阅读说明：本技术 具有污垢脱落性能的鞋类物品 (Article of footwear with soil release properties ) 是由 卡莱布·W·戴尔 扎迦利·C·莱特 杰里米·D·沃克 迈伦·毛雷尔 丹尼斯·席勒 侯赛因· 于 2015-08-27 设计创作，主要内容包括：本申请涉及具有污垢脱落性能的鞋类物品。本公开内容涉及鞋类物品(100)及其部件,包括鞋外底(112),该鞋外底(112)可以在常常导致污垢累积在鞋外底(112)上的条件下使用。特别地,本公开内容涉及鞋类物品(100)及其部件,包括鞋外底(112),所述鞋外底(112)具有包含水凝胶的材料(116),其中所述材料(116)界定所述鞋外底(112)的外表面或侧面。鞋外底(112)可以在诸如运动场的未铺砌表面上穿用期间防止或减少污垢在鞋类上累积。(The present application relates to articles of footwear having soil release properties. The present disclosure relates to articles of footwear (100) and components thereof, including outsoles (112), where the outsoles (112) may be used under conditions that often result in soil accumulation on the outsoles (112). In particular, the present disclosure relates to an article of footwear (100) and components thereof, including an outsole (112), the outsole (112) having a material (116) comprising a hydrogel, wherein the material (116) defines an exterior surface or side of the outsole (112). The outsole (112) may prevent or reduce the accumulation of soil on the footwear during wear on unpaved surfaces such as athletic fields.)

1. An outsole for an article of footwear, the outsole comprising:

a first surface of the outsole configured to face a ground; and

a second surface of the outsole opposite the first surface, the outsole configured to be secured to an upper of an article of footwear; wherein the outsole comprises a material defining at least a portion of the first surface, and the material compositionally comprises a hydrogel, wherein the material has a mass of greater than 20 g/(m)²×min^0.5) Or in the range of from 1 g/(m)²×min^0.5) To 1500 g/(m)²×min^0.5) According to the water absorption rate test using the footwear sampling procedure.

2. Such as rightThe outsole of claim 1, wherein the rate of water absorption of the material is greater than 100 g/(m)²×min^0.5)。

3. The outsole of claim 1, wherein the material has a range of from 30 g/(m)²×min^0.5) To 1200 g/(m)²×min^0.5) The water absorption rate of (c).

4. The outsole of claim 1, wherein the material has a range of from 30 g/(m)²×min^0.5) To 800 g/(m)²×min^0.5) The water absorption rate of (c).

5. The outsole of claim 1, wherein the material has a range of from 100 g/(m)²×min^0.5) To 800 g/(m)²×min^0.5) The water absorption rate of (c).

6. The outsole of claim 1, wherein the material has a range of from 100 g/(m)²×min^0.5) To 600 g/(m)²×min^0.5) The water absorption rate of (c).

7. The outsole of claim 1, wherein the material has a range of from 150 g/(m)²×min^0.5) To 400 g/(m)²×min^0.5) The water absorption rate of (c).

8. The outsole of any of claims 1-7, the material having a 1 hour expansion thickness increase of greater than 20%, as characterized by the expandability test using the footwear sampling procedure.

9. The outsole of claim 8, wherein the material has a 1 hour inflated thickness increase of at least 150%.

10. The outsole of claim 8, wherein the material has a 1 hour inflated thickness increase ranging from 50% to 400%.

Brief Description of Drawings

For a more complete understanding of this disclosure, reference should be made to the following detailed description and accompanying drawings, in which:

FIG. 1 is a bottom isometric view of an article of footwear having an outsole including a material (e.g., in the form of a film) according to the present disclosure, in one aspect of the present disclosure;

FIG. 2 is a bottom view of the outsole of the article of footwear shown in FIG. 1, with the upper of the footwear omitted;

FIG. 3 is a lateral side view of the outsole shown in FIG. 2;

FIG. 4 is a medial side view of the outsole shown in FIG. 2;

FIG. 5 is an enlarged cross-sectional view of a portion of a shoe outsole illustrating a material in accordance with the present disclosure secured to a backing plate adjacent to traction elements (e.g., wedges) in a dry state.

Fig. 5A is an enlarged cross-sectional view of the portion of the outsole shown in fig. 5, where the material is partially saturated and inflated.

FIG. 5B is an enlarged cross-sectional view of the portion of the outsole shown in FIG. 5, where the material is fully saturated and inflated.

Fig. 6-9 are enlarged cross-sectional views of the portion of the outsole shown in fig. 5, illustrating soil-shedding performance of the outsole during a foot strike motion on an unpaved surface.

FIG. 10 is a side cross-sectional view of an outsole including soil release material with soil being released from the outsole during impact with a ground surface in accordance with one aspect of the present disclosure;

FIG. 11 is a bottom view of an article of footwear having an outsole including a material having discrete and separate sub-sections according to the present disclosure, in another aspect of the present disclosure;

FIG. 12 is an enlarged cross-sectional view of a portion of an outsole including material in accordance with the present disclosure present in a recessed pocket of an outsole backing plate in another aspect of the present disclosure;

FIG. 13 is an enlarged cross-sectional view of a portion of an outsole including an outsole backing plate having one or more indentations and a material in accordance with the present disclosure present in and above the indentations in another aspect of the present disclosure;

FIG. 14 is an enlarged cross-sectional view of a portion of an outsole including an outsole backing plate having one or more indentations with locking members and a material in accordance with the present disclosure present in and above the indentations in another aspect of the present disclosure;

FIG. 15 is a bottom view of an article of footwear in another aspect of the present disclosure, illustrating an example golf shoe application;

FIG. 16 is a bottom perspective view of an article of footwear in another aspect of the present disclosure, illustrating an example baseball shoe application;

FIG. 17 is a bottom perspective view of an article of footwear illustrating an exemplary soccer shoe application in another aspect of the present disclosure;

FIG. 18 is a bottom perspective view of an article of footwear in another aspect of the present disclosure, illustrating an example walking shoe application;

FIG. 19 is a photograph of exemplary material of the present disclosure; and

fig. 20A-20H include photographs of an article of footwear with and without a material according to the present disclosure after wear and use during wet and muddy playing conditions.

The article of footwear shown in the figures is illustrated for use with the right foot of a user. However, it should be understood that the following discussion applies correspondingly to left foot articles of footwear.

Description of the invention

It has now been found that certain materials comprising hydrogels, when disposed on a ground-facing surface of an outsole of an article of footwear, can be effective in preventing or reducing soil accumulation on the outsole during wear on unpaved surfaces. In addition, it has been found that the selection of certain materials, in terms of their physical properties as measured using the test methods described herein, can be used to achieve specific performance benefits for the outsole and/or the article of footwear as disclosed herein. Accordingly, the present disclosure describes outsoles formed from these materials that include hydrogels, articles of footwear manufactured using these outsoles, uses of these materials in outsoles, and methods of making and using outsoles and articles of footwear. The hydrogel-containing material defines at least a portion of a surface or side of the outsole. In other words, the material is present at or forms all or part of the outer surface of the outsole. When the outsole is included in an article of footwear, the material defines at least a portion of an outer surface of the article or a ground-facing side of the article.

As can be appreciated, preventing or reducing the accumulation of dirt on the bottom of the footwear may provide a number of benefits. Preventing or reducing soil accumulation on the outsole during wear on unpaved surfaces can also significantly affect the weight of accumulated soil adhering (adhere) to the outsole during wear, reducing fatigue of the wearer due to adhered soil. Preventing or reducing the accumulation of soil on the outsole may help maintain traction during wear. For example, preventing or reducing the accumulation of soil on the outsole during wear on unpaved surfaces may improve or maintain the performance of traction elements present on the outsole. Preventing or reducing the accumulation of soil on the outsole may improve or maintain the wearer's ability to manipulate the athletic device, such as a ball, with the outsole of the article of footwear when worn while in athletic activities.

In a first aspect, the present disclosure is directed to an outsole for an article of footwear. The outsole may be an outsole comprising a first side and an opposing second side; wherein the first side comprises a material and the material comprises a hydrogel in composition. The outsole may be an outsole comprising a first surface configured to face the ground and a second surface of the outsole opposite the first surface. At least a portion of the first surface of the outsole includes a material defining at least a portion of the first surface, and the material compositionally includes a hydrogel. In other words, the hydrogel material is present at and defines at least a portion of the first surface or first side of the outsole. The outsole may be configured to be secured to an upper of an article of footwear. In particular, the second surface of the outsole may be configured to be secured to an upper of an article of footwear. The outsole may be an outsole that prevents or reduces soil accumulation such that the outsole retains at least 10% less soil by weight than a second outsole that is identical to the outsole except that the second outsole is substantially free of materials comprising hydrogel.

In accordance with the present disclosure, the hydrogel-containing material of the outsole (and thus the portion of the outsole that includes the material) may be a material that may be characterized based on its ability to absorb water. The Material may be a Material having a water absorption capacity at 24 hours of greater than 40% by weight as characterized by a water absorption capacity test using the footwear Sampling Procedure, the coextruded Film Sampling Procedure, the Neat Film Sampling Procedure (Neat Film Sampling Procedure), or the Neat Material Sampling Procedure (Neat Material Sampling Procedure) as described below. Additionally or alternatively, the material may have a water absorption capacity of greater than 100% by weight at 1 hour. The material may have a value of greater than 20g/ (m²×min^0.5) As characterized by a water uptake rate test using a footwear sampling procedure, a co-extruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure. The material may have a mass of greater than 100 g/(m)²×min^0.5) The water absorption rate of (c). The material may be a material having a water absorption capacity at 24 hours of more than 40% by weight and a water absorption capacity at more than 20 g/(m)²×min^0.5) Both the water absorption rate of (c). The material may have a 1 hour expansion thickness increase of greater than 20%, as characterized by the expandability test using a footwear sampling procedure, a coextruded film sampling procedure, or a neat film sampling procedure. The material may be a material having both a 24 hour water absorption capacity of greater than 40% by weight and a 1 hour expanded caliper increase of greater than 20%.

In addition, the hydrogel-containing materials of the present disclosure can be characterized based on their surface properties. The material may be a material wherein at least a portion of the first surface defined by the material has a contact angle in the wet state of less than 80 °, as characterized by a contact angle test using a footwear sampling procedure, a coextruded film sampling procedure, or a neat film sampling procedure; and wherein the material has a water absorption capacity at 24 hours of greater than 40% by weight as characterized by the water absorption capacity test using a footwear sampling procedure, a coextruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure. The material may be a material wherein at least a portion of the first surface defined by the material has a wet state coefficient of friction of less than 0.8, as characterized by a coefficient of friction test using a footwear sampling procedure, a co-extruded film sampling procedure, or a neat film sampling procedure; and wherein the material has a water absorption capacity at 24 hours of greater than 40% by weight as characterized by the water absorption capacity test using a footwear sampling procedure, a coextruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure.

The material may be a material wherein at least a portion of the first surface defined by the material has a contact angle in the wet state of less than 80 °, as characterized by a contact angle test using a footwear sampling procedure, a coextruded film sampling procedure, or a neat film sampling procedure; and wherein the material has a water absorption capacity at 1 hour of greater than 100% by weight as characterized by the water absorption capacity test using a footwear sampling procedure, a coextruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure. The material may be a material wherein at least a portion of the first surface defined by the material has a wet state coefficient of friction of less than 0.8, as characterized by a coefficient of friction test using a footwear sampling procedure, a co-extruded film sampling procedure, or a neat film sampling procedure; and wherein the material has a water absorption capacity at 1 hour of greater than 100% by weight as characterized by the water absorption capacity test using a footwear sampling procedure, a coextruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure.

Further, the hydrogel-containing materials of the present disclosure can be characterized based on changes in properties between their dry state and their wet state. The material may be a material having a wet state glass transition temperature when equilibrated at 90% relative humidity and a dry state glass transition temperature when equilibrated at 0% relative humidity, each as characterized by a glass transition temperature test using a pure material sampling method, wherein the wet state glass transition temperature is greater than 6 ℃ less than the dry state glass transition temperature; and wherein the material also preferably has a water absorption capacity at 24 hours of greater than 40% by weight, as characterized by the water absorption capacity test using a footwear sampling procedure, a coextruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure. The material can have a wet state storage modulus when equilibrated at 90% relative humidity and a dry state storage modulus when equilibrated at 0% relative humidity, each as characterized by a storage modulus test using a pure material sampling procedure, wherein the wet state storage modulus of the material is less than the dry state storage modulus of the material; and wherein the material also preferably has a water absorption capacity at 24 hours of greater than 40% by weight, as characterized by the water absorption capacity test using a footwear sampling procedure, a coextruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure.

The material can be a material having a wet state glass transition temperature when equilibrated at 90% relative humidity and a dry state glass transition temperature when equilibrated at 0% relative humidity, each as characterized by a glass transition temperature test using a pure material sampling method, wherein the wet state glass transition temperature is greater than 6 ℃ less than the dry state glass transition temperature; and wherein the material also preferably has a water absorption capacity at 1 hour of greater than 100% by weight, as characterized by the water absorption capacity test using a footwear sampling procedure, a coextruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure. The material can have a wet state storage modulus when equilibrated at 90% relative humidity and a dry state storage modulus when equilibrated at 0% relative humidity, each as characterized by a storage modulus test using a pure material sampling procedure, wherein the wet state storage modulus of the material is less than the dry state storage modulus of the material; and wherein the material also preferably has a water absorption capacity at 1 hour of greater than 100% by weight, as characterized by the water absorption capacity test using a footwear sampling procedure, a coextruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure.

The materials of the present disclosure may also or alternatively be characterized based on the type of hydrogel they comprise. In certain examples, the hydrogel of the material may comprise or consist essentially of a thermoplastic hydrogel. The hydrogel of the material may comprise or consist essentially of one or more polymers selected from the group consisting of: polyurethanes, polyamide homopolymers, polyamide copolymers, and combinations thereof. For example, the polyamide copolymer can comprise or consist essentially of a polyamide block copolymer.

The outsoles of the present disclosure may also or alternatively be characterized based on their structure, e.g., thickness of material on the ground-facing outsole surface, how the material is disposed on the outsole, whether traction elements are present, whether the material is secured to an outsole backing plate, and the like. The outsole may be an outsole having material present on at least 80% of a ground-facing surface of the outsole. The hydrogel-containing material of the outsole may have a thickness in the dry state ranging from 0.1 millimeters to 2 millimeters. The outsole may include one or more traction elements present on a first surface of the outsole. The outsole may also include outsole backing members. The outsole backing members may form at least a portion of the outsole or be secured to the outsole, with material secured to the outsole backing members such that the material defines at least a portion of the first surface of the outsole.

In a second aspect, the present disclosure is directed to an article of footwear comprising an outsole as disclosed herein. The article of footwear may be an article including an outsole and an upper, wherein the outsole has a first ground-facing surface and a second surface opposite the first surface, wherein the upper is secured to the second surface of the outsole, wherein the hydrogel-containing material defines at least a portion of the first ground-facing surface of the outsole. The material may be a material as described above, for example, with respect to the first aspect of the disclosure. The article of footwear may be an article that prevents or reduces soil accumulation such that the article retains at least 10% less soil by weight as compared to a second article of footwear that is identical to the article except that the outsole of the second article is substantially free of hydrogel-containing material.

In a third aspect, the present disclosure is directed to a method of manufacturing an article of footwear, such as the article of footwear of the second aspect. The method comprises the following steps: the method comprises providing an outsole as disclosed herein, for example with respect to a first aspect of the present disclosure, providing an upper for an article of footwear, and securing the outsole and the upper to one another such that the hydrogel-containing material defines at least a portion of a ground-facing surface of the outsole. The method may be a method comprising the steps of: providing an outsole having a first ground-facing surface of the outsole and a second surface opposite the first surface, wherein the outsole is configured to be secured to an upper for an article of footwear, and wherein the hydrogel-containing material defines at least a portion of the first ground-facing surface of the outsole; and securing the outsole and the upper to one another such that the material defines at least a portion of a ground-facing surface of the outsole of the article of footwear. The method may further comprise the steps of: affixing a material to a first side of a backing substrate formed of a second material comprising a thermoplastic material in composition; thermoforming a material secured to a backing substrate formed of a second material to produce an outsole face precursor (outsole face precursor), wherein the outsole face precursor comprises the material secured to a first side of the backing substrate; placing the outsole face portion into a mold; injecting a third material comprising a thermopolymer in composition onto a second side of the backing substrate of the outsole face while the outsole face is present in the mold to produce an outsole, wherein the outsole comprises: an outsole substrate comprising a backing substrate and a third material; and a material secured to the outsole base.

In a fourth aspect, the present disclosure relates to the use of a material comprising a hydrogel in its construction to prevent or reduce soil accumulation on an outsole or article of footwear. The use relates to the use of a material for preventing or reducing soil accumulation on an outsole or on a first surface of an outsole of an article of footwear, the first surface comprising the material, by providing the material on at least a portion of the first surface of the outsole, wherein the outsole retains at least 10% by weight less soil than a second outsole that is identical to the outsole except that the first surface of the second outsole is substantially free of a material comprising a hydrogel. The use may be in a use of a material comprising a hydrogel in its composition for preventing or reducing accumulation of soil on a first surface of an outsole, the first surface comprising a material, the use being achieved by providing the material on at least a portion of the first surface of the outsole, wherein the outsole retains at least 10% by weight less soil than a second outsole which is identical to the outsole except that the first surface of the second outsole is substantially free of the material comprising the hydrogel. The material may be a material as described above, for example, with respect to the first aspect of the disclosure.

In a fifth aspect, the present disclosure is directed to a method of using an article of footwear. The method comprises the following steps: providing an article of footwear having an upper and an outsole of the present disclosure secured to the upper, wherein the material comprising the hydrogel defines at least a portion of a ground-facing surface of the outsole; exposing the material to water to absorb at least a portion of the water into the material, forming a wetted material; compressing the outsole with the wet material against the ground surface to at least partially compress the wet material; and lifting the outsole from the ground surface to release the compression from the wet material. The material may be a material as described above, for example, with respect to the first aspect of the disclosure. Additional aspects and descriptions of the materials, outsoles, articles, uses, and methods of the present disclosure may be found below with particular reference to the numbered items provided below.

As used herein, the term "outsole" is understood to refer to an outer portion of a sole of an article of footwear. The outer portion of the article with the outsole forms at least a portion of the article that may contact the ground during ordinary use. In addition to the outsole, additional sole-type structures, such as midsoles, rigid plates, cushioning, and the like, may or may not be present in the article of footwear. As used herein, the terms "article of footwear" and "footwear" are intended to be used interchangeably to refer to the same item. Generally, the term "article of footwear" will be used in the first example, and for ease of readability, the term "footwear" may be subsequently used to refer to the same article.

As used herein, the term "material" is understood to refer to a material that comprises a hydrogel in its composition. When present in the outsoles of the present disclosure, the material defines at least a portion of a surface or side of the outsole. In other words, the material forms at least a portion of an outer surface or side of the outsole. The material may be present as one or more layers disposed on the surface of the outsole, where the layers may be provided as a single continuous section on the surface or as multiple discontinuous sections on the surface. The material is not intended to be limited by any application process (e.g., coextrusion, injection molding, lamination, spraying, etc.).

The term "ground-facing" refers to a location that an element is intended to be in during normal use when the element is present in an article of footwear, i.e., the element is positioned toward the ground when the wearer is in a standing position during normal use by the wearer, and thus may contact the ground, including unpaved surfaces, when the footwear is used in a conventional manner, such as standing, walking, or running, on an unpaved surface. In other words, an element is understood to be ground-facing if it is intended to face the ground during normal use by a wearer, even though the element may not necessarily face the ground during various steps of manufacture or shipping. In some cases, the ground-facing surface may be positioned toward the ground during normal use, but may not necessarily contact the ground, due to the presence of elements such as traction elements. For example, on a hard ground or paved surface, the terminal ends of the traction elements on the outsole may directly contact the ground, while the portions of the outsole between the traction elements do not directly contact the ground. As described in this example, the portions of the outsole that are between the traction elements are considered to be ground-facing, although they may not contact the ground directly in all circumstances.

As discussed below, it has been found that these outsoles and articles of footwear can prevent or reduce the accumulation of soil on the outsole during wear on unpaved surfaces. As used herein, the term "soil" may include any of a variety of materials that are typically present on the ground or playing surface and which may otherwise adhere to the outsole or exposed midsole of an article of footwear. The fouling may include: inorganic materials such as mud, sand, dirt and gravel; organic matter, such as grass, turf, foliage, other vegetation, and fecal matter; and combinations of inorganic and organic materials, such as clays. In addition, the dirt may include other materials, such as powdered rubber that may be present on or in the unpaved surface.

While not wishing to be bound by theory, it is believed that hydrogel-containing materials according to the present disclosure may provide compressive compliance (compressive compliance) and/or drainage of absorbed water when sufficiently wetted with water, including water containing dissolved, dispersed, or otherwise suspended materials. In particular, it is believed that the compressive flexibility of the wet material, the drainage of liquid from the wet material, or a combination of both, may disrupt the adhesion of dirt on or at the outsole, or the adherence of particles to one another (cohesion), or may disrupt both adhesion and cohesion. This disruption in the adhesion and/or cohesion of soil is believed to be the responsible mechanism (responsive mechanism) for preventing (or otherwise reducing) the accumulation of soil (due to the presence of the wet material) on the outsole of the footwear.

As can be appreciated, preventing soil from accumulating on the bottom of the footwear may improve the performance of traction elements present on the outsole during wear on unpaved surfaces, may prevent the footwear from gaining weight during wear due to accumulated soil, may maintain ball control performance of the footwear, and thus may provide a significant benefit to the wearer compared to an article of footwear without material present on the outsole.

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

As used herein, the term "providing," such as for "providing an outsole," when recited in a claim, is not intended to require any particular delivery or receipt of the provided item. Rather, for the purposes of clarity and ease of readability, the term "providing" is merely used to recite an item to be referred to in the elements that follow in the claims.

As used herein, the terms "preferred" and "preferably" refer to aspects of the invention that may provide certain benefits under certain circumstances. However, other aspects may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred aspects does not imply that other aspects are not useful, and is not intended to exclude other aspects from the scope of the disclosure.

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

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

The articles of footwear of the present disclosure may be designed for a variety of uses, such as, for example, athletic use, military use, work-related use, recreational use, or recreational use. First, the article of footwear is intended for outdoor use on unpaved surfaces (partial or unitary), such as ground surfaces including one or more of grass, turf, gravel, sand, dirt, clay, mud, and the like, whether as athletic surfaces or as general outdoor surfaces. However, the article of footwear may also be desirable for indoor applications, such as indoor sports that include, for example, a dirty playing surface (e.g., an indoor baseball field with a dirty infield). As used herein, the terms "at least one" and "one or more" of the elements are used interchangeably and have the same meaning, including single and multiple elements, and may also be denoted by the suffix "(s)" at the end of the element. For example, "at least one polyurethane," "one or more polyurethanes," and "polyurethane" may be used interchangeably and have the same meaning.

In a preferred aspect, the article of footwear is designed for use in outdoor athletic activities, such as international football/soccer, golf, american football, baseball, running, track and field events, cycling (e.g., road and mountain biking) and the like. The article of footwear may optionally include traction elements (e.g., lugs, wedges, studs (stud), and spikes) to provide traction on soft and slippery surfaces. Wedges, studs and spikes are often included in footwear designed for use in the following activities: such as international/soccer, golf, american football, rugby, baseball, and the like, which are often played on unpaved surfaces. Lugs and/or enlarged sole patterns are often included in footwear including boot designs for use in rugged outdoor conditions such as cross-country running, hiking, and military use.

Fig. 1-4 illustrate an example article of footwear of the present disclosure, referred to as article of footwear 100, and depicted as footwear for use in an international/soccer application. As shown in fig. 1, footwear 100 includes an upper 110 and an outsole 112 as part of an article of footwear, where outsole 112 includes a plurality of traction elements 114 (e.g., cleats) and a hydrogel-containing material 116 at an exterior or ground-facing side or surface thereof. While many of the embodied footwear of the present disclosure preferably include traction elements such as cleats, it should be understood that in other aspects, the incorporation of cleats is optional.

Upper 110 of footwear 100 has a body 118, and body 118 may be made from materials known in the art for making articles of footwear and configured to receive a user's foot. For example, upper body 118 may be made from or include one or more components made from one or more of the following: natural leather; knitted (knit), braided (woven), woven (woven) or non-woven (non-woven) textiles made wholly or partially of natural fibers; a knitted, braided, woven or non-woven textile made wholly or partially of a synthetic polymer; films of synthetic polymers, and the like; and combinations thereof. Upper 110 and the components of upper 110 may be manufactured according to conventional techniques (e.g., molding, extrusion, thermoforming, sewing, knitting, etc.). Although shown in fig. 1 as a generic design, upper 110 may alternatively have any desired aesthetic design, functional design, trade mark indicators, and the like.

Outsole 112 may be secured directly or otherwise to upper 110 using any suitable mechanism or method. As used herein, the term "secured to," for example, with respect to an outsole secured to an upper (e.g., operatively secured to an upper), collectively refers to directly connected, indirectly connected, integrally formed, and combinations thereof. For example, for an outsole secured to an upper, the outsole may be directly attached to the upper (e.g., using an adhesive), the outsole may be indirectly attached to the upper (e.g., using a midsole), may be integrally formed with the upper (e.g., as a single component), and combinations thereof.

For example, upper 110 may be sewn to outsole 112, or upper 110 may be glued to outsole 112, e.g., at or near bite line 120 of upper 110. Footwear 100 may also include a midsole (not shown) that is secured between upper 110 and outsole 112 or may be surrounded by outsole 112. When a midsole is present, upper 110 may be stitched, glued, or otherwise attached to the midsole at any suitable location, such as at or below bite line 120.

As further shown in fig. 1 and 2, the arrangement of outsole 112 may be divided into a forefoot region 122, a midfoot region 124, and a heel region 126. Forefoot region 122 is disposed proximate a forefoot of the wearer, midfoot region 124 is disposed between forefoot region 122 and heel region 126, and heel region 126 is disposed proximate a heel of the wearer and opposite forefoot region 122. Outsole 112 may also include a forward edge 128 at forefoot region 122 and a rearward edge 130 at heel region 126. In addition to these longitudinal designations, the left/right sides of outsole 112 may also be designated by medial side 132 and lateral side 134, respectively.

Each of these designations may also apply to upper 110 and more generally to footwear 100, and are not intended to particularly define the structure or boundaries of footwear 110, upper 110, or outsole 112. As used herein, directional orientations of the article, such as "up," "down," "top," "bottom," "left," "right," and the like, are used for ease of discussion and are not intended to limit use of the article to any particular orientation. Further, references to "ground-facing surface," "ground-facing side," and similar terms refer to the surface or side of the footwear that faces the ground when standing during normal use by the wearer. These terms are also used for ease of discussion, and are not intended to limit use of the article to any particular orientation.

Outsole 112 may optionally include a backing plate 136, which in the illustrated example extends through forefoot region 122, midfoot region 124, and heel region 126. The backing plate 136 is an exemplary backing member or other outsole substrate used in an article of footwear and may provide structural integrity to the outsole 112. However, the backing plate 136 may also be sufficiently flexible, at least in certain locations, to conform to the curvature of the wearer's foot during dynamic movements that occur while wearing. For example, as shown in fig. 1 and 2, the backing plate 136 may include a flex region 138 at the forefoot region 122, which may facilitate flexing of the wearer's toe relative to the foot in active use of the footwear 100.

The backing plate 136 may have a top (or first) surface (or side) 142 (best shown in fig. 3 and 4), a bottom (or second) surface (or side) 144, and sidewalls 146, wherein the sidewalls 146 may extend around the periphery of the backing plate 136 at the forward edge 128, the rearward edge 130, the inner side 132, and the outer side 134. The top surface 142 is an area of the backing plate 136 (and more generally the outsole 112) that may contact and be secured to the upper 110 and/or to any existing midsole or insole.

The bottom surface 144 is the surface of the backing plate 136 that is covered (or at least partially covered) by the material 116 secured thereto, and if the material 116 is otherwise omitted, that surface would otherwise be configured to contact a ground surface, whether indoors or outdoors. Bottom surface 144 is also a portion of outsole 112 from which traction elements 114 may extend, as discussed below.

The optional backing plate 136 may be fabricated with one or more layers, may be produced from any suitable material, and may provide a good interfacial bond for the material 116, as discussed below. Examples of suitable materials for the backing plate 136 include one or more polymeric materials, such as thermoplastic elastomers; a thermosetting polymer; an elastomeric polymer; a silicone polymer; natural rubber and synthetic rubber; a composite material comprising a polymer reinforced with carbon fibers and/or glass; natural leather; metals such as aluminum, steel, and the like; and combinations thereof.

In a particular aspect, when a backing plate 136 is used, the backing plate 136 is fabricated from one or more polymer materials having a chemistry similar to the chemistry of the material 116. In other words, both the backing plate and the material may comprise or consist essentially of polymers having the same or similar functional groups, and/or may comprise or consist essentially of polymers having the same or similar levels of polarity. For example, both the backing plate and the material may comprise or consist essentially of: one or more polyurethanes (e.g., thermoplastic polyurethanes), one or more polyamides (e.g., thermoplastic polyamides), one or more polyethers (e.g., thermoplastic polyethers), one or more polyesters (e.g., thermoplastic polyesters), and the like. Similar chemistries may be beneficial for improving manufacturing compatibility between the material of the material 116 and the material of the backing plate 136, and for improving their interfacial bond strength. Optionally, one or more tie layers (not shown) may be applied between the backing plate 136 and the material 116 to improve their interlayer bonding.

As used herein, the term "polymer" refers to a molecule having polymerized units of one or more monomeric species. The term "polymer" is to be understood as including both homopolymers and copolymers. The term "copolymer" refers to a polymer having polymerized units of two or more monomeric species, and is understood to include terpolymers and other polymers formed from a plurality of different monomers. As used herein, reference to "a" polymer or other compound refers to one or more molecules of the polymer or compound, rather than being limited to a single molecule of the polymer or compound. Further, one or more molecules may or may not be the same, so long as they fall under the category of compounds. Thus, for example, "a" polylaurolactam is interpreted to include one or more polymer molecules of polylaurolactam, wherein the polymer molecules may or may not be the same (e.g., different molecular weights and/or isomers).

Traction elements 114 may each include any suitable wedge, stud, spike, or similar element configured to enhance traction on the wearer during cutting, turning, stopping, accelerating, and backward movements. The traction elements 114 may be arranged in any suitable pattern along the bottom surface 144 of the backing plate 136. For example, traction elements 114 may be distributed in groups or clusters (clusters) (e.g., clusters of 2-8 traction elements 114) along outsole 112. As best shown in fig. 1 and 2, traction elements 114 may be grouped into tufts 147A at forefoot region 122, tufts 147B at midfoot region 124, and tufts 147C at heel region 126. In this example, six of traction elements 114 are substantially aligned along a medial side 132 of outsole 112, and the other six traction elements 114 are substantially aligned along a lateral side 134 of outsole 112.

Traction elements 114 may alternatively be symmetrically or asymmetrically arranged along outsole 112 between medial side 132 and lateral side 134, as desired. In addition, one or more of traction elements 114 may be disposed along the centerline of outsole 112 between medial side 132 and lateral side 134, such as blade (blade)114A, as desired to enhance or otherwise alter performance.

Alternatively (or in addition), the traction elements may also include one or more forward edge traction elements 114, such as one or more blades 114B, one or more fins 114C, and/or one or more wedges (not shown) secured to the backing plate 136 (e.g., integrally formed with the backing plate 136) at a forward edge region between the forefoot region 122 and the tuft 147A. In this application, material 116 may optionally extend through bottom surface 144 at the front edge region while maintaining good traction performance.

Further, traction elements 114 may each independently have any suitable dimensions (e.g., shape and size). For example, in some designs, each traction element 114 within a given tuft (e.g., tufts 147A, 147B, and 147C) can have the same or substantially the same size, and/or each traction element 114 across the entirety of the outsole 112 can have the same or substantially the same size. Alternatively, traction elements 114 within each tuft may have different sizes, and/or each traction element 114 may have different sizes across the entirety of outsole 112.

Examples of suitable shapes for traction elements 114 include rectangular, hexagonal, cylindrical, conical, circular, square, triangular, trapezoidal, diamond, ovoid, and other regular or irregular shapes (e.g., curved lines, C-shapes, etc. …). Traction elements 114 may also have the same or different heights, widths, and/or thicknesses as one another, as discussed further below. Additional examples of suitable dimensions of traction elements 114 and their placement along the backing plate 136 include those provided in soccer/international soccer shoes available from Nike, inc.

Traction elements 114 may be incorporated into the outsole including optional backing plate 136 by any suitable mechanism such that traction elements 114 preferably extend from bottom surface 144. For example, as discussed below, traction elements 114 may be integrally formed with backing plate 136 through a molding process (e.g., for solid ground (FG) footwear). Alternatively, the outsole or optional backing plate 136 may be configured to receive removable traction elements 114, such as screw-in or snap-in traction elements 114. In these aspects, the backing plate 136 may include receiving holes (e.g., threaded or snap-fit holes, not shown), and the traction elements 114 may be threaded or snapped into the receiving holes to secure the traction elements 114 to the backing plate 136 (e.g., for Soft Ground (SG) footwear).

In further examples, a first portion of traction elements 114 may be integrally formed with the outsole or optional backing plate 136, and a second portion of traction elements 114 may be secured with a screw-in mechanism, a snap-in mechanism, or other similar mechanism (e.g., for SG-specific footwear). Traction elements 114 may also be configured as studs for use with Artificial Ground (AG) footwear, if desired. In some applications, the receiving holes may be raised or otherwise protrude from the general plane of the bottom surface 144 of the backing plate 136. Alternatively, the receiving hole may be flush with the bottom surface 144.

Traction elements 114 may be made of any suitable material for use with outsole 112. For example, traction elements 114 may include one or more of a polymeric material, such as a thermoplastic elastomer; a thermosetting polymer; an elastomeric polymer; a silicone polymer; natural rubber and synthetic rubber; a composite material comprising a polymer reinforced with carbon fibers and/or glass; natural leather; metals such as aluminum, steel, and the like; and combinations thereof. In aspects in which traction elements 114 are integrally formed (e.g., molded together) with backing plate 112, traction elements 114 preferably comprise the same material (e.g., thermoplastic material) as the outsole or backing plate 112. Alternatively, in aspects where traction elements 114 are separate and insertable into receiving holes of backing plate 112, traction elements 114 may comprise any suitable material (e.g., metals and thermoplastic materials) that can be secured in receiving holes of backing plate 112.

The optional backing plate 136 (and more generally the outsole 112) may also include other features in addition to traction elements 114 that may provide support or flexibility to the outsole and/or provide aesthetic design objectives. For example, the outsole or backing plate 136 may also include ridges 148, which ridges 148 may be raised or otherwise protrude from the general plane of the bottom surface 144.

As shown, ridges 148 may extend along the path of deployment of traction elements 114, if desired. These features (e.g., ridges 148) may be integrally formed into the sole or backing plate 136, or alternatively, may be removable features that are securable to the backing plate 136. Suitable materials for these features include those discussed above for traction elements 114.

The backing plate 136 (and more generally the outsole 112) may also include other features, such as enlarged sole patterns, lugs, and the like, configured to contact the ground or playing surface to increase traction, to enhance performance, or for aesthetic design purposes. These other features may be present on the shoe outsole in place of, or in addition to, traction elements 114, and may be formed from the suitable materials discussed above for traction elements 114.

As further shown in fig. 3 and 4, traction elements 114 may be arranged such that when footwear 100 is positioned on flat surface 149, bottom surface 144 of backing plate 136 and material 116 are offset from flat surface 149. This offset is present even when the material 116 is fully saturated and expanded, as discussed below. Thus, traction elements 114 may receive a maximum level of shear and frictional contact with a surface during use, such as by penetrating into dirt during cutting, turning, stopping, accelerating, backward movement, and the like. In comparison, the material 116 in its offset position may remain partially protected from a significant portion of these shear and friction conditions, thereby maintaining its integrity during use.

FIG. 5 is an enlarged cross-sectional view of the material 116 and the bottom surface 144 of the backing plate 136 at one of the traction elements 144. In this illustrated example, traction elements 114, which may represent one or more of the other traction elements 114, are integrally molded with the backing plate 136 and include stems 150 that project downward beyond the bottom surface 144 and the material 116. The stem 150 itself may include an outer side surface 152 and a terminal edge 154. The distal edge 154 of the shank 150 is the distal end of the traction element 114 opposite the bottom surface 144 and is the portion of the traction element 114 that may initially contact and penetrate into a playing or ground surface.

As mentioned above, traction elements 114 may have any suitable size and shape, wherein shaft 150 (and outer side surface 152) may accordingly have a rectangular, hexagonal, cylindrical, conical, circular, square, triangular, trapezoidal, diamond, oval, and other regular or irregular shapes (e.g., curved lines, C-shapes, etc. …). Similarly, the terminal edge 154 may have dimensions and sizes corresponding to those of the outer side surface 152, and may be substantially flat, beveled, rounded, and the like. Further, in certain aspects, the terminal edge 154 can be substantially parallel to the bottom surface 144 and/or the material 116.

Examples of suitable average lengths 156 of each stem 150 relative to bottom surface 144 range from 1 mm to 20 mm, from 3 mm to 15 mm, or from 5 mm to 10 mm, wherein, as mentioned above, each traction element 114 may have different sizes and dimensions (i.e., the stems 150 of the various traction elements 114 may have different lengths).

In the example shown in fig. 1-5, the material 116 is present across the entire bottom surface 144 of the backing plate 136 between the traction elements 114 (and not including the traction elements 114). For example, as shown in fig. 5, material 116 may cover bottom surface 144 at a location around shank 150 of each traction element 114 such that material 116 does not cover outer side surface 152 or terminal edge 154 of traction element 114 except optionally at base region 158 of shank 150. This may maintain the integrity of material 116 and maintain the traction performance of traction element 114. In certain aspects, the material 116 does not cover or contact any portion of the outer side surface 152 of the stem portion 150. In other aspects, base region 158, which material 116 (in a dry state) covers and contacts lateral surface 152, is less than 25%, less than 15%, or less than 10% of the length of shaft 150, as measured from bottom surface 144 at traction elements 114 on average.

As can be seen in fig. 5, material 116 may be a film to minimize or otherwise reduce its effect on traction elements 114. Examples of suitable average thicknesses of the material 116 in a dry state (referred to as the dry-state material thickness 160) range from 0.025 millimeters to 5 millimeters, from 0.5 millimeters to 3 millimeters, from 0.25 millimeters to 1 millimeter, from 0.25 millimeters to 2 millimeters, from 0.25 millimeters to 5 millimeters, from 0.15 millimeters to 1 millimeter, from 0.15 millimeters to 1.5 millimeters, from 0.1 millimeters to 2 millimeters, from 0.1 millimeters to 5 millimeters, from 0.1 millimeters to 1 millimeter, or from 0.1 millimeters to 0.5 millimeters. As depicted, the thickness of the material 116 is measured between the interface bond at the bottom surface 144 of the backing plate 136 and the outer surface of the material 116 (referred to as the material surface 162).

In certain alternative aspects, material 116 may also (or alternatively) be present on one or more regions of traction elements 114. For example, the material may be present at an outer surface of traction elements 114. These aspects may be beneficial, for example, in applications where traction element 114 has a central base with multiple stems 150, the multiple stems 150 protruding from the periphery of the central base. In such an aspect, material 116 may be present on at least a central base of traction elements 114. Furthermore, for some applications, material 116 may also cover all of one or more of traction elements 114 (e.g., on shaft 150).

The presence of material 116 on the ground-facing side of outsole 112 (i.e., on bottom surface 144) allows material 116 to contact soil, including wet soil, during use, which is believed to enhance the soil release properties of footwear 100, as explained below. However, the material 116 may also optionally be present on one or more locations of the side walls 146 of the backing plate 144.

As briefly mentioned above, the material 116 comprises a hydrogel in composition. The presence of the hydrogel in the material may allow the material 116 to imbibe or otherwise absorb water. For example, the material may absorb water from the external environment (e.g., from mud, wet grass, presoaking, and the like).

As used herein, the term "compliance" refers to the stiffness of an elastic material and may be determined by the storage modulus of the material. Generally, when the hydrogel of the material is a crosslinked hydrogel (e.g., including physical crosslinks, covalent crosslinks, or both), the lower the degree of crosslinking in the hydrogel, or the greater the distance between crosslinks in the hydrogel, the greater the flexibility of the material will be. In particular aspects, when the material comprises a crosslinked polymer hydrogel, it is believed that such absorption of water via the material 116 may cause the crosslinked polymer hydrogel to expand and stretch under the pressure of the received water, while maintaining its overall structural integrity through its crosslinking. This stretching and expansion of the hydrogel may cause the material 116 to expand and become more flexible (e.g., compressible, expandable, and stretchable).

In terms of material expansion, the expansion of the material 116 may be observed as an increase in material thickness from a dry-state thickness 160 (shown in fig. 5) of the material 116, through a series of intermediate-state thicknesses (e.g., thickness 163, shown in fig. 5A) when additional water is drawn, and finally to a saturated-state thickness 164 (shown in fig. 5B), the saturated-state thickness 164 being the average thickness of the material 116 when fully saturated with water. For example, the saturation state thickness 164 of a fully saturated material 116 may be greater than 150%, greater than 200%, greater than 250%, greater than 300%, greater than 350%, greater than 400%, or greater than 500% of the dry state thickness 160 of the same material 116.

In certain aspects, the saturated-state thickness 164 of a fully saturated material 116 ranges from 150% to 500%, from 150% to 400%, from 150% to 300%, or from 200% to 300% of the dry-state thickness 160 of the same material 116. Examples of suitable average thicknesses of the material 116 in the wet state (referred to as the saturation state thickness 164) range from 0.2 millimeters to 10 millimeters, from 0.2 millimeters to 5 millimeters, from 0.2 millimeters to 2 millimeters, from 0.25 millimeters to 2 millimeters, or from 0.5 millimeters to 1 millimeter.

In certain aspects, the material 116 may rapidly absorb water in contact with the material 116. For example, the material 116 may absorb water from mud and wet grass, such as during a warm-up phase prior to a competitive race. Alternatively (or in addition), the material 116 may be pre-conditioned with water such that the material 116 is partially or fully saturated, such as by spraying or soaking the outsole 112 with water prior to use.

The total amount of water that the material 116 can absorb depends on a number of factors, such as its composition (e.g., its hydrophilicity), its crosslink density, its thickness, and its interfacial bond with the backing plate 136 when present. For example, it is believed that a material comprising a hydrogel having a higher level of hydrophilicity and a lower level of crosslink density may increase the water absorption capacity of the material 116. On the other hand, the interface joint between the material 116 and the bottom surface 144 of the backing plate 136 (when the backing plate 136 is used) can potentially limit the expansion of the material 116 due to the relatively thin dimensions of the material 116. Thus, as described below, the water absorption capacity and the swelling capacity of the material 116 may differ between the material 116 in a pure film state (a film separated by itself) and the material 116 as present on the backing plate 136.

The water absorption capacity and rate of absorption of material 116 depends on the size and shape of its geometry and is generally based on the same factors. However, it has been found that to account for the partial size when measuring water absorption capacity, intrinsic steady state material properties can be derived. Conservation of mass may therefore be used to define the ratio of the weight of water drawn to the initial dry weight of the material 116 over a very long time scale (i.e., when the ratio no longer changes at a measurable rate).

Conversely, the rate of water uptake is instantaneous and can be defined kinetically. The three main factors of the rate of water absorption of material 116 present at the surface of a given partial geometry of the outsole include time, thickness, and exposed surface area available for water absorption. Again, the weight of water absorbed can be used as a measure of the rate of water absorption, but the water flux can also be explained by normalizing the exposed surface area. For example, a thin rectangular film may be defined by 2xLxW, where L is the length of one side and W is the width. The values are doubled to account for both major surfaces of the film, but the pre-factor can be eliminated when the film has a non-wicking structural layer affixed to one of the major surfaces (e.g., using the outsole backing plate).

Normalization to thickness and time may require more detailed analysis because they are paired variables. As more time passes through the experiment, water penetrates deeper into the membrane, and therefore, there are more functional (e.g., absorbent) materials available at longer time scales. The one-dimensional diffusion model may explain the relationship between time and thickness by material properties such as diffusivity. In particular, when plotted against the square root of time, the weight of water absorbed per exposed surface area should yield a straight line.

However, several factors may arise when the model does not represent the data well. First, over time, the absorbent material becomes saturated and diffusion kinetics change due to the reduction in the concentration gradient of water. Second, as time progresses, the material may be plasticized to increase the rate of diffusion so, again, the model no longer represents a physical process. Finally, competing processes may dominate the phenomenon of water absorption or the phenomenon of weight change, usually by surface phenomena such as physical adsorption on rough surfaces by capillary forces. This is not a diffusion driven process and in fact water is not absorbed into the membrane.

Although the material 116 may expand as the material 116 absorbs water and transitions between different material states having respective thicknesses 160, 163, and 164, the saturation state thickness 164 of the material 116 preferably remains less than the length 156 of the traction element 114. This selection of material 116 and its corresponding dry and saturated thickness ensures that traction elements 114 may continue to provide ground-engaging traction during use of footwear 100, even when material 116 is in a fully expanded state. For example, the average gap difference between the length 156 of traction element 114 and the saturation state thickness 164 of material 116 is desirably at least 8 millimeters. For example, the average gap distance may be at least 9 millimeters, 10 millimeters, or greater.

As also mentioned above, in addition to expansion, the compliance of the material 116 may also increase from a relatively rigid (i.e., dry state) to an increasingly stretchable, compressible, and malleable (i.e., wet state). The increased compliance, in turn, may allow the material 116 to easily compress under an applied pressure (e.g., during a foot strike on the ground) and, in some aspects, quickly drain at least a portion of the water it retains (depending on the degree of compression). While not wishing to be bound by theory, it is believed that such compressive flexibility alone, water drainage alone, or a combination of the two may disrupt the adhesion and/or cohesion of soil at the outsole 112, which prevents or otherwise reduces the accumulation of soil on the outsole 112.

In addition to quickly draining water, in certain examples, the compressible material 116 can quickly reabsorb water when compression is released (e.g., from a foot strike during normal use). Thus, during use in a wet or humid environment (e.g., muddy or wet ground), material 116 may dynamically drain and repeatedly absorb water, particularly from a wet surface, during successive foot strikes. Thus, the material 116 may continue to prevent the accumulation of scale for an extended period of time (e.g., during the entire competitive game), particularly when there is groundwater available for reabsorption.

Fig. 6-9 illustrate an example method of using footwear 100 with muddy or wet ground 166 depicting a potential mechanism by which materials comprising hydrogels as disclosed herein may prevent or reduce the accumulation of soil on outsole 112. It is known that dirt from the ground surface 166 can accumulate on the outsole (e.g., between the traction elements) during normal athletic or recreational use, particularly when the ground surface 166 is wet. It is believed that soil accumulates on the outsole due to the combination of the soil particles adhering to the surface of the outsole and the soil particles adhering to each other. To break these adhesion/cohesion forces, the soil particles need to undergo a sufficiently high stress to exceed their adhesion/cohesion activation energy. When this is achieved, the soil particles may then move or flow under the applied stress, which removes or otherwise removes portions of the soil from the outsole.

However, during typical applications of cleated footwear, such as during competitive sporting events (e.g., international football/soccer games, golf events, and american football games), the act of walking and running is not always sufficient to dislodge soil from the outsole of the shoe. This can lead to soil sticking to the outsole, particularly in areas of the gap where compressive forces in the normal direction are maximized between individual traction elements. As can be appreciated, this dirt can build up quickly, increasing the weight of the footwear and reducing the effectiveness of the traction elements (e.g., because they have less axial or normal extent to be able to engage with the ground 166), each of which can have a significant impact on athletic performance.

However, it is believed that the incorporation of material 116 to a surface or side of outsole 112 (e.g., a ground-facing surface or side of the outsole) disrupts the adhesion and/or cohesion of soil at outsole 112, thereby reducing the adhesion/cohesion activation energy otherwise required to cause the flow of soil particles. As shown in fig. 6, footwear 100 may be provided in a pre-conditioned (e.g., pre-moistened) state in which material 116 is partially or fully saturated with water. This may be accomplished in a variety of ways, such as spraying the outsole 112 with water, soaking the outsole 112 in water, or otherwise exposing the material 116 to water in sufficient amounts for a sufficient duration of time. Alternatively (or in addition), when water or a wet material is present on ground 166, footwear 100 may be used on ground 166 in a conventional manner until material 116 draws a sufficient amount of water from ground 166 or the wet material to reach its preconditioned state.

During a foot strike, downward motion (shown by arrow 168) of footwear 100 causes traction elements 114 to contact ground 166. As shown in FIG. 7, the continued applied pressure of the foot strike may cause traction elements 114 to dig into the softer soil of ground 166 until material surface 162 of material 116 contacts ground 166. As shown in fig. 8, additional applied pressure of the foot strike may compress material 116 into ground 166, thereby at least partially compressing material 116 under the applied pressure (shown by arrow 170).

As can be seen, this compression of the material 116 into the soil of the ground 166 generally compresses the soil, increasing the likelihood that soil particles adhere to the outsole 112 and cohesively adhere (clump together) to one another. However, the compression of the material 116 may also expel at least a portion of the water it absorbs into the dirt of the ground 166 (shown by arrows 172). It is believed that as water drains through the material surface 162 of the material 116, the pressure of the drained water may break the adhesion of the soil to the material surface 162 at this interface.

Further, it is believed that the water may also alter the rheological properties of the soil adjacent to the material surface 162 once expelled into the soil (e.g., wash the soil with water to a relatively muddy or wet state). It is believed that this substantially disperses the soil particles in the water carrier and weakens their adhesion (e.g., mechanical bonds/ionic bonds/hydrogen bonds). Each of these mechanisms based on the drained water is believed to reduce the stress required to break the adhesion of soil to the outsole 112. Also, the stresses typically applied during athletic performance (e.g., while running, holding the ball with footwear, and kicking) may more frequently exceed the activation energy of the adhesion/bonding.

As shown in fig. 9, when footwear 100 is lifted (shown by arrow 174) after a foot strike, it is believed that the compression applied to material 116 is released and, thus, material 116 may freely expand. In some examples, it has been found that when outsole 112 is lifted away from ground surface 166, a thin layer of water may remain in contact with material surface 162, which may quickly resorb into material 116. This rapid resorption of water from the material surface 162 after the compression is removed (e.g., within about 1 second, 2 seconds, or 5 seconds) can cause the material 116 to rapidly expand, returning at least partially to its previously expanded state (depending on the amount of re-imbibed water), as shown by arrow 176.

Such cyclic compression and expansion from repeated, rapid, and/or forceful foot strikes during use of footwear 100 may also mechanically disrupt the adhesion of any soil still adhered to material surface 162, despite relatively small thicknesses of material 116 being in any of its various states of water saturation (e.g., partially saturated to fully saturated). In particular, it is believed that in some cases, increased compliance when compressed in the normal or vertical direction results in a non-uniform shear state in the fouling, which may also result in increased interfacial shear stress and a reduction in fouling buildup.

In certain aspects, the material 116 may expand during water reabsorption (and also during initial absorption) in a non-uniform manner. In such aspects, the absorbed water may tend to travel in a path perpendicular to the material surface 162, and thus, once drawn, may generally not move in a generally lateral direction in the plane of the material 116. This relative lack of uneven, vertical water absorption and lateral water transport within the material can create an irregular or rough texture or small ridges on the material surface 162. It is also believed that the presence of these small ridges on the irregular material surface 162 due to non-uniform expansion potentially further disrupts the adhesion of soil at the material surface 162 and thus may loosen the soil and further promote soil shedding. An uneven, ridged material surface 162 can also be seen in the photograph of fig. 19 of an exemplary water-saturated material 116 according to the present disclosure.

In addition to the absorption, compression, expulsion, reabsorption, and expansion cycles discussed above, the increased flexibility of the material 116, e.g., the flexibility of elongation in the longitudinal direction, may allow the material 116 to be more malleable and stretchable when expanded. For example, as shown in fig. 10, during rotation of the foot in foot strike (e.g., when the foot rolls substantially from heel to toe during a stride), the outsole 112 and material 116 correspondingly flex (e.g., causing a compressive force, shown by arrow 170).

When partially or fully saturated with water, the increased elongation or stretching of the material 116 may increase the degree to which the material 116 stretches during this bending, which may cause additional shear on any dirt adhered to the material surface 162. As shown, the undulating ground impact creates a curved outsole 112 and curved compressible material 116, which can cause water to drain therefrom and create a transverse material tensile force to pull the dirt apart and cause the dirt to fall off. The compressive force (shown by arrows 170) on the material 116 that may help to expel water may be particularly strong at the point of contact with the ground 166 and/or where the radius of curvature of the curved outsole 112/curved material 116 is relatively small or at its minimum.

It is believed that the aforementioned properties of the material 116 relating to compression/expansion flexibility and elongation flexibility are closely interrelated, and that they may depend on the properties of the same material 116 (e.g., a hydrophilic material capable of rapidly absorbing and expelling a relatively large amount of water compared to the size and thickness of the material). Differences exist in their mechanisms for preventing soil accumulation, such as surface adhesion failure versus shear induction. It is believed that water reabsorption potentially serves to rapidly expand or swell the material 116 after the material 116 is compressed to expel the water. Rapid water absorption may provide a mechanism for material 116 to replenish water content during a foot strike. The rapid replenishment of the water content of the material 116 may restore the material 116 to its flexible state, returning it to a state in which tensile and shear forces may assist in the shedding of debris. In addition, the re-replenishment of the water content of the material 116 may allow for subsequent water discharge to provide additional mechanisms for preventing scale build-up (e.g., application of water pressure and modification of scale rheological properties). Thus, the water suction/drainage cycles may provide a unique combination for preventing soil accumulation on the outsole 112 of the footwear 100.

In addition to being effective in preventing soil buildup, material 116 has also been found to be sufficiently durable for its intended application on the ground-contacting side of outsole 112. The durability is based in part on the nature and strength of the interfacial bond of the material 116 to the bottom surface 144 of the backing plate 136, as well as the physical properties of the material 116 itself. For many examples, the material 116 may not delaminate from the backing plate 136 during the useful life of the material 116, and the material 116 may be substantially wear resistant and abrasion resistant (e.g., maintain its structural integrity without breaking or tearing).

In various aspects, the useful life of material 116 (as well as outsole 112 and footwear 100 comprising material 116) is at least 10 hours, 20 hours, 50 hours, 100 hours, 120 hours, or 150 hours of wear. For example, in some applications, the useful life of the material 116 ranges from 20 hours to 120 hours. In other applications, the useful life of the material 116 ranges from 50 hours to 100 hours of wear.

Interestingly, for many examples, the dry and wet states of material 116 may allow material 116 to be dynamically adapted in terms of durability to cause dry and wet surface activity (surface play). For example, when used on a dry floor 166, the material 116 may also be dry, which makes it harder and more wear resistant. Alternatively, the material 116 may rapidly absorb water to achieve a partially or fully saturated condition, which may be a state of swelling and/or flexibility, when used on a wet ground 166 or when wet material is present on a dry ground 166. However, the wet floor 166 imposes less wear on the expanded and flexible material 116 than the dry floor 166 does. Thus, the material 116 may be used in a variety of conditions as desired. Nonetheless, footwear 100 and outsole 112 are particularly beneficial for use in wet environments, such as wet environments with mud surfaces, grass surfaces, and the like.

Although material 116 is shown above in fig. 1-4 as extending across the entire bottom surface 144 of outsole 112 of footwear 100, in alternative aspects, material 116 may alternatively be present as one or more segments that are present at separate, discrete locations on bottom surface 144 of outsole 112. For example, as shown in fig. 11, material 116 may optionally be present as: first segment 116A secured to bottom surface 144 at forefoot region 122, e.g., in the gap areas between traction elements 114 of tuft 147A; a second section 116B secured to bottom surface 144 at midsole region 124, e.g., in the gap regions between traction elements 114 of tuft 147B; and/or third segment 116C secured to bottom surface 144 at heel region 126, e.g., in the areas of the gaps between traction elements 114 of tuft 147C. In each of these examples, the remaining area of the bottom surface 144 may be free of the material 116.

In certain arrangements, the material 116 is present as one or more sections secured to the bottom surface 144 at a region 178 between the tufts 147A and 147B, at a region 180 between the tufts 147B and 147C, or both secured to the bottom surface 144. For example, material 116 may include: a first section that exists on bottom surface 144 around the location of section 116A, region 178, and section 116B, and the location of region 178; and a second section corresponding to section 116B (at cluster 147C). As also shown in fig. 11, the sections of material 116 (e.g., sections 116A, 116B, and 116C) may optionally have surface dimensions that conform to the overall geometry of the backing plate 136, e.g., to conform to the contours of the ridges 148, traction elements 114, and the like.

In another arrangement, the bottom surface 144 includes a leading edge region between the leading edge 128 and the tuft 147A (and optionally a leading portion of the tuft 147A) that is free of the material 116. Since some of the examples of material 116 may be slippery when partially or fully saturated, having material 116 present in the front edge region of bottom surface 144 may potentially affect traction and ball control during motion. Moreover, dirt accumulation is generally most pronounced in the interstitial regions of the tufts 147A, 147B, and 147C as compared to the leading edge 128.

In addition, the optional backing plate 136 may also include one or more recessed pockets, such as the pocket 188 shown in FIG. 12, in which the material 116 or sub-sections of the material 116 may reside. This can potentially increase the durability of the material 116 by protecting the material 116 from lateral delamination stresses. For example, the backing plate 136 may include pockets 188 in the interstitial regions of the clusters 147C, wherein the subsections 116C of the material 116 may be secured to the bottom surface 144 within the pockets 188. In this case, the dry-state thickness 160 of the material 116 may vary relative to the depth 190 of the pocket 188.

In certain aspects, the depth 190 of the pocket 188 may range from 80% to 120%, from 90% to 110%, or from 95% to 105% of the dry-state thickness 160 of the material 116. Further, in aspects in which the backing plate 136 includes a plurality of pockets 188, each pocket 188 may have the same depth 190, or the depth 190 may be independently varied as desired. As can be appreciated, when the material 116 is partially or fully saturated, the increased incorporation of the material 116 due to the recessed pocket 188 can potentially reduce the expansion of the material 116. However, a significant portion of material 116 may be sufficiently offset from the walls of pocket 188 that these interfacial bonds (relative to dry-state thickness 160) will minimally affect the swelling and water absorption properties of material 116.

Fig. 13 shows an alternative design for the engagement between the material 116 and the bottom surface 144. In this case, the backing plate 136 may include one or more recessed indentations 192 in any suitable pattern, and wherein portions of the material 116 extend into the indentations 192 to increase the surface area of the interface bond between the material 116 and the bottom surface 144 of the backing plate 136. For example, indentations 192 may be present as: one or more geometrically shaped holes (e.g., circular, rectangular, or other geometric shapes) or irregularly shaped holes in the backing plate 136, one or more grooves or channels extending partially or fully along the backing plate 136 (in a lateral, longitudinal, or diagonal direction), and the like.

In these aspects, the material 116 may have two (or more) thicknesses depending on whether a given portion of the material 116 extends into one of the indentations. For ease of discussion and readability, dry-state thickness 160 of material 116 as used herein refers to a portion of material 116 (in the dry state) that does not extend into one of the indentations, such as at location 194. Thus, the dry-state thickness 160 shown in fig. 13 is the same as the dry-state thickness 160 shown in fig. 5 above.

Each indentation 192 may independently have a depth 196 that may range from 1% to 200%, from 25% to 150%, or from 50% to 100% of the dry-state thickness 160 of the material 116. In these locations, the dry-state thickness of the material 116 is the sum of the dry-state thickness 160 and the depth 196. An interesting result of this arrangement is that the material 116 can potentially expand to different partially or fully saturated thicknesses 164. In particular, because the amount of material 116 expands depends on the initial dry-state thickness of material 116, and because the portion of material 116 at indentations 192 has a greater dry-state thickness than the portion of material 116 at locations 194, this may result in a non-planar expansion of material 116, as depicted by dashed line 198. The particular size of the non-planar expansion may vary depending on: the relative dry-state thickness of material 116, the depth 196 of indentations 192, the degree of saturation of material 116, the particular composition of material 116, and the like.

Fig. 14 illustrates the variation on indentations 192 shown in fig. 13 above. In the design shown in FIG. 14, the indentations 192 may also extend in-plane with the backing plate 136 to form locking members 200 (e.g., arms or flanged heads). Such a design may also be produced with co-extrusion or injection molding techniques, and may further assist in mechanically locking the material 116 to the backing plate 136.

As discussed above, outsole 112 with material 116 is particularly suited for use in international/soccer ball applications. However, material 116 may also be used in combination with other types of footwear 100, such as articles of footwear 100 for golf balls (shown in fig. 15), for baseball (shown in fig. 16), and for american football (shown in fig. 17), each of which may include traction elements 114, such as cleats, studs, and the like.

Fig. 15 illustrates an aspect in which material 116 is positioned on one or more portions of outsole 112 and/or traction elements 114 of golf footwear 100. In some cases, material 116 is present on one or more locations of the ground-facing surface of outsole 112 other than traction elements 114 (e.g., a non-cleated surface, such as that generally shown in fig. 1 with respect to international/soccer footwear 100). Alternatively or additionally, the material 116 may be present on the ground-facing surface of the outsole 112 as one or more material sections 116D on one or more surfaces between the sole patterns 202.

Alternatively or additionally, material 116 may be incorporated onto one or more surfaces of traction elements 114. For example, the material 116 may also be on a central region of the traction elements 114 between the stems/spikes 150A, such as the surface opposite the region where the traction elements 114 are mounted to the backing plate 136 of the outsole 112. In many traction elements for golf footwear, traction element 114 has a substantially flat central base region 158A and a plurality of stems/spikes 150A arranged around the perimeter of central region 158A. In such traction elements, the material 116 may be located on a central substantially flat base region 158A.

In such an aspect, the remaining area of the outsole 112 may be free of material 116. For example, the cleat 114 with the material 116 may be a separate component that may be secured to the outsole 112 (e.g., screwed or snapped in), wherein the outsole 112 itself may be free of the material 116. In other words, the material covered cleats 114 may be provided as components for use with standard footwear (e.g., golf shoes or other footwear) that does not otherwise incorporate the material 116.

Fig. 16 illustrates an aspect in which material 116 is positioned on one or more portions of outsole 112 of baseball article of footwear 100. In some cases, material 116 is present on one or more locations of the ground-facing surface of outsole 112 other than cleats 114 (e.g., non-cleated surfaces, such as generally shown in fig. 1 with respect to international/soccer footwear 100). Alternatively or additionally, material 116 may be present as one or more material segments 116D on one or more recessed surfaces 204 in the ground-facing surface of outsole 112, recessed surfaces 204 may include cleats 114 therein (e.g., material 116 is located only in one or more of recessed surfaces 204, but not substantially on the cleats).

Fig. 17 illustrates an aspect in which material 116 is positioned on one or more portions of outsole 112 of article of american football footwear 100. In some cases, material 116 is present on one or more locations of the ground-facing surface of outsole 112 other than cleats 114 (e.g., non-cleated surfaces, such as generally shown in fig. 1 with respect to international/soccer footwear 100). Alternatively or additionally, material 116 may be present as one or more material segments 116D on one or more recessed surfaces 204 in the ground-facing surface of outsole 112, recessed surfaces 204 may include cleats 114 therein (e.g., material 116 is located only in one or more of recessed surfaces 204, but not substantially on the cleats).

Fig. 18 illustrates an aspect in which material 116 is positioned on one or more portions of outsole 112 of an article of walking footwear 100 (e.g., a walking shoe or boot). As shown, traction elements 114 are in the form of lugs 114D, lugs 114D being integrally formed with bottom surface 144 of outsole 112 and projecting from bottom surface 144 of outsole 112. In some cases, material 116 is present on bottom surface 144 of outsole 112 at one or more locations other than lugs 114D. For example, the material 116 may be located on the recessed surface 204 between adjacent lugs 114D (e.g., but not substantially on the lugs 114D).

The foregoing discussion of footwear 100 and outsole 112 has been made above in the context of footwear having traction elements (e.g., traction elements 114) such as cleats, studs, spikes, lugs, and the like. However, footwear 100 with material 116 may also be designed for any suitable activity, such as running, track events, football, cycling, tennis, and the like. In these aspects, one or more sections of material 116 are preferably located in the gap regions between traction elements, such as in the gap grooves of the sole pattern of a running shoe.

As discussed above, the material of the present disclosure, such as material 116 used with outsole 112 (and footwear 100), may be constructed to include a hydrogel that allows the material to absorb water. As used herein, the terms "absorb (take up)", "absorb (take)" and similar terms refer to the absorption of a liquid (e.g., water) into a material from an external source, e.g., by imbibition, adsorption, or both. Further, as briefly mentioned above, the term "water" refers to an aqueous liquid, which may be pure water, or may be an aqueous carrier having a relatively small amount of dissolved, dispersed, or otherwise suspended materials (e.g., particulates, other liquids, and the like).

The ability of a material (e.g., material 116) to absorb water when used on an outsole and correspondingly swell and increase flexibility may reflect its ability to prevent soil buildup during use with an article of footwear (e.g., footwear 100). As discussed above, when a material absorbs water (e.g., by wicking, adsorption, capillary action, etc.), the water absorbed by the material transitions the material from a dry, relatively more rigid state to a relatively more flexible, partially or fully saturated state. When the material is subsequently subjected to compressive or bending pressure application, the volume of the material may be reduced, for example to expel at least a portion of its water.

It is believed that this drained water reduces the binding force/adhesion of soil particles at the outsole, which alone or more preferably in combination with material flexibility, may prevent or otherwise reduce soil accumulation at the outsole. Thus, the material may undergo dynamic transitions during and between foot strikes, such as when the wearer is running or walking, and these dynamic transitions may also create forces that dislodge accumulated soil or otherwise reduce the accumulation of soil on the outsole.

Based on the mechanisms of the various interactions involved in reducing or preventing the accumulation of soil on the outsoles of the present disclosure, it has been discovered that different properties of the materials used to form all or a portion of the outsole can be used to select, for example, a desired performance benefit, such as preventing or reducing the adhesion of soil to the outsole or increasing the flexibility or durability of the material. For example, an article of footwear (e.g., footwear 100), an outsole (e.g., outsole 114), and a material (e.g., material 116) of the present disclosure may be characterized according to the following: the water absorption capacity and rate of water absorption of the material, the swelling capacity, the contact angle when wet, the coefficient of friction when wet and dry, the decrease in storage modulus from dry to wet, the decrease in glass transition temperature from dry to wet, and the like.

As used herein, the terms "footwear sampling procedure", "co-extruded film sampling procedure", "neat material sampling procedure", "water absorption capacity test", "water absorption rate test", "swell capacity test", "contact angle test", "coefficient of friction test", "storage modulus test", "glass transition temperature test", "impact energy test", and "soil shedding footwear test" refer to the respective sampling procedure and test methodology described in the performance analysis and characterization procedure section below. These sampling procedures and testing methodologies characterize the properties of the recited materials, outsoles, footwear, and the like, and need not be performed as an active step in the claims. It is to be understood that any of the tests disclosed herein can be performed using any of the sampling procedures disclosed herein to determine properties of an outsole or properties of an outsole that can be attributed to an outsole or an article of footwear based on measurements made in a simulated environment (e.g., using samples prepared according to a co-extruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure). In other words, measurements obtained on pure material may be attributed to an outsole comprising material that defines at least a portion of a surface or side of the outsole. In addition, measurements made in a simulated environment may be used to select a desired performance property for an outsole comprising a material that defines at least a portion of a surface or side of the outsole.

For example, in certain aspects, a material (e.g., a material present as a sample of a portion of an outsole prepared according to a footwear sampling procedure, the outsole being such that the material is present at or defines a side or surface of the outsole from which the sample was collected) has a 24-hour water absorption capacity of greater than 40% by weight, as characterized by a water absorption capacity test using the footwear sampling procedure, each as described below. In certain aspects, it is believed that if a particular outsole is unable to absorb more than 40% by weight of water over a 24 hour period due to its rate of water absorption being too low or its ability to absorb water being too low (e.g., due to its thinness, insufficient material may be present, or the overall ability of the material to absorb water being too low), then the outsole may not be effective in preventing or reducing soil buildup.

In further aspects, the material (including the side or surface of the outsole formed from the material) has a 24 hour water absorption capacity of greater than 50% by weight, greater than 100% by weight, greater than 150% by weight, or greater than 200% by weight. In other aspects, the outsole has a 24 hour water absorption capacity of less than 900% by weight, less than 750% by weight, less than 600% by weight, or less than 500% by weight.

In a particular aspect, the material (including the side or surface of the outsole formed from the material) has a 24 hour water absorption capacity ranging from 40% by weight to 900% by weight. For example, the outsole may have a water absorption capacity ranging from 100% by weight to 900% by weight, from 100% by weight to 750% by weight, from 100% by weight to 700% by weight, from 150% by weight to 600% by weight, from 200% by weight to 500% by weight, or from 300% by weight to 500% by weight.

These water absorption capacities are determined by the water absorption capacity test using the footwear sampling procedure and may be applied to samples taken at any suitable representative location along the outsole of the shoe, where the samples may be obtained in accordance with the footwear sampling procedure. In some cases, samples may be collected from one or more of the forefoot region, midfoot region, and/or heel region; collected from each of a forefoot region, a midfoot region, and a heel region; collected from within one or more of the traction element clusters at the forefoot region, midfoot region, and/or heel region (between the traction elements); collecting clusters of self-attaching friction elements; the collection on the planar area of the traction element (for aspects where material is present on the traction element), and combinations thereof.

As discussed below, the water absorption capacity of a material (including the side or surface of an outsole formed from the material) may alternatively be measured in a simulated environment, for example using a material coextruded with a backing substrate. The backing substrate may be made of any suitable material compatible with the materials used to form the outsole backing plate, for example. Thus, suitable 24 hour water uptake capacities for materials coextruded with the backing substrate, as characterized by the water uptake capacity test using the coextruded film sampling procedure, include those discussed above for the water uptake capacity test using the footwear sampling procedure.

Additionally, it has been found that when the material is secured to another surface, such as by being thermally or adhesively bonded to an outsole substrate (e.g., an outsole backing plate), the interfacial bond formed between the material and the outsole substrate can limit the extent to which the material can absorb water and/or swell. Thus, it is believed that materials such as those incorporated into outsole substrates or coextruded backing substrates can potentially have lower water absorption capacity and/or lower expansion capacity than the same materials in pure material form, including pure film form.

Thus, the water absorption capacity and water absorption rate of a material can also be characterized based on the material being in a pure form (e.g., a separate membrane that is not bound to another material). The material in pure form can have a 24 hour water absorption capacity of greater than 40% by weight, greater than 100% by weight, greater than 300% by weight, or greater than 1000% by weight, as characterized by the water absorption capacity test using a pure membrane sampling procedure or a pure material sampling procedure. The material in pure form may also have a 24 hour water absorption capacity of less than 900% by weight, less than 800% by weight, less than 700% by weight, less than 600% by weight or less than 500% by weight.

In particular aspects, the material in pure form has a 24-hour water absorption capacity ranging from 40% by weight to 900% by weight, from 150% by weight to 700% by weight, from 200% by weight to 600% by weight, or from 300% by weight to 500% by weight.

The material (including the side or surface of the outsole formed from the material) may also have a weight per square (g/(m) of greater than 20 g/(m)²-minutes^1/2) As characterized by the water uptake rate test using the footwear sampling procedure. As discussed above, in certain aspects, the outsole (e.g., material 116) may absorb water between compression cycles of foot strikes, which is believed to at least partially replenish material between foot strikes.

Thus, in further aspects, the material (including the side or surface of the outsole formed from the material) has a weight average of greater than 20 grams/(meter)²-minutes^1/2) Greater than 100 grams/(meter)²-minutes^1/2) More than 200 g/(m)²-minutes^1/2) More than 400 g/(m)²-minutes^1/2) Or greater than 600 g/(m)²-minutes^1/2) The water absorption rate of (c). In a particular aspect, the outsole has a range of from 1 to 1,500 grams/(meter)²-minutes^1/2) 20 to 1,300 g/(m)²-minutes^1/2) From 30 to 1,200 g/(m)²-minutes^1/2) From 30 to 800 g/(m)²-minutes^1/2) From 100 to 800 g/(m)²-minutes^1/2) From 100 to 600 g/(m)²-minutes^1/2) From 150 to 450 g/(m)²-minutes^1/2) From 200 to 1,000 g/(m)²-minutes^1/2) From 400 to 1,000 g/(m)²-minutes^1/2) Or from 600 to 900 g/(m)²-minutes^1/2) The water absorption rate of (c).

As characterized by the water uptake rate test using the coextruded film sampling procedure, and as provided in pure form, as characterized by the water uptake rate test using the neat film sampling procedure, as suitable water uptake rates of materials affixed to the coextruded backing substrate, each include those discussed above for the water uptake rate test using the footwear sampling procedure.

In certain aspects, the material (including the sides or surfaces of the outsole formed from the material) may also expand, increasing the thickness and/or volume of the material due to water absorption. This swelling of the material may be a convenient indicator that the material is absorbing water and may help make the material flexible. In certain aspects, the outsole has a 1 hour increase in material thickness (or inflated thickness increase) of greater than 20% or greater than 50%, e.g., ranging from 30% to 350%, from 50% to 400%, from 50% to 300%, from 100% to 200%, or from 150% to 250%, as characterized by the inflation capability test using a footwear sampling procedure. In further aspects, the outsole has a 24 hour increase in material thickness ranging from 45% to 400%, from 100% to 350%, or from 150% to 300%.

In addition, the material (including the side or surface of the outsole formed from the material) may have a 1 hour increase in volume (or increase in volume expansion) of the material greater than 50%, for example ranging from 10% to 130%, from 30% to 100%, or from 50% to 90%. Further, the outsole may have a 24 hour volume increase of material ranging from 25% to 200%, from 50% to 150%, or from 75% to 100%.

For coextruded film mimetics, as characterized by the dilatancy test using the coextruded film sampling procedure, suitable 1 hour and 24 hour material thickness and volume increases for materials affixed to the coextruded backing substrate include those discussed above with respect to the dilatancy test using the footwear sampling procedure.

The material in pure form may have a 1 hour increase in material thickness ranging from 35% to 400%, from 50% to 300%, or from 100% to 200%, as characterized by the dilatancy test using the pure membrane sampling procedure. In certain further aspects, the material in pure form can have a 24 hour increase in material thickness ranging from 45% to 500%, from 100% to 400%, or from 150% to 300%. Accordingly, the material in pure form may have a 1 hour increase in volume of the material ranging from 50% to 500%, from 75% to 400%, or from 100% to 300%.

As also discussed above, in certain aspects, a surface of the material forms a side or surface of the outsole, wherein the side or surface has hydrophilic properties. The hydrophilic properties of the surface of a material can be characterized by determining the static sessile drop contact angle (static sessile drop contact angle) of the surface of the material. Thus, in certain examples, the surface of the material in the dry state has a static sessile drop contact angle (or contact angle in the dry state) of less than 105 °, or less than 95 °, less than 85 °, as characterized by the contact angle test. The contact angle test may be performed on samples obtained according to a footwear sampling procedure, a coextruded film sampling procedure, or a neat film sampling procedure. In certain further examples, the material in a dry state has a static sessile drop contact angle ranging from 60 ° to 100 °, from 70 ° to 100 °, or from 65 ° to 95 °.

In other examples, the surface of the material in the wet state has a static sessile drop contact angle (or contact angle in the wet state) of less than 90 °, less than 80 °, less than 70 °, or less than 60 °. In certain further examples, the surface in the wet state has a static sessile drop contact angle ranging from 45 ° to 75 °. In some cases, the dry state static sessile drop contact angle of the surface is at least 10 °, at least 15 °, or at least 20 °, such as from 10 ° to 40 °, from 10 ° to 30 °, or from 10 ° to 20 °, greater than the wet state static sessile drop contact angle of the surface.

Surfaces of the material, including surfaces of the outsole, may also exhibit a low coefficient of friction when the material is wet. Examples of suitable coefficients of friction (or dry state coefficients of friction) for materials in the dry state are less than 1.5, for example ranging from 0.3 to 1.3, or from 0.3 to 0.7, as characterized by the coefficient of friction test. The coefficient of friction test may be performed on samples obtained according to a footwear sampling procedure, a co-extruded film sampling procedure, or a neat film sampling procedure. Examples of suitable coefficients of friction (or wet state coefficients of friction) for a material in a wet state are less than 0.8 or less than 0.6, for example ranging from 0.05 to 0.6, from 0.1 to 0.6, or from 0.3 to 0.5. Furthermore, the material may exhibit a reduction in its coefficient of friction from its dry state to its wet state, for example a reduction ranging from 15% to 90%, or from 50% to 80%. In some cases, the dry state coefficient of friction of the material is greater than the wet state coefficient of friction, e.g., by a value of at least 0.3 or 0.5, e.g., 0.3 to 1.2 or 0.5 to 1.

Furthermore, the compliance of a material, including an outsole comprising the material, can be characterized based on the storage modulus of the 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) and by a reduction in its storage modulus between the dry and wet states. In particular, the material may have a reduction in storage modulus (Δ Ε') from a dry state relative to a wet state. As the water concentration in the material increases, the decrease in storage modulus corresponds to an increase in compliance because less stress is required for a given strain/deformation.

In certain aspects, the material exhibits a reduction in storage modulus from its dry state to its wet state (50% RH) of greater than 20%, greater than 40%, greater than 60%, greater than 75%, greater than 90%, or greater than 99% relative to the storage modulus in the dry state and as characterized by the storage modulus test using the neat film sampling method. In certain further aspects, the dry state storage modulus of the material is greater than its wet state (50% RH) storage modulus by greater than 25 megapascals (MPa), greater than 50MPa, greater than 100MPa, greater than 300MPa, or greater than 500MPa, for example ranging from 25MPa to 800MPa, from 50MPa to 800MPa, from 100MPa to 800MPa, from 200MPa to 800MPa, from 400MPa to 800MPa, from 25MPa to 200MPa, from 25MPa to 100MPa, or from 50MPa to 200 MPa. Additionally, the dry state storage modulus can range from 40MPa to 800MPa, from 100MPa to 600MPa, or from 200MPa to 400MPa as characterized by the storage modulus test. In addition, the storage modulus in the wet state may range from 0.003MPa to 100MPa, from 1MPa to 60MPa, or from 20MPa to 40 MPa.

In other aspects, the material exhibits a reduction in storage modulus from its dry state to its wet state (90% RH) of greater than 20%, greater than 40%, greater than 60%, greater than 75%, greater than 90%, or greater than 99% relative to the storage modulus in the dry state and as characterized by the storage modulus test using the neat film sampling method. In further aspects, the dry state storage modulus of the material is greater than its wet state (90% RH) storage modulus by greater than 25 megapascals (MPa), greater than 50MPa, greater than 100MPa, greater than 300MPa, or greater than 500MPa, for example ranging from 25MPa to 800MPa, from 50MPa to 800MPa, from 100MPa to 800MPa, from 200MPa to 800MPa, from 400MPa to 800MPa, from 25MPa to 200MPa, from 25MPa to 100MPa, or from 50MPa to 200 MPa. Additionally, the dry state storage modulus can range from 40MPa to 800MPa, from 100MPa to 600MPa, or from 200MPa to 400MPa as characterized by the storage modulus test. In addition, the storage modulus in the wet state may range from 0.003MPa to 100MPa, from 1MPa to 60MPa, or from 20MPa to 40 MPa.

In addition to the reduction in storage modulus, the material may also exhibit a reduction in its glass transition temperature from the dry state (when equilibrated at 0% Relative Humidity (RH)) to the wet state (when equilibrated at 90% RH). While not wishing to be bound by theory, it is believed that the water absorbed by the material plasticizes the material, which lowers its storage modulus and its glass transition temperature, making the material more flexible (e.g., compressible, extensible, and stretchable).

In certain aspects, the material can exhibit a decrease in glass transition temperature (Δ Τ) from its dry state (0% RH) glass transition temperature to its wet state glass transition (90% RH) temperature_g) The reduction in glass transition temperature is greater than a 5 ℃ difference, greater than a 6 ℃ difference, greater than a 10 ℃ difference, or greater than a 15 ℃ difference, as characterized by a glass transition temperature test using a pure membrane sampling method or a pure material sampling procedure. For example, a decrease in glass transition temperature (. DELTA.T)_g) Ranges of (d) may be from greater than 5 ℃ difference to 40 ℃ difference, from greater than 6 ℃ difference to 50 ℃ difference, from greater than 10 ℃ difference to 30 ℃ difference, from greater than 30 ℃ difference to 45 ℃ difference, or from 15 ℃ difference to 20 ℃ difference. The material may also exhibit a dry glass transition temperature ranging from-40 ℃ to-80 ℃, or from-40 ℃ to-60 ℃.

Alternatively (or additionally), the glass transition temperature is reduced (Δ T)_g) May range from a 5 ℃ difference to a 40 ℃ difference, from a 10 ℃ difference to a 30 ℃ difference, or from a 15 ℃ difference to a 20 ℃ difference. The material may also exhibit a dry glass transition temperature ranging from-40 ℃ to-80 ℃, or from-40 ℃ to-60 ℃.

In further aspects, the material may exhibit a soil shedding ability with relative impact energy ranging from 0 to 0.9, from 0.2 to 0.7, or from 0.4 to 0.5, as characterized by an impact energy test using a footwear sampling procedure, a co-extruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure. In addition, the material (e.g., material 116) is preferably sufficiently durable and has sufficient bonding to the outsole backing plate for use over an extended duration of time during play activities. For example, it has been found that the materials of the present disclosure can continue to perform in certain aspects for more than 80 hours or 100 hours without significant visible wear or delamination, as discussed above.

In a particular aspect, the material comprises, in composition, a hydrogel and one or more additives. As used herein, the term "hydrogel" refers to a composition that is capable of absorbing at least 10% by weight of water based on the dry weight of the composition. The hydrogel may be a polymeric hydrogel. The hydrogel may comprise a crosslinked or crosslinkable polymer network, wherein the crosslinks interconnect the various polymer chains to form the polymer network, and wherein the crosslinks may be physical crosslinks, covalent crosslinks, or may include both physical and covalent crosslinks (within the same polymer network). The hydrogel may constitute greater than 50% by weight, or greater than 75% by weight, or greater than 85% by weight, or greater than 95% by weight of the overall material for the outsole. In certain aspects, the material of the outsole consists essentially of a hydrogel.

For physical crosslinks, the copolymer chains may form entangled regions and/or crystalline regions through, for example, non-covalent bonding interactions such as ionic, polar, and/or hydrogen bonding. In particular aspects, the crystalline regions create physical crosslinks between copolymer chains. The crystalline region may include hard segments, as described below.

In certain aspects, the hydrogel may exhibit sol-gel reversibility, allowing it to function as a thermoplastic polymer, which may be advantageous for manufacturing and recycling capabilities. Thus, in certain aspects, the hydrogel of the material includes a physically cross-linked polymer network to function as a thermoplastic hydrogel.

Physically crosslinked hydrogels can be characterized by hard and soft segments, which can exist as phase separated regions within the polymer network when the hydrogel is in a solid (non-molten) state. The hard segments may form part of the backbone of the polymer chain, and may exhibit high polarity, allowing the hard segments of multiple polymer chains to aggregate together, or interact with each other, to form semi-crystalline regions of the polymer network.

"semi-crystalline" or "crystalline" regions have an ordered molecular structure with a well-defined melting point (sharpmelt point), remaining in the solid state until a given amount of heat is absorbed and then rapidly changing to a low viscosity liquid. The "pseudo-crystalline" regions have the properties of crystals, but do not exhibit a true crystal diffraction pattern. For ease of reference, the term "crystalline regions" will be used herein to collectively refer to crystalline regions, semi-crystalline regions, and pseudo-crystalline regions of the polymer network.

In contrast, the soft segments can be longer, more flexible, hydrophilic regions of the polymer network that allow the polymer network to expand and swell under the pressure of absorbed water. The soft segment may constitute an amorphous hydrophilic region of the hydrogel. The soft segment or amorphous region may also form part of the backbone of the polymer chain along with the hard segment. Further, one or more portions of the soft segment or amorphous region may be grafted or otherwise extended as side chains extending from the backbone at the soft segment. The soft segment or amorphous region can be covalently bonded to the hard segment or crystalline region (e.g., via a urethane bond). For example, a plurality of amorphous hydrophilic regions may be covalently bonded to crystalline regions of the hard segment.

Thus, in various aspects, the hydrogel comprises a crosslinked polymer network comprising a plurality of copolymer chains, wherein at least a portion of the copolymer chains each comprise a hard segment physically crosslinked to other hard segments of the copolymer chains and a soft segment covalently bonded to the hard segment, e.g., via a urethane or ester group. In certain instances, the hydrogel comprises a plurality of copolymer chains, wherein at least a portion of the copolymer chains each comprise a first segment physically crosslinked to at least one other copolymer chain of the plurality of copolymer chains and a hydrophilic segment (e.g., a polyether segment) covalently bonded to the first segment, e.g., via a urethane group or an ester group.

In various aspects, the hydrogel comprises a plurality of copolymer chains, wherein at least a portion of the copolymer chains each comprise a first segment that forms at least a crystalline region with other hard segments of the copolymer chains; a second segment covalently bonded to the first segment, such as a soft segment (e.g., a segment having a polyether chain or one or more ether groups), wherein the soft segment forms an amorphous region of the hydrogel. In some cases, the hydrogel includes a plurality of copolymer chains, wherein at least a portion of the copolymer chains have a hydrophilic segment.

The soft segments or amorphous regions of the copolymer chains can constitute a substantial part of the polymer network, allowing their hydrophilic segments or groups to attract water molecules. In certain aspects, the soft segment or amorphous region is present in the copolymer chain at a ratio (relative to the hard segment or crystalline region) of at least 20:1 by weight or greater than 20:1 by weight, ranging from 20:1 to 110:1 by weight, or from 40:1 to 80:1 by weight, or from 60:1 to 80:1 by weight.

For covalent crosslinks, one polymer chain is linked to one or more other polymer chains with one or more covalent bonds, typically with a linker segment or chain. Covalently crosslinked hydrogels (e.g., thermoset and photocurable hydrogels) can be prepared by covalently linking polymer chains together using one or more polyfunctional compounds such as, for example, molecules having at least two ethylenically unsaturated groups, at least two ethylene oxide groups (e.g., diepoxides), or a combination thereof (e.g., glycidyl methacrylate); and may also contain any suitable intermediate chain segment, such as C_1-30、C_2-20Or C_2-10Hydrocarbon, polyether or polyester chain segments.

The polyfunctional compound may comprise at least three functional groups selected from the group consisting of: isocyano (isocyanodyl), hydroxyl, amino, sulfhydryl, carboxyl or derivatives thereof, and combinations thereof. In certain aspects, such as when the polymer network includes a polyurethane, the polyfunctional compound may be a polyol having three or more hydroxyl groups (e.g., glycerol, trimethylolpropane, 1,2, 6-hexanetriol, 1,2, 4-butanetriol, trimethylolethane) or a polyisocyanate having three or more isocyanate groups. In certain instances, such as when the polymer network comprises a polyamide, the polyfunctional compound can include, for example, carboxylic acids having three or more carboxyl groups or activated forms thereof, polyamines having three or more amino groups, and polyols having three or more hydroxyl groups (e.g., glycerol, trimethylolpropane, 1,2, 6-hexanetriol, 1,2, 4-butanetriol, trimethylolethane). In each case, for example when the polymer network comprises a polyolefin, the polyfunctional compound may be a compound having two ethylenically unsaturated groups.

When the hydrogel of the material is crosslinked, it has been found that the crosslink density of the crosslinked hydrogel can affect the structural integrity and water absorption capacity of the material (e.g., material 116). If the crosslink density is too high, the resulting material may be rigid and less flexible, which may reduce its water absorption and expansion capabilities. On the other hand, if the crosslink density is too low, the resulting material may lose its structural integrity when saturated. Thus, the hydrogel of the material preferably has a balanced crosslink density such that the material retains its structural integrity when partially or fully saturated with water, yet is sufficiently flexible.

The hydrogel of the material (e.g., material 116) can include any suitable polymer chains that provide the functional properties disclosed herein (e.g., absorb water, swell, and more generally, prevent soil accumulation). For example, the hydrogel may be a polymer hydrogel comprising or consisting essentially of: one or more polymer chains such as one or more polyurethanes, one or more polyamides, one or more polyolefins, and combinations thereof (e.g., polyurethane and polyamide based hydrogels). The polymer hydrogel may comprise or consist essentially of one or more polysiloxane chains (i.e., the hydrogel may comprise or consist essentially of a silicone hydrogel). The polymer hydrogel may comprise or consist essentially of one or more ionomer polymer chains (i.e., the hydrogel may comprise or consist essentially of an ionomer hydrogel). In these aspects, the hydrogel can comprise a plurality of copolymer chains, wherein at least a portion of the copolymer chains each comprise a polyurethane segment, a polyamide segment, a polyolefin segment, a polysiloxane segment, an ionomer segment, and combinations thereof. The segment can include one or more polyurethanes, one or more polyamides, one or more polyolefins, and combinations thereof.

In certain aspects, the hydrogel comprises a polymer network having one or more polyurethane copolymer chains (i.e., a plurality of polyurethane chains), referred to as a "polyurethane hydrogel. Polyurethane hydrogels may be physically and/or covalently crosslinked. Polyurethane hydrogels can be produced by polymerizing one or more isocyanates with one or more polyols to produce copolymer chains having urethane linkages (-n (co) O-) as shown in formula 1 below, wherein the isocyanates each preferably contain two or more isocyanate (-NCO) groups per molecule, for example, 2,3, or 4 isocyanate groups per molecule (although monofunctional isocyanates can also optionally be included, for example, as chain terminating units).

In these aspects, each R₁Independently an aliphatic or aromatic segment, and each R₂Is a hydrophilic segment.

Any of the functional groups or compounds described herein may be substituted or unsubstituted, unless otherwise specified. A "substituted" group or compound, such as alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxy, ester, ether, or carboxylate, refers to a group of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxy, ester, ether, or carboxylate having at least one hydrogen group substituted with a non-hydrogen group (i.e., substituent). Examples of non-hydrogen groups (or substituents) include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ether, aryl, heteroaryl, heterocycloalkyl, hydroxyl, oxy (or oxo), alkoxy, ester, thioester, acyl, carboxyl, cyano, nitro, amino, amido, sulfur, and halogen. When the substituted alkyl group includes more than one non-hydrogen group, the substituents may be bound to the same carbon or two or more different carbon atoms.

Additionally, the isocyanate may also be chain extended with one or more chain extenders to bridge two or more isocyanates. This can result in a polyurethane copolymer chain as shown in formula 2 below, where R is₃Including chain extenders.

Each segment R in the formulae 1 and 2₁Or the first segment may independently include a straight or branched C, based on the particular isocyanate used_3-30And may be aliphatic, aromatic, or comprise a combination of aliphatic and aromatic moieties. The term "aliphatic" refers to saturated or unsaturated organic molecules that do not include cyclic conjugated ring systems with delocalized pi electrons. In contrast, the term "aromatic" refers to a cyclic conjugated ring system with delocalized pi electrons that exhibits greater stability than a hypothetical ring system with localized pi electrons (a homeotic ring system).

In the aliphatic context (from aliphatic isocyanates), each segment R₁May include straight chain aliphatic groups, branched chain aliphatic groups, cycloaliphatic groups, or combinations thereof. For example, each segment R₁May include straight or branched C_3-20Alkylene segment (e.g., C)_4-15Alkylene or C_6-10Alkylene), one or more C_3-8Cycloalkylene segments (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinations thereof.

Examples of suitable aliphatic diisocyanates for producing the polyurethane copolymer chain include Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Butylene Diisocyanate (BDI), diisocyanatocyclohexylmethane (HMDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI), diisocyanatomethylcyclohexane, diisocyanatomethyltricyclodecane, Norbornane Diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4' -dicyclohexylmethane diisocyanate (H12MDI), diisocyanatododecane, lysine diisocyanate, and combinations thereof.

In the aromatic sector (from aromatic isocyanates), each segment R₁One or more aromatic groups may be included, such as phenyl, naphthyl, tetrahydronaphthyl, phenanthryl, biphenylene, indanyl, indenyl, anthracenyl, and fluorenyl groups. Unless otherwise specified, the aromatic group may be an unsubstituted aromatic group or a substituted aromatic group, and may also include a heteroaromatic group. "heteroaromatic" refers to a monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ring system in which one to four ring atoms are selected from oxygen, nitrogen, or sulfur, and the remaining ring atoms are carbon, and in which the ring system is connected to the remainder of the molecule through any of the ring atoms. Examples of suitable heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl and benzothiazolyl.

Examples of suitable aromatic diisocyanates for producing polyurethane copolymer chains include Toluene Diisocyanate (TDI), TDI adduct with Trimethylolpropane (TMP), methylene diphenyl diisocyanate (MDI), Xylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), Hydrogenated Xylene Diisocyanate (HXDI), naphthalene 1, 5-diisocyanate (NDI), 1, 5-tetrahydronaphthalene diisocyanate, p-phenylene diisocyanate (PPDI), 3 ' -dimethyldiphenyl-4, 4 ' -diisocyanate (DDDI), 4 ' -dibenzyl diisocyanate (DBDI), 4-chloro-1, 3-phenylene diisocyanate, and combinations thereof. In certain aspects, the copolymer chains are substantially free of aromatic groups.

In certain preferred aspects, the polyurethane copolymer chains consist ofIncluding HMDI, TDI, MDI, H₁₂Aliphatic materials, and combinations thereof.

Examples of suitable triisocyanates for producing polyurethane copolymer chains include TDI, HDI, and IPDI adduct with Trimethylolpropane (TMP), uretdione (i.e., dimerized isocyanate), polymeric MDI, and combinations thereof.

Segment R in formula 2₃Straight or branched chain C may be included based on the particular chain extender polyol used_2-C₁₀Examples of suitable chain extender polyols for producing polyurethane copolymer 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- α -diol, bis (2-hydroxyethyl) ethers of xylene- α -diol, and combinations thereof).

Segment R in formulae 1 and 2₂May include polyethers, polyesters, polycarbonates, aliphatic or aromatic groups substituted with one or more hydrophilic side groups selected from the group consisting of: hydroxyl, polyether, polyester, polylactone (e.g., polyvinylpyrrolidone (PVP)), amino, carboxylic acid ester, sulfonate ester, phosphate ester, ammonium (e.g., tertiary and quaternary ammonium), zwitterion (e.g., betaine, e.g., poly (carboxybetaine) (pCB), and ammonium phosphonate, e.g., phosphatidylcholine), and combinations thereof. Thus, R₂The hydrophilic segment(s) of (a) may form part of the hydrogel backbone or be grafted to the hydrogel backbone as a pendant group. In certain aspects, the hydrophilic pendant group or segment is bonded to an aliphatic or aromatic group through a linker. Each chain segment R₂May be present in an amount of 5 to 85% by weight, from 5 to 70% by weight, or from 10 to 50% by weight, based on the total weight of the reactant monomers.

In certain aspects, at least one R₂The segment comprises 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 (PTMO), and combinations thereof. The term "alkyl" as used herein refers to straight and branched chain saturated hydrocarbon groups containing from one to thirty carbon atoms, for example, from one to twenty carbon atoms or from one to ten carbon atoms. Term C_nMeaning that the alkyl group has "n" carbon atoms. E.g. C₄Alkyl refers to an alkyl group having 4 carbon atoms. C_1-7Alkyl refers to alkyl groups having some carbon atoms that encompass the entire range (i.e., 1 to 7 carbon atoms) as well as 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-dimethylpentyl, and 2-ethylhexyl. Unless otherwise specified, an alkyl group may be an unsubstituted alkyl group or a substituted alkyl group.

In some cases, at least one R₂The segment comprises a polyester segment. The polyesters can be derived from the polyesterification of one or more diols (e.g., ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2-methyl-1, 5-pentanediol, diethylene glycol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with one or more dicarboxylic acids (e.g., 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 polyesters may also be derived from polycarbonate prepolymers such as poly (hexamethylene carbonate) ethylene glycol, poly (propylene carbonate) ethylene glycol, poly (tetramethylene carbonate) ethylene glycol, and poly (nonane methylene carbonate) ethylene glycol. Suitable polyesters may include, for exampleFor 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 (nonane methylene carbonate), and combinations thereof.

In each case, at least one R₂The segments comprise polycarbonate segments. The polycarbonate can be derived from the reaction of one or more glycols (e.g., ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2-methyl-1, 5-pentanediol, diethylene glycol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with ethylene carbonate.

In various aspects, at least one R₂The segment includes an aliphatic group substituted with one or more hydrophilic groups selected from the group consisting of: hydroxyl, polyether, polyester, polylactone (e.g., polyvinylpyrrolidone), amino, carboxylate, sulfonate, phosphate, ammonium (e.g., tertiary and quaternary ammonium), zwitterions (e.g., betaines, such as poly (carboxybetaine) (pCB) and ammonium phosphonates, such as phosphatidylcholine), and combinations thereof. In certain aspects, the aliphatic group is linear and can include, for example, C_1-20Alkylene chain or C_1-20Alkenylene chains (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, vinylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). The term "alkylene" refers to a divalent hydrocarbon. Term C_nMeaning that the alkylene group has "n" carbon atoms. E.g. C_1-6Alkylene refers to alkylene groups 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.

In some cases, at least one R₂The chain segment comprises a segment selected fromAn aromatic group substituted with one or more hydrophilic groups of the group consisting of: hydroxyl, polyether, polyester, polylactone (e.g., polyvinylpyrrolidone), amino, carboxylate, sulfonate, phosphate, ammonium (e.g., tertiary and quaternary ammonium), zwitterions (e.g., betaines, such as poly (carboxybetaine) (pCB) and ammonium phosphonates, such as phosphatidylcholine), and combinations thereof. Suitable aromatic groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, phenanthryl, biphenylene, indanyl, indenyl, anthracenyl, fluorenylpyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, and benzothiazolyl.

The aliphatic and aromatic groups are substituted with an appropriate number of hydrophilic side groups and/or charged groups in order to provide the resulting hydrogel with the properties described herein. In certain aspects, the hydrophilic side group is one or more (e.g., 2,3,4,5,6, 7, 8, 9, 10 or more) hydroxyl groups. In various aspects, a hydrophilic pendant group is one or more (e.g., 2,3,4,5,6, 7, 8, 9, 10, or more) amino groups. In some cases, a pendant hydrophilic group is one or more (e.g., 2,3,4,5,6, 7, 8, 9, 10, or more) carboxylate groups. For example, the aliphatic group may include polyacrylic acid. In some cases, the pendant hydrophilic groups are one or more (e.g., 2,3,4,5,6, 7, 8, 9, 10, or more) sulfonate groups. In some cases, a hydrophilic pendant group is one or more (e.g., 2,3,4,5,6, 7, 8, 9, 10, or more) phosphate groups. In certain aspects, the hydrophilic pendant groups are one or more ammonium groups (e.g., tertiary and/or quaternary ammonium). In other aspects, the pendant hydrophilic group is one or more zwitterions (e.g., betaines, such as poly (carboxybetaines) (pCB) and ammonium phosphonates, such as phosphatidylcholine), and combinations thereof.

In certain aspects, R₂The segment includes charged groups capable of binding to counter ions to ionically crosslink the polymer and form an ionomer. In these aspects, for example, R₂Are aliphatic or aromatic groups having amino side groups, carboxylate side groups, sulfonate side groups, phosphate side groups, ammonium side groups, zwitterionic side groups, or combinations thereof. For example, R₂May be an aliphatic group or an aromatic group having one or more pendant carboxylate groups.

In each case, the pendant hydrophilic groups are at least one polyether, for example two polyethers. In other cases, the pendant hydrophilic group is at least one polyester. In each case, the hydrophilic pendant group is a polylactone (e.g., polyvinylpyrrolidone). Each carbon atom of the hydrophilic pendant group can optionally be substituted with, for example, C_1-6Alkyl substitution. In some of these aspects, the aliphatic group and the aromatic group can be a graft polymer in which the pendant groups are homopolymers (e.g., polyethers, polyesters, polyvinylpyrrolidones).

In certain preferred aspects, the hydrophilic pendant groups are polyethers (e.g., polyethylene oxide and polyethylene glycol), polyvinylpyrrolidone, polyacrylic acid, or combinations thereof.

The pendant hydrophilic groups can be bonded to aliphatic or aromatic groups through a linking group. The linking group can be any bifunctional small molecule (e.g., C) capable of linking the pendant hydrophilic group to an aliphatic or aromatic group_1-20). For example, the linking group can include a diisocyanate, as previously described herein, which forms a urethane bond when attached to the hydrophilic side group and to the aliphatic or aromatic group. In certain aspects, the linking group can be 4, 4' -diphenylmethane diisocyanate (MDI), as shown below.

In certain exemplary aspects, the hydrophilic pendant group is polyethylene oxide and the linker group is MDI, as shown below.

In some cases, the hydrophilic pendant group is functionalized to enable it to bind to an aliphatic or aromatic group, optionally through a linking group. In various aspects, for example, when the hydrophilic pendent group comprises an alkenyl group, the alkenyl group may undergo a michael addition with a thiol-containing bifunctional molecule (i.e., a molecule having a second reactive group such as a hydroxyl or amino group) to produce a hydrophilic group that can react with the polymer backbone using the second reactive group, optionally through a linker. For example, when the hydrophilic side group is polyvinylpyrrolidone, it can react with a thiol group on mercaptoethanol to produce a hydroxyl-functionalized polyvinylpyrrolidone, as shown below.

In certain of the aspects disclosed herein, at least one R is₂The segment is polytetramethylene oxide. In other exemplary aspects, at least one R₂The segment may be an aliphatic polyol functionalized with polyethylene oxide or polyvinylpyrrolidone, such as the polyol described in european patent No. 2462908. For example, R₂The segment may be derived from the reaction product of a polyol (e.g., pentaerythritol or 2,2, 3-trihydroxypropanol) and MDI-derivatized methoxypolyethylene glycol (to obtain a compound as shown in formula 6 or 7) or MDI-derivatized polyvinylpyrrolidone that has been previously reacted with mercaptoethanol (to obtain a compound as shown in 8 or 9), as shown below.

In each case, at least one R₂Is a polysiloxane. In these cases, R₂Silicon derivable from formula 10Ketone monomers such as the silicone monomers disclosed in U.S. patent No. 5,969,076.

Wherein:

a is 1 to 10 or greater (e.g., 1,2, 3,4,5,6, 7, 8, 9, or 10);

each R⁴Independently of each other is hydrogen, C_1-18Alkyl radical, C_2-18Alkenyl, aryl or polyether; and is

Each R⁵Independently is C_1-10Alkylene, polyether or polyurethane.

In certain aspects, each R is⁴Independently is H, C_1-10Alkyl radical, C_2-10Alkenyl, aryl, polyethylene, polypropylene or polybutylene. For example, each R⁴May be independently selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, vinyl, propenyl, phenyl and polyethylene.

In various aspects, each R⁵Independently is C_1-10Alkylene (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, or decylene). In other cases, each R⁵Is a polyether (e.g., polyethylene, polypropylene, or polybutylene). In each case, each R⁵Is a polyurethane.

In some cases, the hydrogel includes a crosslinked polymer network that includes copolymer chains that are derivatives of polyurethane. Such a crosslinked polymer network may be produced by polymerizing one or more isocyanates with one or more polyamino compounds, polymercapto compounds, or combinations thereof, as shown in formulas 11 and 12 below:

wherein the variables are as described above. Additionally, the isocyanate may also be chain extended with one or more polyamino or polythiol chain extenders to bridge two or more isocyanates, such as previously described for the polyurethane of formula 2.

In certain aspects, the polyurethane hydrogel is comprised of MDI, PTMO, and 1, 4-butanediol, as described in U.S. patent No. 4,523,005.

In certain aspects, the polyurethane hydrogel is physically crosslinked (hard segments) by, for example, non-polar or polar interactions between urethane groups or on the polymer, and is a Thermoplastic Polyurethane (TPU), or specifically, it may be referred to as a hydrophilic thermoplastic polyurethane. In these aspects, the component R in formula 1₁With the component R in formula 2₁And R₃Forming part of the polymer, often referred to as "hard segment", with component R₂Forming the portion of the polymer often referred to as the "soft segment". In these aspects, the soft segment can be covalently bonded to the hard segment.

Commercially available thermoplastic polyurethane hydrogels suitable for current use include, but are not limited to, those having the trade name "TECOPHILIC", such as TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60(Lubrizol, Countryside, IL), "ESTANE" (e.g., ALR G500; Lubrizol, Countryside, IL).

In various aspects, the polyurethane hydrogel is covalently crosslinked, as previously described herein.

In certain aspects, the polyamide segment of the polyamide hydrogel comprises or consists essentially of a polyamide. Polyamide hydrogels may be formed from the polycondensation of a polyamide prepolymer with a hydrophilic prepolymer to form a block copolyamide.

In certain aspects, the polyamide segments of the polyamide hydrogel may be derived from the condensation of a polyamide prepolymer, such as a lactam, an amino acid, and/or a diamino compound, with a dicarboxylic acid or an activated form thereof. The resulting polyamide segment comprises amide linkages (- (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 polyamide hydrogel may be the same or different.

In certain aspects, the polyamide segments are derived from the polycondensation of lactams and/or amino acids and include amide segments having the structure shown in formula 13 below, wherein R is₆Is a segment of a block copolymer derived from a lactam or an amino acid, and R₂Is a segment derived from a hydrophilic prepolymer:

in certain aspects, R₆Derived from a lactam. In some cases, R₆Derived from C_3-20Lactams, or C_4-15Lactams or C_6-12A lactam. For example, R₆May be derived from caprolactam or laurolactam. In some cases, R₆' is derived from one or more amino acids. In each case R₆Derived from C_4-25Amino acid, or C_5-20Amino acid or C_8-15An amino acid. For example, R₆' may be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

In some cases, formula 13 includes a polyamide-polyether block copolymer segment, as shown below:

wherein m is 3 to 20 and n is 1 to 8. In certain exemplary aspects, m is 4-15, or 6-12 (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.

In various aspects, the polyamide segments of the polyamide hydrogel are derived from the condensation of a diamino compound with a dicarboxylic acid or an activated form thereof and include amide segments having the structure shown in formula 15 below, wherein R is₇Is a segment of a block copolymer derived from a diamino compound, R₈Is a segment derived from a dicarboxylic acid compoundAnd R is₂Is a segment derived from a hydrophilic prepolymer:

in certain aspects, R₇Derived from diamino compounds comprising a compound having C_4-15Carbon atom, or C_5-10Carbon atom, or C_6-9Aliphatic radical of carbon atoms. In certain aspects, diamino compounds include aromatic groups such as phenyl, naphthyl, xylyl, and tolyl. Suitable diamino compounds include, but are not limited to, Hexamethylenediamine (HMD), tetramethylenediamine, Trimethylhexamethylenediamine (TMD), m-xylylenediamine (MXD), and 1, 5-pentaaminediamine (1, 5-pentaaminediamine). In various aspects, R₈Derived from dicarboxylic acids or activated forms thereof, including compounds having C_4-15Carbon atom, or C_5-12Carbon atom, or C_6-10Aliphatic radical of carbon atoms. In certain aspects, the dicarboxylic acid or activated form thereof comprises an aromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Suitable carboxylic acids or activated forms thereof include, but are not limited to, adipic acid, sebacic acid, terephthalic acid, and isophthalic acid. In certain aspects, the copolymer chains are substantially free of aromatic groups.

In certain preferred aspects, each polyamide segment is independently derived from a polyamide prepolymer selected from the group consisting of: 12-aminolauric acid, caprolactam, hexamethylenediamine and adipic acid.

Additionally, the polyamide hydrogel may also be chain extended with one or more polyamino, polycarboxy (or derivatives thereof), or amino acid chain extenders, as previously described herein. In certain aspects, the chain extender may include a diol, dithiol, aminoalcohol, aminoalkylthiol, hydroxyalkylthiol, phosphite, or bisacyllactam compound (e.g., triphenyl phosphite, N' -terephthaloyl bis-laurolactam, and diphenyl isophthalate).

Each of the components R of the formulae 13 and 15₂Independently a polyether, a polyester, a polycarbonate, an aliphatic group, or an aromatic group, wherein the aliphatic or aromatic group is substituted with one or more hydrophilic side groups, as previously described herein, wherein the side groups may optionally be bonded to the aliphatic or aromatic group through a linking group, as previously described herein.

In certain preferred aspects, R₂A compound derived from a group selected from: polyethylene oxide (PEO), polypropylene oxide (PPO), Polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), polyethylene oxide functionalized aliphatic or aromatic groups, polyvinylpyrrolidone functionalized aliphatic or aromatic groups, and combinations thereof. In each case R₂A compound derived from a group selected from: polyethylene oxide (PEO), polypropylene oxide (PPO), polytetramethylene oxide (PTMO), polyethylene oxide functionalized aliphatic or aromatic groups, and combinations thereof. For example, R₂May be derived from a compound selected from the group consisting of: polyethylene oxide (PEO), polytetramethylene oxide (PTMO), and combinations thereof.

In certain aspects, the polyamide hydrogel is physically crosslinked by, for example, nonpolar or polar interactions between polyamide groups on the polymer, and is a thermoplastic polyamide, or in particular, a hydrophilic thermoplastic polyamide. In these aspects, the component R in formula 13₆With the component R in the formula 15₇And R₈Forming part of the polymer, often referred to as "hard segment", with component R₂Forming the portion of the polymer often referred to as the "soft segment". Thus, in certain aspects, the hydrogel can include a physically crosslinked polymer network having one or more polymer chains with amide linkages.

In certain aspects, the hydrogel comprises a plurality of block copolymer chains, wherein at least a portion of the block copolymer chains each comprise a polyamide block and a hydrophilic block (e.g., a polyether block) covalently bonded to the polyamide block to produce a thermoplastic polyamide block copolymer hydrogel (i.e., a polyamide-polyether block copolymer). In these aspects, the polyamide segments can interact with each other to form crystalline regions. Thus, the polyamide block copolymer chains may each comprise a plurality of polyamide segments forming crystalline regions with other polyamide segments of the polyamide block copolymer chains and a plurality of hydrophilic segments covalently bonded to the polyamide segments.

In certain aspects, the polyamide is polyamide-11 or polyamide-12 and the polyether is selected from the group consisting of polyethylene oxide, polypropylene oxide, and polytetramethylene oxide. Commercially available thermoplastic polyamide hydrogels suitable for current use include those available from Arkema, inc., Clear Lake, TX under the trade names "PEBAX" (e.g., "PEBAX MH 1657" and "PEBAX MV 1074"), and "SERENE" coatings (Sumedics, Eden Prairie, MN).

In various aspects, the polyamide hydrogel is covalently crosslinked, as previously described herein.

In certain aspects, the hydrogel comprises or consists essentially of a polyolefin hydrogel. The polyolefin hydrogels may be formed by free radical, cationic, and/or anionic polymerization via methods known to those skilled in the art (e.g., using peroxide initiators, heat, and/or light).

In certain aspects, the hydrogel can comprise one or more, polyolefin chains. For example, the polyolefin may include polyacrylamide, polyacrylate, polyacrylic acid and derivatives or salts thereof, polyacrylic acid halide (polyacrylhalide), polyacrylonitrile, polyallyl alcohol, polyallyl ether, polyallyl ester, polyallyl carbonate, polyallyl urethane, polyallyl sulfone, polyallyl sulfonic acid, polyallyl amine, polyallyl cyanide, polyvinyl ester, polyvinyl thioester, polyvinyl pyrrolidone, polyalpha-olefin, polystyrene, and combinations thereof. Thus, the polyolefin may be derived from a monomer selected from the group consisting of: acrylamide, acrylic esters, acrylic acid and derivatives or salts thereof, acryloyl halides (acrylohalides), acrylonitrile, allyl alcohol, allyl ether, allyl esters, allyl carbonates, allyl carbamates, allyl sulfones, allyl sulfonic acids, allyl amines, allyl cyanides, vinyl esters, vinyl thioesters, vinyl pyrrolidones, alpha-olefins, styrene, and combinations thereof.

In certain aspects, the polyolefin is derived from acrylamide. Suitable acrylamides may include, but are not limited to, acrylamide, methacrylamide, ethylacrylamide, N-dimethylacrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, N-isopropylmethacrylamide, N-phenylacrylamide, N-diphenylmethacrylamide, N- (triphenylmethyl) methacrylamide, N-hydroxyethylacrylamide, 3-acryloylamino-1-propanol, N-acryloylamido-ethoxyethanol, N- [ tris (hydroxymethyl) methyl ] acrylamide, N- (3-methoxypropyl) acrylamide, N- [3- (dimethylamino) propyl ] methacrylamide, (3-acrylamidopropyl) trimethylammonium chloride, N- (N-t-butylacrylamide), N- (N-isopropylacrylamide, N-diphenylmethacrylamide, N- (triphenylmethyl) methacrylamide, N-hydroxyethylacrylamide, N-acryloylamino-1-propanol, N-acryloylamido-ethoxyethanol, N- [ tris (hydroxymethyl) methyl ] acrylamide, N- (3-methoxypropyl) acrylamide, N- [, Diacetone acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, salts of 2-acrylamido-2-methyl-1-propanesulfonic acid, 4-acryloyl morpholine, and combinations thereof. For example, the acrylamide prepolymer may be acrylamide or methacrylamide.

In some cases, the polyolefin is derived from an acrylate (e.g., an acrylate and/or an alkyl acrylate). Suitable acrylates include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, isooctyl acrylate, isodecyl acrylate, octadecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 4-t-butylcyclohexyl acrylate, 3,5, 5-trimethylhexyl acrylate, isobornyl acrylate, vinyl methacrylate, allyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, and mixtures thereof, Cyclohexyl methacrylate, 3, 5-trimethylcyclohexyl methacrylate, or combinations thereof and the like. For example, the acrylate prepolymer may be methyl acrylate, ethyl acrylate, or 2-hydroxyethyl methacrylate.

In some cases, the polyolefin is derived from acrylic acid or a derivative or salt thereof. Suitable acrylic acids include, but are not limited to, acrylic acid, sodium acrylate, methacrylic acid, sodium methacrylate, 2-ethacrylic acid, 2-propylacrylic acid, 2-bromoacrylic acid, 2- (bromomethyl) acrylic acid, 2- (trifluoromethyl) acrylic acid, acryloyl chloride, methacryloyl chloride, and 2-ethacryloyl chloride.

In various aspects, the polyolefin can be derived from allyl alcohol, allyl ether, allyl ester, allyl carbonate, allyl carbamate, allyl sulfone, allyl sulfonic acid, allyl amine, allyl cyanide, or combinations thereof. For example, the polyolefin segment may be derived from allyloxyethanol, 3-allyloxy-1, 2-propanediol, allylbutyl ether, allylbenzyl ether, allylethyl ether, allylphenyl ether, allyl 2,4, 6-tribromophenyl ether, 2-allyloxybenzaldehyde, 2-allyloxy-2-hydroxybenzophenone, allyl acetate, allyl acetoacetate, allyl chloroacetate, allyl cyanoacetate, allyl 2-bromo-2-methylpropionate, allyl butyrate, allyl trifluoroacetate, allyl methyl carbonate, t-butyl N-allylcarbamate, allyl methyl sulfone, 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt, etc., of, Allylamine, allylamine salts, and allyl cyanide.

In certain instances, the polyolefin can be derived from vinyl esters, vinyl thioesters, vinyl pyrrolidones (e.g., N-vinyl pyrrolidone), and combinations thereof. For example, the vinyl monomer may be vinyl chloroformate, vinyl acetate, vinyl decanoate, vinyl neodecanoate, vinyl neononanoate, vinyl pivalate, vinyl propionate, vinyl stearate, vinyl valerate, vinyl trifluoroacetate, vinyl benzoate, vinyl 4-t-butylbenzoate, vinyl cinnamate, butyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, ethylene glycol vinyl ether, 2-ethylhexyl vinyl ether, ethyl-1-propenyl ether, isobutyl vinyl ether, propyl vinyl ether, 2-chloroethyl vinyl ether, 1, 4-butanediol vinyl ether, 1, 4-cyclohexanedimethanol vinyl ether, di (ethylene glycol) vinyl ether, diethyl vinyl orthoformate, vinyl acetate, vinyl decanoate, vinyl neodecanoate, vinyl neononanoate, vinyl pivalate, vinyl propionate, vinyl stearate, vinyl valerate, vinyl trifluoroacetate, vinyl benzoate, vinyl sulfide, vinyl halide, and vinyl chloride.

In certain aspects, the polyolefin may be derived from an alpha-olefin, such as 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-pentadecene, 1-heptadecene, and 1-octadecene.

In each case comprising R₇Suitable styrene monomers include styrene, α -bromostyrene, 2, 4-diphenyl-4-methyl-1-pentene, α -methylstyrene, 4-acetoxystyrene, 4-benzhydrylstyrene, 4-t-butylstyrene, 2, 4-dimethylstyrene, 2, 5-dimethylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2- (trifluoromethyl) styrene, 3- (trifluoromethyl) styrene, 4- (trifluoromethyl) styrene, 2,4, 6-trimethylstyrene, vinylbenzyl chloride, 4-benzyloxy-3-methoxystyrene, 4-t-butoxystyrene, 3, 4-dimethoxystyrene, 4-ethoxystyrene, 4-vinylanisole, 2-bromostyrene, 3-bromostyrene, 4-chloro- α -methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-difluorostyrene, 2, 6-dichlorostyrene, 2, 6-bromostyrene, 2, 3-bromostyrene, 2, 6-dimethylaminoethyl-2, 3, 5-propenyl-N- [3, 4-dimethyl-3, 6-propenyl ] styrene, N-ethyl-3, 4-chloro-3-dimethoxystyrene, 4-vinylstyrene, 4-phenylethylene, 4-chloro-3, 6-bromostyrene, 4-dimethylaminoethyl-2, 3, N-propenyl-2, 5-propenyl-2, 3-dimethylaminoethyl-2, 4-vinylphenethylene, 3, 4-propenyl-3, 4-chloro-3-chloro-3-2, 4-chloro-]Styrene, 3-vinylaniline, 4-vinylaniline, (vinylbenzyl) trimethylammonium chloride, 4- (diphenylphosphino) styrene, 3-isopropenyl- α -dimethylbenzyl isocyanate, 3-nitrostyrene, 9-vinylanthracene, 2-vinylnaphthalene, 4-vinylbenzocyclobutene, 4-vinylbiphenyl, and vinylbenzoic acid.

In certain aspects, the polyolefin comprises a hydrophilic moiety. The hydrophilic portion of the polyolefin hydrogel may be a pendant group of the polyolefin backbone, or the hydrophilic portion may function as a covalent crosslinking agent for the polyolefin hydrogel. In certain aspects, the hydrophilic portion of the polyolefin hydrogel comprises a pendant polyether group, a pendant polyester group, a pendant polycarbonate group, a pendant hydroxyl group, a pendant lactone (e.g., pyrrolidone) group, a pendant amino group, a pendant carboxylate group, a pendant sulfonate group, a pendant phosphate group, a pendant ammonium (e.g., tertiary and quaternary ammonium) group, a pendant zwitterion (e.g., a betaine, such as poly (carboxybetaine) (pCB), and an ammonium phosphonate, such as phosphatidylcholine), or a combination thereof. The polyolefin hydrogel comprising hydrophilic pendant moieties may be formed as previously described by copolymerizing polyolefin monomers with a second polymeric olefin monomer having hydrophilic side chains, such as acrylic acid or polyvinylpyrrolidone.

In certain instances, the polyolefin hydrogel comprises a plurality of polyolefin chains, wherein at least a portion of the polyolefin chains each comprise a first segment physically crosslinked to at least one other polyolefin chain of the plurality of polyolefin chains and one or more hydrophilic segments covalently bonded to the first segment.

In other aspects, the hydrophilic portion of the polyolefin hydrogel is a hydrophilic crosslinker. Cross-linking agents can include polyethers, polyesters, polycarbonates, hydroxyl groups, lactones (e.g., pyrrolidones), amino groups, carboxylates, sulfonates, phosphates, ammonium (e.g., tertiary and quaternary ammonium), zwitterions (e.g., betaines, such as poly (carboxybetaines) (pCB), and ammonium phosphonates, such as phosphatidylcholine), and combinations thereof. The hydrophilic crosslinking agent may be derived from a molecule having at least two ethylenically unsaturated groups such as polyethylene glycol dimethacrylate.

Suitable commercially available polyolefin materials include, but are not limited to, Dow Chemical, Midland MI "POLYOX" product series, and styrenic block copolymers. Examples of styrenic copolymers include, but are not limited to, TPE-s (e.g., styrene-butadiene-styrene (SBS) block copolymers such as "SOFPRENE" and styrene-ethylene-butylene-styrene (SEBS) block copolymers such as "LAPRENE", so.f.ter.group, Lebanon, TN); thermoplastic copolyester elastomers (e.g., thermoplastic elastomer vulcanizates (TPE-V or TPV)), such as "FORPRENE", so.f. ter. group), "term-V", Termopol, isotanbul Turkey; and TPE block copolymers such as "SANTOPRENE" (ExxonMobil, Irving, TX).

In certain aspects, monomers or prepolymers, such as the polyolefin prepolymers described above, are copolymerized with silicone prepolymers to form silicone hydrogels. In these aspects, the silicone prepolymer, the polyolefin prepolymer, or both can function as a crosslinker.

Examples of silicone monomers include, but are not limited to, 3-methacryloxypropyl TRIS (trimethylsiloxy) silane (TRIS), and monomethacryloxypropyl terminated polydimethylsiloxane (mPDMS), vinyl [3- [3,3, 3-trimethyl-1, 1 bis (trimethylsiloxy) -disiloxy ] propyl ] carbamate, 3-methacryloxypropyl-bis (trimethylsiloxy) methylsilane, and methacryloxypropyl pentamethyldisiloxane.

In other aspects, the hydrogel comprises or consists essentially of: an ionomer hydrogel comprising a plurality of ionomer chains. Ionomers are copolymers formed from units of neutral charge and ionized units bound to the polymer backbone, for example, as pendant groups. Typically, the ionized units comprise carboxylic acid groups. The synthesis of ionomers typically includes the steps of first introducing ionized units (e.g., acid groups) into the polymer chain and then neutralizing a portion of the ionized units (e.g., with metal cations). The ionomer may comprise units of acrylic acid, methacrylic acid, or both. The ionomer may comprise a copolymer of ethylene and methacrylic acid.

As discussed above, the material may also optionally include one or more additives, such as antioxidants, colorants, stabilizers, antistatic agents, wax packaging, antiblocking agents, crystal nucleating agents, melt strength enhancers, strain resistant agents, strain blockers, hydrophilicity enhancing additives, and combinations thereof.

Examples of particularly suitable additives include hydrophilicity-enhancing additives, e.g., one or more surfactantsA grade absorber polymer (e.g., a special grade absorber polyacrylic acid or copolymer thereof). Examples of hydrophilicity-enhancing additives include "CREASORB" or "CREABLOCK" in Evonik, Mobile, AL, BASF, "HYSORB" in Wyandotte, MI, M²Polymer Technologies, Inc., Dundee Township, IL, "WASTE LOCK PAM", and Sumitomo Seika, New York, N.Y. "AQUA KEEP" are commercially available under the trademark "AQUA KEEP". The incorporation of hydrophilicity-enhancing additives can aid the hydrogel by increasing the water absorption rate and/or capacity of the material. Examples of suitable concentrations of hydrophilicity-enhancing additives in the material range from 0.1% to 15% by weight, from 0.5% to 10% by weight, or from 1% to 5% by weight, based on the total weight of the material.

In some aspects, the material may define an outer or ground-facing surface of the outsole. Alternatively, the water permeable membrane may define the outer or ground-facing surface of the outsole and may be in direct contact with the material. For example, at least a portion of the outer surface of the outsole may be bounded by the first side of the water-permeable membrane, with material present between the backing plate/outsole substrate and the membrane.

The level of water permeability of the water permeable membrane is preferably sufficient for water to rapidly pass from the outer surface of the outsole (i.e., the first side of the membrane), through the second side of the membrane, and distribute into the material. For example, the level of water permeability of the water permeable membrane may be sufficient to have a 24 hour water absorption capacity of greater than 40% by weight for a sample of the outsole obtained according to the footwear sampling procedure. The level of water permeability of the water permeable membrane may be sufficient to have a 1 hour water uptake capacity of greater than 40% by weight for a sample of the outsole obtained according to the footwear sampling procedure.

The article of footwear of the present disclosure may be manufactured using a variety of different footwear manufacturing techniques. For example, the material (e.g., material 116) and optional backing plate or substrate may be formed using methods such as injection molding, cast molding, thermoforming, vacuum forming, extrusion, spraying, and the like.

In certain aspects, the outsole is formed using a co-extruded outsole plate. In this case, the material may be coextruded with the thermoplastic material used to form the thin backing substrate, where the resulting coextruded material may be provided in the form of a web or sheet. The mesh or sheet may then be placed in a vacuum thermoforming tool to create a three-dimensional geometry of the ground-facing side of the outsole (referred to as an outsole face precursor). The backing substrate provides a first function in this step by creating a structural support for the relatively thin and weak material. The outsole face precursor may then be cut to form its perimeter and apertures to receive the traction elements, thereby providing an outsole face.

The outsole portion may then be placed in a mold cavity, with the material preferably positioned away from the injection gate. Another thermoplastic material may then be back injected (back injected) into the mold to bond to the backing substrate opposite the material. This shows a second function of the backing substrate, i.e. to protect the material from injection pressure. The injected thermoplastic material may be the same or different from the material used to create the backing substrate. Preferably, they may comprise the same or similar materials (e.g., both thermoplastic polyurethanes). Thus, the backing substrate and the injected material in the mold form an outsole backing plate that is secured to the material (during the co-extrusion step).

In other aspects, the outsole is formed using injection molding. In this case, the base material is preferably injected into a mold to create the outsole backing plate. The outsole backing plate may then be back injected with the material to create a material that adheres to the outsole backing plate.

In any of the above aspects, after the outsole is made, the outsole may be secured, directly or indirectly, to the footwear upper (i.e., the upper portion of the article of footwear that generally forms the cavity into which the wearer's foot may be inserted during wear) to provide an article of footwear of the present disclosure. In particular, the material may function as a ground-facing surface of the outsole that is positioned on the side of the outsole backing plate opposite the upper.

Procedure for Property analysis and characterization

Various properties of an outsole of footwear according to the present disclosure may be determined according to the following methodology. In some cases, the properties determined using these test methods may be from outsole or article of footwear samples collected according to a footwear sampling procedure. In other cases, the properties determined using these test methods may be from samples of material taken according to a co-extruded film sampling procedure, a neat film sampling procedure, or a neat material sampling procedure. The properties obtained by these tests are understood to be representative of the outsole of the present disclosure, whether or not the tests are performed on samples taken from the outsole or samples of material.

1.Sampling procedure

As previously mentioned, it has been found that the interface joint can limit the extent to which the material can absorb water and/or swell when the material is secured to another substrate. Thus, various properties of the outsoles of the present disclosure may be characterized using samples prepared using the following sampling procedure:

A.footwear sampling procedure

This procedure can be used to obtain samples of the outsoles of the present disclosure when the outsole comprising the material is a component of footwear (i.e., an outsole that is not secured to an upper) or a component of an article of footwear (e.g., where the material is bonded to an outsole substrate, such as an outsole backing plate). Outsole samples (e.g., at 25 ℃ and 20% relative humidity) containing materials in a non-wet state were cut from an article of footwear using a blade. This process is performed by separating the outsole from the associated footwear upper and removing any material from the outsole top surface (e.g., corresponding to top surface 142) that may absorb water and potentially bias the outsole's moisture uptake measurements. For example, the outsole top surface may be peeled, wiped, scraped, or otherwise cleaned to remove any upper adhesives, yarns (yarn), fibers, foam, and the like that may potentially absorb water on their own.

The resulting sample includes the material and any outsole substrate bonded to the material, and maintains an interfacial bond between the material and the associated outsole substrate. Thus, the test may simulate how an outsole (i.e., a portion of an outsole that includes material such that the material defines a surface or side of the outsole) would be performed as part of an article of footwear. In addition, the sample is also useful where the interfacial bond between the material and the optional outsole substrate is less defined, such as where the material is highly diffused into the material of the outsole substrate (e.g., using a concentration gradient).

The sample is taken, for example, in a forefoot region, a midfoot region, or a heel region of an outsole at a location along the shoe that provides a substantially constant material thickness (within +/-10% of the average material thickness) for a material as present on the outsole, and has a 4 square centimeter (cm)²) Surface area of (a). In the material not to have a length of 4cm²With any section of surface area present on the outsole and/or with a material thickness of 4cm²Where the section of surface area is not substantially constant, sample sizes having smaller cross-sectional surface areas can be taken and the area-specific measurements adjusted accordingly.

B.Co-extruded film sampling procedure

This procedure can obtain a sample of the material of the present disclosure as it is coextruded to a backing substrate to form all or part of an outsole of the present disclosure. The backing substrate may be made of a material that matches the material, such as the material used to form the outsole backing plate of the material.

It has been found that samples taken from coextruded films are a suitable alternative to samples taken from an outsole or article of footwear. In addition, the sample is also useful where the interfacial bond between the material and the backing substrate is less defined, such as where the material is highly diffused into the composition of the backing substrate (e.g., using a concentration gradient).

In this case, the material is co-extruded with the backing substrate as a web or sheet having a substantially constant thickness (within +/-10% of the average material thickness) to the material, and cooled so that the resulting webOr sheet curing. Samples of material secured to the backing substrate, with sample size surface area of 4cm, were then cut from the resulting web or sheet²Such that the material of the resulting sample remains secured to the backing substrate.

C.Pure membrane sampling procedure

This procedure can be used to obtain samples of the materials of the present disclosure when the materials are isolated in pure form (i.e., without any bound substrate). In this case, the material is extruded as a web or sheet having a material thickness that is substantially constant for the material (within +/-10% of the average material thickness), and cooled to solidify the resulting web or sheet. Then, having a length of 4cm²From the resulting web or sheet, a sample of the material of surface area is cut.

Alternatively, if the material source is not available in pure form, the material may be cut from the outsole substrate of the footwear outsole, or from the backing substrate of a coextruded sheet or web, thereby separating the material. In either case, having a width of 4cm²And then cutting from the resulting separated material.

D.Pure material sampling procedure

This procedure can be used to obtain samples of the materials of the present disclosure. In this case, the material is provided in the form of a medium, such as flakes, granules, powder, pellets, and the like. If the material source is not available in pure form, the material may be cut, scraped, or ground from the outsole of the footwear outsole, or from the backing substrate of the coextruded sheet or web, thereby separating the material.

2.Water absorption Capacity test

This test measures the water absorption capacity of a sample of material after a given soaking duration. The sample may be a sample of the outsole or article of footwear collected using the footwear sampling procedure discussed above, may be a sample of the material as present in the coextruded film collected using the coextruded film sampling procedure, may be a sample of the material as present in the neat film collected using the neat film sampling procedure, or may be a sample in neat form collected using the neat material sampling procedureA sample of the material in its form. The sample is initially dried at 60 ℃ until no weight change is observed for successive measurement intervals at least 30 minutes apart (e.g., a 24 hour drying cycle at 60 ℃ is generally a suitable duration). The total weight of the sample was then dried (Wt,_{sample, drying}) Measured in grams. The dried sample was then allowed to cool to 25 ℃ and was completely immersed in a deionized water bath maintained at 25 ℃. After a given soaking duration, the sample was removed from the deionized water bath, blotted dry with a cloth to remove surface water, and the total weight of the soaked sample (Wt,_{sample, wetting}) Measured in grams.

Any suitable soaking duration may be used. For many of the materials of the present disclosure, a 24 hour soak duration is considered sufficient for the material to achieve saturation (i.e., the material will be in its saturated state). As used herein, the phrase "having a water absorption capacity of … … for 5 minutes" refers to a soaking duration of 5 minutes, "having a water absorption capacity of … … for 1 hour" refers to a soaking duration of 1 hour, the phrase "having a water absorption capacity of … … for 24 hours" refers to a soaking duration of 24 hours, and the like.

As can be appreciated, the total weight of the sample collected pursuant to the footwear sampling procedure or the co-extruded film sampling procedure includes, for example, the weight of the dried or soaked material (Wt,_{drying the material}Or a value of one of the values of Wt,_{material, wetting}) And the weight of the outsole or backing substrate (Wt,_substrate). To determine the weight change of the material due to water absorption, the weight of the substrate (Wt,_substrate) It needs to be subtracted from the sample measurement.

The weight of the substrate (Wt,_substrate) Using sample surface area (e.g. 4 cm)²) The average measured thickness of the substrate in the sample and the average density of the substrate material. Alternatively, if the density of the material used for the substrate is unknown or available, the weight of the substrate (Wt,_substrate) Determined by taking a second sample using the same sampling procedure as used for the primary sample and having the same dimensions (surface area and thickness of material/substrate) as the primary sample. Then, firstThe material of the second sample was cut from the substrate of the second sample with a blade to provide a separate substrate. The separated substrate is then dried at 60 ℃ for 24 hours, which may be carried out in the same time as the main sample is dried. Then, the weight of the separated substrate (Wt,_substrate) Measured in grams.

Then, the obtained basis weight (Wt,_substrate) From the weight of the dried and soaked main sample (Wt,_{sample, drying}And a value of Wt, and,_{sample, wetting}) Subtracted to provide the weight of the material as dried and soaked (Wt,_{drying the material}And a value of Wt, and,_{material, wetting}) As depicted below by equations 1 and 2:

Wt,_{drying the material}＝Wt,_{Sample, drying}-Wt,_Substrate

(equation 1)

Wt,_{Material, wetting}＝Wt,_{Sample, wetting}-Wt,_Substrate

(equation 2)

For samples collected according to either the neat film sampling procedure or the neat material sampling procedure, the substrate weight (Wt,_substrate) Is zero. Thus, equation 1 collapses (collapse) to Wt,_{drying the material}＝Wt,_{Sample, drying}And equation 2 is collapsed to Wt,_{material, wetting}＝Wt,_{Sample, wetting}。

Then, the weight of the dried material (Wt,_{drying the material}) From the weight of the soaked material (Wt,_{material, wetting}) Is subtracted to provide the weight of water absorbed by the material, which is then divided by the weight of the dry material (Wt,_{drying the material}) To provide the water absorption capacity in percent for a given soaking duration, as depicted below by equation 3:

for example, "a 1 hour water absorption capacity of 50% means that after 1 hour of soaking, the soaked material in the sample is 1.5 times more than its weight in the dry state, where there is a 1:2 weight ratio of water to material. Similarly, "24 hour water absorption capacity of 500% means that after 24 hours of soaking, the soaked material in the sample weighs 5 times more than its dry state weight, with a 4:1 weight ratio of water to material present.

3.Water absorption Rate test

This test measures the rate of water absorption of a sample of outsole or material by modeling the weight gain as a function of soak time for a sample with a one-dimensional diffusion model. The samples may be collected using any of the footwear sampling procedures, co-extruded film sampling procedures, or neat film sampling procedures discussed above. The sample is initially dried at 60 ℃ until no weight change is observed for successive measurement intervals of at least 30 minutes apart (a 24 hour drying cycle at 60 ℃ is generally of suitable duration). The total weight of the sample was then dried (Wt,_{sample, drying}) Measured in grams. In addition, the average thickness of the material of the dried sample was measured for calculating the water absorption rate, as explained below.

The dried sample was then allowed to cool to 25 ℃ and was completely immersed in a deionized water bath maintained at 25 ℃. Between soak durations of 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, and 25 minutes, the sample was removed from the deionized water bath, blotted with a cloth to remove surface water, and the total weight of the soaked sample (Wt,_{sample, Wet, t}) Measured 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).

Exposed surface area of soaked sample (A)_t) Measurements were also made with calipers used to determine specific gravity increase, as explained below. Exposed surface area refers to the surface area that is in contact with deionized water when fully submerged in the bath. For samples obtained using the footwear sampling procedure and the coextruded film sampling procedure, the samples had only one major surface exposed. However, for samples obtained using a pure membrane sampling procedure, both major surfaces were exposed. For convenience, the surface area of the peripheral edges of the samples was ignored due to their relatively small size.

The measured sample was completely immersed back into the deionized water bath between measurements. Durations of 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, and 25 minutes refer to the soaking duration that accumulates when the sample is fully submerged in the deionized water bath (i.e., after the first minute of soaking and the first measurement, the sample is placed back into the bath for one more minute of soaking, then measured at the 2 minute mark).

As discussed above, in the water absorption capacity test, the total weight of the sample collected according to the footwear sampling procedure or the coextruded film sampling procedure includes, for example, the weight of the dried or soaked material (Wt,_{drying the material}Or a value of one of the values of Wt,_{material, wet, t}) And the weight of the outsole or backing substrate (Wt,_substrate). To determine the weight change of the material due to water absorption, the weight of the substrate (Wt,_substrate) It needs to be subtracted from the sample weight measurement. This can be done using the same procedure discussed above in the water absorption capacity test, to provide a resulting weight Wt of material for each measurement of soaking duration,_{drying the material}And a value of Wt, and,_{material, wet, t}。

Then, the specific gravity of the water absorbed from each soaked sample was increased (Ws,_{material, t}) Is calculated as the weight of the soaked sample (Wt,_{material, wet, t}) And the weight of the initial dry sample (Wt,_{drying the material}) The difference between, wherein the resulting difference is then divided by the exposed surface area of the soaked sample (A)_t) As depicted below by equation 4:

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 noted above.

The rate of water absorption of the material in the sample is then increased as a specific gravity (Ws,_{material, t}) The slope of the square root over time (in minutes) is determined as determined by least squares linear regression of the data points. To the within this disclosureThe material of the container, the specific gravity increase (Ws,_{material, t}) The plot of the square root over time (in minutes) provides a substantially linear initial slope (to provide the water uptake rate by linear regression analysis). However, after a period of time depending on the thickness of the material, the specific gravity increase will slow, indicating a decrease in the rate of water absorption, until a state of saturation is reached. It is believed that this is because water is sufficiently diffused throughout the material when it approaches saturation, and will vary depending on the material thickness.

Thus, for materials having an average dry material thickness (as measured above) of less than 0.3 millimeters, only specific gravity increase data points at 1 minute, 2 minutes, 4 minutes, and 9 minutes were used in the linear regression analysis. In these cases, the data points at 16 and 25 minutes may begin to diverge significantly from the linear slope due to the near saturation of the water uptake and are omitted from the linear regression analysis. In contrast, for materials having an average dry material thickness (as measured above) of 0.3 millimeters or more, specific gravity increase data points at 1 minute, 2 minutes, 4 minutes, 9 minutes, 16 minutes, and 25 minutes were used in the linear regression analysis. The resulting slope defining the rate of water uptake of the sampled material has units of weight/(surface area-square root of time), e.g., grams/(meter)²-minutes^1/2)。

In addition, the surface of certain materials or substrates may create 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 material or substrate. Thus, samples of these materials or substrates may show a rapid increase in specific gravity for 1-minute samples, and possibly for 2-minute samples. After that, however, the additional weight increase is negligible. Thus, if the specific gravity increase data points at 1 minute, 2 minutes, and 4 minutes continue to show an increase in water absorption, then only linear regression analysis is applied. If not, then the water absorption rate under the test methodology is considered to be about zero grams/(meter)²-minutes^1/2)。

4.Test for expansion Capacity

This test measures the expansion capability of a sample of shoe outsole or material in terms of the material thickness and the increase in volume of the material after a given soak duration of the sample (e.g., collected using the footwear sampling procedure, the co-extruded film sampling procedure, or the neat material sampling procedure discussed above). The sample is initially dried at 60 ℃ until no weight change is observed for successive measurement intervals of at least 30 minutes apart (a 24 hour drying cycle is generally of suitable duration). The dimensions of the dried sample are then measured (e.g., thickness, length, and width for rectangular samples; thickness and diameter for circular samples, etc. …). The dried sample was then completely immersed in a deionized water bath maintained at 25 ℃. After a given soaking duration, the sample was removed from the deionized water bath, blotted dry with a cloth to remove surface water, and the same dimensions of the soaked sample were re-measured.

Any suitable soaking duration may be used. Thus, as used herein, the phrase "5 minute expanded thickness (or volume) increase of … …" refers to a soaking duration of 5 minutes, "1 hour expanded thickness (or volume) increase of … …" refers to a test duration of 1 hour, and the phrase "24 hour expanded thickness (or volume) increase of … …" refers to a test duration of 24 hours, and the like.

The swelling of the material in the sample is determined by (i) an increase in the thickness of the material between the dried material and the soaked material, by (ii) an increase in the volume of the material between the dried material and the soaked material, or (iii) both. The increase in material thickness between the dried material and the soaked material is calculated by subtracting the measured material thickness of the initial dried material from the measured material thickness of the soaked material. Similarly, the increase in material volume between the dry material and the soaked material is calculated by subtracting the measured material volume of the initial dry material from the measured material volume of the soaked material. The increase in material thickness and volume can also be expressed as a percentage increase relative to the thickness or volume of the dry material, respectively.

5.Contact Angle testing

The test measures the contact angle of a sample surface (e.g., of the surface of an outsole of the present disclosure, wherein the surface is defined by a material of the present disclosure, or a surface of a coextruded film formed from the material, or a surface of a clear film formed from the material) based on a measurement of the static sessile drop contact angle of the sample (e.g., collected with the footwear sampling procedure, the coextruded film sampling procedure, or the clear film sampling procedure discussed above). The contact angle refers to the angle at which the liquid interface meets the solid surface of the sample and is an indicator of how hydrophilic the surface is.

For the dry test (i.e., to determine the contact angle in the dry state), the sample was initially equilibrated at 25 ℃ and 20% humidity for 24 hours. For the wetting test (i.e., to determine the contact angle in the wet state), the sample was completely submerged in a deionized water bath maintained at 25 ℃ for 24 hours. Thereafter, the sample was removed from the bath and blotted dry with a cloth to remove surface water and clamped to a glass slide if necessary to prevent curling.

The dried or wet sample is then placed on a movable stage of a contact angle goniometer, such as a goniometer commercially available from Rame-Hart Instrument Co., Succasunna, NJ under the trade name "RAME-HART F290". A 10-microliter drop of deionized water was then placed on the sample using a syringe and an automated pump. An image of the drop is then taken immediately (before the material can absorb the drop) and the contact angle of the two edges of the drop is measured from the image. The increase in contact angle between the dry sample and the wet sample was calculated by subtracting the measured contact angle of the wet material from the measured contact angle of the dry material.

6.Coefficient of friction test

The test measures the coefficient of friction of a sample surface (e.g., a shoe exterior surface according to the present disclosure, a surface of a coextruded film formed from a material of the present disclosure, or a surface of a neat film formed from a material of the present disclosure) of a sample (e.g., collected with a footwear sampling procedure, a coextruded film sampling procedure, or a neat material sampling procedure discussed above). For the dry test (i.e., to determine the coefficient of friction in the dry state), the samples were initially equilibrated at 25 ℃ and 20% humidity for 24 hours. For the wetting test (i.e., to determine the coefficient of friction in the wet state), the sample was completely submerged in a deionized water bath maintained at 25 ℃ for 24 hours. Thereafter, the sample was removed from the bath and blotted dry with a cloth to remove surface water.

The measurements were performed using an aluminum sled mounted on an aluminum test rail for performing a sliding friction test in the sample by sliding the sample on the aluminum surface of the test rail. The test track measures 127 mm wide by 610 mm long. The aluminum skid measures 76.2 mm x76.2 mm with a 9.5 mm radius cut to the leading edge. The contact area of the aluminum sled with the rail is 76.2 mm x 66.6 mm, or 5,100 mm square).

The dry or wet sample was attached to the bottom of the slide using a room temperature curing two part epoxy adhesive available under the trade name "LOCTITE 608" from Henkel, Dusseldorf, Germany. The binder serves to maintain planarity of the wet sample, which may curl when saturated. Polystyrene foam having a thickness of about 25.4 millimeters is attached to the top surface of the skid plate of the structural support (opposite the test specimen).

The sliding friction test was performed using a screw driven load frame. The streamer is attached to the sled with a base supported in a polystyrene foam structural support and wrapped around pulleys to tow the sled through the aluminum test rail. The sliding or friction force is measured using a load cell having a capacity of 2,000 newtons. For a total sliding weight of 20.9 kilograms (205 newtons), the normal force is controlled by placing the weight on top of the aluminum skid plate, supported by a polystyrene foam structural support. The crosshead of the test frame was increased at a rate of 5 mm/sec and the total test displacement was 250 mm. The coefficient of friction is calculated based on the steady state force parallel to the direction of travel required to pull the sled at a constant speed. The coefficient of friction itself is obtained by adding an additional force to the steady state pull force. Any instantaneous values associated with the static friction coefficient at the start of the test are ignored.

7.Storage modulus test

This test measures the resistance (stress to strain ratio) of a sample of the material to be deformed when a vibratory or shock force is applied to the sample, and is a good indicator of the compliance of the material in the dry and wet states. For this test, a pure membrane sampling procedure was used to provide the sample in the form of a membrane, the sample being modified such that the surface area of the test sample is rectangular with dimensions of 5.35 mm wide and 10 mm long. The material thickness may 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 material thickness.

The storage modulus (E') of the sample in megapascals (MPa) was determined by Dynamic Mechanical Analysis (DMA) using a DMA ANALYZER commercially available from TA Instruments, new castle, DE under the trade name "Q800 DMA ANALYZER" equipped with a relative humidity accessory to maintain the sample at a constant temperature and relative humidity during analysis.

Initially, the thickness of the test sample was measured using calipers (used in the modulus calculation). The test sample was then clamped into a DMA analyzer, which was operated under the following stress/strain conditions during analysis: isothermal temperature of 25 ℃, frequency of 1 hz, strain amplitude of 10 microns, preload of 1 newton, and force track of 125%. DMA analysis was performed at a constant 25 ℃ temperature according to the following time/Relative Humidity (RH) profile: (i) 0% RH for 300 minutes (representing a dry state for storage modulus determination), (ii) 50% RH for 600 minutes, (iii) 90% RH for 600 minutes (representing a wet state for storage modulus determination), and (iv) 0% RH for 600 minutes.

The E' value (in MPa) is determined from the DMA curve according to standard DMA techniques at the end of each time segment with a constant RH value. I.e. with the E ' value of 0% RH (i.e. storage modulus in the dry state) being the value at the end of step (i), with the E ' value of 50% RH being the value at the end of step (ii), and with the E ' value of 90% RH (i.e. storage modulus in the wet state) being the value at the end of step (iii) in a specific time/relative humidity curve.

A sample of a material can be characterized by its dry-state storage modulus, its wet-state storage modulus, or a decrease in storage modulus between the dry-state material and the wet-state material, where the wet-state storage modulus is less than the dry-state storage modulus. This reduction in storage modulus can be exemplified as the difference between the dry state storage modulus and the wet state storage modulus, or as a percentage change from the dry state storage modulus.

8.Glass transition temperature test

This test measures the glass transition temperature (T) of a sample of material_g) Wherein the material is provided in pure form, for example using a pure film sampling procedure or a pure material sampling procedure, with a sample weight of 10 milligrams. Samples were measured in both the dry and wet states (i.e., after exposure to a humid environment as described herein).

The glass transition temperature was determined using DMA using a DMA ANALYZER commercially available from TA Instruments, New Castle, DE under the trade name "Q2000 DMA ANALYZER", equipped with an aluminum sealing disk with a pinhole cover, and the sample chamber was purged with 50 ml/min of nitrogen during analysis. Samples in the dry state were prepared by holding at 0% RH until a constant weight (less than 0.01% weight change over a 120 minute period). Samples in the wet state were prepared by conditioning at a constant 25 ℃ 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. Step (iii) of the conditioning procedure may be terminated early if the sample weight is measured during conditioning and is measured to be substantially constant over an interval of 100 minutes within 0.05%.

After preparing the sample in either the dry or wet state, the sample is analyzed by DSC to provide a heat flow versus temperature curve. DSC analysis was performed using the following time/temperature profile: (i) equilibrating at-90 ℃ for 2 minutes, (ii) ramping up to 250 ℃ at +10 ℃/minute, (iii) ramping down to-90 ℃ at-50 ℃/minute, and (iv) ramping up to 250 ℃ at +10 ℃/minute. Glass transition temperature values (in degrees celsius) were determined from DSC curves according to standard DSC techniques.

9.Impact energy test

The test measures the ability of a sample of material (e.g., outsole, coextruded film, or clear film) to shed soil under specific test conditions, where the sample is prepared using a coextruded film sampling procedure or a clear film sampling procedure (to obtain a suitable sample surface area). Initially, the sample was completely immersed in a water bath maintained at 25 ℃ for 24 hours, and then removed from the bath and blotted dry with cloth to remove surface water.

The wet test sample was then adhered to an aluminum block model shoe outsole having a thickness of 25.4 millimeters and a surface area of 76.2 millimeters x76.2 millimeters using a room temperature cured two part epoxy adhesive commercially available from Henkel, dusseldorf, Germany under the trade name "LOCTITE 608". The binder serves to maintain planarity of the soaked sample, which may curl when saturated.

Four polyurethane wedges, 0.5 inch (12.7 mm) tall wedges commercially available from Markrest sports Goods Company, St. Louis, MO under the trade designation "MARKWORT M12-EP", were then threaded into the bottom of the block in a square pattern at a 1.56 inch (39.6 mm) pitch. As a control reference, four identical wedges were attached to an aluminum block model outsole without a sample of the attached material.

To block the model shoe outsole wedge, a bed of wet dirt having a height of about 75 millimeters was placed on top of a flat plastic plate. The SOIL was model 50051562 commercially available from Timberline (Old Castle, inc., Atlanta, a subsidiary of GA) under the trademark "Timberline TOP SOIL" and sieved with a square mesh having a 1.5 mm pore size on each side. Water is then added to the dry soil to produce a wet soil having a water content of 20-22%. The model outsole is then compressed under weight and twisting motion into wet soil until the wedges contact the plastic plate. The weight is removed from the model outsole and then the model outsole is twisted 90 degrees in the plane of the plate and then raised vertically. If no wet soil blocked the model shoe outsole, no additional testing was performed.

However, if wet soil did clog the model shoe outsole, the wet soil was knocked loose by dropping a 25.4 millimeter diameter steel ball weighing 67 grams onto the top side of the model shoe outsole (opposite the test specimen and the clogged soil). The initial drop height was 152 millimeters (6 inches) above the model outsole. If the wet soil does not become loose, the ball drop height is increased by another 152 mm (6 inches) and dropped again. This procedure of increasing the ball drop height by 152 millimeter (6 inch) increments was repeated until the wet soil on the bottom of the outsole model was knocked loose.

The test was run 10 times per test sample. For each run, the height at which the ball fell can be determined by multiplying the height at which the ball fell by the ball mass (67 grams) and the acceleration of gravity (9.8 meters/second)²) And converted into non-blocking impact energy. The unobstructed impact energy in joules is equal to the height of a ball drop in inches multiplied by 0.0167. This procedure was performed on both the model outsole with the material sample and the control model outsole without material, and the relative ball drop height, and therefore the relative impact energy, was determined as the ball drop height of the model outsole with the material sample divided by the control model outsole without material. A result of zero relative ball drop height (or relative impact energy) indicates that initially no soil was clogged to the model outsole when the model outsole was compressed into the test soil (i.e., where the test ball drop and control model outsole portions were omitted).

10.Soil release footwear test

This test measures the soil release ability of a cleated article of footwear and does not require any sampling procedure. Initially, the outsole of the footwear (while still attached to the upper) was completely immersed in a water bath maintained at 25 ℃ for 20 minutes, and then removed from the bath and blotted dry with cloth to remove surface water, and its initial weight was measured.

The footwear with the soaked outsole is then placed on a last (i.e., foot form) and secured to a test fixture commercially available from Instron Corporation, Norwood, MA under the trade name "Instron 8511And (4) placing. The footwear was then lowered so that the wedges were completely submerged in the soil, and then raised and lowered into the soil at 10 mm increments, 10 repetitions at 1 hz. The wedge was submerged in the soil and the wedge rotated 20 degrees in each direction 10 times at 1 hertz. The SOIL was model 50051562 commercially available from Timberline (Old Castle, Inc., Atlanta, a subsidiary of GA) under the trade name "TIMBERLINE TOP SOIL" and the water content was adjusted so that the shear strength value on a shear tester (shear vane tester) available from Test Mark industries (East pallestine, OH) was 3 kg/cm²And 4 kg/cm²In the meantime.

After the test is complete, the footwear is carefully removed from the last and its post-test weight is measured. The difference between the tested weight and the initial weight of the footwear resulting from soil accumulation is then determined.

Examples

The present disclosure is more particularly described in the following embodiments that are intended as illustrations only, since numerous modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are based on basis weight, and all reagents used in the examples were obtained or purchased from chemical suppliers described below, or may be synthesized by conventional techniques.

1.Shoe outsole moisture absorption analysis

The water absorption capacity of the test samples of examples 1-5 was measured over various soaking durations. Each test sample was taken from an international football/soccer shoe outsole with an outsole of the present disclosure. Each outsole was originally manufactured by co-extruding the material with a backing substrate having a substrate thickness of 0.4 millimeters, wherein the backing substrate material was an aromatic thermoplastic polyurethane commercially available from Lubrizol Corporation, Wickliffe, OH under the trade name "ESTANE 2103-87 AE".

For examples 1-3, the material was a thermoplastic polyurethane hydrogel commercially available from Lubrizol Corporation, Wickliffe, OH under the trade designation "TECOPHILIC TG-500" that included copolymer chains with aliphatic hard segments and hydrophilic soft segments (with polyether chains). For examples 4 and 5, the material was a lower water absorption thermoplastic polyurethane hydrogel commercially available from Lubrizol corporation, Wickliffe, OH under the trade name "TECOPHILIC HP-60D-60".

For each example, the resulting coextruded web was then sheeted, vacuum thermoformed, and trimmed to size for the outsole surface. The outsole surface is then reinjected with another thermoplastic polyurethane, commercially available from Bayer MaterialScience AG, levirkusen, Germany under the trade name "DESMOPAN DP 8795A", to produce an outsole having a material defining a ground-facing surface, and the extruded backing substrate and the reinjection material collectively form an outsole backing plate. A footwear upper is then adhered to the top side of the resulting outsole to provide an article of footwear.

The test specimens for each example were then collected as described above in the footwear sampling procedure, except for the dimensions of the specimens described below. In particular, a circular test specimen comprising the material and the outsole backing plate was cut from the footwear. This is done by initially cutting the upper from the outsole near the bite line where the outsole and upper meet.

A small pilot hole is then created in the center of the sample (creating an inner diameter for the sample) to facilitate cutting of a ring-shaped sample having the desired outer diameter. After cutting, all removable layers remaining on the top side of the outsole backing plate were peeled away from the test specimens, including the insole board, strobel (strobel) and insole board, while some residual adhesive was retained on the specimens. Each sample was collected from its respective region (i.e., near the longitudinal centerline) and generally centered between the wedges.