[0283] Swelling capacity test scheme

[0284] This test measures the swelling ability of a component based on the increase in thickness and volume of a sample (e.g., obtained using the footwear sampling procedure discussed above) after a given soak duration. The sample is initially dried at 60 degrees Celsius until there is no weight change for at least 30-minute intervals of consecutive measurement periods (a 24-hour drying period is typically a suitable duration). Then the dimensions of the dried sample are measured (e.g., the thickness, length, and width of a rectangular sample; the thickness and diameter of a circular sample, etc.). The dried sample is then completely immersed in a deionized water bath maintained at 25 degrees Celsius. After a given soak duration, the sample is removed from the deionized water bath, blotted dry with a cloth to remove surface water, and the same dimensions of the soaked sample are measured again.

[0285] Any suitable soak duration can be used. Thus, as used herein, the expression "having a swelling thickness (or volume) increase at 5 minutes" refers to a 5-minute soak duration, the expression "having a swelling thickness (or volume) increase at 1 hour" refers to a 1-hour test duration, the expression "having a swelling thickness (or volume) increase at 24 hours" refers to a 24-hour test duration, and the like.

[0286] The swelling of a component is determined by: (1) the increase in thickness between the dry component and the soaked component, (2) the increase in volume between the dry component and the soaked component, or (3) both. The increase in thickness between the dry component and the soaked component is calculated by subtracting the measured thickness of the initial dry component from the measured thickness of the soaked component. Similarly, the increase in volume between the dry component and the soaked component is calculated by subtracting the measured volume of the initial dry component from the measured volume of the soaked component. The increases in thickness and volume can also be expressed as percentage increases relative to the dry thickness or dry volume, respectively.

[0287] Contact angle test

[0288] This test measures the contact angle of the delaminated material based on the measurement of the static sessile liquid droplet contact angle of a sample (e.g., obtained using the footwear sampling procedure or co-extruded film sampling procedure discussed above). The contact angle refers to the angle at which the liquid interface meets the solid surface and is an indicator of how hydrophilic the surface is.

[0289] For the dry test (i.e., determining the dry contact angle), the sample is initially equilibrated at 25 degrees Celsius and 20% humidity for 24 hours. For the wet test (i.e., determining the wet contact angle), the sample is completely immersed in a deionized water bath maintained at 25 degrees Celsius for 24 hours. After that, the sample is removed from the bath and blotted dry with a cloth to remove surface water and, if necessary, clamped between glass slides to prevent curling.

[0290] Then the dry or wet sample is placed on the moveable stage of a contact angle goniometer commercially available under the trade name “RAME-HART F290” from Rame-Hart Instrument Co., Succasunna, N.J. Then, a 10-μL droplet of deionized water is placed on the sample using a syringe and an automatic pump. Then an image of the droplet is immediately taken (before the film can absorb the droplet), and the contact angles at the two edges of the water droplet are measured from this image. The decrease in the contact angle between the dry and wet samples is calculated by subtracting the measured contact angle of the wet delaminated material from the measured contact angle of the dry delaminated material.

[0291] Coefficient of friction test

[0292] This test measures the coefficient of friction of a sample (e.g., obtained using the footwear sampling procedure, co-extruded film sampling procedure, or pure film sampling procedure discussed above) for a coefficient of friction test. For the dry test (i.e., determining the dry coefficient of friction), the sample is initially equilibrated at 25 degrees Celsius and 20% humidity for 24 hours. For the wet test (i.e., determining the wet coefficient of friction), the sample is completely immersed in a deionized water bath maintained at 25 degrees Celsius for 24 hours. After that, the sample is removed from the bath and blotted dry with a cloth to remove surface water.

[0293] The measurement is performed using an aluminum sled mounted on an aluminum test track, which is used to perform a sliding friction test on the test sample on 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 the leading edge cut to have a radius of 9.5 mm. The contact area of the aluminum sled with the track is 76.2 mm × 66.6 mm, or 5,100 square millimeters.

[0294] Attach the dry or wet sample to the bottom of the sled using a two-component room-temperature curing epoxy adhesive commercially available from Henkel, Dusseldorf, Germany under the trade name “LOCTITE 608”. The adhesive is used to maintain the planarity of the wet sample, which may curl when saturated. Attach polystyrene foam with a thickness of approximately 25.4 mm to the top surface of the sled (opposite the test sample) for structural support.

[0295] The sliding friction test is conducted using a screw-driven load frame. The tow cable is attached to the sled using a mount supported in the polystyrene foam structural support and wrapped around a pulley to drag the sled across the aluminum test track. The sliding force or frictional force is measured using a load transducer with a capacity of 2000 Newtons. The normal force is controlled by placing weights on top of the aluminum sled supported by the polystyrene foam structural support, with the total sled weight being 20.9 kg (205 Newtons). The crosshead of the test frame is increased at a rate of 5 mm / s, and the total test displacement is 250 mm. The coefficient of friction is calculated based on the steady-state force parallel to the direction of motion required to tow the sled at a constant speed. The coefficient of friction itself is obtained by dividing the steady-state tensile force by the applied normal force. Any transient values related to the static coefficient of friction at the start of the test are ignored.

[0296] Storage modulus test

[0297] This test measures the resistance of the delaminated material to deformation (the ratio of stress to strain) when a vibratory force or oscillating force is applied to it and is a good indicator of the film compliance in both the dry and wet states. For this test, a pure film sampling procedure is used to provide the sample in pure form, which is modified such that the surface area of the test sample is rectangular with dimensions of 5.35 mm wide and 10 mm long. The thickness of the delaminated material can range from 0.1 mm to 2 mm, and the specific range is not particularly limited as the final modulus results are normalized according to the thickness of the delaminated material.

[0298] The storage modulus (E') of the sample in megapascals is determined by dynamic mechanical analysis (DMA) using a DMA analyzer commercially available from TA Instruments, New Castle, Del. under the trade name “Q800 DMA ANALYZER”, which is equipped with a relative humidity attachment to maintain the sample at a constant temperature and relative humidity during the analysis.

[0299] Initially, the thickness of the test sample (for use in modulus calculations) was measured using calipers. The test sample was then clamped into a DMA analyzer, which operated under the following stress / strain conditions during analysis: an isothermal temperature of 25 degrees Celsius, a frequency of 1 Hertz, a strain amplitude of 10 microns, a preload of 1 Newton, and a force track of 125 percent. The DMA analysis was conducted at a constant temperature of 25 degrees Celsius according to the following time / relative humidity (RH) profile: (i) 0% RH for 300 minutes (representing the dry state for storage modulus determination), (ii) 50% RH for 600 minutes, (iii) 90% RH for 600 minutes (representing the wet state for storage modulus determination), and (iv) 0% RH for 600 minutes.

[0300] At the end of each time segment with a constant RH value, the E’ value (in megapascals) was determined from the DMA curve according to standard DMA techniques. That is, in the specified time / relative humidity profile, the E’ value at 0% RH (i.e., the dry state storage modulus) was the value at the end of step (i), the E’ value at 50% RH was the value at the end of step (ii), and the E’ value at 90% RH (i.e., the wet state storage modulus) was the value at the end of step (iii).

[0301] The delaminated material can be characterized by its dry state storage modulus, its wet state storage modulus, or the reduction in storage modulus between the delaminated material in the dry state and the delaminated material in the wet state, where the wet state storage modulus is less than the dry state storage modulus. This reduction in storage modulus can be listed as the difference between the dry state storage modulus and the wet state storage modulus, or as the percentage change relative to the dry state storage modulus.

[0302] Glass transition temperature test

[0303] This test measures the glass transition temperature (T g ) of the outsole component film of the sample, where the outsole component film was provided in pure form, such as using a pure film sampling procedure or a pure material sampling procedure, with a sample weight of 10 milligrams. The sample was measured both in the dry state and in the wet state (i.e., after exposure to a humid environment as described herein).

[0304] The glass transition temperature is determined using DMA. The DMA uses a DMA analyzer commercially available from TA Instruments, New Castle, Del. under the trade name “Q2000 DMA ANALYZER”. The DMA analyzer is equipped with an aluminum seal disk with a pinhole lid, and the sample chamber is purged with nitrogen at 50 mL / min during analysis. Samples in the dry state are prepared by holding at 0% RH until constant weight (weight change less than 0.01 percent over a 120-minute period). Samples in the wet state are prepared by conditioning at a constant 25 degrees Celsius according to the following time / relative humidity (RH) profile: (i) 250 minutes at 0% RH, (ii) 250 minutes at 50% RH, and (iii) 1,440 minutes at 90% RH. The conditioning procedure of step (iii) can be terminated early if the sample weight is measured during conditioning and is measured to be substantially constant within 0.05 percent over 100-minute intervals.

[0305] After preparing the sample in the dry or wet state, the sample is analyzed by DSC to provide a curve of heat flow versus temperature. The DSC analysis is carried out using the following time / temperature profile: (i) equilibration at -90 degrees Celsius for 2 minutes, (ii) ramping at +10 degrees Celsius / minute to 250 degrees Celsius, (iii) ramping at -50 degrees Celsius / minute to -90 degrees Celsius, and (iv) ramping at +10 degrees Celsius / minute to 250 degrees Celsius. The glass transition temperature value (in degrees Celsius) is determined from the DSC curve according to standard DSC techniques.

[0306] The present disclosure is also described in the following items.

[0307] Item 1. A layered material comprising: an outer-facing layer of a first material comprising a hydrogel material and a second layer comprising a thermoplastic hot melt adhesive layer.

[0308] Item 2. The layered material according to any one of the preceding items, further comprising one or more inner layers between the outer-facing layer and the thermoplastic hot melt adhesive layer.

[0309] Item 3. The layered material according to any one of the preceding items, wherein one of the one or more inner layers is a connecting layer comprising a connecting material.

[0310] Item 4. The layered material according to any one of the preceding items, wherein one of the one or more inner layers is an elastic layer comprising an elastomeric material.

[0311] Item 5. The layered material according to any one of the preceding items, wherein the elastomeric material is a thermoplastic polymer.

[0312] Item 6. The layered material according to any one of the preceding items, wherein the thermoplastic polymer comprises polyurethane.

[0313] Item 7. The layered material according to any one of the preceding items, wherein the polyurethane is thermoplastic polyurethane (TPU).

[0314] Item 8. The layered material according to any one of the preceding items, wherein one of the one or more inner layers is a regrind layer comprising regrind material.

[0315] Item 9. The layered material according to any one of the preceding items, wherein two or more inner layers are disposed between the out-facing layer and the thermoplastic hot melt adhesive layer, and the inner layers are selected from the connecting layer, the regrind layer, and the elastomer layer.

[0316] Item 10. The layered material according to any one of the preceding items, wherein three or more inner layers are disposed between the out-facing layer and the thermoplastic hot melt adhesive layer, and the inner layers are selected from the connecting layer, the regrind layer, and the elastomer layer.

[0317] Item 11. The layered material according to any one of the preceding items, wherein the hydrogel material comprises polyurethane hydrogel.

[0318] Item 12. The layered material according to any one of the preceding items, wherein the polyurethane hydrogel is a reaction polymer of a diisocyanate and a polyol.

[0319] Item 13. The layered material according to any one of the preceding items, wherein the hydrogel material comprises polyamide hydrogel.

[0320] Item 14. The layered material according to any one of the preceding items, wherein the polyamide hydrogel is a condensation reaction polymer of a diamine compound and a dicarboxylic acid.

[0321] Item 15. The layered material according to any one of the preceding items, wherein the hydrogel material comprises polyurea hydrogel.

[0322] Item 16. The layered material according to any one of the preceding items, wherein the polyurea hydrogel is a reaction polymer of a diisocyanate and a diamine.

[0323] Item 17. The layered material according to any one of the preceding items, wherein the hydrogel material comprises polyester hydrogel.

[0324] Item 18. The layered material according to any one of the preceding items, wherein the polyester hydrogel is a reaction polymer of a dicarboxylic acid and a diol.

[0325] Item 19. The layered material according to any one of the preceding items, wherein the hydrogel material comprises a polycarbonate hydrogel.

[0326] Item 20. The layered material according to any one of the preceding items, wherein the polycarbonate hydrogel is a reaction polymer of a diol and phosgene or a carbonic acid diester.

[0327] Item 21. The layered material according to any one of the preceding items, wherein the hydrogel material comprises a polyetheramide hydrogel.

[0328] Item 22. The layered material according to any one of the preceding items, wherein the polyetheramide hydrogel is a reaction polymer of a dicarboxylic acid and a polyether diamine.

[0329] Item 23. The layered material according to any one of the preceding items, wherein the hydrogel material comprises a hydrogel formed from an addition polymer of an ethylenically unsaturated monomer.

[0330] Item 24. The layered material according to any one of the preceding items, wherein the hydrogel material comprises a hydrogel formed from a copolymer, wherein the copolymer is a combination of two or more types of polymers within each polymer chain.

[0331] Item 25. The layered material according to any one of the preceding items, wherein the copolymer is selected from the group consisting of: a polyurethane / polyurea copolymer, a polyurethane / polyester copolymer, and a polyester / polycarbonate copolymer.

[0332] Item 26. The layered material according to any one of the preceding items, wherein the thermoplastic hot melt adhesive material comprises one or more thermoplastic polymers selected from the group consisting of polyester, polyether, polyamide, polyurethane, and polyolefin.

[0333] Item 27. The layered material according to any one of the preceding items, wherein the one or more thermoplastic polymers comprise one or more thermoplastic polyesters.

[0334] Item 28. The layered material according to any one of the preceding items, wherein the one or more thermoplastic polyesters comprise polyethylene terephthalate (PET).

[0335] Item 29. The layered material according to any one of the preceding items, wherein the one or more thermoplastic polymers comprise one or more thermoplastic polyamides.

[0336] Item 30. The laminated material according to any one of the preceding items, wherein the one or more thermoplastic polyamides include nylon 6,6, nylon 6, nylon 12, and combinations thereof.

[0337] Item 31. The laminated material according to any one of the preceding items, wherein the one or more thermoplastic polymers include one or more thermoplastic polyurethanes.

[0338] Item 32. The laminated material according to any one of the preceding items, wherein the one or more thermoplastic polymers include one or more thermoplastic copolymers.

[0339] Item 33. The laminated material according to any one of the preceding items, wherein the one or more thermoplastic copolymers include thermoplastic copolymers selected from the group consisting of: thermoplastic copolyesters, thermoplastic coethers, thermoplastic copolyamides, thermoplastic copolyurethanes, and combinations thereof.

[0340] Item 34. The laminated material according to any one of the preceding items, wherein the one or more thermoplastic copolymers include thermoplastic copolyesters.

[0341] Item 35. The laminated material according to any one of the preceding items, wherein the one or more thermoplastic copolymers include thermoplastic coethers.

[0342] Item 36. The laminated material according to any one of the preceding items, wherein the one or more thermoplastic copolymers include thermoplastic copolyamides.

[0343] Item 37. The laminated material according to any one of the preceding items, wherein the one or more thermoplastic copolymers include thermoplastic copolyurethanes.

[0344] Item 38. The laminated material according to any one of the preceding items, wherein the one or more thermoplastic polymers include one or more thermoplastic polyetheramide (PEBA) polymers.

[0345] Item 39. The laminated material according to any one of the preceding items, wherein the thermoplastic hot melt adhesive material includes a low processing temperature polymer composition.

[0346] Item 40. The laminated material according to any one of the preceding items, wherein the melting temperature T of the low processing temperature polymer composition m is less than 135 degrees Celsius.

[0347] Item 41. The laminated material according to any one of the preceding items, wherein the low processing temperature polymer composition exhibits a melting temperature ranging from about 80 degrees Celsius to about 135 degrees Celsius.

[0348] Item 42. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition exhibits a glass transition temperature T of about 50 degrees Celsius or lower. g .

[0349] Item 43. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition exhibits a glass transition temperature T of about 25 degrees Celsius or lower. g .

[0350] Item 44. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition exhibits a melt flow index of about 0.1 g / 10 min to about 60 g / 10 min at 160 degrees Celsius using a test weight of 2.16 kg.

[0351] Item 45. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition exhibits a melt flow index of about 2 g / 10 min to about 50 g / 10 min at 160 degrees Celsius using a test weight of 2.16 kg.

[0352] Item 46. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition exhibits a melting enthalpy of at least about 5 J / g.

[0353] Item 47. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition exhibits a melting enthalpy ranging from about 8 J / g to about 45 J / g.

[0354] Item 48. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition exhibits a modulus of about 1 MPa to about 500 MPa.

[0355] Item 49. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition exhibits a modulus of about 40 MPa to about 110 MPa.

[0356] Item 50. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition withstands 5,000 or more cycles in the cold sole material flexure test without exhibiting visible cracking or stress whitening.

[0357] Item 51. The layered material according to any one of the preceding items, wherein the low processing temperature polymer composition withstands 150,000 cycles in the cold sole material flexure test without exhibiting visible cracking or stress whitening.

[0358] Item 52. The layered material according to any one of the preceding items, wherein the connecting material comprises a thermoplastic polymer.

[0359] Item 53. The layered material according to any one of the preceding items, wherein the thermoplastic polymer is selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, polyolefins, and combinations thereof.

[0360] Item 54. The layered material according to any one of the preceding items, wherein the connecting material comprises one or more polymers selected from the group consisting of aliphatic thermoplastic polyurethanes, aliphatic polyamides, and combinations thereof.

[0361] Item 55. The layered material according to any one of the preceding items, wherein the aliphatic polyamide comprises a caprolactam functional group.

[0362] Item 56. The layered material according to any one of the preceding items, wherein the aliphatic polyamide is nylon.

[0363] Item 57. The layered material according to any one of the preceding items, wherein the one or more thermoplastic polyamides comprise nylon 6,6, nylon 6, nylon 12, and combinations thereof.

[0364] Item 58. The layered material according to any one of the preceding items, wherein the connecting layer comprises an ethylene vinyl alcohol copolymer.

[0365] Item 59. The layered material according to any one of the preceding items, wherein the thermoplastic polyurethane (TPU) contains more than one alkoxy segment and more than one diisocyanate segment, and wherein the more than one diisocyanate segment is connected to each other by a chain-extending segment.

[0366] Item 60. The layered material according to any one of the preceding items, wherein the TPU is a reaction polymer of a diisocyanate and a polyol.

[0367] Item 61. The layered material according to any one of the preceding items, wherein the diisocyanate segment comprises an aliphatic diisocyanate segment, an aromatic diisocyanate segment, or both.

[0368] Item 62. The layered material according to any one of the preceding items, wherein the diisocyanate segment comprises an aliphatic diisocyanate segment.

[0369] Item 63. The layered material according to any one of the preceding items, wherein the aliphatic diisocyanate segment comprises a hexamethylene diisocyanate (HDI) segment.

[0370] Item 64. The layered material according to any one of the preceding items, wherein most of the diisocyanate segments are HDI segments.

[0371] Item 65. The layered material according to any one of the preceding items, wherein the aliphatic diisocyanate segments include isophorone diisocyanate (IPDI) segments.

[0372] Item 66. The layered material according to any one of the preceding items, wherein the diisocyanate segments include aromatic diisocyanate segments.

[0373] Item 67. The layered material according to any one of the preceding items, wherein the aromatic diisocyanate segments include diphenylmethane diisocyanate (MDI) segments.

[0374] Item 68. The layered material according to any one of the preceding items, wherein the aromatic diisocyanate segments include toluene diisocyanate (TDI) segments.

[0375] Item 69. The layered material according to any one of the preceding items, wherein the alkoxy segments include ester segments and ether segments.

[0376] Item 70. The layered material according to any one of the preceding items, wherein the alkoxy segments include ester segments.

[0377] Item 71. The layered material according to any one of the preceding items, wherein the alkoxy segments include ether segments.

[0378] Item 72. The layered material according to any one of the preceding items, wherein the regrind material includes two or more of the following: the hydrogel material, the thermoplastic hot melt adhesive material, the elastomeric material, and the bonding material.

[0379] Item 73. A structure comprising the layered material according to any one of Items 1-72.

[0380] Item 74. The structure according to any one of the preceding items, wherein the structure is a footwear item, a component of footwear, a clothing item, a component of clothing, a sports equipment item, or a component of sports equipment.

[0381] Item 75. The structure according to any one of the preceding items, wherein the structure is a footwear item.

[0382] Item 76. The structure according to any one of the preceding items, wherein the layered material is attached to an outsole component of the footwear item.

[0383] Item 77. The structure according to any one of the preceding items, wherein the side of the footwear item configured to face the ground includes the layered material, and the outermost layer forms at least a portion of the outer surface of the side.

[0384] Item 78. The structure according to any one of the preceding items, wherein the upper of the footwear item includes the layered material, and the outermost layer forms at least a portion of the outer surface of the upper.

[0385] Item 79. The structure according to any one of the preceding items, wherein the footwear item includes one or more attachment friction elements, and the attachment friction elements are on the side of the footwear item configured to face the ground.

[0386] Item 80. The structure according to any one of the preceding items, wherein the attachment friction elements are selected from the group consisting of: anti-slip members, studs, spikes, and lugs.

[0387] Item 81. The structure according to any one of the preceding items, wherein the attachment friction elements are integrally formed with the outsole component of the footwear item.

[0388] Item 82. The structure according to any one of the preceding items, wherein the attachment friction elements are removable attachment friction elements.

[0389] Item 83. The structure according to any one of the preceding items, wherein the layered material is not disposed on the tips of the attachment friction elements configured to contact the ground.

[0390] Item 84. The structure according to any one of the preceding items, wherein the outermost layer is disposed in a region separating the attachment friction elements and optionally on one or more sides of the attachment friction elements, and the attachment friction elements are in a region of the outsole component of the footwear item different from the region of the outermost layer (e.g., in the midfoot region and not in the toe region, the heel region, or both) (e.g., the toe region, the heel region, or both).

[0391] Item 85. A method of manufacturing an item, comprising: attaching a first component and the layered material according to any one of Items 1-72 to each other to form the item.

[0392] Item 86. The method according to any one of the preceding items, wherein the item is a footwear item, a clothing item, or a sports equipment item.

[0393] Item 87. The method according to any one of the preceding items, wherein the first component is an upper component for a footwear item.

[0394] Item 88. The method according to any one of the preceding items, wherein the first component is an outsole component for a footwear item.

[0395] Item 89. The method according to any one of the preceding items, wherein the attaching step is attaching the outsole component and the layered material such that the outward-facing layer forms at least a portion of a side of the outsole component configured to face the ground.

[0396] Item 90. The method according to any one of the preceding items, wherein the footwear item includes one or more traction elements, and wherein the traction elements are on the side of the outsole component configured to face the ground.

[0397] Item 91. The method according to any one of the preceding items, wherein the traction elements are selected from the group consisting of: anti-slip members, studs, spikes, and lugs.

[0398] Item 92. The method according to any one of the preceding items, wherein the traction elements are integrally formed with the outsole component of the footwear item.

[0399] Item 93. The method according to any one of the preceding items, wherein the traction elements are removable traction elements.

[0400] Item 94. The method according to any one of the preceding items, wherein the layered material is not disposed on tips of the traction elements configured to contact the ground.

[0401] Item 95. The method according to any one of the preceding items, wherein the layered material is disposed in areas separating the traction elements and optionally on one or more sides of the traction elements, and optionally wherein the layered material (e.g., in a midfoot region of the shoe) is not disposed in the same regions (e.g., a toe region, a heel region, or both) as the traction elements.

[0402] Item 96. An article, comprising: a product of the method according to any one of Items 85 - 95.

[0403] Item 97. A process for manufacturing an article, the process comprising: placing a first element on a molding surface; placing a thermoplastic hot melt adhesive layer according to any one of Items 1-72 in contact with at least a portion of the first element on the molding surface; when the thermoplastic hot melt adhesive layer is in contact with a component on the molding surface, raising the temperature of the thermoplastic hot melt adhesive layer to a temperature at or above the activation temperature of the thermoplastic hot melt adhesive; and after raising the temperature of the thermoplastic hot melt adhesive, while the thermoplastic hot melt adhesive layer remains in contact with a component on the molding surface, lowering the temperature of the thermoplastic hot melt adhesive to a temperature below the melting temperature T m of the thermoplastic hot melt adhesive; thereby bonding the layered material to the component to form a bonded component.

[0404] Item 98. The process according to any one of the preceding items, wherein the activation temperature of the thermoplastic hot melt adhesive is a temperature at or above the Vicat softening temperature T vs or melting temperature T m of the thermoplastic hot melt adhesive.

[0405] Item 99. The process according to any one of the preceding items, wherein the activation temperature of the thermoplastic hot melt adhesive is a temperature lower than at least one of 1) the creep relaxation temperature T cr ; 2) the heat distortion temperature T hd ; or 3) the Vicat softening temperature T vs of the hydrogel material of the layered material.

[0406] Item 100. The process according to any one of the preceding items, wherein the first element is selected from a first formed part, a first film, a first textile, a first yarn, and a first fiber, the first element comprising a first element material; and raising the temperature of the thermoplastic hot melt adhesive to a temperature at or above its activation temperature comprises raising the temperature of the first element to a temperature higher than the melting temperature T m of the first element material.

[0407] Item 101. A structure comprising an article formed by the process according to Items 97-100.

[0408] Item 102. The structure according to any one of the preceding items, wherein the article is a footwear article, a component of footwear, a clothing article, a component of clothing, a sports equipment article, or a component of sports equipment.

[0409] Item 103. The structure according to any one of the preceding items, wherein the article is a footwear article.

[0410] Item 104. The structure according to any one of the preceding items, wherein the article is an outsole component for a footwear article.

[0411] Item 105. The structure according to any one of the preceding items, wherein the footwear article includes one or more attachment friction elements, and wherein the attachment friction elements are on a side of the footwear article configured to face the ground.

[0412] Item 106. The structure according to any one of the preceding items, wherein the attachment friction elements are selected from the group consisting of: anti-slip members, studs, spikes, and lugs.

[0413] Item 107. The structure according to any one of the preceding items, wherein the attachment friction elements are integrally formed with the outsole component of the footwear article.

[0414] Item 108. The structure according to any one of the preceding items, wherein the attachment friction elements are removable attachment friction elements.

[0415] Item 109. The structure according to any one of the preceding items, wherein the layered material is not disposed on a tip of the attachment friction element configured to contact the ground.

[0416] Item 110. The structure according to any one of the preceding items, wherein the layered material is disposed in a region separating the attachment friction elements and optionally on one or more sides of the attachment friction elements, optionally wherein the layered material (e.g., in a midfoot region of the shoe) is disposed in a region different from the attachment friction elements (e.g., in a toe region, a heel region, or both).

[0417] Item 111. A component comprising: the layered material of Items 1-72, the layered material including an out-facing layer comprising a hydrogel material and a second material comprising a thermoplastic hot melt adhesive, the layered material having an outer perimeter, wherein the out-facing layer is present on at least a portion of a side of the component; and a second polymer material, the second polymer material being attached to the thermoplastic hot melt adhesive layer and the outer perimeter of the layered material.

[0418] Item 112. The component according to any one of the preceding items, wherein the component is a footwear article, a component of a footwear article, a clothing article, a component of a clothing article, a sports equipment article, or a component of a sports equipment article.

[0419] Item 113. The component according to any one of the preceding items, wherein the component is an outsole component for a footwear item, and the outward-facing layer is present on at least a portion of the side of the outsole component configured to face the ground.

[0420] Item 114. The component according to any one of the preceding items, wherein the outsole component includes two or more attachment friction elements, and the layered material is disposed in a zone separating the attachment friction elements and optionally on one or more sides of the attachment friction elements, optionally wherein the layered material (e.g., located in the midfoot region of the shoe) is disposed in a different region from the attachment friction elements (e.g., located in the toe region, the heel region, or both).

[0421] Item 115. A method of manufacturing a component, the method comprising: placing the layered material according to Items 1-72, including an outer perimeter, an outward-facing layer comprising a hydrogel material, and a second layer comprising a thermoplastic hot melt adhesive, into a mold such that a portion of the outward-facing layer contacts a portion of a molding surface; constraining the portion of the outward-facing layer against the portion of the molding surface when a second polymer material is flowed into the mold; curing the second polymer material in the mold to thereby bond the second polymer material to the thermoplastic hot melt adhesive layer and the outer perimeter of the layered material, producing the component, wherein the portion of the outward-facing layer forms the outermost layer of the component; and removing the component from the mold.

[0422] Item 116. The method according to any one of the preceding items, wherein during the flowing, the temperature of the second polymer material is at or above the activation temperature of the thermoplastic hot melt adhesive.

[0423] Item 117. The method according to any one of the preceding items, wherein during the constraining, the temperature of the thermoplastic hot melt adhesive is at or above the activation temperature of the thermoplastic hot melt adhesive.

[0424] Item 118. The method according to any one of the preceding items, wherein the activation temperature of the thermoplastic hot melt adhesive is at or above the Vicat softening temperature T vs or the melting temperature T m of the thermoplastic hot melt adhesive.

[0425] Item 119. The method according to any one of the preceding items, wherein the activation temperature of the thermoplastic hot melt adhesive is lower than 1) the creep relaxation temperature T cr ; 2) the heat distortion temperature T hd ; or 3) the Vicat softening temperature T of the hydrogel materialvs The temperature of at least one of them.

[0426] Item 120. The method according to any one of the preceding items, wherein during the constraint and the flow, the temperature of the layered material is maintained below 1) the creep relaxation temperature T of the hydrogel material of the layered material cr ; 2) the heat distortion temperature T hd ; or 3) the Vicat softening temperature T vs The temperature of at least one of them.

[0427] Item 121. The method according to any one of the preceding items, wherein the component is an article of footwear, a component of an article of footwear, an article of clothing, a component of an article of clothing, an item of sports equipment or a component of an item of sports equipment.

[0428] Item 122. The method according to any one of the preceding items, wherein the component is an outsole component for an article of footwear, and the outward-facing layer is present on at least a portion of the side of the outsole component configured to face the ground.

[0429] Item 123. The method according to any one of the preceding items, wherein the outsole component includes two or more attachment friction elements, and the layered material is disposed in a region separating the attachment friction elements and optionally on one or more sides of the attachment friction elements.

[0430] Item 124. An article of footwear, comprising: an outsole component on a side of the article of footwear, wherein the side is configured to face the ground, wherein the outsole component includes a layered material having an outward-facing layer and a second layer opposite the outward-facing layer, wherein the outward-facing layer includes at least a portion of the outer surface of the article of footwear, wherein the outward-facing layer includes a hydrogel material, and the second layer includes a thermoplastic hot melt adhesive material, and wherein the article of footwear includes one or more attachment friction elements on the side of the article of footwear configured to face the ground.

[0431] Item 125. The article according to any one of the preceding items, wherein the outward-facing layer is disposed in a region of the article of footwear separating the attachment friction elements and optionally on one or more sides of the attachment friction elements, optionally wherein the attachment friction elements are not located in the same region as the outward-facing layer.

[0432] Item 126. The article according to any one of the preceding items, wherein the footwear article includes a toe region, a midfoot region, and a heel region, wherein the layered material is disposed in the midfoot region and optionally not in the toe region, the heel region, or both, and optionally wherein the attachment friction element is not located in the midfoot region and optionally wherein the attachment friction element is located in the toe region, the heel region, or both.

[0433] Item 127. The article according to any one of the preceding items, wherein the layered material is not disposed on the tip of the attachment friction element configured to contact the ground.

[0434] Item 128. The article according to any one of the preceding items, wherein the attachment friction element is selected from the group consisting of: anti-slip members, studs, spikes, and lugs.

[0435] Item 129. The article according to any one of the preceding items, wherein the attachment friction element is integrally formed with the outsole member of the shoe, the attachment friction element is attached to the footwear article adjacent to the outsole member, or the attachment friction element is a removable attachment friction element.

[0436] Item 130. The article according to any one of the preceding items, wherein the upper of the footwear article includes the layered material and the outward-facing layer forms at least a part of the outer surface of the upper.

[0437] Item 131. The article according to any one of the preceding items, wherein one or more inner layers are disposed between the outward-facing layer and the thermoplastic hot melt adhesive layer, and the inner layer is selected from the group consisting of a bonding layer, a regrind layer, and an elastomeric layer.

[0438] Item 132. The article according to any one of the preceding items, wherein the hydrogel material is selected from the group consisting of: polyurethane hydrogel, polyamide hydrogel, polyurea hydrogel, polyester hydrogel, polycarbonate hydrogel, polyetheramide hydrogel, hydrogels formed from addition polymers of ethylenically unsaturated monomers, copolymers thereof, and combinations thereof, and optionally wherein the hydrogel material includes polyurethane hydrogel.

[0439] Item 133. The article according to any one of the preceding items, wherein the hydrogel material includes a hydrogel formed from a copolymer, and the copolymer is a combination of two or more types of polymers within each polymer chain.

[0440] Item 134. The article according to any one of the preceding items, wherein the copolymer is selected from the group consisting of: polyurethane / polyurea copolymer, polyurethane / polyester copolymer, and polyester / polycarbonate copolymer.

[0441] Item 135. The article according to any one of the preceding items, wherein the thermoplastic hot melt adhesive material comprises one or more thermoplastic polymers selected from the group consisting of polyester, polyether, polyamide, polyurethane, and polyolefin, optionally wherein the thermoplastic hot melt adhesive material comprises one or more thermoplastic polyurethanes.

[0442] Item 136. The article according to any one of the preceding items, wherein the thermoplastic hot melt adhesive material comprises a low processing temperature polymer composition, wherein the low processing temperature polymer composition exhibits a melting temperature ranging from about 80 degrees Celsius to about 135 degrees Celsius, the low processing temperature polymer composition exhibits a glass transition temperature T of about 50 degrees Celsius or lower g , the low processing temperature polymer composition exhibits a melt flow index of about 0.1 g / 10 min to about 60 g / 10 min at 160 degrees Celsius using a test weight of 2.16 kg, the low processing temperature polymer composition exhibits a melting enthalpy of at least about 5 J / g, the low processing temperature polymer composition exhibits a modulus of about 1 MPa to about 500 MPa, the low processing temperature polymer composition withstands 5,000 or more cycles in the cold sole material flexure test without exhibiting visible cracking or stress whitening, or a combination thereof.

[0443] Item 137. The article according to any one of the preceding items, wherein the connecting material comprises a thermoplastic polymer, wherein the thermoplastic polymer is selected from the group consisting of polyester, polyether, polyamide, polyurethane, polyolefin, and combinations thereof.

[0444] Item 138. The article according to any one of the preceding items, wherein the regrind layer comprises a regrind material, the regrind material comprising two or more of the following: the hydrogel material, the thermoplastic hot melt adhesive material, an elastomeric material, and a connecting material.

[0445] Item 139. A method of manufacturing a footwear article, comprising: attaching a shoe outsole component and a layered material to each other to form the article, wherein the layered material comprises an out-facing layer and a second layer opposite the out-facing layer, wherein the out-facing layer comprises a hydrogel material and the second layer comprises a thermoplastic hot melt adhesive material, wherein the footwear article comprises one or more attachment friction elements on a side of the footwear article configured to face the ground.

[0446] Item 140. The method according to any one of the preceding items, wherein the attaching step comprises attaching the outsole component and the layered material to each other such that the out-facing layer forms at least a part of the side of the outsole component configured to face the ground.

[0447] Item 141. The method according to any one of the preceding items, wherein the out-facing layer is arranged in a zone separating the attachment friction elements and optionally on one or more sides of the attachment friction elements, optionally wherein the attachment friction elements are not located in the same area as the out-facing layer.

[0448] Item 142. The method according to any one of the preceding items, wherein the footwear item comprises a toe region, a midfoot region, and a heel region, wherein the layered material is arranged in the midfoot region and optionally not in the toe region, the heel region, or both, optionally wherein the attachment friction elements are located in the toe region and the heel region, optionally wherein the attachment friction elements are not located in the midfoot region.

[0449] Item 143. The method according to any one of the preceding items, wherein one or more inner layers are arranged between the out-facing layer and the second layer, wherein the inner layer is selected from a bonding layer, a regrind layer, and an elastomeric layer.

[0450] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It should be understood that such range formats are used for convenience and brevity and are thus to be interpreted in a flexible manner as including not only the numerical values explicitly recited as range limits but also all the individual numerical values or sub-ranges subsumed within that range as if each numerical value and sub-range were explicitly recited. By way of illustration, the concentration range “from about 0.1 percent to about 5 percent” should be interpreted to include not only the explicitly recited concentrations of about 0.1 wt% to about 5 wt% but also the individual concentrations (e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and sub-ranges (e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4 percent) indicated within the range. In aspects, the term “about” may include conventional rounding according to the significant digits of the numerical value. Additionally, the phrase “from about ‘x’ to ‘y’” includes “from about ‘x’ to about ‘y’”.

[0451] Numerous variations and modifications can be made to the aspects described above. All such modifications and variations are intended to be included within the scope of the present disclosure and are protected by the appended claims.

Claims

1. A layered material (10d), comprising: - an outer-facing layer (12) of a first material comprising a hydrogel material, - a thermoplastic hot melt adhesive layer (16), and - three or more inner layers (14a, 14b, 14c) disposed between the outer-facing layer (12) and the thermoplastic hot melt adhesive layer (16), wherein the inner layers (14a, 14b, 14c) comprise a tie layer, a regrind layer, and an elastomer layer; wherein the regrind layer comprises regrind hydrogel material.

2. The layered material according to claim 1, wherein the elastomer layer comprises an elastomeric material, and the elastomeric material is a thermoplastic polymer.

3. The layered material according to claim 2, wherein the thermoplastic polymer is thermoplastic polyurethane (TPU).

4. The layered material according to any one of claims 1-3, wherein: - the hydrogel material is selected from the group consisting of: polyurethane hydrogel, polyamide hydrogel, polyurea hydrogel, polyester hydrogel, polycarbonate hydrogel, polyetheramide hydrogel, hydrogels formed from addition polymers of ethylenically unsaturated monomers; or - the hydrogel material comprises a hydrogel formed from a copolymer, wherein the copolymer is a combination of two or more types of polymers within each polymer chain.

5. The layered material according to claim 4, wherein the copolymer is selected from the group consisting of: polyurethane / polyurea copolymer, polyurethane / polyester copolymer, and polyester / polycarbonate copolymer.

6. The layered material according to any one of claims 1-3 and 5, wherein the thermoplastic hot melt adhesive layer comprises a thermoplastic hot melt adhesive material, and wherein: - the thermoplastic hot melt adhesive material comprises one or more thermoplastic polymers selected from the group consisting of polyester, polyether, polyamide, polyurethane, and polyolefin; and / or - The thermoplastic hot melt adhesive material comprises a low processing temperature polymer composition, wherein the low processing temperature polymer composition exhibits: a melting temperature from 80 degrees Celsius to 135 degrees Celsius, a glass transition temperature T of 50 degrees Celsius or lower g , a melt flow index of 0.1 g / 10 min to 60 g / 10 min using a test weight of 2.16 kg at 160 degrees Celsius, a melting enthalpy of at least 5 J / g, and / or a modulus of 1 megapascal to 500 megapascals.

7. The layered material according to claim 4, wherein the thermoplastic hot melt adhesive layer comprises a thermoplastic hot melt adhesive material, and wherein: - the thermoplastic hot melt adhesive material comprises one or more thermoplastic polymers selected from the group consisting of polyester, polyether, polyamide, polyurethane, and polyolefin; and / or - The thermoplastic hot melt adhesive material comprises a low processing temperature polymer composition, wherein the low processing temperature polymer composition exhibits: a melting temperature from 80 degrees Celsius to 135 degrees Celsius, a glass transition temperature T of 50 degrees Celsius or lower g , a melt flow index of 0.1 g / 10 min to 60 g / 10 min using a test weight of 2.16 kg at 160 degrees Celsius, a melting enthalpy of at least 5 J / g, and / or a modulus of 1 megapascal to 500 megapascals.

8. The layered material according to any one of claims 1-3, 5, and 7, wherein the tie layer comprises a tie material, and the tie material comprises a thermoplastic polymer, wherein the thermoplastic polymer for the tie material is selected from the group consisting of polyester, polyether, polyamide, polyurethane, polyolefin, and combinations thereof.

9. The layered material according to claim 4, wherein the tie layer comprises a tie material, and the tie material comprises a thermoplastic polymer, wherein the thermoplastic polymer for the tie material is selected from the group consisting of polyester, polyether, polyamide, polyurethane, polyolefin, and combinations thereof.

10. The layered material according to claim 6, wherein the connecting layer comprises a connecting material, and the connecting material comprises a thermoplastic polymer, and the thermoplastic polymer for the connecting material is selected from the group consisting of polyesters, polyethers, polyamides, polyurethanes, polyolefins, and combinations thereof.

11. The layered material according to any one of claims 1 - 3, 5, 7, and 9 - 10, wherein the regrind layer further comprises a thermoplastic hot melt adhesive material, an elastomeric material, and / or a connecting material.

12. The layered material according to claim 4, wherein the regrind layer further comprises a thermoplastic hot melt adhesive material, an elastomeric material, and / or a connecting material.

13. The layered material according to claim 6, wherein the regrind layer further comprises a thermoplastic hot melt adhesive material, an elastomeric material, and / or a connecting material.

14. The layered material according to claim 8, wherein the regrind layer further comprises a thermoplastic hot melt adhesive material, an elastomeric material, and / or a connecting material.

15. A component comprising the layered material according to any one of claims 1 to 14, wherein the layered material (10d) has an outer perimeter; the outermost layer (12) is present on at least a portion of the side of the component; and a second polymer material is attached to the thermoplastic hot melt adhesive layer (16) and the outer perimeter of the layered material.

16. The component according to claim 15, wherein the component is a component of a footwear item, a component of a clothing item, or a component of a sports equipment item.

17. A method of manufacturing the component according to claim 15 or claim 16, the method comprising: placing the layered material (10d) into a mold such that a portion of the outermost layer (12) contacts a portion of a molding surface; constraining the portion of the outermost layer (12) against the portion of the molding surface when flowing a second polymer material into the mold; curing the second polymer material in the mold to thereby bond the second polymer material to the thermoplastic hot melt adhesive layer (16) and the outer perimeter of the layered material, producing the component, wherein the portion of the outermost layer forms the outermost layer of the component; and removing the component from the mold.

18. The method according to claim 17, wherein during said flow, the temperature of said second polymeric material is at or above the activation temperature of the thermoplastic hot melt adhesive of the thermoplastic hot melt adhesive layer, wherein said activation temperature of said thermoplastic hot melt adhesive is at or above the Vicat softening temperature T vs or the melting temperature T m of the temperature.

19. The method according to claim 17 or claim 18, wherein the activation temperature of the thermoplastic hot melt adhesive of the thermoplastic hot melt adhesive layer is lower than 1) the creep relaxation temperature T of the hydrogel material cr ; 2) the heat distortion temperature T hd ; or 3) the Vicat softening temperature T vs of at least one; and / or wherein during the restraint and the flow, the temperature of the laminated material is maintained below 1) the creep relaxation temperature T of the hydrogel material of the laminated material cr ; 2) the heat distortion temperature T hd ; or 3) the Vicat softening temperature T vs of at least one.

20. A process for manufacturing an article, the process comprising: placing a first element on a molding surface; placing the thermoplastic hot melt adhesive layer (16) of the layered material (10d) according to any one of claims 1 to 14 in contact with at least a portion of the first element on the molding surface; when the thermoplastic hot melt adhesive layer (16) is in contact with at least a portion of the first element on the molding surface, raising the temperature of the thermoplastic hot melt adhesive of the thermoplastic hot melt adhesive layer to a temperature at or above the activation temperature of the thermoplastic hot melt adhesive; And after raising the temperature of the thermoplastic hot melt adhesive, while the thermoplastic hot melt adhesive layer remains in contact with the first element on the molding surface, reducing the temperature of the thermoplastic hot melt adhesive to a temperature below the melting temperature T m of the thermoplastic hot melt adhesive; thereby bonding the laminated material (10d) to the first element to form a bonded component.

21. The process according to claim 20, wherein the activation temperature of the thermoplastic hot melt adhesive is at or above the Vicat softening temperature T of the thermoplastic hot melt adhesive vs or the melting temperature T m of the thermoplastic hot melt adhesive, and / or wherein the activation temperature of the thermoplastic hot melt adhesive is lower than 1) the creep relaxation temperature T cr ; 2) the heat distortion temperature T hd ; or 3) the Vicat softening temperature T vs of the hydrogel material of the delaminated material (10d); or at least one of the temperatures of 22. The process according to claim 20 or claim 21, wherein the first element is selected from a first forming part, a first film, a first textile, a first yarn and a first fiber, the first element comprising a first element material; and raising the temperature of the thermoplastic hot melt adhesive to a temperature at or above the activation temperature of the thermoplastic hot melt adhesive comprises raising the temperature of the first element to a temperature higher than the melting temperature T m of the first element material.

23. A footwear item comprising the layered material according to any one of claims 1 to 14.

24. The footwear article according to claim 23, wherein: - the layered material is attached to an outsole component of the footwear article; - a side of the footwear article configured to face the ground includes the layered material, and the outermost layer forms at least a portion of the outer surface of the side; and / or - an upper of the footwear article includes the layered material, and the outermost layer forms at least a portion of the outer surface of the upper.

25. An article of clothing or an article of sports equipment comprising the layered material according to any one of claims 1 to 14.

26. A method of manufacturing a footwear article, an article of clothing or an article of sports equipment, comprising: attaching a component of the footwear article, a component of the article of clothing or a component of the article of sports equipment and the layered material (10d) according to any one of claims 1 to 14 to each other to form the footwear article, the article of clothing or the article of sports equipment.

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