Patent Application
20220015505
The design and manufacture of footwear and sporting equipment involves a variety of factors from the aesthetic aspects, to the comfort and feel, to the performance and durability. While design and fashion may be rapidly changing, the demand for increasing performance in the footwear and sporting equipment market is unchanging. In addition, the market has shifted to demand lower-cost and recyclable materials still capable of meeting increasing performance demands. To balance these demands, designers of footwear and sporting equipment employ a variety of materials and designs for the various components.
Further aspects of the present disclosure will be readily appreciated upon review of the detailed description, described below, when taken in conjunction with the accompanying drawings.
The present disclosure is generally directed to an article of manufacture, or components thereof having surface-defining materials that are capable of taking up water. Particular polymeric hydrogels, and hydrogel materials (i.e., compositions comprising at least one polymeric hydrogel), when disposed on an externally-facing surface of an article, can be effective at preventing or reducing the accumulation of soil on the externally-facing surface of the article. However, applicants have found that the polymeric hydrogel and/or hydrogel material can sometimes detach or delaminate from other materials or components in sole structures, including polyolefin-based materials or components.
The present disclosure provides composite elements which include a hydrogel layer comprising a hydrogel material, where the hydrogel layer is operably coupled with a textile, as well as sole structures for an article of footwear incorporating the composite elements, and methods of forming and using the composite elements and sole structures. In the composite element, the hydrogel layer and the textile are operably coupled so that the hydrogel layer penetrates the textile structure, so that the hydrogel layer extends through a first side of the textile, and at least partially into a core of the textile, but does not extend all the way through the textile, e.g., onto a second side of the textile. Not wishing to be bound by any particular theory, it is believed that providing the hydrogel layer coupled in this manner to a textile as part of the disclosed composite element can lead to improved mechanical bonding between the textile and the hydrogel layer as well as between the textile and the plate portion of a sole structure, thereby reducing or eliminating the detachment or delamination of the polymeric hydrogel and/or hydrogel material from the composite element and from the plate when the composite element is used in a sole structure. In a particular aspect, using an air-permeable textile (i.e., a textile which is air-permeable prior to being coupled to the hydrogel layer and/or the plate) can lead to further improvements in the levels of mechanical bonding between the hydrogel layer and the textile, and between the textile and the plate.
In various aspects, this disclosure provides sole structures comprising the composite element operably coupled with a plate comprising a second polymeric material. In the aspects, the hydrogel material of the hydrogel layer at least partially defines an externally-facing surface of the sole structure, including ground-facing surfaces of the sole structure. Typically, the hydrogel material of the hydrogel layer will be absent from externally-facing surfaces which are configured to be ground-contacting, such as the surfaces of traction elements which are configured to contact the ground during normal wear. The textile of the composite element assists with coupling the hydrogel layer with the plate, as the first side of the textile as well as the core of the textile increase the available surface area with which the hydrogel layer can mechanically bond, as compared to a substantially flat surface (for example, in a film). This mechanically bonded structure of the composite element reduces or eliminates delamination of the hydrogel layer, which, in turn improves the soil-shedding capabilities of the hydrogel layer. The textile of the composite element also assists with coupling the composite element to the plate. Since the hydrogel layer does not extend onto the second side of the textile, at least the second side of the textile, and in some aspects a portion of the core, increase the available surface area with which the material(s) of the plate (or an adhesive layer) can mechanically bond to the composite element, and thus to the hydrogel layer. When using polymeric materials which have significantly different surface energies, such as, for example, relatively hydrophilic polymeric hydrogels in the hydrogel materials of the hydrogel layer, such as polyurethane hydrogels, and relatively hydrophobic materials in the plate, such as polyolefins, it has been found that the increased bonding strength provided by the presence of these mechanical bonds significantly improves the bond strength between these otherwise relatively incompatible materials. Conventional adhesives used in the footwear industry (e.g., polyurethane-based contact adhesives and/or hot melt adhesives) to be used to supplement the mechanical bonds, but in many cases, the strength of these mechanical bonds, particularly when they are thermal bonds formed by melting or softening the hydrogel material and/or the plate material, is sufficiently great that no additional adhesives need to be used. Further aspects, geometries, and features of this layered structure will be discussed herein.
As can be appreciated, preventing or reducing soil accumulation on articles can provide many benefits. Preventing or reducing soil accumulation on articles during use on unpaved, muddy, or wet surfaces can significantly affect the weight of accumulated soil adhered to the article during use. Preventing or reducing soil accumulation on an article can help improve safety. Further, preventing or reducing soil accumulation on the article can make it easier to clean the article following use.
The present disclosure can be described in accordance with the following numbered aspects, which should not be confused with the claims.
In accordance with Aspect 1, the present disclosure is directed to a composite element comprising:
a textile comprising a textile material and having a first side, a second side, and a core located between the first side and the second side;
a hydrogel layer comprising a hydrogel material and having a first side and a second side that is operably coupled to the textile along the first side of the textile;
wherein a portion of the hydrogel layer extends through the first side of the textile and at least partially into the core of the textile, but does not extend onto the second side of the textile.
In accordance with Aspect 2, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the textile, before its first side is operably coupled with the hydrogel layer, has a core thickness measured between the first side and the second side of the textile of about 0.1 millimeter to about 5 millimeters, or about 0.2 millimeter to about 3 millimeters, or about 0.3 millimeter to about 2 millimeters.
In accordance with Aspect 3, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the textile, before its first side is operably coupled with the hydrogel layer, is an air-permeable textile, optionally wherein the textile, before its first side is operably coupled with the hydrogel layer, has an air permeability of from about 10 to about 250 cubic centimeters/square centimeters/second, or about 50 to about 150 cubic centimeters/square centimeters/second, as determined using ASTM D737-4.
In accordance with Aspect 4, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the textile material has a textile material melting temperature or a textile material Vicat softening temperature that is at least 20 degrees Celsius, or at least 50 degrees Celsius, or at least 75 degrees Celsius, or at least 100 degrees Celsius greater than a melting temperature or Vicat softening temperature of the hydrogel material of the hydrogel layer.
In accordance with Aspect 5, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel layer penetrates at least 10 percent, or at least 20 percent, or at least 30 percent, or at least 40 percent, or at least 50 percent, or at least 60 percent of the core thickness of the textile.
In accordance with Aspect 6, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel layer penetrates less than 90 percent, or less than 80 percent, or less than 70 percent, or less than 60 percent, or less than 50 percent, or less than 40 percent, or less than 30 percent of the core thickness of the textile.
In accordance with Aspect 7, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the textile comprises at least one textile chosen from a woven textile, a non-woven textile, a knit textile, a braided textile, a crochet textile, or a combination thereof.
In accordance with Aspect 8, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the textile comprises at least one non-woven textile chosen from carded, air laid, wet laid, spun bond, melt blown materials, or a combination thereof.
In accordance with Aspect 9, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the textile comprises one or more natural or synthetic fibers or yarns, optionally wherein the textile comprises one or more synthetic fibers, and the one or more synthetic fibers comprise a polymeric material including a polymer chosen from a polyester, a polyamide, a polyolefin, or a combination thereof.
In accordance with Aspect 10, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the textile comprises one or more recycled fibers.
In accordance with Aspect 11, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the textile has a basis weight of about 5 to about 500 grams/meter squared, or, wherein the hydrogel layer has a dry-state thickness ranging from 0.1 millimeters (mm) to 2 mm, or wherein hydrogel material has a melt flow index of from about 35 to about 55 grams per 10 minutes, according to the Melt Flow Index Test Protocol, or any combination thereof.
In accordance with Aspect 12, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel material exhibits a wet-state glass transition temperature equilibrated at 90 percent relative humidity and a dry-state glass transition temperature equilibrated at 0 percent relative humidity, as characterized by the Glass Transition Temperature Test Protocol with the Neat Material Sampling Procedure;
wherein the wet state glass transition temperature is more than 6 degrees Celsius lower than the dry-state glass transition temperature.
In accordance with Aspect 13, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel material has a wet-state storage modulus when equilibrated at 90 percent relative humidity and a dry-state storage modulus when equilibrated at 0 percent relative humidity, as characterized by the Storage Modulus Test Protocol with the Neat Material Sampling Procedure;
wherein the wet-state storage modulus is less than the dry-state storage modulus of the hydrogel material.
In accordance with Aspect 14, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel material comprises a thermoplastic hydrogel.
In accordance with Aspect 15, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel material comprises one or more polymers selected from a polyurethane, a polyamide homopolymer, a polyamide, and any combination thereof.
In accordance with Aspect 16, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel material comprises a polyurethane hydrogel.
In accordance with Aspect 17, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel material comprises a polyamide block copolymer hydrogel.
In accordance with Aspect 18, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel layer comprises a mixture or dispersion of the hydrogel material with an elastomeric material.
In accordance with Aspect 19, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel layer comprises a mixture of a first cured rubber and from about 30 weight percent to about 70 weight percent of the hydrogel material, based on the total weight of the mixture, wherein the hydrogel material comprises a polyurethane hydrogel.
In accordance with Aspect 20, the present disclosure is directed to the composite element of any one of Aspects 1 to 20, wherein the hydrogel material is distributed throughout the hydrogel layer and entrapped by a first polymeric network including the first cured rubber.
In accordance with Aspect 21, the present disclosure is directed to an article comprising:
a composite element comprising:
a first textile comprising a first textile material and having a first side, a second side, and a core located between the first side and the second side;
a hydrogel layer, comprising a hydrogel material and having a first side and a second side that is operably coupled to the textile along the first side of the first textile;
wherein a portion of the hydrogel layer extends through the first side of the first textile and at least partially into the core of the first textile, but does not extend onto the second side of the first textile;
wherein at least a portion of the first side of the hydrogel layer provides a first externally-facing surface of the article; and
a second element comprising a second polymeric material, the second element having a first side and a second side, wherein at least a portion of the first side of the second element is operably coupled with the second side of the first textile.
In accordance with Aspect 22, the present disclosure is directed to the article of Aspect 21, wherein the article is an article of footwear, a component of an article of footwear, an article of apparel, a component of an article of apparel, an article of sporting equipment, or a component of an article of sporting equipment.
In accordance with Aspect 23, the present disclosure is directed to the article of Aspect 21, wherein the composite element is a composite element according to any one of Aspects 1 to 20.
In accordance with Aspect 24, the present disclosure is directed to a sole structure for an article of footwear, the sole structure comprising:
a composite element comprising:
a first textile comprising a first textile material and having a first side, a second side, and a core located between the first side and the second side;
a hydrogel layer, comprising a hydrogel material and having a first side and a second side that is operably coupled to the textile along the first side of the first textile;
wherein a portion of the hydrogel layer extends through the first side of the first textile and at least partially into the core of the first textile, but does not extend onto the second side of the first textile;
wherein at least a portion of the first side of the hydrogel layer provides a first ground-facing surface of the sole structure; and
a sole component comprising a second polymeric material, the sole component having a first side and a second side, wherein at least a portion of the first side of the sole component is operably coupled with the second side of the first textile.
In accordance with Aspect 25, the present disclosure is directed to the sole structure of Aspect 24, wherein the sole component is a full plate or a partial plate, or wherein the sole component b) comprises one or more traction elements, or comprises a pod comprising a plurality of connected traction elements, or wherein the sole component is a full or partial plate comprising one or more traction elements.
In accordance with Aspect 26, the present disclosure is directed to the sole structure of Aspect 24, wherein the composite element comprises a composite element according to any one of Aspects 1 to 20.
In accordance with Aspect 27, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the sole structure further comprises a second textile comprising a second textile material and having a first side, a second side, and a core located between the first side and the second side, wherein the second side of the second textile is operably coupled with the second side of the sole component.
In accordance with Aspect 28, the present disclosure is directed to the sole structure of Aspect 27, wherein the second textile is a composite element according to any one of Aspects 1 to 20.
In accordance with Aspect 29, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the second polymeric material comprises a thermoplastic polymer, optionally wherein the thermoplastic polymer is a thermoplastic polyolefin, optionally wherein the thermoplastic polyolefin is a thermoplastic polyolefin copolymer.
In accordance with Aspect 30, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the second polymeric material comprises a polyoefin.
In accordance with Aspect 31, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the second polymeric material comprises a copolymer.
In accordance with Aspect 32, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the second polymeric material comprises a polyolefin copolymer, and optionally an effective amount of a polymeric resin modifier, optionally wherein the effective amount of the polymeric resin modified is at least 5 weight percent based on the total weight of the second polymeric material.
In accordance with Aspect 33, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein second polymeric material has a melt flow index of from about 35 to about 55 grams per 10 minutes, according to the Melt Flow Index Test Protocol.
In accordance with Aspect 34, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the second polymeric material has an abrasion loss of a about 0.05 cubic centimeters (cm3) to about 0.1 cubic centimeters (cm3), about 0.07 cubic centimeters (cm3) to about 0.1 cubic centimeters (cm3), about 0.08 cubic centimeters (cm3) to about 0.1 cubic centimeters (cm3), or about 0.08 cubic centimeters (cm3) to about 0.11 cubic centimeters (cm3) pursuant to ASTM D 5963-97a using the Neat Material Sampling Procedure.
In accordance with Aspect 35, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the effective amount of the polymeric resin modifier is an amount effective to allow the second polymeric material to pass a flex test pursuant to the Cold Ross Flex Test Protocol using the Plaque Sampling Procedure; optionally wherein the effective amount of the polymeric resin modifier is an amount effective to allow the second polymeric material to pass a flex test pursuant to the Cold Ross Flex Test Protocol using the Plaque Sampling Procedure without a significant change in an abrasion loss as compared to an abrasion loss of a similar polymeric material that is identical to the second polymeric material except without the polymeric resin modifier when measured pursuant to ASTM D 5963-97a using the Neat Material Sampling Procedure.
In accordance with Aspect 36, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the abrasion loss of the second polymeric material is about 0.08 cubic centimeters to about 0.1 cubic centimeters.
In accordance with Aspect 37, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polyolefin copolymer is a random copolymer, optionally wherein the polyolefin copolymer comprises a plurality of repeat units, with each of the plurality of repeat units individually derived from an alkene monomer having about 1 to about 6 carbon atoms, optionally wherein the polyolefin copolymer is a random copolymer and comprises a plurality of repeat units, with each of the plurality of repeat units individually derived from an alkene monomer having about 1 to about 6 carbon atoms, optionally wherein the polyolefin copolymer comprises a plurality of repeat units, with each of the plurality of repeat units individually derived from a monomer selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-butene, and a combination thereof.
In accordance with Aspect 38, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polyolefin copolymer comprises a plurality of repeat units each individually selected from Formula 1A-1D
In accordance with Aspect 39, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polyolefin copolymer comprises a plurality of repeat units each individually having a structure according to Formula 2
where R1 is a hydrogen or a substituted or unsubstituted, linear or branched, C1-C12 alkyl or heteroalkyl.
In accordance with Aspect 40, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein polymers in the second polymeric material consist essentially of polyolefin copolymers.
In accordance with Aspect 41, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polyolefin copolymer is a random copolymer of a first plurality of repeat units and a second plurality of repeat units, and wherein each repeat unit in the first plurality of repeat units is derived from ethylene and the each repeat unit in the second plurality of repeat units is derived from a second olefin, optionally wherein the second olefin is selected from the group consisting of propylene, 4-methyl-1-pentene, 1-butene, and other linear or branched terminal alkenes having about 3 to 12 carbon atoms.
In accordance with Aspect 42, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A, and wherein each of the repeat units in the second plurality of repeat units has a structure selected from Formula 1B-1D
optionally wherein each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A, and wherein each of the repeat units in the second plurality of repeat units has a structure according to Formula 2
where R1 is a hydrogen or a substituted or unsubstituted, linear or branched, C2-C12 alkyl or heteroalkyl.
In accordance with Aspect 43, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polyolefin copolymer comprises about 80 percent to about 99 percent, about 85 percent to about 99 percent, about 90 percent to about 99 percent, or about 95 percent to about 99 percent polyolefin repeat units by weight based upon a total weight of the polyolefin copolymer, optionally wherein the polyolefin copolymer comprises about 1 percent to about 5 percent, about 1 percent to about 3 percent, about 2 percent to about 3 percent, or about 2 percent to about 5 percent ethylene by weight based upon a total weight of the polyolefin copolymer.
In accordance with Aspect 44, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polyolefin copolymer is substantially free of polyurethanes, or wherein polymer chains of the polyolefin copolymer are substantially free of urethane repeat units, or wherein the second polymeric material is substantially free of polymer chains including urethane repeat units, or any combination thereof.
In accordance with Aspect 45, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polyolefin copolymer is substantially free of polyamide, wherein polymer chains of the polyolefin copolymer are substantially free of amide repeat units, or wherein the second polymeric material is substantially free of polymer chains including amide repeat units, or any combination thereof.
In accordance with Aspect 46, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the polyolefin copolymer comprises a polypropylene copolymer, optionally wherein the polypropylene copolymer comprises about 80 percent to about 99 percent, about 85 percent to about 99 percent, about 90 percent to about 99 percent, or about 95 percent to about 99 percent polypropylene repeat units by weight based upon a total weight of the polypropylene copolymer, optionally wherein the polypropylene copolymer comprises about 1 percent to about 5 percent, about 1 percent to about 3 percent, about 2 percent to about 3 percent, or about 2 percent to about 5 percent ethylene by weight based upon a total weight of the polypropylene copolymer.
In accordance with Aspect 47, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polypropylene copolymer is a random copolymer comprising about 2 percent to about 3 percent of a first plurality of repeat units by weight and about 80 percent to about 99 percent by weight of a second plurality of repeat units based upon a total weight of the polypropylene copolymer; wherein each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A and each of the repeat units in the second plurality of repeat units has a structure according to Formula 1B
In accordance with Aspect 48, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein polymers in the second polymeric material consist essentially of propylene repeat units, optionally wherein the second polymeric material consists essentially of polypropylene copolymers, optionally wherein the polypropylene copolymer is a random copolymer of ethylene and propylene, optionally wherein the second polymeric material comprises an elastomeric material, optionally an olefin elastomer.
In accordance with Aspect 49, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the second polymeric material comprises a polystyrene, a polyethylene, an ethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene, a poly-4-methylpent-1-ene, a polyisoprene, a polybutadiene, an ethylene-methacrylic acid copolymer, a copolymer thereof, or a blend or mixture thereof; optionally wherein the second polymeric material comprises repeating units of styrene, butene, isobutylene, isoprene, butadiene, or a combination thereof; optionally wherein the second polymeric material comprises a block copolymer comprising a polystyrene block; wherein the block copolymer comprises a copolymer of styrene and one or both of ethylene and butylene; optionally wherein the second polymeric material comprises an ethylene-propylene diene rubber (EPDM) dispersed in a polypropylene.
In accordance with Aspect 50, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the second polymeric material comprises a polyurethane, a polyamide, a polyester, a polyether, a polyurea, or a copolymer thereof, or a combination thereof.
In accordance with Aspect 51, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the abrasion loss of the second polymeric material is within about 20 percent of an abrasion loss of the otherwise same second polymeric material except without the resin modifier when measured pursuant to ASTM D 5963-97a using the Neat Material Sampling Procedure; or wherein the second polymeric material has a percent crystallization of about 35 percent, about 30 percent, about 25 percent, or less when measured according to the Crystallinity Test Protocol using the Neat Material Sampling Procedure; or wherein the second polymeric material has a percent crystallization that is at least 4 percentage points less than a percent crystallization of the otherwise same second polymeric material except without the polymeric resin modifier when measured according to the Crystallinity Test Protocol using the Neat Material Sampling Procedure.
In accordance with Aspect 52, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the effective amount of the polymeric resin modifier is about 5 percent to about 30 percent, about 5 percent to about 25 percent, about 5 percent to about 20 percent, about 5 percent to about 15 percent, about 5 percent to about 10 percent, about 10 percent to about 15 percent, about 10 percent to about 20 percent, about 10 percent to about 25 percent, or about 10 percent to about 30 percent by weight based upon a total weight of the second polymeric material, or wherein the effective amount of the polymeric resin modifier is about 20 percent, about 15 percent, about 10 percent, about 5 percent, by weight, or less based upon a total weight of the second polymeric material.
In accordance with Aspect 53, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polymeric resin modifier comprises about 10 percent to about 15 percent ethylene repeat units by weight based upon a total weight of the polymeric resin modifier; optionally wherein the polymeric resin modifier comprises about 10 percent to about 15 percent repeat units according to Formula 1A by weight based upon a total weight of the polymeric resin modifier
In accordance with Aspect 54, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the second polymeric material has a total ethylene repeat unit content of about 3 percent to about 7 percent by weight based upon a total weight of the second polymeric material, or wherein the polymeric resin modifier has an ethylene repeat unit content of about 10 percent to about 15 percent by weight based upon a total weight of the polymeric resin modifier.
In accordance with Aspect 55, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polymeric resin modifier is a copolymer comprising isotactic repeat units derived from an olefin, wherein the polymeric resin modifier is a copolymer comprising repeat units according to Formula 1B, and wherein the repeat units according to Formula 1B are arranged in an isotactic stereochemical configuration
In accordance with Aspect 56, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein an otherwise same second polymeric material except without the polymeric resin modifier does not pass the cold Ross flex test using the Cold Ross Flex Test Protocol and the Neat Material Sampling Procedure.
In accordance with Aspect 57, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polymeric resin modifier is a copolymer comprising isotactic propylene repeat units and ethylene repeat units, optionally. wherein the polymeric resin modifier is a copolymer comprising a first plurality of repeat units and a second plurality of repeat units; wherein each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A and each of the repeat units in the second plurality of repeat units has a structure according to Formula 1B, and wherein the repeat units in the second plurality of repeat units are arranged in an isotactic stereochemical configuration
In accordance with Aspect 58, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the polymeric resin modifier is a metallocene catalyzed polymer, optionally a metallocene catalyzed copolymer, optionally a metallocene catalyzed propylene copolymer.
In accordance with Aspect 59, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the second polymeric material further comprises a clarifying agent, optionally wherein the clarifying agent is present in an amount from about 0.5 percent by weight to about 5 percent by weight or about 1.5 percent by weight to about 2.5 percent by weight based upon a total weight of the polyolefin resin, optionally wherein the clarifying agent is selected from the group consisting of a substituted or unsubstituted dibenzylidene sorbitol, 1,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene], and a derivative thereof.
In accordance with Aspect 60, the present disclosure is directed to the sole structure according to any one of Aspects 24 to 78, wherein the clarifying agent comprises an acetal compound that is the condensation product of a polyhydric alcohol and an aromatic aldehyde, wherein the polyhydric alcohol is selected from the group consisting of acyclic polyols such as xylitol and sorbitol and acyclic deoxy polyols such as 1,2,3-trideoxynonitol or 1,2,3-trideoxynon-1-enitol, optionally wherein the aromatic aldehyde is selected from the group consisting of benzaldehyde and substituted benzaldehydes.
In accordance with Aspect 61, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first textile or the second textile or both comprises a decorative element, optionally wherein the decorative element is a printed element, a dyed element, or a structurally colored element, or an embroidered element, or any combination thereof, optionally wherein the decorative element is visible from the ground-facing side of the sole structure.
In accordance with Aspect 62, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first textile or the second textile or both comprises an adhesive layer, and the adhesive layer is on the first side of the first textile, or the second side of the first textile, or on the first side of the second textile, or on the second side of the second textile, or any combination thereof.
In accordance with Aspect 63, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the sole structure further comprises a first adhesive layer that operably couples the second side of the hydrogel layer with the first side of the first textile; a second adhesive layer that operably couples the second side of the first textile with the first side of the sole component; or a third adhesive layer that operably couples the second side of the second textile to the second side of the sole component, or a fourth adhesive layer positioned on the first side of the second textile, or any combination thereof.
In accordance with Aspect 64, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, or both penetrate at least a portion of a core thickness of the first textile; or the third adhesive layer, or the fourth adhesive layer, or both penetrate at least a portion of a core thickness of the third textile; or any combination thereof.
In accordance with Aspect 65, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, or both penetrate at least 10 percent, or at least 20 percent, or at least 30 percent, or at least 40 percent of the core thickness of the first textile; or the third adhesive layer or the fourth adhesive layer, or both penetrate at least 10 percent, or at least 20 percent, or at least 30 percent, or at least 40 percent of the core thickness of the second textile; or any combination thereof.
In accordance with Aspect 66, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, or both penetrate less than 80 percent, or less than 70 percent, or less than 60 percent, or less than 50 percent, or less than 40 percent, or less than 30 percent of the core thickness of the first textile; or the third adhesive layer, or the fourth adhesive layer or both penetrate less than 80 percent, or less than 70 percent, or less than 60 percent, or less than 50 percent, or less than 40 percent, or less than 30 percent of the core thickness of the second textile; or any combination thereof.
In accordance with Aspect 67, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, the third adhesive layer, the fourth adhesive layer, or any combination thereof, have a thickness of from about 0.2 millimeters to about 2.0 millimeters.
In accordance with Aspect 68, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, the third adhesive layer, the fourth adhesive layer, or any combination thereof, have a thickness of from about 0.4 millimeters to about 1.5 millimeters.
In accordance with Aspect 69, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first adhesive layer, the second adhesive layer, the third adhesive layer, the fourth adhesive layer, or any combination thereof, comprise a contact adhesive, or comprise a hot melt adhesive, optionally wherein the hot melt adhesive comprises a polyurethane, optionally wherein the hot melt adhesive has a melt flow index of from about 35 to about 55 grams per 10 minutes, according to the Melt Flow Index Test Protocol.
In accordance with Aspect 70, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first ground-facing surface of the sole structure provides at least about 80 percent of a total ground-facing surface of the sole structure.
In accordance with Aspect 71, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the first side of the sole component comprises a second portion that provides a second surface of the sole structure, and the second surface of the sole structure is configured to be a ground-contacting surface.
In accordance with Aspect 72, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the second surface comprises one or more traction elements, optionally wherein the one or more traction elements are integrally formed with the sole component; or wherein the sole component comprises one or more openings configured to receive a detachable traction element; optionally wherein the one or more traction elements include lugs, cleats, studs, spikes, or a combination thereof.
In accordance with Aspect 73, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the hydrogel layer has an outer perimeter, and the one or more traction elements of the sole component are disposed outside of the outer perimeter of the hydrogel layer; optionally wherein the hydrogel layer has a void defined at least in part by an inner perimeter, and at least one of the one or more traction elements of the sole component at occupies at least a portion of the void in the hydrogel layer.
In accordance with Aspect 74, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the hydrogel layer has a dry-state thickness ranging from 0.1 millimeters (mm) to 2 mm.
In accordance with Aspect 75, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein hydrogel material has a melt flow index of from about 35 to about 55 grams per 10 minutes, according to the Melt Flow Index Test Protocol.
In accordance with Aspect 76, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the hydrogel layer has a water uptake capacity at 1 hour of greater than 40 percent by weight as characterized by the Water Uptake Capacity Test Protocol with the Component Sampling Procedure; or wherein the hydrogel layer has a water uptake rate greater than 20 g/m2/√min as characterized by the Water Uptake Rate Test Protocol with the Component Sampling Procedure; or wherein the hydrogel layer has a swell thickness increase at 1 hour greater than 20 percent as characterized by the Swelling Capacity Test Protocol with the Component Sampling Procedure; or. wherein at least a portion of the external surface of the hydrogel layer exhibits one or more of a wet-state contact angle less than 80° as characterized by the Contact Angle Test Protocol and a wet-state coefficient of friction less than 0.8 as characterized by the Coefficient of Friction Test Protocol, with the Component Sampling Procedure; or wherein the hydrogel material exhibits a wet-state glass transition temperature equilibrated at 90 percent relative humidity and a dry-state glass transition temperature equilibrated at 0 percent relative humidity, as characterized by the Glass Transition Temperature Test Protocol with the Neat Material Sampling Procedure;
wherein the wet state glass transition temperature is more than 6 degrees Celsius lower than the dry-state glass transition temperature; or wherein the hydrogel material has a wet-state storage modulus when equilibrated at 90 percent relative humidity and a dry-state storage modulus when equilibrated at 0 percent relative humidity, as characterized by the Storage Modulus Test Protocol with the Neat Material Sampling Procedure;
wherein the wet-state storage modulus is less than the dry-state storage modulus of the hydrogel material; or any combination thereof.
In accordance with Aspect 77, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the hydrogel material comprises a thermoplastic hydrogel, optionally wherein the hydrogel material comprises one or more polymers chosen from a polyurethane, a polyamide homopolymer, a polyamide copolymer, or any combination thereof; optionally wherein the hydrogel material comprises a thermoplastic polyurethane, or wherein the hydrogel material comprises a polyamide block copolymer.
In accordance with Aspect 78, the present disclosure is directed to the sole structure of any one of Aspects 24 to 78, wherein the hydrogel material comprises a mixture or dispersion of a polymeric hydrogel with an elastomeric material; optionally wherein the hydrogel material comprises a mixture of a first cured rubber and from about 30 weight percent to about 70 weight percent of a polymeric hydrogel, based on the total weight of the mixture, wherein the polymeric hydrogel comprises a polyurethane hydrogel; optionally wherein the polymeric hydrogel is distributed throughout the hydrogel material and entrapped by a first polymeric network including the first cured rubber.
In accordance with Aspect 79, the present disclosure is directed to an article of footwear comprising an upper operably coupled with the sole structure of any one of Aspects 24 to 78.
In accordance with Aspect 80, the present disclosure is directed to the article of footwear of any one of Aspects 79 to 81, wherein the sole structure comprises a sole component operably coupled to a second textile, the second textile includes a fourth adhesive layer present on the first side of the second textile, and the fourth adhesive layer operably couples the upper to the sole structure.
In accordance with Aspect 81, the present disclosure is directed to the article of footwear of any one of Aspects 79 to 81, wherein the article includes a mechanical bond or an adhesive bond between the second side of the sole component and the upper.
In accordance with Aspect 82, the present disclosure is directed to a method of making a composite element, the method comprising:
operably coupling a hydrogel layer comprising a hydrogel material with a first side of a textile;
wherein a portion of the hydrogel layer extends through a first side of the textile, and at least partially through a core of the textile, but does not extend onto a second side of the textile.
In accordance with Aspect 83, the present disclosure is directed to the method of any of Aspects 82-84, wherein the step of operably coupling the hydrogel layer with first side of the textile comprises spraying, dipping, brushing, or printing the hydrogel material onto the first side of the textile; or wherein the step of operably coupling the hydrogel layer with first side of the textile comprises extruding, pouring, or injection molding the hydrogel material onto the first side of the textile; or wherein the step of operably coupling the hydrogel layer with first side of the textile comprises mechanically, chemically, and/or thermally bonding a hydrogel material to the first side of the textile; or wherein the step of operably coupling the hydrogel layer with first side of the textile comprises increasing the temperature of the hydrogel material to a first temperature that is equal to or greater than a melting temperature or Vicat softening temperature of the hydrogel material, but which is below a Vicat softening temperature of the textile material; and contacting the softened or molten hydrogel layer with the first side of the textile so that at least a portion of the hydrogel material penetrates the first side of the textile; or wherein the step of operably coupling the hydrogel layer includes melting both the hydrogel material and the textile material, contacting the molten hydrogel material with the molten textile material, and intermingling polymer chains of the molten hydrogel material and polymer chains of the molten textile material; or wherein the step of operably coupling the hydrogel layer with first side of the textile further comprises: after contacting the textile material with the molten or softened hydrogel material, reducing the temperature of the hydrogel material to a second temperature that is below the melting temperature or Vicat softening temperature of the hydrogel material, thereby solidifying the molten or softened hydrogel material.
In accordance with Aspect 84, the present disclosure is directed to the method of any one of Aspects 82 to 84, wherein the textile material has a textile melting temperature or a textile Vicat softening temperature that is at least 20 degrees Celsius, or at least 30 degrees Celsius, or at least 40 degrees Celsius, or at least 50 degrees Celsius, or at least 60 degrees Celsius, or at least 70 degrees Celsius, or at least 80 degrees Celsius, or at least 90 degrees Celsius, or at least 100 degrees Celsius greater than a melting temperature or Vicat softening temperature of the hydrogel material.
In accordance with Aspect 85, the present disclosure is directed to a method of making an article, the method comprising:
operably coupling a first composite element to a second component; the composite element comprising a textile and a hydrogel layer; the textile comprising a textile material and having a first side, a second side, and a core located between the first side and the second side; the hydrogel layer comprising a hydrogel material and having a first side and a second side, the second side of the hydrogel layer being operably coupled to the textile along the first side of the textile; wherein, in the composite element, a portion of the hydrogel layer extends through the first side of the textile and at least partially into the core of the textile, but does not extend onto the second side of the textile;
wherein the operably coupling comprises forming a bond between the second side of the textile of the composite element and the second component such that the hydrogel layer of the composite element defines at least a portion of an externally-facing surface of the second component.
In accordance with Aspect 86, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the step of operably coupling comprises forming a mechanical bond between the second side of the textile and a second polymeric material.
In accordance with Aspect 87, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the article is an article of footwear, a component of an article of footwear, an article of apparel, a component of an article of apparel, an article of sporting equipment, or a component of an article of sporting equipment.
In accordance with Aspect 88, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the article is a sole structure of an article of footwear, and optionally wherein the externally-facing surface is a ground-facing surface of the sole structure.
In accordance with Aspect 89, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the step of operably coupling comprises placing the first composite element into a mold so that a portion of the first side of the hydrogel layer contacts a portion of a molding surface of the mold, forming a prepared molding surface;
charging a second polymeric material onto the prepared molding surface of the mold;
at least partially solidifying the charged second polymeric material in the mold and thereby operably coupling the composite element and the at least partially solidified second polymeric material, forming a sole structure comprising the hydrogel layer of the composite element defining at least a portion of a ground-facing surface of the sole structure; and removing the sole structure from the mold.
In accordance with Aspect 90, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the method further comprises restraining the composite element in the mold so that at least a portion of the first side of the hydrogel layer contacts the molding surface while charging the second polymeric material.
In accordance with Aspect 91, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the composite element is a composite element according to any one of Aspects 1 to 20.
In accordance with Aspect 92, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the sole structure is a sole structure according to any one of Aspects 26 to 78.
In accordance with Aspect 93, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the second polymeric material is a thermosetting material, and the step of at least partially solidifying the charged second material comprises at least partially curing the charged second material into a thermoset second material.
In accordance with Aspect 94, the present disclosure is directed to the method of any one of Aspects 85 to 114, further comprising increasing the temperature of the second polymeric material to a molding temperature that is above a melting temperature or Vicat softening temperature of the second polymeric material.
In accordance with Aspect 95, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the step of increasing the temperature of the second polymeric material to the molding temperature is conducted prior to or during the step of charging the second polymeric material.
In accordance with Aspect 96, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the step of increasing the temperature of the second polymeric material to the molding temperature is conducted while the second polymeric material is in contact with the prepared molding surface.
In accordance with Aspect 97, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein after the temperature of the second polymeric material is increased to the molding temperature, at least a portion of the second polymeric material penetrates the second side of the textile.
In accordance with Aspect 98, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the second polymeric material is a thermoplastic material, and the step of solidifying the second polymeric material comprises decreasing the temperature of the second polymeric material to a second temperature that is below the melting temperature or Vicat softening temperature of the second polymeric material.
In accordance with Aspect 99, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the first composite element further comprises a hot melt adhesive layer on the second side of the textile, and the step of increasing the temperature to the molding temperature comprises increasing the temperature of the hot melt adhesive to a temperature that is above the melting temperature of the hot melt adhesive, so that the adhesive bonds with the second polymeric material.
In accordance with Aspect 100, the present disclosure is directed to the method of any one of Aspects 85 to 114, further comprising the method of making the composite element according to any one of Aspects 82 to 84.
In accordance with Aspect 101, the present disclosure is directed to the method of any one of Aspects 85 to 114, further comprising increasing the temperature of the second polymeric material to a third temperature that is above Vicat softening temperature of the second polymeric material.
In accordance with Aspect 102, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein after the temperature of the second polymeric material is increased to the molding temperature, at least a portion of the second polymeric material penetrates into the core of the textile.
In accordance with Aspect 103, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein solidifying the second polymeric material comprises decreasing the temperature of the second polymeric material to a temperature that is below the Vicat softening temperature of the second polymeric material.
In accordance with Aspect 104, the present disclosure is directed to the method of any one of Aspects 85 to 114, further comprising providing an adhesive layer on the first side of the textile, the second side of the textile, or both.
In accordance with Aspect 105, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the step of charging the second polymeric material into the mold comprises closing the mold and injecting the second polymeric material into the closed mold using an injection molding process.
In accordance with Aspect 106, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein charging the second polymeric material into the mold comprises charging the second polymeric material into the mold, closing the mold before, during or after the charging, and applying compression to the closed mold.
In accordance with Aspect 107, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the step of restraining the first side of the hydrogel layer against the portion of the molding surface comprises using a vacuum, using one or more retractable pins, or using both a vacuum and one or more retractable pins.
In accordance with Aspect 108, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the molding surface is in the predetermined shape of the sole component.
In accordance with Aspect 109, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein at least a portion of the molding surface has a predetermined curvature.
In accordance with Aspect 110, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein placing the composite element in the mold and/or restraining the portion of the first side of the hydrogel layer against the portion of the molding surface includes bending or curving the hydrogel layer to conform to a curvature of the molding surface while maintaining the hydrogel layer at a temperature in a range of about 10 degrees Celsius to about 80 degrees Celsius.
In accordance with Aspect 111, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein one or more traction elements are integrally formed with the sole structure during the molding step; separately added as snap-fit or screw-on components after the sole structure is removed from the mold; or a combination thereof; wherein the one or more traction elements are integrally formed with the sole structure using the second polymeric material.
In accordance with Aspect 112, the present disclosure is directed to the method of any one of Aspects 85 to 114, further comprising placing one or more preformed traction element tips into the mold prior to charging the second polymeric material.
In accordance with Aspect 113, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the traction elements comprise a traction element material, and the traction element material has a higher average durometer hardness, or lower average abrasion loss, or both, as compared to the second polymeric material.
In accordance with Aspect 114, the present disclosure is directed to the method of any one of Aspects 85 to 114, wherein the traction elements are lugs, cleats, studs, spikes, or a combination thereof.
In accordance with Aspect 115, the present disclosure is directed to a method of manufacturing an article of footwear, the method comprising:
securing an upper to a sole structure, the sole structure comprising a hydrogel layer having a first side and a second side that is operably coupled with a first side of a textile, and a sole component comprising a second polymeric material that is operably coupled with a second side of the textile, such that the first side of the hydrogel layer of the sole structure defines a ground-facing surface of the article of footwear.
In accordance with Aspect 116, the present disclosure is directed to the method of any one of Aspects 115 to 120, wherein the method further comprises:
attaching a midsole to the sole structure and/or the upper prior to securing the sole structure to the upper, such that the midsole resides between the sole structure and the upper.
In accordance with Aspect 117, the present disclosure is directed to the method of any one of Aspects 115 to 120, wherein the upper comprises, a natural leather, a thermoset polymer, a thermoplastic polymer, or a mixture thereof.
In accordance with Aspect 118, the present disclosure is directed to the method of any one of Aspects 115 to 120, wherein the upper comprises a textile selected from a knit textile, a woven textile, a non-woven textile, a braided textile, or a combination thereof; optionally wherein the textile includes one or more natural or synthetic fibers or yarns; optionally wherein the synthetic fibers or yarns comprise a thermoplastic polyurethane (TPU), a polyamide, a polyester, a polyolefin, or a mixture thereof.
In accordance with Aspect 119, the present disclosure is directed to the method of any one of Aspects 115 to 120, wherein securing the sole structure to the upper includes the use of an adhesive, a primer, or a combination thereof.
In accordance with Aspect 120, the present disclosure is directed to an article of footwear manufactured according to any of Aspects 115 to 120.
Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular aspects described, and as such may, of course, vary. Other systems, methods, features, and advantages of polymeric hydrogels, composite elements, and articles and components formed thereof will be or become apparent to one with skill in the art upon examination of the drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only, and is not intended to be limiting. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein.
Composite Element
Referring to
The presence of the core of the textile further increases the surface area available for forming mechanical bonds. In some aspects, the hydrogel layer can penetrate at least 10 percent, at least 20 percent, at least 30 percent, or at least 40 percent of the core thickness of the textile. In another aspect, the hydrogel layer can penetrate less than 80 percent, less than 70 percent, less than 60 percent, less than 50 percent, less than 40 percent, or less than 30 percent of the core thickness of the textile.
In some aspects, the hydrogel layer can have a dry-state thickness ranging from about 0.1 millimeters to about 2 millimeters, or from about 0.3 millimeters to about 1.5 millimeters, or from about 0.5 millimeters to about 1.0 millimeters.
The polymeric hydrogel is present in the composite element in an amount of about 0.5 weight percent to about 85 weight percent based on the overall weight of the composite element. Alternatively, the polymeric hydrogel is present in an amount that ranges from about 5 weight percent to about 80 weight percent based on the overall weight of the composite element; alternatively, about 10 weight percent to about 70 weight percent, or about 20 weight percent to about 70 weight percent, or about 30 weight percent to about 70 weight percent, or about 45 to about 70 weight percent.
For the purpose of this disclosure, the term “weight” refers to a mass value, such as having the units of grams, kilograms, and the like. Further, the recitations of numerical ranges by endpoints include the endpoints and all numbers within that numerical range. For example, a concentration ranging from 40 percent by weight to 60 percent by weight includes concentrations of 40 percent by weight, 60 percent by weight, and all concentrations there between (e.g., 40.1 percent, 41 percent, 45 percent, 50 percent, 52.5 percent, 55 percent, 59 percent, etc.).
In an aspect, the disclosed hydrogel material can have a melt flow index of from about 35 to about 55 grams per 10 minutes (at 190 degrees Celsius, 21.6 kg) according to the Melt Flow Index Test Protocol disclosed herein. In another aspect, the melt flow index can be about 35 grams per 10 minutes, about 40 grams per 10 minutes, about 45 grams per 10 minutes, about 50 grams per 10 minutes, or about 55 grams per 10 minutes.
Sole Structures and Articles of Footwear Made Therefrom
In some aspects, the disclosure is directed to articles of footwear comprising an upper and a sole structure including the composite element. As used herein, the terms “article of footwear” and “footwear” are intended to be used interchangeably to refer to the same article. Typically, the term “article of footwear” will be used in a first instance, and the term “footwear” can be subsequently used to refer to the same article for ease of readability.
The sole structures have a plate operably coupled with the composite element, where the hydrogel material provides a ground-facing surface of the sole structure. Sole structures having a hydrogel material on a ground-facing surface can prevent or reduce soil accumulation on the ground-facing surface of the article during use on unpaved, muddy, or wet surfaces. However, applicants have found that the hydrogel material of the hydrogel layer can sometimes detach or delaminate from other materials or components in sole structures. Not wishing to be bound by any particular theory, it is believed that providing the hydrogel material in the hydrogel layer as part of the disclosed composite element can lead to improved bonding, reducing or eliminating the detachment or delamination of the polymeric hydrogel, the hydrogel material, and/or the hydrogel layer from other materials or components.
The sole component can further comprise one or more traction elements or a pod that includes a plurality of traction elements connected to each other. In an aspect, the sole structure further comprises a second textile comprising a second textile material and having a first side, a second side, and a core located between the first side and the second side, and wherein the second side of the second textile is operably coupled with the second side of the sole component.
The terms “externally-facing”, “ground-facing”, and “ground-contacting” as used herein in reference to certain structures, layers, or surfaces refers to the position the element is intended to be in when the element is present in an article during normal use. As used herein, “externally-facing” refers to an element which forms an outer-most surface of an article. If the article is footwear, “externally-facing” can refer to an outer-most surface of the upper, the sole structure, or both. If the article is footwear, “ground-contacting” refers to an element which includes an outer-most surface which is configured to directly contact the ground, and which directly contacts the ground during normal wear on a flat, paved surface. For example, the terminal end of a traction element (i.e., the portion of a traction element which extends farthest out from the base of an outsole) and directly contacts the ground when used in a conventional manner, such as standing, walking, or running on a paved or unpaved surfaces. If the article is footwear, “ground-facing” refers to an element which includes an outer-most surface which is positioned toward the ground, during normal wear, but which does not directly contact the ground when the article of footwear is in direct contact with a flat, paved surface. Under some conditions, such as went worn on soft ground, a ground-facing surface may come into direct contact with the ground during normal wear, such as when worn on soft turf or under muddy conditions. Ground-facing surfaces often collect soil and/or debris during wear on soft ground. Examples of ground-facing surfaces include the sides of a traction element, or an area of an outsole located between traction elements. In other words, even though the element may not necessarily be externally-facing or be facing or contacting the ground during various steps of manufacturing or shipping, if the element is intended to be externally-facing, or to face the ground or contact the ground during normal use by a wearer, the element is understood to be externally-facing, and, more specifically, may be “ground-facing” or “ground-contacting”.
The article of footwear can be designed for a variety of uses, such as sporting, athletic, military, work-related, recreational, or casual use. Primarily, the article of footwear is intended for outdoor use on unpaved surfaces (in part or in whole), such as on a ground surface including one or more of grass, turf, gravel, sand, dirt, clay, mud, pavement, and the like, whether as an athletic performance surface or as a general outdoor surface. However, the article of footwear may also be desirable for indoor applications, such as indoor sports including dirt playing surfaces for example (e.g., indoor baseball fields with dirt infields).
The article of footwear can be designed for use in indoor or outdoor sporting activities, such as global football/soccer, golf, American football, rugby, baseball, running, track and field, cycling (e.g., road cycling and mountain biking), and the like. The article of footwear can optionally include traction elements (e.g., lugs, cleats, studs, and spikes as well as tread patterns) to provide traction on soft and slippery surfaces, where articles of the present disclosure can be used or applied between or among the traction elements and optionally on the sides of the traction elements but on the surface of the traction element that contacts the ground or surface. Cleats, studs and spikes are commonly included in footwear designed for use in sports such as global football/soccer, golf, American football, rugby, baseball, and the like, which are frequently played on unpaved surfaces. Lugs and/or exaggerated tread patterns are commonly included in footwear including boots design for use under rugged outdoor conditions, such as trail running, hiking, and military use.
Referring to
The sole structure 213 is described in more detail with reference to
The sole structure 213 can be secured to the upper 250. In some aspects, the lower surface of the upper 250 can be secured to the second upper surface 2160 of the plate 216, by an intermingled bond. In an aspect, an intermingled bond is formed by melding or intermingling polymers in the upper 250 and the polymeric resin of the plate 216. In an aspect, when material from the upper penetrates (e.g., any polymeric material, hydrogel material, resin, yarn, or the like) any distance into the second side 2160 of the plate 216, a mechanical bond is formed. In an aspect, a mechanical bond is formed whenever there exists an entanglement of component parts from two or more elements (e.g., upper and sole structure) such that they cannot be separated. In some aspects, the lower surface of the upper 250 can be adhesively bonded to the second upper surface 2160 of the plate 216 by providing an adhesive between the upper 250 and the polymeric resin of the plate 216. In some aspects, when an adhesive is used, a mechanical bond is formed; that is, the adhesive separately forms mechanical bonds with both the upper and sole structure. In some aspects, when an adhesive is used, a chemical bond is formed. In an aspect, an adhesive can be applied to both the upper 250 and the polymeric resin of the plate 216 and these two parts can be placed in contact with one another during curing of the adhesive. In one aspect, this contact during curing results in the formation of a chemical bond. In at least one aspect, a textile is disposed between plate 216 and upper 250 to assist with bonding.
In some aspects, the second side 204 of the textile 202 can be bonded by intermingling with a material present of the first side 2162 of the plate 216. In some aspects, the second side 204 of the textile 202 can be mechanically bonded to the first side 2162 of the plate 216 by intermingling polymers in the textile 202 and the polymeric resin of the plate 216. In some aspects, the second side 204 of the textile 202 can be adhesively bonded to the first side 2162 of the plate 216. In some aspects, the bonding can include both mechanical and adhesive bonding.
The plate 216 includes a second polymeric material. In some aspects, the second polymeric material of the plate 216 extends through the second side 204 of the textile 202, forming a mechanical bond between the plate and the composite element. In some aspects, the second polymeric material of the plate 216 also extends at least partially through the core 205 of the textile. In some aspects, the second polymeric material of the plate can penetrate at least 10 percent, at least 20 percent, at least 30 percent, or at least 40 percent of the core thickness 208 of the textile 202. In another aspect, the second polymeric material of the plate 216 can penetrate less than 80 percent, less than 70 percent, less than 60 percent, less than 50 percent, less than 40 percent, or less than 30 percent of the core thickness 208 of the textile 202.
According to another aspect of the present disclosure, a sole structure for an article of footwear comprises two or more composite elements, for example, a composite element in the toe portion, the heel portion, the medial portion of the sole structure, or a combination thereof. Each of the composite elements has a hydrogel layer operably coupled with a textile, and is oriented so that the hydrogel material of the hydrogel layer defines a ground-facing surface of the sole structure. The second polymeric material of the plate is operably coupled with the second side of the textile of the two or more composite elements. In some aspects, the second polymeric material of the plate is also operably coupled to the entire external perimeter of each of the two or more composite elements.
As described herein, an article can include two or more different types of composite elements, where the hydrogel layers of each have different water uptake capacities so that different physical characteristics are exhibited by the different types of composite elements.
Referring to
In some aspects, an article of footwear can have a rand operably coupled with the upper and the sole structure. Generally speaking, a rand is a component of an article of footwear that is disposed on an exterior surface of the article of footwear. The rand may be disposed on the upper, on the sole structure, or both. In some aspects, the rand may overlap the biteline where an outsole and upper are attached, and may extend vertically above and/or below the biteline. A rand may be continuous around the article of footwear, or may be discontinuous or located only in select areas. For example, a rand may extend around the entire outer periphery of the article through each of the forefoot portion, the midfoot portion, and the heel portion. In other embodiments, a rand may be present only on the forefoot portion of the upper, or on the forefoot portion and the heel portion of the article. A rand may comprise any material that provides properties and characteristics necessary or desirable for that area of the article of footwear, such as, for example, additional bonding strength between the upper and the sole structure, additional abrasion resistance, additional water resistance, or a combination thereof. In some aspects, the rand may have a decorative appearance, such as by coloring or printing. In some aspects, the rand may have a textured surface.
In some aspects, the upper of an article of footwear 200 can include a removable sock liner (not pictured). As is known in the art, a sock liner conforms to and lines the inner bottom surface of a shoe and is the component contacted by the sole (or socked sole) of a wearer's foot.
In an aspect, the hydrogel layer of the composite material provides at least about 50, at least about 60, at least about 70, at least about 80 percent, at least about 90, of the total ground-facing surface of the sole structure. In another aspect, the first side of the plate provides a second ground-facing surface of the sole structure.
According to another aspect of the present disclosure, the sole structure further comprises one or more traction elements with the one or more composite elements of the sole structure being configured to fit between or around the traction elements. The traction elements can have a ground-contacting surface that does not include the composite element. The composite element can include a void having an interior perimeter, and the traction elements is present in the void, or passes through the void of the composite element. When desirable, the traction element can comprise the second polymeric material, which is operably coupled with the interior perimeter of the composite element. The second polymeric material can also define the ground-facing surfaces of the traction element (e.g., the sides of the traction element), and/or the ground-contacting surface or surfaces of the traction element (e.g., the tip or tips of the traction element).
In an aspect the composite element has an outer perimeter, and the one or more elements of the plate are disposed outside of the outer perimeter of the composite element. In another aspect, the composite element can have a void region defined at least in part by an inner perimeter, and at least one of the one or more traction elements couples with plate in the void region in the composite element.
In some aspects, a portion of composite element can be cut or stamped or molded to form the shape of the composite element as present in the sole structure. In some aspects, the composite element is configured to fit between or around one or more traction elements; i.e., the perimeter of the composite element can be shaped to go between or around the base of a traction element, or one or more interior portions of the film component can be cut out e.g., forming a hole or a void, to go between or around the base of one or more traction elements, or both.
Referring now to
According to various aspects, at least a portion of the external surface of the sole structure can comprise a pattern or a texture. When desirable, this pattern can represent a tread pattern. In some aspects, the external surface of the outsole comprises one or more traction elements wherein the portion of said traction elements that contact the ground are substantially free of the hydrogel material and/or the composite element. In aspects, the traction elements comprise a material that is harder than the hydrogel material and/or the composite element. In some aspects, the one or more traction elements can have a conical or rectangular shape as further described below. The traction elements can provide enhanced traction between the sole structure and the ground. The traction elements also can provide support or flexibility to the sole structure and/or provide an aesthetic design or look to the footwear article.
According to the various aspects, the traction elements can include, but are not limited to, various shaped projections, such as cleats, studs, spikes, or similar elements configured to enhance traction between the sole structure and the ground for a wearer during cutting, turning, stopping, accelerating, and backward movement. According to the aspects, the traction elements can be arranged in any necessary or desirable pattern along the bottom surface of the sole structure. For instance, the traction elements can be distributed in groups or clusters along the sole structure (e.g., clusters of 2-8 traction elements). In certain aspects, the traction elements can be arranged along the outsole symmetrically or non-symmetrically between a medial side and a lateral side of the article of footwear. In certain aspects, one or more of the traction elements can be arranged along a centerline of the sole structure between the medial side and the lateral side.
According to some aspects, the traction elements comprise a traction element polymeric material. In an aspect, the traction element polymeric material and the polymeric component of the second polymeric material can contain different types of polymers. In another aspect, the traction element polymeric material and the polymeric component of the second polymeric material can contain the same types of polymers in different proportions. In some aspects, one or more of the traction elements can comprise the same material as the second polymeric material. In some aspects, one or more of the traction elements can be formed integrally with the sole structure during the molding steps as described in the methods of manufacturing the outsole defined herein. In yet other aspects, at least one of the traction elements can be substantially free of the second polymeric material. In some aspects, the one or more traction elements are made of a material that is harder than the second polymeric material of the plate.
For example, in certain aspects the traction elements can include one or more types of polymers. General types of polymers suitable for use in the composite elements, sole structures, and articles of footwear described herein include thermoplastic polymers; thermoplastic elastomers; thermoset polymers; elastomeric polymers; silicone polymers; natural and synthetic rubbers; composite elements including polymers reinforced with carbon fiber and/or glass; natural leather; metals such as aluminum, steel and the like; and combinations thereof. In some aspects, the traction elements are integrally formed with the sole structure (e.g., molded together), the traction elements can include the same materials as the component (e.g., thermoplastic or thermoset polymers). In some aspects, the traction elements are separately provided (i.e., not molded with the outsole) and can be otherwise operably coupled with the sole structure. For example, the sole structure can contain certain fittings or receptacles or receiving holes with which the traction elements can be coupled. In these aspects the traction elements can comprise any suitable materials that can secured in the receiving holes of the sole structure (e.g., metals and polymers) either as snap-fit, screw-on, or the like.
In some aspects, the traction elements can each independently have any necessary or desired dimension (e.g., shape and size). Examples of shapes for the traction elements include rectangular, hexagonal, cylindrical, conical, circular, square, triangular, trapezoidal, diamond, ovoid, as well as other regular or irregular shapes (e.g., curved lines, C-shapes, etc.). In some aspects, the traction elements can have the same or different heights, widths, and/or thicknesses as each other. Further examples of suitable dimensions for the traction elements and their arrangements along the sole structure include those provided in soccer/global football footwear commercially available under the tradenames “TIEMPO”, “HYPERVENOM”, “MAGISTA”, and “MERCURIAL” from Nike, Inc. of Beaverton, Oreg.
In various aspects, the traction elements can be incorporated into the sole structure by any necessary or desired mechanism such that the traction elements extend from the bottom surface of the outsole. In some aspects, the traction elements can be integrally formed with the sole structure through a molding process. In some aspects, the sole structure can be configured to receive removable traction elements, such as screw-in or snap-in traction elements. In these aspects, the sole structure can include receiving holes (e.g., threaded or snap-fit holes) or fittings, and the traction elements can be screwed or snapped into or otherwise coupled with the receiving holes or fittings to secure the traction elements to the sole structure.
In further aspects, a first portion of the traction elements can be integrally formed with the sole structure and a second portion of the traction elements can be secured with screw-in, snap-in, or other similar mechanisms. The traction elements can also be configured as short studs for use with artificial ground (AG) footwear, if desired. In some aspects, the receiving holes or fittings can be raised or otherwise protrude from the general plane of the external surface of the sole structure. In some aspects, the receiving holes can be flush with the external surface. In some aspects, the sole structure can comprise a combination of these features and elements.
According to various aspects, the one or more traction elements have a length (the dimension by which it protrudes from the externally-facing surface of the sole structure) that is greater than the hydrated or saturated-state thickness of the sole structure. The materials present in the sole structure and its corresponding dry and saturated thicknesses can be selected to ensure that the traction elements continue to provide ground-engaging traction during use of the footwear, even when the hydrogel layer is in a fully swollen state. For example, the sole structure can be characterized by a “clearance” which is the difference between the length of one or more traction elements and the thickness of the sole structure (in its dry state, hydrated state, or saturated state). In some aspects, the average clearance for the saturated-state of the sole structure is desirably at least 8 millimeters (mm). In some aspects, the average clearance of the sole structure in its saturated state can be at least 9 mm, at least 10 mm, or more.
Decorative Features
In some aspects, disclosed herein are a composite element and/or a sole structure comprising the composite element as described herein, wherein the textile comprises a decorative element. The decorative element can be a printed element, a dyed element, a structurally colored element, an embroidered element, or any combination thereof. In some aspects, the decorative element is visible from the ground-facing side of the sole structure.
Properties of the Composite Element and Sole Structures
It has been found the composite element and articles incorporating the composite element (e.g. footwear) can prevent or reduce the accumulation of soil on the externally-facing surface of the composite element during wear on unpaved surfaces. As used herein, the term “soil” can include any of a variety of materials commonly present on a ground or playing surface and which might otherwise adhere to an outsole or exposed midsole of a footwear article. Soil can include inorganic materials such as mud, sand, dirt, and gravel; organic matter such as grass, turf, leaves, other vegetation, and excrement; and combinations of inorganic and organic materials such as clay. Additionally, soil can include other materials such as pulverized rubber which may be present on or in an unpaved surface.
As one skilled in the art will appreciate, preventing or reducing soil accumulation on articles of footwear can provide many benefits. Preventing or reducing soil accumulation on the outsoles of articles of footwear during wear on unpaved surfaces also can significantly affect the weight of accumulated soil adhered to the outsole during wear, reducing fatigue to the wearer caused by the adhered soil. Preventing or reducing soil accumulation on the outsole can help preserve traction during wear. For example, preventing or reducing soil accumulation on the outsole can improve or preserve the performance of traction elements present on the ground-facing surface of the outsole during wear on unpaved surfaces. When worn while playing sports, preventing or reducing soil accumulation on outsoles can improve or preserve the ability of the wearer to manipulate sporting equipment such as a ball with the article of footwear. Further, preventing or reducing soil accumulation on the outsole can make it easier to clean the article of footwear following use.
Disruption of Soil Adhesion
While not wishing to be bound by theory, it is believed that the hydrogel layer of the composite element, and thus the composite element of the present disclosure itself, when sufficiently wet with water (including water containing dissolved, dispersed or otherwise suspended materials) can provide compressive compliance and/or expulsion of uptaken water. In particular, it is believed that the compressive compliance of the wet hydrogel layer, the expulsion of liquid from the wet hydrogel material and/or composite element, a change in topography of the externally-facing surface, or combination thereof, can disrupt the adhesion of soil on or at the externally-facing surface, or the cohesion of the particles to each other on the externally-facing surface, or can disrupt both the adhesion and cohesion. This disruption in the adhesion and/or cohesion of soil is believed to be a responsible mechanism for preventing (or otherwise reducing) the soil from accumulating on the externally-facing surface (due to the presence of the wet material).
This disruption in the adhesion and/or cohesion of soil is believed to be a responsible mechanism for preventing (or otherwise reducing) the soil from accumulating on the externally-facing surface (due to the presence of the polymeric hydrogel in the hydrogel material of the present disclosure). As can be appreciated, preventing soil from accumulating on articles, including on articles of footwear, apparel or sporting equipment particularly, can improve the performance of traction elements present on the articles (e.g., on a sole) during use or wear on unpaved surfaces, can prevent the article from gaining weight due to accumulated soil during use or wear, can preserve performance of the article and thus can provide significant benefits to a user or wearer as compared to an article without the elastomeric material present.
Water Uptake and Swelling
The swelling of the polymeric hydrogel in the hydrogel material present in the hydrogel layer of the composite element can be observed as an increase in thickness of the polymeric hydrogel itself (e.g., in neat form), as an increase in thickness of the hydrogel material itself (e.g., in neat form), as an increase in thickness of the hydrogel layer of the composite element, and/or as an increase in thickness of the composite element itself, from its dry-state thickness, through a range of intermediate-state thicknesses as additional water is absorbed, and finally to a saturated-state thickness which is an average thickness of the polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element when the polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element is fully saturated with water. For example, the saturated-state thickness (or length, and/or height) for the fully saturated polymeric hydrogel, hydrogel material, hydrogel layer, and/or composite element can be greater than 25 percent, greater than 50 percent, greater than 100 percent, greater than 150 percent, greater than 200 percent, greater than 250 percent, greater than 300 percent, greater than 350 percent, greater than 400 percent, or greater than 500 percent, of the dry-state thickness for the same polymeric hydrogel, hydrogel material, hydrogel layer, and/or composite element, as characterized by the Swelling Capacity Test. The saturated-state thickness (or length, and/or height) for the fully saturated polymeric hydrogel, hydrogel material, hydrogel layer, and/or composite element can be about 150 percent to 500 percent, about 150 percent to 400 percent, about 150 percent to 300 percent, or about 200 percent to 300 percent of the dry-state thickness for the same polymeric hydrogel, hydrogel material, hydrogel layer, and/or composite element.
The polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can have an increase in thickness (or length, and/or height) at 1 hour of greater than 20 percent, greater than 30 percent, greater than 40 percent, or greater than 50 percent, as characterized by the Swelling Capacity Test. The polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can have an increase in thickness (or length, and/or height) at 1 hour of about 35 percent to 400 percent, about 50 percent to 300 percent, or about 100 percent to 200 percent, as characterized by the Swelling Capacity Test. The polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can have an increase in thickness (or length, and/or height) at 24 hours of about 45 percent to 500 percent, about 100 percent to 400 percent, or about 150 percent to 300 percent. Correspondingly, the polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can have an increase in volume at 1 hour of about 50 percent to 500 percent, about 75 percent to 400 percent, or about 100 percent to 300 percent.
Even though the polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can swell as it takes up water and transitions between the different material states with corresponding thicknesses, the saturated-state thickness of the composite element preferably remains less than the length of the traction element. This selection of the composite element and its corresponding dry and saturated thicknesses ensures that the traction elements can continue to provide ground-engaging traction during use of the footwear, even when the composite element is in a fully swollen state. For example, the average clearance difference between the lengths of the traction elements and the saturated-state thickness of the composite element is desirably at least 8 millimeters. For example, the average clearance distance can be at least 9 millimeters, 10 millimeters, or more.
The polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can quickly take up water that is in contact with the polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element. For instance, the composite element comprising the hydrogel material can take up water from mud and wet grass, such as during a warmup period prior to a competitive match. Alternatively (or additionally), the hydrogel material can be pre-conditioned with water so that the hydrogel material or hydrogel layer of the composite element is partially or fully saturated, such as by spraying or soaking the structure with water prior to use.
The polymeric hydrogel, the hydrogel material, and/or the hydrogel layer can exhibit an overall water uptake capacity of about 10 weight percent to 225 weight percent as measured in the Water Uptake Capacity Test over a soaking time of 24 hours using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure, as will be defined below. The overall water uptake capacity (at 24 hours) exhibited by the polymeric hydrogel, the hydrogel material, and/or the hydrogel layer can be in the range of about 10 weight percent to about 225 weight percent; about 30 weight percent to about 200 weight percent; about 50 weight percent to about 150 weight percent; or about 75 weight percent to about 125 weight percent. The water uptake capacity, as measured by the Water Uptake Capacity test at 24 hours, exhibited by the polymeric hydrogel, the hydrogel material, and/or the hydrogel layer can be about 20 weight percent or more, about 40 weight percent or more, about 60 weight percent or more, about 80 weight percent or more, or about 100 weight percent or more. For the purpose of this disclosure, the term “overall water uptake capacity” is used to represent the amount of water by weight taken up by the polymeric hydrogel, the hydrogel material, and/or the hydrogel layer as a percentage by weight of the sample when dry. The procedure for measuring overall water uptake capacity includes measurement of the “dry” weight of a sample of the polymeric hydrogel, the hydrogel material, and/or the hydrogel layer, immersion of the sample in water at ambient temperature (˜23 degrees Celsius) for a predetermined amount of time, followed by re-measurement of the weight of the sample when “wet”. The procedure for measuring the overall weight uptake capacity according to the Water Uptake Capacity Test is described below.
The sample of the polymeric hydrogel or the hydrogel material itself, in neat form (e.g., the polymeric hydrogel prior to being compounded into the hydrogel material, and/or the hydrogel material prior to being formed into the hydrogel layer); or of the hydrogel layer itself (e.g., prior to being coupled with the textile), can exhibit an overall water uptake capacity of about 10 weight percent to 3000 weight percent as measured in the Water Uptake Capacity Test over a soaking time of 24 hours using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure, as will be defined below. The overall water uptake capacity (at 24 hours) exhibited by the polymeric hydrogel, the hydrogel material, and/or the hydrogel layer can be in the range of about 50 weight percent to about 2500 weight percent; about 100 weight percent to about 2000 weight percent; about 200 weight percent to about 1500 weight percent; or about 300 weight percent to about 1000 weight percent. The water uptake capacity, as measured by the Water Uptake Capacity test at 24 hours, exhibited by the polymeric hydrogel, the hydrogel material, or the hydrogel layer can be about 20 weight percent or more, about 40 weight percent or more, about 60 weight percent or more, about 80 weight percent or more, or about 100 weight percent or more. The water uptake capacity, as measured by the Water Uptake Capacity test at 24 hours, exhibited by the polymeric hydrogel, the hydrogel material, and/or the hydrogel layer can be about 100 weight percent or more, about 200 weight percent or more, about 300 weight percent or more, about 400 weight percent or more, or about 500 weight percent or more. For the purpose of this disclosure, the term “overall water uptake capacity” is used to represent the amount of water by weight taken up by the polymeric hydrogel the hydrogel material, and/or the hydrogel layer as a percentage by weight of the sample when dry. The procedure for measuring overall water uptake capacity includes measurement of the “dry” weight of the sample, immersion of the sample in water at ambient temperature (˜23 degrees Celsius) for a predetermined amount of time, followed by re-measurement of the weight of the sample when “wet”. The procedure for measuring the overall weight uptake capacity according to the Water Uptake Capacity Test using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure is described below.
The polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can have a “time value” equilibrium water uptake capacity, where the time value corresponds to the duration of soaking or exposure to water (e.g., for example in use of footwear being exposed to water). For example, a “30 second equilibrium water uptake capacity” corresponds to the water uptake capacity at a soaking duration of 30 seconds, a “2 minute equilibrium water uptake capacity” corresponds to the water uptake capacity at a soaking duration of 2 minutes, and so on at various time duration of soaking. A time duration of “0 seconds” refers to the dry-state and a time duration of 24 hours corresponds to the saturated state of the composite element at 24 hours. Additional details are provided in the Water Uptake Capacity Test Protocol described herein. In some aspects, the polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can have a one hour water uptake capacity of greater than 40 percent.
The polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can also be characterized by a water uptake rate. The water uptake rate of the polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can be 10 g/m2/√min to 120 g/m2/√min as measured in the Water Uptake Rate Test using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure. The water uptake rate is defined as the weight (in grams) of water absorbed per square meter (m2) of the sample over the square root of the soaking time (√min). Alternatively, the water uptake rate can range from about 12 g/m2/√min to about 100 g/m2/√min; alternatively, from about 20 g/m2/√min to about 90 g/m2/√min; alternatively, up to about 60 g/m2/√min.
The overall water uptake capacity and the water uptake rate can be dependent upon the amount of the polymeric hydrogel that is present in the hydrogel material, on the volume of hydrogel material present in the composite element, and/or on the thickness of the hydrogel layer in the composite element. The polymeric hydrogel and/or the hydrogel material can be characterized by a water uptake capacity of 50 weight percent to 2500 weight percent as measured according to the Water Uptake Capacity Test using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure. The water uptake capacity of the polymeric hydrogel is determined based on the amount of water by weight taken up by the polymeric hydrogel (in neat form) as a percentage by weight of dry polymeric hydrogel. The water uptake capacity of the hydrogel material is determined based on the amount of water by weight taken up by the hydrogel material (in neat form) as a percentage by weight of dry hydrogel material. Alternatively, the water uptake capacity exhibited by the polymeric hydrogel and/or the hydrogel material can be in the range of about 100 weight percent to about 1500 weight percent; or in the range of about 300 weight percent to about 1200 weight percent.
The polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can exhibit no appreciable weight loss in a Water Cycling Test. The Water Cycling Test as further defined below involves a comparison of the initial weight of the sample to that of the composite element sample after being soaked in a water bath for a predetermined amount of time, dried and then reweighed. Alternatively, the composite element polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite material can exhibit a Water Cycling weight loss from 0 weight percent to about 15 weight percent as measured pursuant to the Water Cycling Test and using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure. Alternatively, the water cycling weight loss is less than 15 weight percent; alternatively, less than 10 weight percent.
Hydrophilic Properties of the Composite Element
The first side of the composite element (i.e., the side of the composite element which includes the hydrogel layer and which is configured to form a ground-facing surface of a sole structure) may also be characterized by the degree to which it exhibits a mud pull-off force that is less than about 12 Newtons (N). Alternatively, the mud pull-off force is less than about 10 N; alternatively, in the range of about 1 N to about 8 N. The mud pull-off force is determined by the Mud Pull-Off Test using the Component Sampling Procedure as described below.
The hydrogel material alone or as present in the hydrogel layer of the composite element exhibit hydrophilic properties. The hydrophilic properties can be characterized by determining the static sessile drop contact angle of the hydrogel material's surface. Accordingly, in some examples, the hydrogel material in a dry state has a static sessile drop contact angle (or dry-state contact angle) of less than 105 degrees, or less than 95 degrees, less than 85 degrees, as characterized by the Contact Angle Test. The Contact Angle Test can be conducted on a sample obtained in accordance with the Material Sampling Procedure, the Plaque Sampling Procedure, and/or the Component Sampling Procedure. In some further examples, the hydrogel material in a dry state has a static sessile drop contact angle ranging from 60 degrees to 100 degrees, from 70 degrees to 100 degrees, or from 65 degrees to 95 degrees.
In other aspects, the hydrogel material alone or present in the hydrogel layer of the composite element, in a wet state, has a static sessile drop contact angle (or wet-state contact angle) of less than 90 degrees, less than 80 degrees, less than 70 degrees, or less than 60 degrees. In some further aspects, the hydrogel material in a wet state has a static sessile drop contact angle ranging from 45 degrees to 75 degrees. In some cases, the dry-state static sessile drop contact angle of the hydrogel material is greater than the wet-state static sessile drop contact angle by at least 10 degrees, at least 15 degrees, or at least 20 degrees, for example from 10 degrees to 40 degrees, from 10 degrees to 30 degrees, or from 10 degrees to 20 degrees.
The hydrogel material alone or present in the hydrogel layer of the composite element can also exhibit a low coefficient of friction when it is wet. Examples of suitable coefficients of friction for the hydrogel material in a dry state (or dry-state coefficient of friction) are less than 1.5, for instance 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 can be conducted on a sample obtained in accordance with the Material Sampling Procedure, or the Plaque Sampling Procedure, or the Component Sampling Procedure. Examples of suitable coefficients of friction for the hydrogel material in a wet state (or wet-state coefficient of friction) are less than 0.8 or less than 0.6, for instance ranging from 0.05 to 0.6, from 0.1 to 0.6, or from 0.3 to 0.5. Furthermore, the hydrogel material can exhibit a reduction in its coefficient of friction from its dry state to its wet state, such as a reduction ranging from 15 percent to 90 percent, or from 50 percent to 80 percent. In some cases, its dry-state coefficient of friction is greater than its wet-state coefficient of friction, for example being higher by a value of at least 0.3 or 0.5, such as 0.3 to 1.2 or 0.5 to 1.
Furthermore, the compliance of the hydrogel material alone or present in the composite element can be characterized based on its storage modulus in the dry state (when equilibrated at 0 percent relative humidity (RH)), and in a partially wet state (e.g., when equilibrated at 50 percent RH or at 90 percent RH), and by reductions in its storage modulus between the dry and wet states. In particular, the hydrogel material can have a reduction in storage modulus (ΔE′) from the dry state relative to the wet state. A reduction in storage modulus as the water concentration in the hydrogel material corresponds to an increase in compliance, because less stress is required for a given strain/deformation.
The polymeric hydrogel and/or the hydrogel material can exhibit a reduction in the storage modulus from its dry state to its wet state (50 percent RH) of more than 20 percent, more than 40 percent, more than 60 percent, more than 75 percent, more than 90 percent, or more than 99 percent, relative to the storage modulus in the dry state, and as characterized by the Storage Modulus Test with the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure.
In some further aspects, the dry-state storage modulus of the polymeric hydrogel and/or the hydrogel material is greater than its wet-state (50 percent RH) storage modulus by more than 25 megapascals (MPa), by more than 50 MPa, by more than 100 MPa, by more than 300 MPa, or by more than 500 MPa, for example ranging from 25 MPa to 800 MPa, from 50 MPa to 800 MPa, from 100 MPa to 800 MPa, from 200 MPa to 800 MPa, from 400 MPa to 800 MPa, from 25 MPa to 200 MPa, from 25 MPa to 100 MPa, or from 50 MPa to 200 MPa. Additionally, the dry-state storage modulus can range from 40 MPa to 800 MPa, from 100 MPa to 600 MPa, or from 200 MPa to 400 MPa, as characterized by the Storage Modulus Test. Additionally, the wet-state storage modulus can range from 0.003 MPa to 100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.
The polymeric hydrogel and/or the hydrogel material can exhibit a reduction in the storage modulus from its dry state to its wet state (90 percent RH) of more than 20 percent, more than 40 percent, more than 60 percent, more than 75 percent, more than 90 percent, or more than 99 percent, relative to the storage modulus in the dry state, and as characterized by the Storage Modulus Test with the Material Sampling Procedure, the Plaque Sampling Procedure, of the Component Sampling Procedure. The dry-state storage modulus of the polymeric hydrogel or hydrogel material can be greater than its wet-state (90 percent RH) storage modulus by more than 25 megaPascals (MPa), by more than 50 MPa, by more than 100 MPa, by more than 300 MPa, or by more than 500 MPa, for example ranging from 25 MPa to 800 MPa, from 50 MPa to 800 MPa, from 100 MPa to 800 MPa, from 200 MPa to 800 MPa, from 400 MPa to 800 MPa, from 25 MPa to 200 MPa, from 25 MPa to 100 MPa, or from 50 MPa to 200 MPa. Additionally, the dry-state storage modulus can range from 40 MPa to 800 MPa, from 100 MPa to 600 MPa, or from 200 MPa to 400 MPa, as characterized by the Storage Modulus Test. Additionally, the wet-state storage modulus can range from 0.003 MPa to 100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.
In addition to a reduction in storage modulus, the polymeric hydrogel and/or the hydrogel material of the hydrogel layer of the composite element can also exhibit a reduction in its glass transition temperature from the dry state (when equilibrated at 0 percent relative humidity (RH) to the wet state (when equilibrated at 90 percent RH).
The polymeric hydrogel and/or the hydrogel material of the hydrogel layer of the composite element can exhibit a reduction in glass transition temperature (ΔTg) from its dry-state (0 percent RH) glass transition temperature to its wet-state glass transition (90 percent RH) temperature of more than a 5 degrees Celsius difference, more than a 6 degrees Celsius difference, more than a 10 degrees Celsius difference, or more than a 15 degrees Celsius difference, as characterized by the Glass Transition Temperature Test with the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure. For instance, the reduction in glass transition temperature can range from more than a 5 degrees Celsius difference to a 40 degrees Celsius difference, from more than a 6 degrees Celsius difference to a 50 degrees Celsius difference, form more than a 10 degrees Celsius difference to a 30 degrees Celsius difference, from more than a 30 degrees Celsius difference to a 45 degrees Celsius difference, or from a 15 degrees Celsius difference to a 20 degrees Celsius difference. The polymeric hydrogel and/or hydrogel material can also exhibit a dry glass transition temperature ranging from −40 degrees Celsius to −80 degrees Celsius, or from −40 degrees Celsius to −60 degrees Celsius.
Alternatively (or additionally), the reduction in glass transition temperature can range from a 5 degrees Celsius difference to a 40 degrees Celsius difference, form a 10 degrees Celsius difference to a 30 degrees Celsius difference, or from a 15 degrees Celsius difference to a 20 degrees Celsius difference. The elastomeric material can also exhibit a dry glass transition temperature ranging from −40 degrees Celsius to −80 degrees Celsius, or from −40 degrees Celsius to −60 degrees Celsius.
The total amount of water that the polymeric hydrogel, the hydrogel material, the hydrogel layer, and/or the composite element can take up depends on a variety of factors, such as the composition of the hydrogel material (e.g., the types and amounts of ingredients present in the hydrogel material in addition to the polymeric hydrogel), the type of polymeric hydrogel used (e.g., its hydrophilicity), the concentration of the polymeric hydrogel present in the hydrogel material, the concentration of the hydrogel material in the hydrogel layer, the thickness of the hydrogel layer, and the like. The water uptake capacity and the water uptake rate of a sample and/or a component are dependent on the size and shape of its geometry, and are typically based on the same factors. Conversely, the water uptake rate is transient and can be defined kinetically. The three factors for water uptake rate for a given sample and/or component having a given geometry include time, thickness, and the surface area of the exposed region available for taking up water.
As also mentioned above, in addition to swelling, the compliance of polymeric hydrogel, the hydrogel material, and/or the hydrogel layer can also increase from being relatively stiff (i.e., dry-state) to being increasingly stretchable, compressible, and malleable (i.e., wet-state). The increased compliance accordingly can allow the hydrogel layer of the composite element to readily compress under an applied pressure (e.g., during a foot strike on the ground), and in some examples, to quickly expel at least a portion of its retained water (depending on the extent of compression). While not wishing to be bound by theory, it is believed that this compressive compliance alone, water expulsion alone, or both in combination can disrupt the adhesion and/or cohesion of soil, which prevents or otherwise reduces the accumulation of soil on the surface of a component comprising the composite element.
In addition to quickly expelling water, in particular examples, the compressed composite element is capable of quickly re-absorbing water when the compression is released (e.g., liftoff from a foot strike during normal use). As such, during use in a wet or damp environment (e.g., a muddy or wet ground), the composite element can dynamically expel and repeatedly take up water over successive foot strikes, particularly from a wet surface. As such, the composite element described herein can continue to prevent soil accumulation over extended periods of time (e.g., during an entire competitive match), particularly when there is ground water available for re-uptake.
As used herein, the terms “take up”, “taking up”, “uptake”, “uptaking”, and the like refer to the drawing of a liquid (e.g., water) from an external source into the composite element and the hydrogel, such as by absorption, adsorption, or both. Furthermore, as briefly mentioned above, the term “water” refers to an aqueous liquid that can be pure water, or can be an aqueous carrier with lesser amounts of dissolved, dispersed or otherwise suspended materials (e.g., particulates, other liquids, and the like).
In addition to being effective at preventing soil accumulation, the composite element has also been found to be sufficiently durable for its intended use on a ground-facing surface of the article of footwear. In various aspects, the useful life of the composite element (and footwear containing it) is at least 10 hours, 20 hours, 50 hours, 100 hours, 120 hours, or 150 hours of wear.
Textile
Having described the various aspects, additional details regarding the textile are provided. In an aspect, the textile may include any textile that permits penetration by the hydrogel layer. Generally speaking, a “textile” may be defined as any article manufactured from fibers, filaments, or yarns characterized by flexibility, fineness, and a high ratio of length to thickness, such as, for example, a rolled good. Textiles generally fall into two categories. The first category includes textiles produced directly from webs of filaments or fibers by randomly interlocking the fibers or filaments to construct non-woven fabrics and felts. The second category includes textiles formed through a mechanical manipulation of yarn, thereby producing a woven fabric, a knitted fabric, a braided fabric, a crocheted fabric, and the like.
The terms “filament,” “fiber,” or “fibers” as used herein refer to materials that are in the form of discrete elongated pieces that are significantly longer than they are wide. The fiber can include natural, manmade or synthetic fibers. The fibers may be produced by conventional techniques, such as extrusion, electrospinning, interfacial polymerization, pulling, and the like. The fibers can include carbon fibers, boron fibers, silicon carbide fibers, titania fibers, alumina fibers, quartz fibers, glass fibers, such as E, A, C, ECR, R, S, D, and NE glasses and quartz, or the like. The fibers can be fibers formed from synthetic polymers capable of forming fibers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters, polyolefins (e.g., polyethylene, polypropylene), aromatic polyamides (e.g., an aramid polymer such as para-aramid fibers and meta-aramid fibers), aromatic polyimides, polybenzimidazoles, polyetherimides, polytetrafluoroethylene, acrylic, modacrylic, poly(vinyl alcohol), polyamides, polyurethanes, and copolymers such as polyether-polyurea copolymers, polyester-polyurethanes, polyether block amide copolymers, or the like. The fibers can be natural fibers (e.g., silk, wool, cashmere, vicuna, cotton, flax, hemp, jute, sisal). The fibers can be man-made fibers from regenerated natural polymers, such as rayon, lyocell, acetate, triacetate, rubber, and poly(lactic acid). The fibers can be made from commodity synthetic polymeric materials such as polyesters or polyamides.
The fibers can have an indefinite length. For example, man-made and synthetic fibers are generally extruded in substantially continuous strands. Alternatively, the fibers can be staple fibers, such as, for example, cotton fibers, or can be extruded synthetic polymer fibers cut to form staple fibers of relatively uniform length. The staple fiber can have a have a length of about 1 millimeter to 100 centimeters or more as well as any increment therein (e.g., 1 millimeter increments).
The fiber can have any of a variety of cross-sectional shapes. Natural fibers can have a natural cross-section, or can have a modified cross-sectional shape (e.g., with processes such as mercerization). Man-made or synthetic fibers can be extruded to provide a strand having a predetermined cross-sectional shape. The cross-sectional shape of a fiber can affect its properties, such as its softness, luster, and wicking ability. The fibers can have round or essentially round cross sections. Alternatively, the fibers can have non-round cross sections, such as flat, oval, octagonal, rectangular, wedge-shaped, triangular, dog-bone, multi-lobal, multi-channel, hollow, core-shell, or other shapes.
The fiber can be processed. For example, the properties of fibers can be affected, at least in part, by processes such as drawing (stretching) the fibers, annealing (hardening) the fibers, and/or crimping or texturizing the fibers.
In some cases a fiber can be a multi-component fiber, such as one comprising two or more polymeric materials. The two or more polymeric materials can be present in a core-sheath, islands-in-the-sea, segmented-pie, striped, or side-by-side configuration. A multi-component fiber can be processed in order to form a plurality of smaller fibers (e.g., microfibers) from a single fiber, for example, by remove a sacrificial material.
As used herein, the term “yarn” refers to an assembly formed of one or more fibers, wherein the strand has a substantial length and a relatively small cross-section, and is suitable for use in the production of textiles by hand or by machine, including textiles made using weaving, knitting, crocheting, braiding, sewing, embroidery, or ropemaking techniques. Thread is a type of yarn commonly used for sewing.
Yarns can be made using fibers formed of natural, man-made and synthetic materials. Synthetic fibers are most commonly used to make spun yarns from staple fibers, and filament yarns. Spun yarn is made by arranging and twisting staple fibers together to make a cohesive strand. The process of forming a yarn from staple fibers typically includes carding and drawing the fibers to form sliver, drawing out and twisting the sliver to form roving, and spinning the roving to form a strand. Multiple strands can be plied (twisted together) to make a thicker yarn. The twist direction of the staple fibers and of the plies can affect the final properties of the yarn. A yarn can be formed of a single long, substantially continuous filament, which is conventionally referred to as a “monofilament yarn,” or a plurality of individual filaments grouped together. A yarn can also be formed of two or more long, substantially continuous filaments which are grouped together by grouping the filaments together by twisting them or entangling them or both. As with staple yarns, multiple strands can be plied together to form a thicker yarn.
Once formed, the yarn can undergo further treatment such as texturizing, thermal or mechanical treating, or coating with a material such as a synthetic polymer. The fibers, yarns, or textiles, or any combination thereof, used in the disclosed articles can be sized. Sized fibers, yarns, and/or textiles are coated on at least part of their surface with a sizing composition selected to change the absorption or wear characteristics, or for compatibility with other materials. The sizing composition facilitates wet-out and wet-through of the coating or resin upon the surface and assists in attaining desired physical properties in the final article. An exemplary sizing composition can comprise, for example, epoxy polymers, urethane-modified epoxy polymers, polyester polymers, phenol polymers, polyamide polymers, polyurethane polymers, polycarbonate polymers, polyetherimide polymers, polyamideimide polymers, polystylylpyridine polymers, polyimide polymers bismaleimide polymers, polysulfone polymers, polyethersulfone polymers, epoxy-modified urethane polymers, polyvinyl alcohol polymers, polyvinyl pyrrolidone polymers, and mixtures thereof.
Two or more yarns can be combined, for example, to form composite yarns such as single- or double-covered yarns, and corespun yarns. Accordingly, yarns may have a variety of configurations that generally conform to the descriptions provided herein.
The yarn can comprise at least one thermoplastic material (e.g., one or more of the fibers can be made of thermoplastic material). The yarn can be made of a thermoplastic material. The yarn can be coated with a layer of a material such as a thermoplastic material.
The linear mass density or weight per unit length of a yarn can be expressed using various units, including denier (D) and tex. Denier is the mass in grams of 9000 meters of yarn. The linear mass density of a single filament of a fiber can also be expressed using denier per filament (DPF). Tex is the mass in grams of a 1000 meters of yarn. Decitex is another measure of linear mass, and is the mass in grams for a 10,000 meters of yarn.
As used herein, tenacity is understood to refer to the amount of force (expressed in units of weight, for example: pounds, grams, centinewtons or other units) needed to break a yarn (i.e., the breaking force or breaking point of the yarn), divided by the linear mass density of the yarn expressed, for example, in (unstrained) denier, decitex, or some other measure of weight per unit length. The breaking force of the yarn is determined by subjecting a sample of the yarn to a known amount of force, for example, using a strain gauge load cell such as an INSTRON brand testing system (Norwood, Mass., USA). Yarn tenacity and yarn breaking force are distinct from burst strength or bursting strength of a textile, which is a measure of how much pressure can be applied to the surface of a textile before the surface bursts.
Generally, in order for a yarn to withstand the forces applied in an industrial knitting machine, the minimum tenacity required is approximately 1.5 grams per Denier. Most yarns formed from commodity polymeric materials generally have tenacities in the range of about 1.5 grams per Denier to about 4 grams per Denier. For example, polyester yarns commonly used in the manufacture of knit uppers for footwear have tenacities in the range of about 2.5 to about 4 grams per Denier. Yarns formed from commodity polymeric materials which are considered to have high tenacities generally have tenacities in the range of about 5 grams per Denier to about 10 grams per Denier. For example, commercially available package dyed polyethylene terephthalate yarn from National Spinning (Washington, N.C., USA) has a tenacity of about 6 grams per Denier, and commercially available solution dyed polyethylene terephthalate yarn from Far Eastern New Century (Taipei, Taiwan) has a tenacity of about 7 grams per Denier. Yarns formed from high performance polymeric materials generally have tenacities of about 11 grams per Denier or greater. For example, yarns formed of aramid fiber typically have tenacities of about 20 grams per Denier, and yarns formed of ultra-high molecular weight polyethylene (UHMWPE) having tenacities greater than 30 grams per Denier are available from Dyneema (Stanley, N.C., USA) and Spectra (Honeywell-Spectra, Colonial Heights, Va., USA).
Various techniques exist for mechanically manipulating yarns to form a textile. Such techniques include, for example, interweaving, intertwining and twisting, and interlooping. Interweaving is the intersection of two yarns that cross and interweave at right angles to each other. The yarns utilized in interweaving are conventionally referred to as “warp” and “weft.” A woven textile includes include a warp yarn and a weft yarn. The warp yarn extends in a first direction, and the weft strand extends in a second direction that is substantially perpendicular to the first direction. Intertwining and twisting encompasses various procedures, such as braiding and knotting, where yarns intertwine with each other to form a textile. Interlooping involves the formation of a plurality of columns of intermeshed loops, with knitting being the most common method of interlooping. The textile may be primarily formed from one or more yarns that are mechanically-manipulated, for example, through interweaving, intertwining and twisting, and/or interlooping processes, as mentioned above.
The textile can be a nonwoven textile. Generally, a nonwoven textile or fabric is a sheet or web structure made from fibers and/or yarns that are bonded together. The bond can be a chemical and/or mechanical bond, and can be formed using heat, solvent, adhesive or a combination thereof. Exemplary nonwoven fabrics are flat or tufted porous sheets that are made directly from separate fibers, molten plastic and/or plastic film. They are not made by weaving or knitting and do not necessarily require converting the fibers to yarn, although yarns can be used as a source of the fibers. Nonwoven textiles are typically manufactured by putting small fibers together in the form of a sheet or web (similar to paper on a paper machine), and then binding them either mechanically (as in the case of felt, by interlocking them with serrated or barbed needles, or hydro-entanglement such that the inter-fiber friction results in a stronger fabric), with an adhesive, or thermally (by applying binder (in the form of powder, paste, or polymer melt) and melting the binder onto the web by increasing temperature). A nonwoven textile can be made from staple fibers (e.g., from wetlaid, airlaid, carding/crosslapping processes), or extruded fibers (e.g., from meltblown or spunbond processes, or a combination thereof), or a combination thereof. Bonding of the fibers in the nonwoven textile can be achieved with thermal bonding (with or without calendering), hydro-entanglement, ultrasonic bonding, needlepunching (needlefelting), chemical bonding (e.g., using binders such as latex emulsions or solution polymers or binder fibers or powders), meltblown bonding (e.g., fiber is bonded as air attenuated fibers intertangle during simultaneous fiber and web formation). The non-woven textile can comprise a textile material comprising one or more polyurethane, polyester, polyether, polyamide, or polyolefin. The polymeric component of the textile material can comprise or consist essentially of polyurethanes, or polyesters, or polyamides, or polyolefins.
In any of these aspects, the textile can have a basis weight of from about 5 to about 500 grams/meter squared, or from about 5 to about 400 grams/meter squared, or from about 10 to about 300 grams/meter squared, or from about 20 to about 200 grams/meter squared.
In one aspect, the textile, prior to operably coupling with the hydrogel layer, can have a core thickness measured between the first side and the second side of from about 0.5 millimeter to about 5 millimeters, or of about 0.5 millimeter to about 3 millimeters, or about 0.5 millimeter to about 2 millimeters, or about 0.5 millimeter to about 1.5 millimeters, or about 0.75 millimeter to about 3 millimeters.
In an aspect, the textile, before it is operably coupled with the hydrogel layer, is air permeable. Use of an air permeable textile (i.e., a textile which is air permeable prior to being operably coupled with the hydrogel layer in the composite element) can promote penetration of the hydrogel layer through the first side of the textile and at least partially into the core of the textile. In one aspect, prior to operably coupling the first side of the textile with the hydrogel layer, the textile can have an air permeability of from about 10 to about 250 cubic centimeters/square centimeters/second, or about 50 to about 150 cubic centimeters/square centimeters/second, or about 70 to about 120 cubic centimeters/square centimeters/second. In some aspects, the air permeability of the textile can vary across the textile.
In some aspects, the textile material, i.e., a chemical composition present in the textile, can have a textile material melting temperature or a textile material Vicat softening temperature that is greater than the melting temperature or Vicat softening temperature of the polymeric hydrogel, the hydrogel material, and/or the hydrogel layer. Use of a textile material which does not melt or soften at or near the temperature at which the hydrogel material is applied to the textile to form the hydrogel layer can promote penetration of the hydrogel material into the core of the textile without reducing the surface area of the textile available to form a mechanical bond with the hydrogel layer, which in turn can increase the strength of the bond between the hydrogel layer and the textile in the composite element. The textile material melting temperature or the textile material Vicat softening temperature can be at least 20 degrees Celsius, at least 30 degrees Celsius, at least 40 degrees Celsius, at least 50 degrees Celsius, at least 70 degrees Celsius, at least 80 degrees Celsius, at least 90 degrees Celsius, or at least 100 degrees Celsius greater than the melting temperature or Vicat softening temperature of the polymeric hydrogel, of the hydrogel material, and/or of the hydrogel layer. In any of these aspects, the melting temperature can be determined using the Melting Temperature (Tm) Test Protocol and the Vicat softening temperature can be determined using the Vicat Softening Temperature (Tvs) Test Protocol using the Material Sampling Procedure, the Plaque Sampling Procedure, and the Component Sampling Procedure described herein.
In one aspect, the textile comprises two or more layers of textile, each layer comprising a textile material. Each layer independently may comprise a woven textile, a non-woven textile, a knit textile, a braided textile, a crochet textile, or a combination thereof. By way of example, the textile may comprise a first textile layer comprising a nonwoven textile comprising a first textile material, and a second textile layer comprising a knit textile comprising a second textile material; or a first layer comprising a first non-woven textile comprising a first textile material, and a second layer comprising a second non-woven textile comprising a second textile material. When the textile comprises two or more layers of textiles I, the two or more layers may be operably coupled. One layer of the multi-layer textile may independently have the textile characteristics described herein, or the entire multi-layer textile may have the characteristics described herein.
In some aspects, the textile can include one or more natural or synthetic fibers or yarns comprising a polymeric material. In aspects where the textile includes one or more synthetic fibers, the synthetic fiber can be chosen from a polyester, a polyamide, a polyolefin, or a combination thereof. In some aspects, the textile can comprise one or more recycled fibers. In one aspect, a “recycled fiber” as used herein can refer to fibers reclaimed from pre-consumer waste. In another aspect, a “recycled fiber” can refer to a fiber reclaimed from post-consumer waste textile. In a further aspect, fibers can be reclaimed from pre- and/or post-consumer waste, for example, by shredding or deconstructing a textile to produce loose fibers, by dissolving or melting existing textiles or fibers to form a reclaimed composition, and by reforming fibers from the reclaimed composition.
Polymeric Hydrogels, Hydrogel Materials, and Hydrogel Layers
In an aspect, the hydrogel layer of the disclosed composite element can consist essentially of or can comprise a hydrogel material. The hydrogel material includes one or more polymeric hydrogels. Thus, the polymeric component of the hydrogel material can consist of a single polymeric hydrogel, or can consist of a plurality of polymeric hydrogels, or can consist of a mixture of one or more polymeric hydrogels and one or more non-hydrogel polymers. The one or more polymeric hydrogel can include a thermoplastic hydrogel. In addition to one or more polymeric hydrogels, the hydrogel material can include one or more additional ingredients such as, for example, a non-hydrogel polymeric material, and/or one or more non-polymeric ingredients such as colorants, fillers, and processing aids. In a further aspect, the hydrogel material or the hydrogel layer or both can include one or more polymers or copolymers selected from a polyurethane, a polyamide, a polyimide, or a combination thereof. For example, the hydrogel layer, or the hydrogel material, or both, may further comprise a tie material. The tie material can promote bonding between the hydrogel layer and the textile, or between the hydrogel layer and a second polymeric material present in a plate. The tie material can be a component of the hydrogel material (e.g., the tie material can be in admixture with the hydrogel material in a single hydrogel layer), or can form a separate portion of the hydrogel layer (e.g., the hydrogel layer can be a multi-layer structure including a first layer comprising the hydrogel material and a second layer comprising the tie material). In one aspect, the polymeric hydrogel of the hydrogel material, or the polymeric component of the hydrogel material, comprises or consists essentially of a polyurethane hydrogel. In another aspect, the polymeric hydrogel of the hydrogel material, or the polymeric component of the hydrogel material, comprises or consists essentially of a polyamide block copolymer hydrogel.
The hydrogel material can be a thermoplastic material, comprising a thermoplastic polymeric hydrogel. The hydrogel material may comprise at least one thermoplastic non-hydrogel polymer in addition to the thermoplastic polymeric hydrogel. In general, a thermoplastic material softens or melts when heated and returns to a solid state when cooled. The thermoplastic material transitions from a solid state to a softened state when its temperature is increased to a temperature at or above its Vicat softening temperature, and a molten liquid state when its temperature is increased to a temperature at or above its melting temperature. When sufficiently cooled, the thermoplastic material transitions from the softened or liquid state to the solid state. As such, the thermoplastic material may be softened or melted, molded, cooled, re-softened or re-melted, re-molded, and cooled again through multiple cycles. For amorphous thermoplastic polymers, the solid state is understood to be the “rubbery” state above the glass transition temperature of the polymer. The thermoplastic material can have a melting temperature from about 90 degrees C. to about 190 degrees C. when determined in accordance with ASTM D3418-97 as described herein below. The thermoplastic material can have a melting temperature from about 90 degrees C. to about 140 degrees C., or about 90 degrees C. to about 100 degrees C., or about 93 degrees C. to about 99 degrees C. when determined in accordance with ASTM D3418-97 as described herein below. The thermoplastic material can have a melting temperature from about 100 degrees C. to about 150 degrees C., or about 100 degrees C. to about 130 degrees C., or about 110 degrees C. to about 120 degrees C., or 112 degrees C. to about 118 degrees C. when determined in accordance with ASTM D3418-97 as described herein below.
The glass transition temperature is the temperature at which an amorphous polymer transitions from a relatively brittle “glassy” state to a relatively more flexible “rubbery” state. The thermoplastic material can have a glass transition temperature from about −20 degrees C. to about 30 degrees C. when determined in accordance with ASTM D3418-97 as described herein below. The thermoplastic material can have a glass transition temperature from about −15 degrees C. to about −5 degrees C., or from about −13 degrees C. to about −7 degrees C. when determined in accordance with ASTM D3418-97 as described herein below. The thermoplastic material can have a glass transition temperature from about 15 degrees C. to about 25 degrees C., or from about 17 degrees C. to about 23 degrees C. when determined in accordance with ASTM D3418-97 as described herein below.
The polymeric hydrogel can be an aliphatic or aromatic polyurethane hydgrogel, including a thermoplastic aliphatic or aromatic polyurethane hydrogel, that comprises a combination of hard segments and soft segments, wherein the hard segments include one or more segments having isocyanate groups. The hard segments may include segments formed from hexamethylene diisocyanate (HDI) or 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI), alone or in combination with 1,4-butanediol (1,4-BD) as a chain extender as shown in formula (F-1A). The segments having isocyanate groups include segments having isocyanate groups that are directly bonded to segments formed from the 1,4-BD. In one aspect, the soft segments may be formed from poly(ethylene oxide) (PEO) as shown in formula (F-1B). The reaction product (i.e., the polymeric hydrogel) formed of both hard segments, HS, and the soft segments, SS, may correspond to the formula shown in (F-1C), wherein the SS and HS correspond to the formulas shown in (F-1D) and (F-1E), respectively. Such polymeric hydrogel formed of soft segments and hard segments exhibits an average ratio of a number of soft segments to a number of hard segments (SS:HS) present in the polymer chains of the polymeric hydrogel. The SS:HS ratio can be in in the range of about 6:1 to about 100:1; alternatively, in the range of about 15:1 to about 99:1; alternatively, in the range of about 30:1 to about 95:1; alternatively, in the range of about 50:1 to about 90:1; alternatively in the range of 75:1 to 85:1. As the SS:HS ratio increases, more of the soft segment (e.g., PEO) is present in the structure of the polymeric hydrogel. While not wishing to be bound by theory, it is believed that the higher the SS:HS ratio, the higher water uptake capacity is for the polymeric hydrogel. A chemical description of formulas F-1A to F-1E is provided below.
The polymeric hydrogel can comprise a polyurethane hydrogel, a polyamide hydrogel, a polyurea hydrogel, a polyester hydrogel, a polycarbonate hydrogel, a polyetheramide hydrogel, a hydrogel formed of addition polymers of ethylenically unsaturated monomers, copolymers thereof (e.g., co-polyesters, co-polyethers, co-polyamides, co-polyurethanes, co-polyolefins), and combinations thereof. As the hydrogel material comprises the polymeric hydrogel, the hydrogel material comprises a polymeric component consisting of all the polymers present in the hydrogel material. Similarly, the hydrogel component of the hydrogel material consists of all the polymeric hydrogels present in the hydrogel material. The polymeric component of the hydrogel material can comprise or consist of a polyurethane hydrogel, a polyamide hydrogel, a polyurea hydrogel, a polyester hydrogel, a polycarbonate hydrogel, a polyetheramide hydrogel, a hydrogel formed of addition polymers of ethylenically unsaturated monomers, copolymers thereof (e.g., co-polyesters, co-polyethers, co-polyamides, co-polyurethanes, co-polyolefins), and combinations thereof. The polymeric component of the hydrogel material can further comprise additional polymeric ingredients. The hydrogel material can further comprise non-polymeric ingredients. Alternatively, the hydrogel material can consist essentially of the polymeric component, i.e., the hydrogel material can be substantially free of non-polymeric ingredients. Similarly, the hydrogel material can consist essentially of the hydrogel component, i.e., the hydrogel material can be substantially free of non-hydrogel polymers and non-polymeric ingredients. Additional details are provided herein.
As described herein, the hydrogel material comprises a polymeric hydrogel. The hydrogel component of the hydrogel material can comprise or consist essentially of one or more polyurethane hydrogels. Polyurethane hydrogels are prepared from one or more diisocyanate and one or more diol, including one or more hydrophilic diol, and thus can be said to include segments derived from diisocyantes and from diols. The polymeric hydrogel may also be prepared from a hydrophilic diol and a hydrophobic diol, where the hydrophobic diol is relatively more hydrophobic as compared to the hydrophilic diol. The polymerization is normally carried out using roughly an equivalent amount of the diol(s) and diisocyanate(s). Examples of hydrophilic diols include polyethylene glycols and copolymers of ethylene glycol and propylene glycol. The diisocyanate can be selected from a wide variety of aliphatic or aromatic diisocyanates. The relative hydrophobicity of the resulting polymeric hydrogel is determined by the amount and type of the hydrophilic diols, the type and amount of the hydrophobic diols, and the type and amount of the diisocyanates present in the polymer chain of the resulting polymeric hydrogel.
The polymeric hydrogel, and/or the hydrogel component of the hydrogel mixture, can comprise or consist essentially of one or more polyurea hydrogels. Polyurea hydrogels are prepared from one or more diisocyanate and one or more hydrophilic diamine. The polymeric hydrogel may also include a hydrophobic diamine in addition to the hydrophilic diamines. The polymerization is normally carried out using roughly an equivalent amount of the diamine(s) and diisocyanate(s). Typical hydrophilic diamines include amine-terminated polyethylene oxides and amine-terminated copolymers of polyethylene oxide/polypropylene. Examples are JEFFAMINE diamines sold by Huntsman (The Woodlands, Tex., USA). The diisocyanate can be selected from a wide variety of aliphatic or aromatic diisocyanates. The relative hydrophobicity of the resulting polymeric hydrogel is determined by the amount and type of the hydrophilic diamine, the type and amount of the hydrophobic amine, and the type and amount of the diisocyanate present in the polymer chain of the resulting polymeric hydrogel.
The polymeric hydrogel, and/or the hydrogel component of the hydrogel mixture, can comprise or consist essentially of one or more polyester hydrogels. Polyester hydrogels can be prepared from dicarboxylic acids (or dicarboxylic acid derivatives) and diols where part or all of the diol is a hydrophilic diol. Examples of hydrophilic diols include polyethylene glycols and copolymers of ethylene glycol and propylene glycol. A second relatively hydrophobic diol can also be used to control the polarity of the polymeric hydrogel. One or more diacid can be used which can be either aromatic or aliphatic. Of particular interest are block polyesters prepared from hydrophilic diols and lactones of hydroxyacids. The lactone is polymerized on each end of the hydrophilic diol to produce a triblock polymer. In addition, these triblock segments can be linked together to produce a multiblock polymeric hydrogel by reaction with a dicarboxylic acid.
The polymeric hydrogel, and/or the hydrogel component of the hydrogel mixture, can comprise or consist essentially of one or more polycarbonate hydrogels. Polycarbonates are typically prepared by reacting a diol with phosgene or a carbonate diester. A hydrophilic polycarbonate is produced when part or all of the diol is a hydrophilic diol. Examples of hydrophilic diols include hydroxyl terminated polyethers of ethylene glycol and polyethers of ethylene glycol with propylene glycol. A second relatively hydrophobic diol can also be included to control the polarity of the polymeric hydrogel.
The polymeric hydrogel, and/or the hydrogel component of the hydrogel mixture, can comprise or consist essentially of one or more polyetheramide hydrogels. Polyetheramides are prepared from dicarboxylic acids (or dicarboxylic acid derivatives) and polyether diamines (a polyether terminated on each end with an amino group). Hydrophilic amine-terminated polyethers produce polymeric hydrogels. Relatively hydrophobic diamines can be used in conjunction with hydrophilic diamines to control the hydrophilicity of the polymeric hydrogel. In addition, the type dicarboxylic acid segment can be selected to control the polarity of the polymer and the physical properties of the polymeric hydrogel. Typical hydrophilic diamines include amine-terminated polyethylene oxides and amine-terminated copolymers of polyethylene oxide/polypropylene. Examples are JEFFAMINE diamines sold by Huntsman (The Woodlands, Tex., USA).
The polymeric hydrogel, and/or the hydrogel component of the hydrogel mixture, can comprise one or more comb polymers. Addition polymers of ethylenically unsaturated monomers are examples of comb polymers. Comb polymers are produced when one of the monomers is a macromer (an oligomer with an ethylenically unsaturated group one end). In one case the main chain is hydrophilic while the side chains are relatively hydrophobic. Alternatively, the comb backbone can be relatively hydrophobic while the side chains are hydrophilic. An example is a polymeric hydrogel having a backbone of a hydrophobic monomer such as styrene, with a side chain including a methacrylate monoester of polyethylene glycol.
The polymeric hydrogel, and/or the hydrogel component of the hydrogel mixture, can comprise or consist essentially of one or more polymeric hydrogels formed of addition polymers of ethylenically unsaturated monomers. The addition polymers of ethylenically unsaturated monomers can be random polymers. The polymeric hydrogels can include prepared by free radical polymerization of one of more hydrophilic ethylenically unsaturated monomer and one or more hydrophobic ethylenically unsaturated monomers. Examples of hydrophilic monomers include acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, sodium p-styrene sulfonate, [3-(methacryloylamino)propyl]trimethylammonium chloride, 2-hydroxyethyl methacrylate, acrylamide, N,N-dimethylacrylamide, 2-vinylpyrrolidone, (meth)acrylate esters of polyethylene glycol, and (meth)acrylate esters of polyethylene glycol monomethyl ether. Examples of relatively hydrophobic monomers include (meth)acrylate esters of C1 to C4 alcohols, polystyrene, polystyrene methacrylate macromonomer and mono(meth)acrylate esters of siloxanes. The water uptake and physical characteristics of the polymeric hydrogel can be tuned by selection of the monomer and the amounts of each monomer type used to prepare the polymer chain of the polymeric hydrogel.
The addition polymers of ethylenically unsaturated monomers can be block polymers. Block polymers of ethylenically unsaturated monomers can be prepared by methods such as anionic polymerization or controlled free radical polymerization. Polymeric hydrogels are produced when the resulting polymer chain of the polymeric hydrogel has both hydrophilic blocks and relatively hydrophobic blocks. The polymeric hydrogel can be a diblock polymer (A-B) polymer, a triblock polymer (A-B-A) or a multiblock polymer. Triblock polymers with relatively hydrophobic end blocks and one or more hydrophilic center block(s) can be used. Block polymers can be prepared by other means as well. Partial hydrolysis of polyacrylonitrile polymers produces multiblock polymers with hydrophilic domains (e.g., hydrolyzed domains) separated by relatively hydrophobic domains (e.g., unhydrolyzed domains) such that the partially hydrolyzed polymer has hydrogel properties. The hydrolysis can convert acrylonitrile segments to hydrophilic acrylamide or acrylic acid segments in a multiblock pattern.
The polymeric hydrogel, and/or the hydrogel component of the hydrogel mixture, can comprise or consist essentially of a copolymeric hydrogel, i.e., a polymeric hydrogel which includes a copolymer in its polymer chain structure. Copolymers combine two or more types of polymers within each polymer chain. Examples include polyurethane/polyurea copolymeric hydrogels, polyurethane/polyester copolymeric hydrogels, and polyester/polycarbonate copolymeric hydrogels.
The hydrogel material can comprise or consist essentially of one or more polymeric hydrogels combined with an elastomeric material such as a rubber, including a cured or uncured rubber. In some examples, wherein the hydrogel material comprises a cured rubber, the hydrogel material can be an elastomeric hydrogel material, i.e., a hydrogel material having elastomeric properties. The rubber can be a natural rubber or a synthetic rubber, such as, for example, a butadiene rubber or an isoprene rubber. In an aspect, the hydrogel material is a hydrogel coating on another material, such as on an elastomeric material. In an aspect, the hydrogel material is a mixture or dispersion of the polymeric hydrogel with or in an elastomeric material. In an aspect, the hydrogel material includes a mixture of a first cured rubber and one or more polymeric hydrogels. In the hydrogel material, the one or more polymeric hydrogels can be distributed throughout the hydrogel material, and can be entrapped by a polymeric network including the cured rubber. For example, the polymeric hydrogel can be physically entangled with a crosslinked network of the cured rubber, and/or can be chemically crosslinked to a crosslinked network of the cured rubber. The polymeric network including the cured rubber can be formed by crosslinking a mixture of uncured rubber and the hydrogel component. The hydrogel component can comprise or consist of one or more polyurethane hydrogels. The hydrogel material can comprise a first concentration of the hydrogel component of from about 1 weight percent to about 70 weight percent based on the total weight of the hydrogel material, or from about 5 weight percent to about 60 weight percent, or from about 10 weight percent to about 50 weight percent, or from about 20 weight percent to about 40 weight percent, based on the total weight of the hydrogel material.
Plate
In some aspects, the composite element is present in a sole structure which includes a plate. In one aspect, the sole component can comprise a full plate extending from the toe region, through the midfoot region, to the heel region of an article of footwear incorporating the sole component. In an aspect, the sole component can include a partial plate covering a portion of the forefoot region, a portion of the heel region, a portion of the midfoot region, or a combination thereof. The plate comprises a second polymeric material. The second polymeric material of the plate comprises at least one polymer. The second polymeric material can include a polymeric component consisting of all the polymers present in the second polymeric material. In addition to the at least one polymer, the second polymeric material can further comprise one or more additional materials such as colorants, fillers, and resin modifiers. The second polymeric material can comprise one or more thermoplastic polymer, and can be a thermoplastic second polymeric material. Alternatively, the second polymeric material can be a thermosetting material which, when cured, is a thermoset material. In such cases, prior to curing, the thermosetting second polymeric material will comprise one or more thermosetting polymers. When cured, the thermoset second polymeric material will comprise one or more thermoset polymers.
In some aspects of the sole structure, the second polymeric material of the plate extends through a first side of a textile of the composite element, thereby forming a mechanical bond between the composite element and the plate. In order to promote formation of this mechanical bond by contacting the textile with the second polymeric material in molten form, the second polymeric material can have a melt flow index of from about 35 to about 55 grams per 10 minutes (at 190 degrees Celsius, 21.6 kg), according to the Melt Flow Index Test Protocol using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure described herein. In one aspect, the melt flow index is about 35 grams per 10 minutes, about 40 grams per 10 minutes, about 45 grams per 10 minutes, about 50 grams per 10 minutes, or about 55 grams per 10 minutes.
The second polymeric material can comprise one or more polyolefin polymers or copolymers, including one or more thermoplastic polyolefin polymers or copolymers. The polymeric component of the second polymeric material can comprise or consist essentially of one or more polyolefin polymers or copolymers. The one or more polyolefin polymers or copolymers can include or consist essentially of a polypropylene, a polystyrene, a polyethylene, an ethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene, a poly-4-methylpent-1-ene, a polyisoprene, a polybutadiene, an ethylene-methacrylic acid copolymer, any copolymers thereof, or a mixture thereof. The polymeric component of the second polymeric material can comprise or consist essentially of a polypropylene homopolymer, a polypropylene copolymer, a polyethylene homopolymer, a polyethylene copolymer, or any combination thereof. The polymeric component of the second polymeric material can comprise or consist essentially a mixture of a polyolefin homopolymer or copolymer and a resin modifier. For example, the polymeric component can comprise or consist essentially of a mixture of a polypropylene homopolymer and a polymeric resin modifier, a mixture of a polypropylene copolymer and a polymeric resin modifier, or a mixture of a polypropylene homopolymer, a polypropylene copolymer, and a polymeric resin modifier.
In some aspects, the at least one polyolefin of the second polymeric material or the polymeric component of the second polymeric material can comprise or consist essentially of an ethylene-propylene rubber (EPDM) dispersed in a polypropylene. In one aspect, the at least one polyolefin or the polymeric component comprises or consists essentially of a block copolymer comprising a polystyrene block. In some aspects, the block copolymer comprises a copolymer of styrene and one or both of ethylene and butylene.
In some aspects, the one or more polymers of the second polymeric material comprises a non-polyolefin polymer. Similarly, the second polymeric material can include a non-polyolefin polymeric component consisting of all the non-polyolefin polymers present in the second polymeric material. For example, the one or more non-polyolefin polymers or the non-polyolefin polymeric component can comprise or consist essentially of a polyurethane, a polyamide, a polyimide, a polyester, a polyether, a polyurea, or any combination thereof. The one or more non-polyolefin polymers or the non-polyolefin polymeric component can comprise or consist of a polyurethane. The polyurethane can be a thermoplastic polyurethane (TPU). The polyurethane can include a polyether-polyurethane or a polyester-polyurethane, or a mixture of both. The one or more non-polyolefin polymers or the non-polyolefin polymeric component can comprise or consist of a polyamide, including a thermoplastic polyamide. The polyamide can comprise or consist essentially of a polyamide homopolymer, or a polyamide copolymer, or a mixture of both The polyamide copolymer can include a polyamide block copolymer, such as a random polyamide block copolymer having polyamide segments and polyether segments.
The one or more polymers of the second polymeric material and/or the polymeric component of the second polymeric material can comprise or consist essentially of one or more of a variety of polyolefin copolymers. The one or more copolymers can include alternating copolymers or random copolymers or block copolymers or graft copolymers. In some aspects, the one or more copolymers include random copolymers. In some aspects, the copolymer includes a plurality of repeat units or segments, with each of the plurality of repeat units individually derived from an alkene monomer having about 1 to about 6 carbon atoms. In other aspects, the copolymer includes a plurality of repeat units, with each of the plurality of repeat units individually derived from a monomer selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-butene, 1-octene, and a combination thereof. In some aspects, the polyolefin copolymer includes a plurality of repeat units each individually selected from Formula 1A-1D. In some aspects, the polyolefin copolymer includes a first plurality of repeat units having a structure according to Formula 1A, and a second plurality of repeat units having a structure selected from Formula 1B-1D.
In some aspects, the polyolefin copolymer includes a plurality of repeat units each individually having a structure according to Formula 2
where R1 is a hydrogen or a substituted or unsubstituted, linear or branched, C1-C12 alkyl. C1-C6 alkyl, C1-C3 alkyl, C1-C12 heteroalkyl, C1-C6 heteroalkyl, or C1-C3 heteroalkyl. In some aspects, each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A above, and each of the repeat units in the second plurality of repeat units has a structure according to Formula 2 above.
In some aspects, the polyolefin copolymer is a random copolymer of a first plurality of repeat units and a second plurality of repeat units, and each repeat unit in the first plurality of repeat units is derived from ethylene and each repeat unit in the second plurality of repeat units is derived from a second olefin. In some aspects, the second olefin is an alkene monomer having about 1 to about 6 carbon atoms. In other aspects, the second olefin includes propylene, 4-methyl-1-pentene, 1-butene, or other linear or branched terminal alkenes having about 3 to 12 carbon atoms. In some aspects, the polyolefin copolymer contains about 80 percent to about 99 percent, about 85 percent to about 99 percent, about 90 percent to about 99 percent, or about 95 percent to about 99 percent polyolefin repeat units by weight based upon a total weight of the polyolefin copolymer. In some aspects, the polyolefin copolymer consists essentially of polyolefin repeat units. In some aspects, polymers in the polyolefin resin composition consist essentially of polyolefin copolymers.
The polyolefin copolymer can include ethylene, i.e. can include repeat units derived from ethylene such as those in Formula 1A. In some aspects, the polyolefin copolymer includes about 1 percent to about 5 percent, about 1 percent to about 3 percent, about 2 percent to about 3 percent, or about 2 percent to about 5 percent ethylene by weight based upon a total weight of the polyolefin copolymer.
The polymeric component of the second polymeric material can be substantially free of polyurethanes and/or polyamides. For example, in some aspects the polyolefin copolymer is substantially free of polyurethanes. In some aspects, the polymer chains of the polyolefin copolymer are substantially free of urethane repeat units. In some aspects, the polymeric component is substantially free of polymer chains including urethane repeat units. In some aspects, the polyolefin copolymer is substantially free of polyamide. In some aspects, the polymer chains of the polyolefin copolymer are substantially free of amide repeat units. In some aspects, the second polymeric material is substantially free of polymer chains including amide repeat units.
In some aspects, the polyolefin copolymer includes polypropylene or is a polypropylene copolymer. In some aspects, the polymeric component of the resin composition comprises or consists essentially of polypropylene copolymers. In some aspects the second polymeric material includes a polypropylene copolymer, and a polymeric resin modifier. In some aspects, the second polymeric material has an abrasion loss as described above, and wherein the polymeric resin modifier is present in an amount effective to allow the second polymeric material to pass a flex test pursuant to the Cold Ross Flex Test using the Plaque Sampling Procedure. In some aspects, the amount of the polymeric resin modifier is an amount effective to allow the resin composition to pass a flex test pursuant to the Cold Ross Flex Test using the Plaque Sampling Procedure without a significant change in an abrasion loss as compared to an abrasion loss of a polymeric material identical to the second polymeric material except without the polymeric resin modifier, when measured pursuant to ASTM D 5963-97a using the Material Sampling Procedure.
The polypropylene copolymer and/or the polymeric component can comprise or consist essentially of a random copolymer, e.g. a random copolymer of ethylene and propylene. The polypropylene copolymer can include about 80 percent to about 99 percent, about 85 percent to about 99 percent, about 90 percent to about 99 percent, or about 95 percent to about 99 percent propylene repeat units by weight based upon a total weight of the polypropylene copolymer. In some aspects, the polypropylene copolymer includes about 1 percent to about 5 percent, about 1 percent to about 3 percent, about 2 percent to about 3 percent, or about 2 percent to about 5 percent ethylene by weight based upon a total weight of the polypropylene copolymer. In some aspects, the polypropylene copolymer is a random copolymer including about 2 percent to about 3 percent of a first plurality of repeat units by weight and about 80 percent to about 99 percent by weight of a second plurality of repeat units based upon a total weight of the polypropylene copolymer; wherein each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A above and each of the repeat units in the second plurality of repeat units has a structure according to Formula 1B above.
The polypropylene copolymers and/or the polymeric component of the second polymeric material can be substantially free of polyurethanes and/or polyamides. For example, in some aspects the polypropylene copolymer and/or the polymeric component is substantially free of polyurethanes. In some aspects, the polymer chains of the polypropylene copolymer are substantially free of urethane repeat units. In some aspects, the polypropylene copolymer is substantially free of polymer chains including urethane repeat units. In some aspects, the polypropylene copolymer is substantially free of polyamide. In some aspects, the polymer chains of the polypropylene copolymer are substantially free of amide repeat units. In some aspects, the polypropylene copolymer is substantially free of polymer chains including amide repeat units.
In an aspect, in the polymeric component of the second polymeric material comprises or consist essentially of polypropylene homopolymers or copolymers including propylene repeat units or both. In another aspect, the polymeric component of the second polymeric material comprises or consists essentially of polypropylene copolymers. In some aspects, the polypropylene copolymer can be a random copolymer of ethylene and propylene.
The combination of abrasion resistance and flexural durability can be related to the overall crystallinity of the second polymeric composition. In some aspects, the second polymeric material has a percent crystallization (percent crystallization) of about 45 percent, about 40 percent, about 35 percent, about 30 percent, about 25 percent or less when measured according to the Crystallinity Test using the Material Sampling Procedure. It has been found that adding the polymeric resin modifier to the second polymeric material in an amount which only slightly decreases the percent crystallinity of the second polymeric material as compared to an otherwise identical second polymeric material except without the polymeric resin modifier can result in second polymeric materials which are able to pass the Cold Ross Flex test while maintaining a relatively low abrasion loss. In some aspects, the polymeric resin modifier leads to a decrease in the percent crystallinity (percent crystallinity) of the second polymeric material. In some aspects, the second polymeric material has a percent crystallization (percent crystallization) that is at least 6, at least 5, at least 4, at least 3, or at least 2 percentage points less than a percent crystallization (percent crystallization) of the otherwise same second polymeric material except without the polymeric resin modifier when measured according to the Crystallinity Test using the Material Sampling Procedure.
In some aspects, the effective amount of the polymeric resin modifier is about 5 percent to about 30 percent, about 5 percent to about 25 percent, about 5 percent to about 20 percent, about 5 percent to about 15 percent, about 5 percent to about 10 percent, about 10 percent to about 15 percent, about 10 percent to about 20 percent, about 10 percent to about 25 percent, or about 10 percent to about 30 percent by weight based upon a total weight of the second polymeric material.
In an aspect, one or more polymers of the second polymeric material can have a total ethylene repeat unit content of from about 3 percent to about 7 percent by weight based upon the total weight of the second polymeric material. In another aspect, the polymeric resin modifier can have an ethylene repeat unit content of from about 10 percent to about 15 percent by weight based upon the total weight of the polymeric resin modifier.
In some aspects, the polymeric resin modifier comprises or consists essentially of a copolymer comprising isotactic repeats derived from an olefin. In some aspects, the polymeric resin modifier comprises or consists essentially of a copolymer comprising repeat units according to Formula 1B above, and wherein the repeat units according to Formula 1B are arranged in an isotactic stereochemical configuration.
In some aspects, the polymeric resin modifier comprises or consists essentially of a copolymer comprising isotactic propylene repeat units and ethylene repeat units. In an aspect, the polymeric resin modifier is a copolymer comprising a first plurality of repeat units and a second plurality of repeat units. In this aspect, each of the repeat units in the first plurality of repeat units has a structure according to Formula 1A above and each of the repeat units in the second plurality of repeat units has a structure according to Formula 1B above, and the repeat units in the second plurality of repeat units are arranged in an isotactic stereochemical configuration.
In an aspect, the second polymeric material comprising a resin modifier as disclosed herein can pass the cold Ross flex test using the Cold Ross Flex Test Protocol and sampled using the Material Sampling Procedure, but an otherwise same second polymeric material but without the polymeric resin modifier does not pass the cold Ross flex test.
Polymeric Material
Now having described aspects of the hydrogel material, the textile material, and the second polymeric material of the plate, additional details are provided regarding the polymeric materials that may be included in the hydrogel material, or the textile material, or the second polymeric material, or the first adhesive material, or the second adhesive material, or any combination thereof, disclosed herein. As described herein, the polymeric material can be the hydrogel material, the textile material, the second polymeric material, or any combination thereof. Similarly, the polymeric component of the polymeric material (i.e., the portion of the polymeric material consisting of all the polymers present in the polymeric material) can be the polymeric component of the hydrogel material, the hydrogel component of the hydrogel material, the polymeric component of the textile material, the polymeric component of the second polymeric material, or any combination thereof. In aspects, the polymeric material can include polymers of the same or different types of monomers (e.g., homopolymers and copolymers, including terpolymers). In some aspects, the polymeric material includes a thermoplastic polymer. In other aspects, the polymeric material includes a thermoset polymer. In some aspects, the polymeric material includes a polyolefin polymer. In certain aspects, the polymeric material can include one or more polymers having different monomeric units randomly distributed in their polymer chains (e.g., a random co-polymer).
For example, the polymeric material can be or include a polymer having repeating polymeric units of the same chemical structure (i.e., segments). Physical crosslinks can be present within the segments or between the segments or both within and between the segments. Some polymers include repeating segments which are relatively harder (hard segments), and repeating polymeric segments which are relatively softer (soft segments). In various aspects, the polymer has repeating hard segments and soft segments. Examples of hard segments include isocyanate segments. Examples of soft segments include an alkoxy group such as polyether segments and polyester segments. As used herein, the polymeric segment can be referred to as being a particular type of polymeric segment such as, for example, an isocyanate segment (e.g., diisocyanate segment), an alkoxy polyamide segment (e.g., a polyether segment, a polyester segment), and the like. It is understood that the chemical structure of the segment is derived from the described chemical structure. For example, an isocyanate segment is a polymerized unit including an isocyanate functional group. When referring to polymeric segments of a particular chemical structure, the polymer can contain up to 10 mole percent of segments of other chemical structures. For example, as used herein, a polyether segment is understood to include up to 10 mole percent of non-polyether segments.
In certain aspects, the polymeric material can include a thermoplastic polyurethane (also referred to as “TPU”). In aspects, the thermoplastic polyurethane can be a thermoplastic polyurethane polymer. In such aspects, the thermoplastic polyurethane polymer can include hard and soft segments. In aspects, the hard segments can comprise or consist of isocyanate segments (e.g., diisocyanate segments). In the same or alternative aspects, the soft segments can comprise or consist of alkoxy segments (e.g., polyether segments, or polyester segments, or a combination of polyether segments and polyester segments). In a particular aspect, the polymeric material can comprise or consist essentially of an elastomeric thermoplastic polyurethane having repeating hard segments and repeating soft segments.
The hydrogel material, the second polymeric material, or both, can include one or more polymer in which the polymer's chain structure includes at least a portion comprising a first hard segment and a first soft segment, wherein the hard segment is physically crosslinked to another hard segment in the same polymer chain or to a hard segment in another polymer, and the soft segment is covalently bonded to the first hard segment. For example, the hard segment and the soft segment can be covalently bonded through a carbamate linkage or an ester linkage.
The hydrogel material, the second polymeric material, or both, can include one or more polymer in which the polymer's chain structure includes a first segment, such as a hard segment, that forms a crystalline or semi-crystalline region of a polymeric network by physically crosslinking with segments of the chain or with other polymer chains; and a second segment, such as a soft segment covalently bonded to the first segment. In this example, the second segment may form amorphous regions of the polymeric network.
Polyolefins
In some aspects, the polymer, the polymeric component of the polymeric material, and/or the polymeric material can comprise or consist essentially of a thermoplastic polyolefin. Exemplary of thermoplastic polyolefins useful can include, but are not limited to, polyethylene, polypropylene, and thermoplastic olefin elastomers (e.g., metallocene-catalyzed block copolymers of ethylene and α-olefins having 4 to about 8 carbon atoms). In a further aspect, the thermoplastic polyolefin is a polymer comprising a polyethylene, an ethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene, a poly-4-methylpent-1-ene, a polyisoprene, a polybutadiene, an ethylene-methacrylic acid copolymer, and an olefin elastomer such as a dynamically cross-linked polymer obtained from polypropylene (PP) and an ethylene-propylene rubber (EPDM), and blends or mixtures of the foregoing. Further exemplary thermoplastic polyolefins include cycloolefins such as cyclopentene or norbornene.
It is to be understood that polyethylene, which optionally can be crosslinked, is inclusive a variety of polyethylenes, including, but not limited to, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMVV), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), and blends or mixtures of any the foregoing polyethylenes. A polyethylene can also be a polyethylene copolymer derived from monomers of monoolefins and diolefins copolymerized with a vinyl, acrylic acid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinyl acetate. Polyolefin copolymers comprising vinyl acetate-derived units can be a high vinyl acetate content copolymer, e.g., greater than about 50 percent by weight vinyl acetate-derived composition.
In some aspects, the thermoplastic polyolefin, as disclosed herein, can be formed through free radical, cationic, and/or anionic polymerization by methods well known to those skilled in the art (e.g., using a peroxide initiator, heat, and/or light). In a further aspect, the disclosed thermoplastic polyolefin can be prepared by radical polymerization under high pressure and at elevated temperature. Alternatively, the thermoplastic polyolefin can be prepared by catalytic polymerization using a catalyst that normally contains one or more metals from group IVb, Vb, VIb or VIII metals. The catalyst usually has one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that can be either p- or s-coordinated complexed with the group IVb, Vb, VIb or VIII metal. In various aspects, the metal complexes can be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. It is understood that the metal catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators can be used, typically a group Ia, IIa and/or IIIa metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes. The activators can be modified conveniently with further ester, ether, amine or silyl ether groups.
Suitable thermoplastic polyolefins can be prepared by polymerization of monomers of monolefins and diolefins as described herein. Exemplary monomers that can be used to prepare disclosed thermoplastic polyolefin include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixtures thereof.
Suitable ethylene-α-olefin copolymers can be obtained by copolymerization of ethylene with an α-olefin such as propylene, butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like having carbon numbers of 3 to 12.
Suitable dynamically cross-linked polymers can be obtained by cross-linking a rubber component as a soft segment while at the same time physically dispersing a hard segment such as PP and a soft segment such as EPDM by using a kneading machine such as a Banbury mixer and a biaxial extruder.
In some aspects, the thermoplastic polyolefin can be a mixture of thermoplastic polyolefins, such as a mixture of two or more polyolefins disclosed herein above. For example, a suitable mixture of thermoplastic polyolefins can be a mixture of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) or mixtures of different types of polyethylene (for example LDPE/HDPE).
In some aspects, the thermoplastic polyolefin can be a copolymer of suitable monoolefin monomers or a copolymer of a suitable monoolefin monomer and a vinyl monomer. Exemplary thermoplastic polyolefin copolymers include, but are not limited to, ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
In some aspects, the thermoplastic polyolefin can be a polypropylene homopolymer, a polypropylene copolymer, a polypropylene random copolymer, a polypropylene block copolymer, a polyethylene homopolymer, a polyethylene random copolymer, a polyethylene block copolymer, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a medium density polyethylene, a high density polyethylene (HDPE), or blends or mixtures of one or more of the preceding polymers.
In some aspects, the polyolefin is a polypropylene. The term “polypropylene,” as used herein, is intended to encompass any polymeric composition comprising propylene monomers, either alone or in mixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers (such as ethylene, butylene, and the like). Such a term also encompasses any different configuration and arrangement of the constituent monomers (such as atactic, syndiotactic, isotactic, and the like).
In some aspects, the polyolefin is a polyethylene. The term “polyethylene,” as used herein, is intended to encompass any polymeric composition comprising ethylene monomeric units, either alone or in mixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomeric units (such as propylene, butylene, and the like). Such a term also encompasses any different configuration and arrangement of the constituent monomeric units (such as atactic, syndiotactic, isotactic, and the like).
Polyurethanes
The polymer, the polymeric component of the polymeric material, the polymeric material, or any combination thereof, can comprise or consist essentially of a polyurethane. The polyurethane can be a thermoplastic polyurethane (also referred to as “TPU”). Alternatively, the polyurethane can be a thermoset polyurethane. Additionally, the polyurethane can be an elastomeric polyurethane, including an elastomeric TPU or an elastomeric thermoset polyurethane. The elastomeric polyurethane can include hard and soft segments. The hard segments can comprise or consist of urethane segments (e.g., isocyanate-derived segments). The soft segments can comprise or consist of alkoxy segments (e.g., polyol-derived segments including polyether segments, or polyester segments, or a combination of polyether segments and polyester segments). The polyurethane can comprise or consist essentially of an elastomeric polyurethane having repeating hard segments and repeating soft segments.
In aspects, one or more of the thermoplastic polyurethanes can be produced by polymerizing one or more isocyanates with one or more polyols to produce polymer chains having carbamate linkages (—N(CO)O—), where the isocyanate(s) each preferably include two or more isocyanate (—NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups per molecule (although, single-functional isocyanates can also be optionally included, e.g., as chain terminating units). Additionally, the isocyanates can also be chain extended with one or more chain extenders to bridge two or more isocyanates.
Each isoncyanate-derived segment of the polyurethane of the can independently include a linear or branched C3-30 segment. Depending upon the particular isocyanate(s) used to form the segment, the isocyanate segment can be aliphatic, aromatic, or include a combination of aliphatic portions(s) and aromatic portion(s). The term “aliphatic” refers to a saturated or unsaturated organic molecule that does not include a cyclically conjugated ring system having delocalized pi electrons. In comparison, the term “aromatic” refers to a cyclically conjugated ring system having delocalized pi electrons, which exhibits greater stability than a hypothetical ring system having localized pi electrons.
Each isocyanate-derived segment can be present in an amount of 5 percent to 85 percent by weight, from 5 percent to 70 percent by weight, or from 10 percent to 50 percent by weight, based on the total weight of the reactant monomers used to form the polyurethane.
In aliphatic embodiments (from aliphatic isocyanate(s)), each isocyanate-derived segment can include a linear aliphatic group, a branched aliphatic group, a cycloaliphatic group, or combinations thereof. For instance, each isocyanate-derived segment can include a linear or branched C3-20 alkylene segment (e.g., C4-15 alkylene or C6-10 alkylene), one or more C3-8 cycloalkylene segments (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinations thereof.
Examples of suitable aliphatic diisocyanates for producing the polyurethane polymer chains include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylenediisocyanate (BDI), bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), bisisocyanatomethylcyclohexane, bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI), cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate (H12M DI), diisocyanatododecane, lysine diisocyanate, and combinations thereof.
In an aspect, the diisocyanate segments can include aliphatic diisocyanate segments. In one aspect, a majority of the diisocyanate segments comprise the aliphatic diisocyanate segments. In an aspect, at least 90 percent of the diisocyanate segments are aliphatic diisocyanate segments. In an aspect, the diisocyanate segments consist essentially of aliphatic diisocyanate segments. In an aspect, the aliphatic diisocyanate segments are substantially (e.g., about 50 percent or more, about 60 percent or more, about 70 percent or more, about 80 percent or more, about 90 percent or more) linear aliphatic diisocyanate segments. In an aspect, at least 80 percent of the aliphatic diisocyanate segments are aliphatic diisocyanate segments that are free of side chains. In an aspect, the aliphatic diisocyanate segments include C2-C10 linear aliphatic diisocyanate segments.
In aromatic embodiments (from aromatic isocyanate(s)), each segment R1 can include one or more aromatic groups, such as phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl, biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unless otherwise indicated, an aromatic group can be an unsubstituted aromatic group or a substituted aromatic group, and can also include heteroaromatic groups. “Heteroaromatic” refers to monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ring systems, where one to four ring atoms are selected from oxygen, nitrogen, or sulfur, and the remaining ring atoms are carbon, and where the ring system is joined to the remainder of the molecule by any of the ring atoms. Examples of suitable heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, and benzothiazolyl.
Examples of suitable aromatic diisocyanates for producing the polyurethane polymer chains include toluene diisocyanate (TDI), TDI adducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate (MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene 1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate, para-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyl diisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate, and combinations thereof. In some embodiments, the polymer chains are substantially free of aromatic groups.
In particular aspects, the polyurethane polymer chains are produced from diisocynates including HMDI, TDI, MDI, H12 aliphatics, and combinations thereof. For example, the low processing temperature polymeric composition of the present disclosure can comprise one or more polyurethane polymer chains are produced from diisocynates including HMDI, TDI, MDI, H12 aliphatics, and combinations thereof.
In certain aspects, polyurethane chains that are crosslinked (e.g., partially crosslinked polyurethane polymers which retain thermoplastic properties) or which can be crosslinked, can be used in accordance with the present disclosure. It is possible to produce crosslinked or crosslinkable polyurethane polymer chains using multi-functional isocyanates. Examples of suitable triisocyanates for producing the polyurethane polymer chains include TDI, HDI, and IPDI adducts with trimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates), polymeric MDI, and combinations thereof.
A portion of the isocyanate-derived segment can include a linear or branched C2-C10 segment, based on the particular chain extender used, and can be, for example, aliphatic, aromatic, or polyether. Examples of suitable chain extenders for producing the polyurethane polymer chains include ethylene glycol, lower oligomers of ethylene glycol (e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol), 1,2-propylene glycol, 1,3-propylene glycol, lower oligomers of propylene glycol (e.g., dipropylene glycol, tripropylene glycol, and tetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol, 1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylated aromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone and resorcinol, xylene-a,a-diols, bis(2-hydroxyethyl) ethers of xylene-a,a-diols, and combinations thereof.
The polyol-derived segment of the polyurethane can include a polyether group, a polyester group, a polycarbonate group, an aliphatic group, or an aromatic group. Each polyol-derived segment can be present in an amount of 5 percent to 85 percent by weight, from 5 percent to 70 percent by weight, or from 10 percent to 50 percent by weight, based on the total weight of the reactant monomers used to form the polyurethane.
In some aspects, the thermoplastic polyurethane includes a polyether segment (i.e., a segment having one or more ether groups). Suitable polyethers include, but are not limited to, polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof. The term “alkyl” as used herein refers to straight chained and branched saturated hydrocarbon groups containing one to thirty carbon atoms, for example, one to twenty carbon atoms, or one to ten carbon atoms. The term Cn means the alkyl group has “n” carbon atoms. For example, 04 alkyl refers to an alkyl group that has 4 carbon atoms. 01-7 alkyl refers to an alkyl group having a number of carbon atoms encompassing 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), t-butyl (1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unless otherwise indicated, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group.
In some aspects of the thermoplastic polyurethane, the at least one polyol-derived segment includes a polyester segment. The polyester segment can be derived from the polyesterification of one or more dihydric alcohols (e.g., ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol-1,5,diethylene glycol,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with one or more dicarboxylic acids (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 polyester also can be derived from polycarbonate prepolymers, such as poly(hexamethylene carbonate) glycol, poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol, and poly(nonanemethylene carbonate) glycol. Suitable polyesters can include, for example, polyethylene adipate (PEA), poly(1,4-butylene adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), polycaprolactone, polyhexamethylene carbonate, poly(propylene carbonate), poly(tetramethylene carbonate), poly(nonanemethylene carbonate), and combinations thereof.
In various of the thermoplastic polyurethanes, at least one polyol-derived segment includes a polycarbonate segment. The polycarbonate segment can be derived from the reaction of one or more dihydric alcohols (e.g., ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2-methylpentanediol-1,5, diethylene glycol, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, and combinations thereof) with ethylene carbonate.
In various examples, the aliphatic group is linear and can include, for example, a 01-20 alkylene chain or a C1-20 alkenylene chain (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). The term “alkylene” refers to a bivalent hydrocarbon. The term Cn means the alkylene group has “n” carbon atoms. For example, C1-6 alkylene refers to an alkylene group having, e.g., 1, 2, 3, 4, 5, or 6 carbon atoms. The term “alkenylene” refers to a bivalent hydrocarbon having at least one double bond.
In various aspects, the aliphatic and aromatic groups can be substituted with one or more pendant relatively hydrophilic and/or charged groups. In some aspects, the pendant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) hydroxyl groups. In various aspects, the pendant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In some cases, the pendant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, the aliphatic group can include one or more polyacrylic acid group. In some cases, the pendant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, the pendant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) phosphate groups. In some examples, the pendant hydrophilic group includes one or more ammonium groups (e.g., tertiary and/or quaternary ammonium). In other examples, the pendant hydrophilic group includes one or more zwitterionic groups (e.g., a betaine, such as poly(carboxybetaine (pCB) and ammonium phosphonate groups such as a phosphatidylcholine group).
Optionally, in some aspects, the polyurethane can include an at least partially crosslinked polymeric network that includes polymer chains that are derivatives of polyurethane. In such cases, the level of crosslinking can be such that the polyurethane retains thermoplastic properties (i.e., the crosslinked thermoplastic polyurethane can be softened or melted and re-solidified under the processing conditions described herein). This crosslinked polymeric network can be produced by polymerizing one or more isocyanates with one or more polyamino compounds, polysulfhydryl compounds, or combinations thereof.
As described herein, the thermoplastic polyurethane can be physically crosslinked through e.g., nonpolar or polar interactions between the urethane or carbamate groups on the polymers. In these aspects, the isocyanate-derived segment of the polymer chain is referred to as the “hard segment”, and polyol-derived segment of the polymer chain is referred to as the “soft segment”. In these aspects, in a polymer chain, the soft segment is covalently bonded to the hard segment. In some aspects, hard segments within an individual polymer chain may physically crosslink, or may physically crosslink with the hard segments of other polymer chains. In some examples, the thermoplastic polyurethane having physically crosslinked hard segments can be a hydrophilic thermoplastic polyurethane (i.e., a thermoplastic polyurethane including hydrophilic groups as disclosed herein), and may be a polyurethane hydrogel (i.e., a polyurethane capable of taking up at least 10 percent of its weight in water).
Polyamides
In various aspects, the polymer, the polymeric component of the polymeric material, the polymeric material, or any combination thereof, can comprise or consist essentially of a polyamide, such as a thermoplastic polyamide. The polyamide can be a polyamide homopolymer having repeating polyamide segments of the same chemical structure. Alternatively, the polyamide can comprise a number of polyamide segments having different polyamide chemical structures (e.g., polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, etc.). The polyamide segments having different chemical structure can be arranged randomly, or can be arranged as repeating blocks.
The polyamide can be a co-polyamide (i.e., a co-polymer including polyamide segments and non-polyamide segments). The polyamide segments of the co-polyamide can comprise or consist of polyamide 6 segments, polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, or any combination thereof. The polyamide segments of the co-polyamide can be arranged randomly, or can be arranged as repeating segments. In a particular example, the polyamide segments can comprise or consist of polyamide 6 segments, or polyamide 12 segments, or both polyamide 6 segment and polyamide 12 segments. In the example where the polyamide segments of the co-polyamide include of polyamide 6 segments and polyamide 12 segments, the segments can be arranged randomly. The non-polyamide segments of the co-polyamide can comprise or consist of polyether segments, polyester segments, or both polyether segments and polyester segments. The co-polyamide can be a co-polyamide, or can be a random co-polyamide. The copolyamide can be formed from the polycodensation of a polyamide oligomer or prepolymer with a second oligomer prepolymer to form a copolyamide (i.e., a co-polymer including polyamide segments. Optionally, the second prepolymer can be a hydrophilic prepolymer.
In aspects, the co-polyamide can be a block co-polyamide. For example, the block co-polyamide can have repeating hard segments, and repeating soft segments. The hard segments can comprise polyamide segments, and the soft segments can comprise non-polyamide segments.
The co-polyamide can be an elastomeric co-polyamide, including a thermoplastic co-polyamide. The elastomeric co-polyamide can comprise or consist of a block co-polyamide having repeating hard segments and repeating soft segments. In block co-polymers, including block co-polymers having repeating hard segments and soft segments, physical crosslinks can be present within the segments or between the segments or both within and between the segments.
In some aspects, the polyamide itself, or the polyamide segment of the thermoplastic co-polyamide can be derived from the condensation of polyamide prepolymers, such as lactams, amino acids, and/or diamino compounds with dicarboxylic acids, or activated forms thereof. The resulting polyamide segments include 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 thermoplastic polyamide can be the same or different.
In various aspects, the polyamide is a poly (ether block amide) polymer. The poly(ether block amide) polymer can be prepared by polycondensation of polyamide blocks containing reactive ends with polyether blocks containing reactive ends. Examples include, but are not limited to: 1) polyamide blocks containing diamine chain ends with polyoxyalkylene blocks containing carboxylic chain ends; 2) polyamide blocks containing dicarboxylic chain ends with polyoxyalkylene blocks containing diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxylated alpha-omega polyoxyalkylenes known as polyether diols; 3) polyamide blocks containing dicarboxylic chain ends with polyether diols, the products obtained in this particular case being polyetheresteramides. The polyamide block of the thermoplastic poly(ether-block-amide) can be derived from lactams, amino acids, and/or diamino compounds with dicarboxylic acids as previously described. The polyether block can be derived from one or more polyethers selected from the group consisting of polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF), polytetramethylene oxide (PTMO), and combinations thereof.
Examples of poly(ether block amide) polymers include those comprising polyamide blocks comprising dicarboxylic chain ends derived from the condensation of α, ω-aminocarboxylic acids, of lactams or of dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid. In poly(ether block amide) polymers of this type, a α, ω-aminocarboxylic acid such as aminoundecanoic acid can be used; a lactam such as caprolactam or lauryllactam can be used; a dicarboxylic acid such as adipic acid, decanedioic acid or dodecanedioic acid can be used; and a diamine such as hexamethylenediamine can be used; or various combinations of any of the foregoing. In various aspects, the copolymer comprises polyamide blocks comprising polyamide 12 or of polyamide 6. The poly(ether block) amide can have a melting point of less than 150 degrees Celsius, or between 90 degrees Celsius and 135 degrees Celsius.
In an aspect, the number average molar mass of the polyamide blocks can be from about 300 grams per mole and about 15,000 grams per mole, from about 500 grams per mole and about 10,000 grams per mole, from about 500 grams per mole and about 6,000 grams per mole, from about 500 grams per mole to 5,000 grams per mole, and from about 600 grams per mole and about 5,000 grams per mole. In a further aspect, the number average molecular weight of the polyether block can range from about 100 grams per mole to about 6,000 grams per mole, from about 400 grams per mole to 3000 grams per mole and from about 200 grams per mole to about 3,000 grams per mole. In a still further aspect, the polyether (PE) content of the poly(ether block amide) polymer can be from about 0.05 to about 0.8 (i.e., from about 5 mole percent to about 80 mole percent). In a yet further aspect, the polyether blocks can be present from about 10 percent by weight to about 50 percent by weight, from about 20 percent by weight to about 40 percent by weight, and from about 30 percent by weight to about 40 percent by weight. The polyamide blocks can be present from about 50 percent by weight to about 90 percent by weight, from about 60 percent by weight to about 80 percent by weight, and from about 70 percent by weight to about 90 percent by weight.
In an aspect, the polyether blocks can contain units other than ethylene oxide units, such as, for example, propylene oxide or polytetrahydrofuran (which leads to polytetramethylene glycol sequences). It is also possible to use simultaneously PEG blocks, i.e. those consisting of ethylene oxide units, PPG blocks, i.e. those consisting of propylene oxide units, and P TmG blocks, i.e. those consisting of tetramethylene glycol units, also known as polytetrahydrofuran. PPG or P TmG blocks are advantageously used. The amount of polyether blocks in these copolymers containing polyamide and polyether blocks can be from about 10 percent by weight to about 50 percent by weight of the copolymer and from about 35 percent by weight to about 50 percent by weight.
Exemplary commercially available co-polyamides include, but are not limited to, those available under the tradenames of VESTAMID (Evonik Industries); PLATAMID (Arkema), e.g., product code H2694; PEBAX (Arkema), e.g., product code “PEBAX MH1657” and “PEBAX MV1074”; PEBAX RNEW (Arkema); GRILAMID (EMS-Chemie AG), or also to other similar materials produced by various other suppliers.
In some examples, the polyamide is physically crosslinked through, e.g., nonpolar or polar interactions between the polyamide groups of the polymers. In examples where the polyamide is a copolyamide, the copolyamide can be physically crosslinked through interactions between the polyamide groups, an optionally by interactions between the copolymer groups. When the copolyamide is physically crosslinked thorough interactions between the polyamide groups, the polyamide segments can form the portion of the polymer referred to as the “hard segment”, and copolymer segments can form the portion of the polymer referred to as the “soft segment”. For example, when the copolyamide is a poly(ether-block-amide), the polyamide segments form the hard segment portion of the polymer, and polyether segments can form the soft segment portion of the polymer. Therefore, in some aspects, the polymer material can include a physically crosslinked polymeric network having one or more polymer chains with amide linkages.
In some aspects, the polyamide segment of the co-polyamide includes polyamide-11 or polyamide-12 and the polyether segment is a segment selected from the group consisting of polyethylene oxide, polypropylene oxide, and polytetramethylene oxide segments, and combinations thereof.
Polyesters
In aspects, the polymer, the polymeric component of the polymeric material, the polymeric material, or any combination thereof can comprise or consist essentially of a polyester such as a thermoplastic polyester. The polyester can be formed by reaction of one or more carboxylic acids, or its ester-forming derivatives, with one or more bivalent or multivalent aliphatic, alicyclic, aromatic or araliphatic alcohols or a bisphenol. The polyester can be a polyester homopolymer having repeating polyester segments of the same chemical structure. Alternatively, the polyester can comprise a number of polyester segments having different polyester chemical structures (e.g., polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, etc.). The polyester segments having different chemical structure can be arranged randomly, or can be arranged as repeating blocks.
Exemplary carboxylic acids that that can be used to prepare the polyester include, but are not limited to, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decane dicarboxylic acid, undecane dicarboxylic acid, terephthalic acid, isophthalic acid, alkyl-substituted or halogenated terephthalic acid, alkyl-substituted or halogenated isophthalic acid, nitro-terephthalic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioether dicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid, 4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylic acid. Exemplary diols or phenols suitable for the preparation of the thermoplastic polyester include, but are not limited to, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol, 1,4-cyclohexane dimethanol, and bis-phenol A.
In some aspects, the polyester is a polybutylene terephthalate (PBT), a polytrimethylene terephthalate, a polyhexamethylene terephthalate, a poly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate (PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), a polybutylene naphthalate (PBN), a liquid crystal polyester, or a blend or mixture of two or more of the foregoing.
The polyester can be a co-polyester (i.e., a co-polymer including polyester segments and non-polyester segments). The co-polyester can be an aliphatic co-polyester (i.e., a co-polyester in which both the polyester segments and the non-polyester segments are aliphatic). Alternatively, the co-polyester can include aromatic segments. The polyester segments of the co-polyester can comprise or consist of polyglycolic acid segments, polylactic acid segments, polycaprolactone segments, polyhydroxyalkanoate segments, polyhydroxybutyrate segments, or any combination thereof. The polyester segments of the co-polyester can be arranged randomly, or can be arranged as repeating blocks.
For example, the polyester can be a block co-polyester having repeating blocks of polymeric units of the same chemical structure (segments) which are relatively harder (hard segments), and repeating blocks of polymeric segments which are relatively softer (soft segments). In block co-polyesters, including block co-polyesters having repeating hard segments and soft segments, physical crosslinks can be present within the blocks or between the blocks or both within and between the blocks. The polyester can comprise or consist essentially of an elastomeric co-polyester having repeating blocks of hard segments and repeating blocks of soft segments.
The non-polyester segments of the co-polyester can comprise or consist of polyether segments, polyamide segments, or both polyether segments and polyamide segments. The co-polyester can be a block co-polyester, or can be a random co-polyester. The co-polyester can be formed from the polycondensation of a polyester oligomer or prepolymer with a second oligomer prepolymer to form a block copolyester. Optionally, the second prepolymer can be a hydrophilic prepolymer. For example, the co-polyester can be formed from the polycondensation of terephthalic acid or naphthalene dicarboxylic acid with ethylene glycol, 1,4-butanediol, or 1-3 propanediol. Examples of co-polyesters include polyethelene adipate, polybutylene succinate, poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene napthalate, and combinations thereof. In a particular example, the co-polyamide can comprise or consist of polyethylene terephthalate.
In some aspects, the thermoplastic polyester is a block copolymer comprising segments of one or more of polybutylene terephthalate (PBT), a polytrimethylene terephthalate, a polyhexamethylene terephthalate, a poly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate (PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), a polybutylene naphthalate (PBN), and a liquid crystal polyester. For example, a suitable thermoplastic polyester that is a block copolymer can be a PET/PEI copolymer, a polybutylene terephthalate/tetraethylene glycol copolymer, a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, or a blend or mixture of any of the foregoing.
In some aspects, the thermoplastic polyester is a biodegradable resin, for example, a copolymerized polyester in which poly(α-hydroxy acid) such as polyglycolic acid or polylactic acid is contained as principal repeating units.
The disclosed polyesters can be prepared by a variety of polycondensation methods known to the skilled artisan, such as a solvent polymerization or a melt polymerization process.
Resin Modifier
The resin modifier can be a polymeric resin modifier (i.e., a resin modifier having a polymeric chain structure). In some aspects, the polymeric resin modifier is a metallocene catalyzed polymer or a metallocene catalyzed copolymer. In another aspect, the polymeric resin modifier can consist essentially of isotactic propylene repeat units with about 11 percent by weight-15 percent by weight of ethylene repeat units based on a total weight of metallocene catalyzed copolymer randomly distributed along the copolymer. In some aspects, the polymeric resin modifier includes about 10 percent to about 15 percent ethylene repeat units by weight based upon a total weight of the polymeric resin modifier. In some aspects, the polymeric resin modifier includes about 10 percent to about 15 percent repeat units according to Formula 1A above by weight based upon a total weight of the polymeric resin modifier. In some aspects, the polymeric resin modifier is a copolymer of repeat units according to Formula 1B above, and the repeat units according to Formula 1B are arranged in an isotactic stereochemical configuration.
In some aspects, the polymeric resin modifier is a copolymer containing isotactic propylene repeat units and ethylene repeat units. In some aspects, the polymeric resin modifier is a copolymer including a first plurality of repeat units and a second plurality of repeat units, wherein the repeat units in the second plurality of repeat units are arranged in an isotactic stereochemical configuration.
In one aspect, the amount of the polymeric resin modifier is an amount effective to allow the polymeric material to pass a flex test pursuant to the Cold Ross Flex Text Protocol using the Plaque Sampling Procedure as described further herein. In another aspect, the amount of the polymeric resin modifier does not cause a significant change in abrasion loss as compared to abrasion loss for a similar polymeric material identical to the disclosed polymeric material except without the polymeric resin modifier when measured pursuant to ASTM D 5963-97a using the Material Sampling Procedure. In one aspect, the abrasion loss of the polymeric material is within about 20 percent of abrasion loss of the otherwise same polymeric material except without the resin modifier when measured pursuant to ASTM D 5963-97A using the Material Sampling Procedure further described herein.
In an aspect, the effective amount of the polymeric resin modifier can be from about 5 percent to about 30 percent, about 5 percent to about 25 percent, about 5 percent to about 20 percent, about 5 percent to about 15 percent, about 5 percent to about 10 percent, about 10 percent to about 15 percent, about 10 percent to about 20 percent, about 10 percent to about 25 percent, or about 10 percent to about 30 percent by weight based upon the total weight of the polymeric material. In another aspect, the effective amount of the polymeric resin modifier can be about 20 percent, about 15 percent, about 10 percent, about 5 percent, or less by weight, based on the total weight of the polymeric material.
Clarifying Agent
In some aspects, it can be beneficial to include a clarifying agent in the polymeric material, including the second polymeric material present in the plate. The clarifying agent can allow for clear visibility through the plate. For example, this can allow for clear visibility of a textile bonded to the plate. The clarifying agent can be present in any suitable amount to provide sufficient optical clarity of the polymeric material. In some aspects, the clarifying agent is present in an amount from about 0.5 percent by weight to about 5 percent by weight or about 1.5 percent by weight to about 2.5 percent by weight based upon a total weight of the polymeric material. The clarifying agent can include those selected from the group of substituted or unsubstituted dibenzylidene sorbitol, 1,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene], and a derivative thereof. The clarifying agent can include an acetal compound that is the condensation product of a polyhydric alcohol and an aromatic aldehyde. The polyhydric alcohol can include those selected from the group consisting of acyclic polyols such as xylitol and sorbitol and acyclic deoxy polyols such as 1,2,3-trideoxynonitol or 1,2,3-trideoxynon-1-enitol. The aromatic aldehyde can include those selected from the group consisting of benzaldehyde and substituted benzaldehydes.
Methods of Making Polymeric Materials
According to various aspects, this disclosure also provides a method for making a polymeric material, such as one or more of the disclosed polymeric materials.
Generally speaking, a method for making a polymeric material includes blending a polymer with. Methods of blending polymers can include film blending in a press, blending in a mixer (e.g. mixers commercially available under the tradename “HAAKE” from Thermo Fisher Scientific, Waltham, Mass.), solution blending, hot melt blending, and extruder blending. In some aspects, the polymer and other ingredients are miscible such that they can be readily mixed by the screw in the injection barrel during injection molding, e.g. without the need for a separate blending step.
The methods can further include extruding the blended polymer material to form an extruded polymer material. The methods of extruding the blended polymer material can include manufacturing long products of relatively constant cross-section (rods, sheets, pipes, films, wire insulation coating). The methods of extruding the blended polymer material can include conveying a softened blended polymer material through a die with an opening. The blended polymer material can be conveyed forward by a feeding screw and forced through the die. Heating elements, placed over the barrel, can soften and melt the blended polymer material. The temperature of the material can be controlled by thermocouples. The product going out of the die can be cooled by blown air or in a water bath to form the extruded polymer material. In one aspect, the polymer material can be the hydrogel material, and extruding the hydrogel material can comprise extruding all of or a portion of the hydrogel layer. For example, the hydrogel material can be extruded into a film used to form all or a portion of the hydrogel layer. In another aspect, the polymer material can be the textile material, and the textile material can be extruded into fibers, and the fibers can in turn be drawn into yarn, or can be used to form a non-woven textile. In yet another aspect, the polymer material can be the second polymeric material, and can be extruded onto the second side of the textile of the composite element. Alternatively, the product going out of the die can be pelletized with little cooling as described below.
The method can further include pelletizing the extruded polymer material to form a pelletized polymer material. Methods of pelletizing can include melt pelletizing (hot cut) whereby the melt coming from a die is almost immediately cut into pellets that are conveyed and cooled by liquid or gas. Methods of pelletizing can include strand pelletizing (cold cut) whereby the melt coming from the die head is converted into strands (the extruded resin composition) that are cut into pellets after cooling and solidification.
The method can further include injection molding the polymer material, such as a pelletized polymer material, to form an article, such as a sole structure. The injection molding can include the use of a non-rotating, cold plunger to force the polymer material through a heated cylinder wherein the polymer material is heated by heat conducted from the walls of the cylinder to the polymer material. The injection molding can include the use of a rotating screw, disposed co-axially of a heated barrel, for conveying the polymer material toward a first end of the screw and to heat the polymer material by the conduction of heat from the heated barrel to the polymer material. As the polymer material is conveyed by the screw mechanism toward the first end, the screw is translated toward the second end so as to produce a reservoir space at the first end. When sufficient melted polymer material is collected in the reservoir space, the screw mechanism can be pushed toward the first end so as to inject the polymer material into a selected mold.
Additional Ingredients
The polymeric material can further comprise one or more additional ingredients. The one or more additional ingredients can be a polymeric ingredient or a non-polymeric ingredient. These additional ingredients can be independently selected from the group including, but not limited to, curing agents, initiators, plasticizers, mold release agents, lubricants, antioxidants, flame retardants, dyes, pigments, reinforcing and non-reinforcing fillers, fiber reinforcements, and light stabilizers.
Adhesive Materials
In some aspects, the composite element or the sole structure or both further comprise a first adhesive layer that operably couples the second side of the hydrogel layer with the first side of the textile, a second adhesive layer that operably couples the second side of the textile with the first side of the plate, or both a first adhesive layer and a second adhesive layer as described. In one aspect, the first adhesive layer, the second adhesive layer, or both, penetrate at least a portion of the thickness of the textile. In some aspects, the sole structure further comprises a third adhesive layer that operably couples the second side of the second textile, when a second textile is included, to the second side of the sole component, or a fourth adhesive layer positioned on the first side of the second textile, when a second textile is included, or any combination thereof. In some aspects, the first adhesive layer, the second adhesive layer, the third adhesive layer, the fourth adhesive layer, or a combination thereof penetrate at least 10 percent, at least 20 percent, at least 30 percent, or at least 40 percent of the thickness of the textiles with which they are in contact. In another aspect, the first adhesive layer, the second adhesive layer, or both penetrate less than about 80 percent, less than about 70 percent, less than about 60 percent, less than about 50 percent, less than about 40 percent, or less than about 30 percent of the core thickness of the textile. In some aspects, the fourth adhesive layer can be used to couple a sole structure to a shoe upper.
In an aspect, the first adhesive layer, the second adhesive layer, or both, have a thickness of from about 0.1 millimeters to about 2.0 millimeters, or of from about 0.1 millimeters to about 1.5 millimeters, or from about 0.1 millimeters to 0.5 millimeters.
Contact Adhesives: In one aspect, the first adhesive material of the first adhesive layer, the second adhesive material of the second adhesive layer, or both, comprise a contact adhesive. The first adhesive material or the second adhesive material or both can comprise a thermoset polymeric material as described above. The adhesive material can comprise an epoxy-based contact adhesive or cement, a urethane-based contact adhesive or cement, an acrylate-based contact adhesive or cement, including cyanoacrylate-based adhesive or cement, a silicone-based contact adhesive or cement, or a combination thereof. The contact adhesive or cement can comprise a polyurethane-based contact adhesive, such as, for example, a conventional polyurethane-based shoe cement.
Hot Melt Adhesives: In one aspect, the first adhesive material of the first adhesive layer, the second adhesive material of the second adhesive layer, or both comprise a hot melt adhesive. The first adhesive material or the second adhesive material or both can comprise a thermoplastic polymeric material as described above. In some aspects, the hot melt adhesive comprises a thermoplastic polyurethane. In another aspect, the hot melt adhesive can have a melt flow index of from about 35 to about 55 grams per 10 minutes (at 190 degrees Celsius, 21.6 kg), or of about 35, 40, 45, 50, or about 55 grams per 10 minutes, according to the Melt Flow Index Test Protocol described herein.
Methods of Making a Composite Element
In an aspect, disclosed herein is a method for making a composite element, the method comprising: operably coupling a hydrogel layer comprising a hydrogel material with a first side of a textile, the textile having the first side, a second side opposing the first side, and a core located between the first side and the second side, wherein the hydrogel layer extends through the first side of the textile and at least partially into the core of the textile, but does not extend onto the second side of the textile.
In one aspect, the step of operably coupling the hydrogel layer with the first side of the textile comprises spraying, brushing, or painting a hydrogel material onto the first side of the textile, or dipping the first side of the textile into the hydrogel material. In an alternative aspect, the step of operably coupling the hydrogel layer with the first side of the textile comprises injection molding or extruding the hydrogel material onto the first side of the textile.
In one aspect, the step of operably coupling the hydrogel layer with the first side of the textile comprises forming a mechanical bond between hydrogel layer and the first side of the textile. The process of forming the mechanical bond between the hydrogel layer and the textile can comprise softening or melting the hydrogel material, applying the softened or melted hydrogel material to the first side of the textile, and allowing the softened or melted hydrogel material to penetrate between and around the fibers of the textile, and to penetrate a portion of the thickness of the core of the textile, without penetrating the entire thickness of the core and onto the second side of the textile, and then solidifying the softened or melted hydrogel material. In other aspects, the process of forming the mechanical bond between the hydrogel layer and the textile can comprise softening or melting an adhesive material present in the hydrogel layer (the adhesive material can be an ingredient of the hydrogel material, or can be a cap layer of the hydrogel layer), applying the softened or melted adhesive material to the first side of the textile, and allowing the softened or melted adhesive material to penetrate between and around the fibers of the textile, and to penetrate a portion of the thickness of the core of the textile, without penetrating the entire thickness of the core and onto the second side of the textile, and then solidifying the softened or melted adhesive material. In one aspect, the process includes, before, during or after a step of contacting the first side of the textile and the hydrogel layer, but before solidifying the hydrogel material or the adhesive material, increasing the temperature of the hydrogel material or the adhesive material to a temperature at or above its Vicat softening temperature, or to a temperature at or above its melting temperature. Pressure or heat or both pressure and heat can be applied during the process, to increase the rate and extent of penetration of the hydrogel material or the adhesive material into the textile core. In one aspect, the step of increasing the temperature of the hydrogel material or the adhesive material comprising increasing its temperature to a temperature at or above its Vicat softening temperature, but which is below the Vicat softening temperature of the textile material. In another aspect, the step of increasing the temperature of the hydrogel material or the adhesive material comprising increasing its temperature to a temperature at or above its melting temperature, but which is below the Vicat softening temperature of the textile material. By maintaining the hydrogel material or the adhesive material below the Vicat softening temperature of the textile material (e.g., at least 20 degrees C. below, or at least 50 degrees C. below, or at least 100 degrees C. below), allows the texture of the first side of the textile, as well as the complex structure of the core of the textile, to remain intact and provide a large surface area (formed by the surfaces of the fibers and the areas between the fibers) onto which the softened or melted hydrogel material or adhesive material can flow, and, when solidified, form a mechanical bond with. Unexpectedly, the strength of the mechanical bond formed in this manner between the textile and the hydrogel material or the adhesive material of the hydrogel layer, is sufficient to prevent delamination of the hydrogel material from the textile, even after repeated wet-dry cycling.
In other aspects, it may be desirable soften the textile material during the process of affixing the hydrogel layer and the textile. In such aspects, the step of increasing the temperature of the hydrogel material or the adhesive material can include increasing its temperature to a temperature which is at or above its Vicat softening temperature or its melting temperature, and which is also at or above the Vicat softening temperature of the textile material.
In other aspects, it may be desirable to form a thermal bond between the hydrogel material or the adhesive material and the textile, in which polymer chains from the hydrogel material or the adhesive material intermingle with polymer chains of the textile material. In such aspects, the step of increasing the temperature of the hydrogel material or the adhesive material can include increasing its temperature to a temperature above its melting temperature and which is also above the melting temperature of the textile material.
Methods of Making the Sole Structures
In an aspect, provided herein is a method of making an article, the method comprising operably coupling a first composite element to a second component. In a further aspect, the composite element comprises a textile and a hydrogel layer, where the textile comprises a textile material and having a first side, a second side, and a core located between the first side and the second side. In another aspect, the hydrogel layer comprises a hydrogel material having a first side and a second side, and the second side of the hydrogel layer is operably coupled to the textile along the first side of the textile. Further, in the composite element, a portion of the hydrogel layer can extend through the first side of the textile at least partially into the core of the textile, but does not extend onto the second side of the textile. In one aspect, operably coupling comprises forming a bond between the second side of the textile and the second component such that the hydrogel layer of the composite element defines at least a portion of an externally-facing surface of the second component. In some aspects, operably coupling comprises forming a mechanical bond between the second side of the textile and a second polymeric material. In one aspect, the article can be an article of footwear, a component of an article of footwear, an article of apparel, a component of an article of apparel, an article of sporting equipment, or a component of an article of sporting equipment. In some aspects, the article is a sole structure of an article of footwear and, optionally, the externally-facing surface is a ground-facing surface of a sole structure.
In one aspect, provided herein is a method for making a sole structure for an article of footwear, the method comprising (i) placing a first composite element into a mold, wherein the composite element comprises a textile having a first side, a core having a thickness, and a second side, and a hydrogel layer that extends through the first side and into the core of the textile without contacting the second side, so that a portion of the first side of the hydrogel layer contacts a portion of a molding surface of the mold, forming a prepared molding surface; (ii) charging a second polymeric material onto the prepared molding surface of the mold; (iii) at least partially solidifying the charged second polymeric material in the mold and operably coupling the composite element and the at least partially solidified second polymeric material, forming a sole structure having an outermost hydrogel layer; and (iv) removing the sole structure from the mold. The composite element and sole structure can be any of those described herein.
In some aspects, a portion of the first side of the hydrogel layer can be restrained against a portion of the molding surface while charging the second polymeric material onto the prepared molding surface of the mold.
In an aspect, the method further includes the step of increasing the temperature of the second polymeric material to a molding temperature that is above the melting temperature or Vicat softening temperature of the second polymeric material. Further in this aspect, after the temperature of the second polymeric material is increased to the first temperature, at least a portion of the second polymeric material can penetrate the second side of the textile. In another aspect, solidifying the second polymeric material comprises decreasing the temperature of the second polymeric material to a second temperature that is below the melting temperature or Vicat softening temperature of the second polymeric material.
In some aspects, the first component further comprises a hot melt adhesive layer on the second side of the textile, and the method further comprises increasing the temperature of the hot melt adhesive to a temperature that is above the melting temperature of the hot melt adhesive, so that the adhesive bonds to the second polymeric material.
In some aspects, a mold having a molding surface is provided, and the composite element is placed in the mold so that the first side of the hydrogel layer contacts a portion of the molding surface of the mold, forming a prepared molding surface.
In aspects where the composite element is substantially planar and the molding surface is curved, the film component can be bent or curved in order to fit into the mold and contact the molding surface. However, it is to be understood that this bending or curving will not involve heating the film component above 80 degrees Celsius (C).
In some aspects, the portion of the first side of the hydrogel layer contacting the molding surface is restrained against the portion of the molding surface while a second polymeric material is charged into the mold. Restraining the portion of the first layer against the molding surface reduces or eliminates the need to thermoform the composite element and can prevent or reduce seepage of the second polymeric material between the composite element and the molding surface during the charging step. In some aspects, the step of restraining the first side of the hydrogel layer against the molding surface can include applying a vacuum to the composite element, or applying pins (e.g., retractable pins) to the composite element, or both.
In some aspects, the charging step can include injecting or pouring the second polymeric material into the mold. Once the second polymeric material has at least partially solidified within the mold, the sole structure can be removed from the mold. The use of the disclosed method avoids issues such as drawing and stretching of the composite element during thermoforming, which can damage the composite element resulting in rejects or scrap. The use of this process also reduces the “thermal history” of the composite element by limiting the number of times the composite element is exposed to temperatures above 80 degrees C. during the manufacturing process, which can result in degradation of the hydrogel material. The use of this process can also reduce the amount of waste material as compared to a conventional thermoforming process.
Methods of Making Components and Articles
According to another aspect of the present disclosure, a method of manufacturing an article of footwear comprises securing an upper to a sole structure, the sole structure comprising a composite element comprising a hydrogel layer including a hydrogel material as described herein, wherein the hydrogel material of the hydrogel layer of the composite element defines at least a portion of a ground-facing surface of the article of footwear.
According to yet another aspect of the present disclosure a sole component for an article of footwear comprises one or more composite elements as described herein, wherein each of the composite elements has an external perimeter and a hydrogel layer such that the hydrogel material of each of the hydrogel layers defines a ground-facing surface of the sole component. A second polymeric material may operably connect the second side of the textile of the composite element to the sole component, including connecting the entire external perimeter of each of the one or more composite elements to the sole component. The sole component may further comprise one or more traction elements with the one or more composite elements being configured to fit between or around the traction elements.
According to some aspects, one or more of the traction elements can comprise an element that is added separately after the sole component is removed from the mold, for example, as snap-fit, screw-on components, or a combination thereof. In these aspects, the separately-added traction elements can be individually selected to comprise the same material as the second polymeric material or a material that is different than or substantially free of the second polymeric material. The separately-added traction elements can be permanently or removably coupled with the sole component and/or the sole structure. When desirable, one or more fittings can be used to removably couple traction elements to the sole component and/or the sole structure. For example, one or more traction element can be placed into the mold prior to adding the second polymeric material in order to be molded with the sole component and/or sole structure. These fittings are configured to couple with the separately-added traction elements, e.g., snap-fit or screw-on components. According to certain aspects, preformed traction element tips, which include the traction element terminal end, can be placed into the mold prior to adding the second polymeric material in order to be molded with the sole structure or the sole component. These pre-formed traction elements can be individually selected to comprise the same material as the second polymeric material or a material that is different than the second polymeric material (e.g., harder than and/or more abrasion-resistant than the second polymeric material) or substantially free of the second polymeric material. For example, the polymeric material of at least the terminal end of a traction element can comprise a polymeric component which differs from the polymeric component of the second polymeric material based on one or more types of polymers present, a concentration of one or more types of polymers present, or both.
The disclosure provides several methods for making components and articles described herein. The methods can include injection molding a polymeric material described herein. The disclosure provides methods for manufacturing a component for an article of footwear, by injection molding a polymeric material described herein.
In certain aspects, the methods comprise forming a sole component such as a plate. For example, a polymeric material can be injection molded to mold a sole component. In this aspect, a mold can be provided having a first mold portion having a first surface, a second surface, and an outer perimeter. The polymeric material can be injected to the first portion of the mold. The resultant injection-molded component is a unitary component, comprising a sole component. In some aspects, the composite element can be placed in the mold prior to injection molding, and the step of injection molding can form the sole component as well as form a bond between the composite element and the sole component. The bond can be a thermal bond formed between a polymeric material present on the second side of the composite element, and between the injection molded polymeric material, such as a second polymeric material as described herein. The bond between the composite element and the sole component can be a mechanical bond formed between the second side of the textile of the composite element and the injected polymeric material.
In some aspects, the composite element and sole component, such as a plate, are provided separately, and affixed, combined or joined so as to be operably coupled. For example, an adhesive can be provided between the composite element (e.g., between the second side of textile of the composite element) and the sole component, to provide an adhesive bond between the composite element and the sole component. Any suitable adhesive that is compatible with both the composite element and the sole component can be used. For example, a cement commonly used in the footwear industry, such as a polyurethane-based cement system alone or with a primer layer, can be used.
In other aspects, affixing the composite element to the sole component can include forming a mechanical bond between the sole component and the composite element. Optionally, pressure can be applied to the composite element, to the sole component, or both, during the formation of the mechanical bond. In some aspects, the mechanical bond can be a thermal bond in which a thermoplastic material is softened to facilitate deformation of the thermoplastic material against one or more of the surfaces to be bonded, and then the thermoplastic material is re-solidified. In other aspects, the mechanical bond can be a thermally intermingled bond in which a thermoplastic material is melted to facilitate intermingling of polymer chains of the thermoplastic material with another polymeric material on one or more of the surfaces to be bonded, and then the thermoplastic material is re-solidified. Affixing the sole component to the composite element can include (i) increasing a temperature of the sole component, (ii) contacting the sole component with the composite element and (iii) keeping the sole component and the composite element in contact with each other while decreasing the temperature of the sole component to a second temperature below the melting or softening point of the polymeric material of the sole component, forming a mechanical bond between the plate and the composite element.
In one aspect, disclosed herein is a method for manufacturing an article of footwear, the method comprising securing a sole structure as disclosed herein and an upper to each other, such that the hydrogel layer of the sole structure defines a ground-facing surface of the article of footwear. In some aspects, the method further includes attaching a midsole to the sole structure and/or the upper prior to securing the sole structure to the upper, such that the midsole resides between the sole structure and the upper.
The methods can further include operably coupling a composite element as described herein to a second element. The second element can include a textile or multilayer film or a sole component for an article of footwear such as, for example, a plate or a traction element. For example, the second element can additionally include an upper. In one aspect, the upper can comprise or further comprise a natural leather, a thermoset polymer, a thermoplastic polymer, or a mixture thereof. The second element can comprise a polymeric material comprising a polyolefin. In some aspects, the second component can comprise a textile selected from: a knit textile, a woven textile, a non-woven textile, a crochet textile, a braided textile, or a combination thereof. In an aspect, the textile includes one or more natural or synthetic fibers or yarns. In some aspects, the synthetic fibers and/or yarns comprise a thermoplastic polyurethane, a polyamide, a polyester, a polyolefin, or a mixture thereof. Securing the sole structure to the second component can include forming a mechanical bond between a side of the sole structure and the second component, such as, for example, between a plate and a strobel. In a further aspect, securing the sole structure to the second component can include the use of an adhesive alone or in combination with a primer. Alternatively, securing the sole structure to the upper can include forming a thermal bond between a thermoplastic material present on an outer surface of the sole structure, and between a thermoplastic material on an outer surface of the second component. Securing the sole structure to the second component can include forming a mechanical bond between a textile forming an outer surface of the sole structure, and a textile forming an outer surface of the upper, such as a strobel, for example, using a hot melt adhesive at the interface between the outer surface of the sole structure and the outer surface of the upper.
As described herein, two elements can be operably coupled to each other. For example, in the composite element, the hydrogel layer and the textile are operably coupled. Similarly, in the sole structure, the composite element and a sole component are operably coupled, and in the article of footwear, the sole structure and the upper are operably coupled. The two elements can be directly coupled or otherwise operably coupled to each other using any suitable mechanism or method. As used herein, the terms “operably coupled”, such as for a sole structure that is operably secured to an upper, refers collectively to direct connections, indirect connections, integral formations, and combinations thereof. For instance, for a sole structure that is operably secured to an upper, the sole structure can be directly connected to the upper. The direct connection can be a mechanical bond. The mechanical bond can include a thermal bond formed by softening and then re-solidifying a thermoplastic material, or a thermal bond formed by melting and then re-solidifying two thermoplastic materials, such as a thermally intermingled bond. The direct connection can include an adhesive layer present at the interface between the two elements (e.g., adhered directly thereto with an adhesive such as a cement (alone or with a primer layer) or a hot melt adhesive), can be integrally formed with the upper (e.g., as a unitary component), and combinations thereof.
The upper of the article of footwear has a body, which can be fabricated from materials known in the art for making articles of footwear, and is configured to receive a user's foot. The upper of a shoe consists of all components of the shoe above the biteline (the interface between the bottom surface of the upper and the top surface of the sole structure). The different components of the upper can include a toe box; a heel region, a heel counter; a tongue; eye stays, a medial side, a lateral side, and a vamp, to name a few. These components can be attached by stitches or by adhesives to become a single unit to which the sole structure is attached.
The upper or components of the upper usually comprise a soft body made up of one or more lightweight materials. The materials used in the upper provide stability, comfort, and a secure fit. For example, the upper can be made from or include one or more components made from one or more of natural or synthetic leather, a thermoset polymer, a thermoplastic polymer, or a mixture thereof. When desirable, the upper can be made using one of these components as textile comprising fibers made from a polymeric material as described herein.
The textile can include; a knit, braided, woven, or nonwoven textile made in whole or in part of a natural fiber; a knit, braided, woven or non-woven textile made in whole or in part of a synthetic polymer, a film of a synthetic polymer, etc.; and combinations thereof. The textile can include one or more natural or synthetic fibers or yarns. The synthetic yarns can comprise, consist of, or consist essentially of thermoplastic polyurethane (TPU), polyamide (e.g., “NYLON” etc.), polyester (e.g., polyethylene terephthalate or PET), polyolefin, or a mixture thereof.
Since the sole structure includes outer most portions of the sole such as the ground-contacting portions of the article of footwear, the sole structure is directly exposed to abrasion and wear. In some aspects, various portions of the sole structure can be constructed with different thickness and can exhibit different degrees of flexibility. The sole structure can comprise materials that are selected to provide necessary or desired properties, such as a degree of waterproofing, durability, and/or a coefficient of friction that is high enough to prevent slipping. In some cases, a polymeric material can be incorporated into the ground-contacting portion of the sole structure to give a hardwearing ground-contacting surface. In some aspects, the ground-contacting portion of the sole structure can be combined with a softer, more flexible midsole for greater comfort. For example, the midsole can comprise a cushioning element such as an air bladder or a foam material. In some aspects, the material of the cushioning element can include, without limitation, a polymeric material comprising one or more polyurethanes, or ethylene vinyl acetates, or copolyesters, or polyolefins, or combinations thereof.
According to another aspect of the present disclosure, the use of a sole structure comprising a hydrogel material forming at least a portion of an externally-facing or ground-facing surface is described. This use involves incorporating the sole structure as described herein as an externally-facing surface in a finished article of footwear in order to prevent or reduce soil accumulation on the externally-facing or ground-facing surface of the sole structure. In some aspects, the sole structure or article of footwear retains at least 5 percent less soil and/or debris by weight; alternatively, at least 10 percent less soil and/or debris by weight, as compared to a conventional sole structure or article of footwear that is similar except that the externally-facing surface or ground-facing surface of the conventional sole structure or article of footwear is substantially free of the hydrogel material.
According to yet another aspect of the present disclosure, the use of an article of footwear comprising a hydrogel material on at least a portion of an externally-facing surface is described. This use involves incorporating the hydrogel layer of a composite element as described herein as an externally-facing surface in a finished article of footwear in order to prevent or reduce soil accumulation on the externally-facing surface of the sole structure and article. In some aspects, the article of footwear retains at least 5 percent less soil by weight; alternatively, at least 10 percent less soil by weight, as compared to a conventional article of footwear that is similar except that the externally-facing surface of the conventional article of footwear is substantially free of the hydrogel material.
Property Analysis and Characterization Procedures
Cold Ross Flex Test Protocol
The cold Ross flex test is determined according the following test method. The purpose of this test is to evaluate the resistance to cracking of a sample under repeated flexing to 60 degrees in a cold environment. A plaque sample of the material for testing is prepared using the Plaque Sampling Procedure and is sized to fit inside the flex tester machine. Each material is tested as five separate samples. The flex tester machine is capable of flexing samples to 60 degrees at a rate of 100±5 cycles per minute. The mandrel diameter of the machine is 10 millimeters. Suitable machines for this test are the Emerson AR-6, the Satra S Tm 141F, the Gotech GT-7006, and the Shin II Scientific SI-LTCO (DaeSung Scientific). The sample(s) are inserted into the machine according to the specific parameters of the flex machine used. The machine is placed in a freezer set to −6 degrees Celsius for the test. The motor is turned on to begin flexing with the flexing cycles counted until the sample cracks. Cracking of the sample means that the surface of the material is physically split. Visible creases of lines that do not actually penetrate the surface are not cracks. The sample is measured to a point where it has cracked but not yet broken in two.
Abrasion Loss Test Protocol ASTM D 5963-97a
Abrasion loss is tested on cylindrical test pieces with a diameter of 16±0.2 millimeter and a minimum thickness of 6 millimeters cut from samples prepared using the Plaque Sampling Procedure which are then cut to size using an ASTM standard hole drill. The abrasion loss is measured using Method B of ASTM D 5963-97a on a Gotech GT-7012-D abrasion test machine. The tests are performed as 22 degrees Celsius with an abrasion path of 40 meters. The Standard Rubber #1 used in the tests has a density of 1.336 grams per cubic centimeter (g/cm3). The smaller the abrasion loss volume, the better the abrasion resistance.
Mud Pull Off Test Protocol
A two-inch diameter sample prepared using the Plaque Sampling Procedure is cut and affixed to the top plate of a set of parallel, flat aluminum test plates on a standard mechanical testing machine (e.g. Instron tensile testing equipment.) A 1-inch diameter mud sample, approximately 7 millimeters in height is loaded onto the bottom plate of the mechanical tester. The soil used to make the mud is commercially available under the tradename “TIMBERLINE TOP SOIL”, model 50051562, from Timberline (subsidiary of Old Castle, Inc., Atlanta, Ga.) and was sifted with a square mesh with a pore dimension of 1.5 millimeter on each side. The mud was previously dried and then diluted to water to 22 percent water by weight. The force transducers are normalized to zero force. The plates are then pressed together to a load of 445 Newtons in the compressive direction. The load is then immediately removed and a small force hysteresis is measured at the mud detachment point that is greater than the tared value of zero in the tensile direction. The maximum force measured is the pull off force for the mud adhesion to the material substrate. The compression/detachment cycle is repeated at least 10 times until a stable value is obtained.
Crystallinity Test Protocol
To determine percent crystallinity of a polymer material including a copolymer, or of the copolymer in neat resin form, and of a homopolymer of the main component of the copolymer (e.g., polypropylene homopolymer polypropylene) prepared using the Material Sampling Procedure are analyzed by differential scanning calorimetry (DSC) over the temperature range from −80 degrees Celsius to 250 degrees Celsius. A heating rate of 10 degrees Celsius per minute is used. The melting endotherm is measured for each sample during heating. Universal Analysis software (TA Instruments, New Castle, Del., USA) is used to calculate percent crystallinity based upon the melting endotherm for the homopolymer (e.g., 207 Joules per gram for 100 percent crystalline polypropylene material). Specifically, the percent crystallinity (percent crystallinity) is calculated by dividing the melting endotherm measured for the copolymer or for the resin composition by the 100 percent crystalline homopolymer melting endotherm.
Creep Relation Temperature Tcr Test Protocol
The creep relation temperature Tcr is determined using a sample prepared using the Material Sampling Procedure according to the exemplary techniques described in U.S. Pat. No. 5,866,058. The creep relaxation temperature Tcr is calculated to be the temperature at which the stress relaxation modulus of the tested material is 10 percent relative to the stress relaxation modulus of the tested material at the solidification temperature of the material, where the stress relaxation modulus is measured according to ASTM E328-02. The solidification temperature is defined as the temperature at which there is little to no change in the stress relaxation modulus or little to no creep about 300 seconds after a stress is applied to a test material, which can be observed by plotting the stress relaxation modulus (in Pa) as a function of temperature (in degrees Celsius).
Vicat Softening Temperature Tvs Test Protocol
The Vicat softening temperature Tvs is be determined according to the test method detailed in ASTM D1525-09 Standard Test Method for Vicat Softening Temperature of Plastics, using Load A and Rate A, using a sample prepared using the Material Sampling Procedure. Briefly, the Vicat softening temperature is the temperature at which a flat-ended needle penetrates the specimen to the depth of 1 millimeter under a specific load. The temperature reflects the point of softening expected when a material is used in an elevated temperature application. It is taken as the temperature at which the specimen is penetrated to a depth of 1 millimeter by a flat-ended needle with a 1 square millimeter circular or square cross-section. For the Vicat A test, a load of 10 Newtons (N) is used, whereas for the Vicat B test, the load is 50 Newtons. The test involves placing a test specimen in the testing apparatus so that the penetrating needle rests on its surface at least 1 millimeter from the edge. A load is applied to the specimen per the requirements of the Vicat A or Vicat B test. The specimen is then lowered into an oil bath at 23 degrees Celsius. The bath is raised at a rate of 50 degrees Celsius or 120 degrees Celsius per hour until the needle penetrates 1 millimeter. The test specimen must be between 3 and 6.5 millimeter thick and at least 10 millimeter in width and length. No more than three layers can be stacked to achieve minimum thickness.
Heat Deflection Temperature Thd Test Protocol
The heat deflection temperature Thd is be determined according to the test method detailed in ASTM D648-16 Standard Test Method for Deflection Temperature of Plastics Under Flexural Load in the Edgewise Position, using a 0.455 megapascals applied stress, with a sample prepared using the Material Sampling Procedure. Briefly, the heat deflection temperature is the temperature at which a polymer or plastic sample deforms under a specified load. This property of a given plastic material is applied in many aspects of product design, engineering, and manufacture of products using thermoplastic components. In the test method, the bars are placed under the deflection measuring device and a load (0.455 megapascals) of is placed on each specimen. The specimens are then lowered into a silicone oil bath where the temperature is raised at 2 degrees Celsius per minute until they deflect 0.25 millimeters per ASTM D648-16. ASTM uses a standard bar 5″×½″×¼″. ISO edgewise testing uses a bar 120 millimeters×10 millimeters×4 millimeters. ISO flatwise testing uses a bar 80 millimeters×10 millimeters×4 millimeters.
Melting Temperature, Glass Transition Temperature, and Enthalpy of Melting Test Protocol
The melting temperature and glass transition temperature are determined using a commercially available Differential Scanning calorimeter (“DSC”) in accordance with ASTM D3418-97, using a sample prepared using the Material Sampling Procedure. Briefly, a 10-15 gram sample is placed into an aluminum DSC pan and then the lead was sealed with the crimper press. The DSC is configured to scan from −100 degrees Celsius to 225 degrees Celsius with a 20 degrees Celsius/minute heating rate, hold at 225 degrees Celsius for 2 minutes, and then cool down to 25 degrees Celsius at a rate of −10 degrees Celsius/minute. The DSC curve created from this scan is then analyzed using standard techniques to determine the glass transition temperature and the melting temperature. The enthalpy of melting is calculated by integrating the area of the melting endotherm peak and normalizing by the sample mass.
Melt Flow Index Test Protocol
The melt flow index is determined according to the test method detailed in ASTM D1238-13 Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer, using Procedure A described therein, with a sample prepared using the Material Sampling Procedure. Briefly, the melt flow index measures the rate of extrusion of thermoplastics through an orifice at a prescribed temperature and load. In the test method, approximately 7 grams of the material is loaded into the barrel of the melt flow apparatus, which has been heated to a temperature specified for the material. A weight specified for the material is applied to a plunger and the molten material is forced through the die. A timed extrudate is collected and weighed. Melt flow rate values are calculated in grams per 10 minutes. Alternatively, melt flow index can be determined using International Standard ISO1133 Determination of the Melt Mass-Flow Rate (MFR) and Melt Volume-Flow Rate (MVR) of Thermoplastics using Procedure A described therein, at 190 degrees Celsius and a load of 2.16 kilograms.
Durometer Hardness Test Protocol
The hardness of a material is determined according to the test method detailed in ASTM D-2240 Durometer Hardness, using a Shore A scale. The sample is prepared using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure.
Flexural Modulus Test Protocol
The flexural modulus (modulus of elasticity) for a material is determined according to the test method detailed in ASTM D790. The sample is prepared using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure. The modulus is calculated by taking the slope of the stress (megapascals) versus the strain in the steepest initial straight-line portion of the load-deflection curve.
Modulus Test Protocol
The (tensile) modulus for a material is determined according to the test method detailed in ASTM D412-98 Standard Test Methods for Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers-Tension, with the following modifications. The sample is prepared using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure. The sample dimension is the ASTM D412-98 Die C, and the sample thickness used is 2.0 millimeters±0.5 millimeters. The grip type used is a pneumatic grip with a metal serrated grip face. The grip distance used is 75 millimeters. The loading rate used is 500 millimeters per minute. The modulus (initial) is calculated by taking the slope of the stress (megapascals) versus the strain in the initial linear region.
Water Uptake Capacity Test Protocol
This test measures the water uptake capacity of a material after a predetermined soaking duration for a sample. The sample is prepared using the Material Sampling Procedure or the Plaque Sampling Procedure. The sample is initially dried at 60 degrees Celsius until there is no weight change for consecutive measurement intervals of at least 30 minutes apart (e.g., a 24-hour drying period at 60 degrees Celsius is typically a suitable duration). The total weight of the dried sample (Wtsample dry) is then measured in grams. The dried sample is allowed to cool down to 25 degrees Celsius, and is fully immersed in a deionized water bath maintained at 25 degrees Celsius. After a given soaking duration, the sample is removed from the deionized water bath, blotted with a cloth to remove surface water, and the total weight of the soaked sample (Wtsample wet) is measured in grams.
Any suitable soaking duration can be used, where a 24-hour soaking duration is believed to simulate saturation conditions for a material (i.e., a hydrophilic resin will be in its saturated state). Accordingly, as used herein, the expression “having a water uptake capacity at 5 minutes” refers to a soaking duration of 5 minutes, the expression “having a water uptake capacity at 1 hour” refers to a soaking duration of 1 hour, the expression “having a water uptake capacity at 24 hours” refers to a soaking duration of 24 hours, and the like. If no time duration is indicated after a water uptake capacity value, the soaking duration corresponds to a period of 24 hours.
As can be appreciated, the total weight of a sample includes the weight of the material as dried or soaked (Wtsample dry or Wtsample wet) and the weight of the substrate (Wt,substrate) needs to be subtracted from the sample measurements.
The weight of the substrate (Wtsubstrate) is calculated using the sample surface area (e.g., 4.0 cm2), an average measured thickness of the hydrogel material portion of the hydrogel layer, and the average density of the hydrogel material. Alternatively, if the density of the material for the substrate is not known or obtainable, the weight of the substrate (Wtsubstrate) is 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 film/substrate thicknesses) as the primary sample. The material of the second sample is then cut apart from the substrate of the second sample with a blade to provide an isolated substrate. The isolated substrate is then dried at 60 degrees Celsius for 24 hours, which can be performed at the same time as the primary sample drying. The weight of the isolated substrate (Wt,substrate) is then measured in grams.
The resulting substrate weight (Wtsubstrate) is then subtracted from the weights of the dried and soaked primary sample (Wtsample dry or Wtsample wet) to provide the weights of the material as dried and soaked (Wtcomponent dry or Wtcomponent wet) as depicted by Equations 1 and 2.
Wt
component dry
=Wt
sample dry
−Wt
substrate (Eq. 1)
Wt
component wet
=Wt
sample wet
−Wt
substrate (Eq. 2)
The weight of the dried component (Wtcomponent dry) is then subtracted from the weight of the soaked component (Wtcomponent wet) to provide the weight of water that was taken up by the component, which is then divided by the weight of the dried component (Wtcomponent dry) to provide the water uptake capacity for the given soaking duration as a percentage, as depicted below by Equation 3.
For example, a water uptake capacity of 50 percent at 1 hour means that the soaked component weighed 1.5 times more than its dry-state weight after soaking for 1 hour. Similarly, a water uptake capacity of 500 percent at 24 hours means that the soaked component weighed 5 times more than its dry-state weight after soaking for 24 hours.
Water Uptake Rate Test Protocol
This test measures the water uptake rate of a material by modeling weight gain as a function of soaking time for a sample with a one-dimensional diffusion model. The sample is prepared using the Material Sampling Procedure or the Plaque Sampling Procedure. The sample is dried at 60 degrees Celsius until there is no weight change for consecutive measurement intervals of at least 30 minutes apart (a 24-hour drying period at 60 degrees Celsius is typically a suitable duration). The total weight of the dried sample (Wtsample dry) is then measured in grams. Additionally, the average thickness of the component for the dried sample is measured for use in calculating the water uptake rate, as explained below.
The dried sample is allowed to cool down to 25 degrees Celsius, and is fully immersed in a deionized water bath maintained at 25 degrees Celsius. Between soaking durations of 1, 2, 4, 9, 16, and 25 minutes, the sample is removed from the deionized water bath, blotted with a cloth to remove surface water, and the total weight of the soaked sample (Wtsample wet) is measured, where “t” refers to the particular soaking-duration data point (e.g., 1, 2, 4, 9, 16, or 25 minutes).
The exposed surface area of the soaked sample is also measured with calipers for determining the specific weight gain, as explained below. The exposed surface area refers to the surface area that comes into contact with the deionized water when fully immersed in the bath. For samples obtained using the Footwear Sampling Procedure, the samples only have one major surface exposed. For convenience, the surface areas of the peripheral edges of the sample are ignored due to their relatively small dimensions.
The measured sample is fully immersed back in the deionized water bath between measurements. The 1, 2, 4, 9, 16, and 25 minute durations refer to cumulative soaking durations while the sample is fully immersed in the deionized water bath (i.e., after the first minute of soaking and first measurement, the sample is returned to the bath for one more minute of soaking before measuring at the 2-minute mark).
As discussed above in the Water Uptake Capacity Test, the total weight of a sample includes the weight of the material as dried or soaked (Wtcomponent wet or Wtcomponent dry) and the weight of the article or backing substrate (Wtsubstrate). In order to determine a weight change of the material due to water uptake, the weight of the substrate (Wtsubstrate) needs to be subtracted from the sample weight measurements. This can be accomplished using the same steps discussed above in the Water Uptake Capacity Test to provide the resulting material weights Wtcomponent wet and Wtcomponent dry for each soaking-duration measurement.
The specific weight gain (Wst) from water uptake for each soaked sample is then calculated as the difference between the weight of the soaked sample (Wtcomponent wet) and the weight of the initial dried sample (Wtcomponent dry) where the resulting difference is then divided by the exposed surface area of the soaked sample (Δt) as depicted in Equation 4.
where t refers to the particular soaking-duration data point (e.g., 1, 2, 4, 9, 16, or 25 minutes), as mentioned above.
The water uptake rate for the material is then determined as the slope of the specific weight gains (Wst) versus the square root of time (in minutes), as determined by a least squares linear regression of the data points. For the material, the plot of the specific weight gains (Wst) versus the square root of time (in minutes) provides an initial slope that is substantially linear (to provide the water uptake rate by the linear regression analysis). However, after a period of time depending on the thickness of the component, the specific weight gains will slow down, indicating a reduction in the water uptake rate, until the saturated state is reached. This is believed to be due to the water being sufficiently diffused throughout the material as the water uptake approaches saturation, and will vary depending on component thickness.
As such, for the component having an average thickness (as measured above) less than 0.3 millimeters, only the specific weight gain data points at 1, 2, 4, and 9 minutes are used in the linear regression analysis. In these cases, the data points at 16 and 25 minutes can begin to significantly diverge from the linear slope due to the water uptake approaching saturation, and are omitted from the linear regression analysis. In comparison, for the component having an average dried thickness (as measured above) of 0.3 millimeters or more, the specific weight gain data points at 1, 2, 4, 9, 16, and 25 minutes are used in the linear regression analysis. The resulting slope defining the water uptake rate for the sample has units of weight per (surface area-square root of time), such as grams per (meter2-minutes1/2) or g/m2/√min.
Furthermore, some surfaces can create surface phenomenon that quickly attract and retain water molecules (e.g., via surface hydrogen bonding or capillary action) without actually drawing the water molecules into the film or substrate. Thus, samples of these films or substrates can show rapid specific weight gains for the 1-minute sample, and possibly for the 2-minute sample. After that, however, further weight gain is negligible. As such, the linear regression analysis is only applied if the specific weight gain in data points at 1, 2, and 4 minutes continue to show an increase in water uptake. If not, the water uptake rate under this test methodology is considered to be about zero g/m2/√min.
Swelling Capacity Test Protocol
This test measures the swelling capacity of a material in terms of increases in thickness and volume after a given soaking duration for a sample. The sample is prepared using the Material Sampling Procedure or the Plaque Sampling Procedure. The sample is initially dried at 60 degrees Celsius until there is no weight change for consecutive measurement intervals of at least 30 minutes apart (a 24-hour drying period is typically a suitable duration). The dimensions of the dried sample are then measured (e.g., thickness, length, and width for a rectangular sample; thickness and diameter for a circular sample, etc.). The dried sample is then fully immersed in a deionized water bath maintained at 25 degrees Celsius. After a given soaking duration, the sample is removed from the deionized water bath, blotted with a cloth to remove surface water, and the same dimensions for the soaked sample are re-measured.
Any suitable soaking duration can be used. Accordingly, as used herein, the expression “having a swelling thickness (or volume) increase at 5 minutes of.” refers to a soaking duration of 5 minutes, the expression “having a swelling thickness (or volume) increase at 1 hour of” refers to a test duration of 1 hour, the expression “having a swelling thickness (or volume) increase at 24 hours of” refers to a test duration of 24 hours, and the like.
The swelling of the component is determined by (1) an increase in the thickness between the dried and soaked component, by (2) an increase in the volume between the dried and soaked component, or (3) both. The increase in thickness between the dried and soaked components is calculated by subtracting the measured thickness of the initial dried component from the measured thickness of the soaked component. Similarly, the increase in volume between the dried and soaked components is calculated by subtracting the measured volume of the initial dried component from the measured volume of the soaked component. The increases in the thickness and volume can also be represented as percentage increases relative to the dry thickness or volume, respectively.
Contact Angle Test Protocol
This test measures the contact angle of a material based on a static sessile drop contact angle measurement for a sample. The sample is prepared using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure. The contact angle refers to the angle at which a liquid interface meets a solid surface, and is an indicator of how hydrophilic the surface is.
For a dry test (i.e., to determine a dry-state contact angle), the sample is initially equilibrated at 25 degrees C. and 20 percent humidity for 24 hours. For a wet test (i.e., to determine a wet-state contact angle), the sample is fully immersed in a deionized water bath maintained at 25 degrees C. for 24 hours. After that, the sample is removed from the bath and blotted with a cloth to remove surface water, and clipped to a glass slide if needed to prevent curling.
The dry or wet sample is then placed on a moveable stage of a contact angle goniometer, such as those commercially available under the tradename “RAM E-HART F290” from Rame-Hart Instrument Co., Succasunna, N.J. A 10-microliter droplet of deionized water is then placed on the sample using a syringe and automated pump. An image is then immediately taken of the droplet (before film can take up the droplet), and the contact angle of both edges of the water droplet are measured from the image. The decrease in contact angle between the dried and wet samples is calculated by subtracting the measured contact angle of the wet composite element from the measured contact angle of the dry composite element.
Coefficient of Friction Test Protocol
This test measures the coefficient of friction of the Coefficient of Friction Test for a sample. The sample is prepared using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure. For a dry test (i.e., to determine a dry-state coefficient of friction), the sample is initially equilibrated at 25 degrees C. and 20 percent humidity for 24 hours. For a wet test (i.e., to determine a wet-state coefficient of friction), the sample is fully immersed in a deionized water bath maintained at 25 degrees C. for 24 hours. After that, the sample is removed from the bath and blotted with a cloth to remove surface water.
The measurement is performed with an aluminum sled mounted on an aluminum test track, which is used to perform a sliding friction test for test sample on an aluminum surface of the test track. The test track measures 127 millimeters wide by 610 millimeters long. The aluminum sled measures 76.2 millimeters.times.76.2 millimeters, with a 9.5 millimeter radius cut into the leading edge. The contact area of the aluminum sled with the track is 76.2 millimeters×66.6 millimeters, or 5,100 square millimeters).
The dry or wet sample is attached to the bottom of the sled using a room temperature-curing two-part epoxy adhesive, such as that commercially available under the tradename “LOCTITE 608” from Henkel, Dusseldorf, Germany. The adhesive is used to maintain the planarity of the wet sample, which can curl when saturated. A polystyrene foam having a thickness of about 25.4 millimeters is attached to the top surface of the sled (opposite of the test sample) for structural support.
The sliding friction test is conducted using a screw-driven load frame. A tow cable is attached to the sled with a mount supported in the polystyrene foam structural support, and is wrapped around a pulley to drag the sled across the aluminum test track. The sliding or frictional force is measured using a load transducer with a capacity of 2,000 Newtons. The normal force is controlled by placing weights on top of the aluminum sled, supported by the polystyrene foam structural support, for a total sled weight of 20.9 kilograms (205 Newtons). The crosshead of the test frame is increased at a rate of 5 millimeters per second, and the total test displacement is 250 millimeters. The coefficient of friction is calculated based on the steady-state force parallel to the direction of movement required to pull the sled at constant velocity. The coefficient of friction itself is found by dividing the steady-state pull force by the applied normal force. Any transient value relating static coefficient of friction at the start of the test is ignored.
Storage Modulus Test Protocol
This test measures the resistance of a material to being deformed (ratio of stress to strain) when a vibratory or oscillating force is applied to it, and is a good indicator of film compliance in the dry and wet states. The sample is prepared using the Material Sampling Procedure, the Plaque Sampling Procedure, or the Component Sampling Procedure. For this test, a sample is provided having a surface area with dimensions of 5.35 millimeters wide and 10 millimeters long. The sample thickness can range from 0.1 millimeters to 2 millimeters, and the specific range is not particularly limited as the end modulus result is normalized according to material thickness.
The storage modulus (E′) with units of megaPascals (MPa) of the sample is determined by dynamic mechanical analysis (DMA) using a DMA analyzer, such as a commercially available analyzer under the tradename “Q800 DMA ANALYZER” from TA Instruments, New Castle, Del., which is equipped with a relative humidity accessory to maintain the sample at constant temperature and relative humidity during the analysis.
Initially, the thickness of the test sample is measured using calipers (for use in the modulus calculations). The test sample is then clamped into the DMA analyzer, which is operated at the following stress/strain conditions during the analysis: isothermal temperature of 25 degrees C., frequency of 1 Hertz, strain amplitude of 10 micrometers, preload of 1 Newton, and force track of 125 percent. The DMA analysis is performed at a constant 25 degree C. temperature according to the following time/relative humidity (RH) profile: (i) 0 percent relative humidity for 300 minutes (representing the dry state for storage modulus determination), (ii) 50 percent relative humidity for 600 minutes, (iii) 90 percent relative humidity for 600 minutes (representing the wet state for storage modulus determination), and (iv) 0 percent relative humidity for 600 minutes.
The E′ value (in megapascals) is determined from the DMA curve according to standard DMA techniques at the end of each time segment with a constant relative humidity value. Namely, the E′ value at 0 percent relative humidity (i.e., the dry-state storage modulus) is the value at the end of step (i), the E′ value at 50 percent relative humidity is the value at the end of step (ii), and the E′ value at 90 percent relative humidity (i.e., the wet-state storage modulus) is the value at the end of step (iii) in the specified time/relative humidity profile.
The material can be characterized by its dry-state storage modulus, its wet-state storage modulus, or the reduction in storage modulus between the dry-state and wet-state, where wet-state storage modulus is less than the dry-state storage modulus. This reduction in storage modulus can be listed as a difference between the dry-state storage modulus and the wet-state storage modulus, or as a percentage change relative to the dry-state storage modulus.
Sampling Procedures
Using the Test Protocols described above, various properties of the materials disclosed herein and articles formed therefrom can be characterized using samples prepared with the following sampling procedures:
Material Sampling Procedure
The Material Sampling Procedure can be used to obtain a neat sample of a polymeric material or of a polymer, or, in some instances, a sample of a material used to form a polymeric material or a polymer. The material is provided in media form, such as flakes, granules, powders, pellets, and the like. If a source of the polymeric material or polymer is not available in a neat form, the sample can be cut from a component or element containing the polymeric material or polymer, such as a composite element or a sole structure, thereby isolating a sample of the material.
Plaque Sampling Procedure and Film Sampling Procedure
A sample of polymer material or a polymer is prepared. A portion of the polymer or polymeric material is then be molded into a film or plaque sized to fit the testing apparatus. For example, when using a Ross flexing tester, the plaque is sized to fit inside the Ross flexing tester used, the plaque having dimensions of about 15 centimeters (cm) by 2.5 centimeters (cm) and a thickness of about 1 millimeter (mm) to about 4 millimeters (mm) by thermoforming the polymeric material in a mold. For a plaque sample of a polymer, the sample can be prepared by melting the polymer, charging the molten polymer into a mold, re-solidifying the polymer in the shape of the mold, and removing the solidified molded sample from the mold. Alternatively, the plaque sample of the polymer can be melted and then extruded into a film which is cut to size. For a plaque sample of a polymer material, the sample can be prepared by mixing together the ingredients of the polymer material, melting the thermoplastic ingredients of the polymer material, charging the molten polymer into a mold, re-solidifying the polymeric material in the shape of the mold, and removing the solidified molded sample from the mold. Alternatively, the plaque sample of the polymer material can be prepared by mixing and melting the ingredients of the polymeric material, and then the molten polymer material can be extruded into a film which is cut to size. For a film sample of a polymer, the film is extruded as a web or sheet having a substantially constant film thickness for the film (within ±10 percent of the average film thickness) and cooled to solidify the resulting web or sheet. A sample of the film having a surface area of 4 square centimeters is then cut from the resulting web or sheet. Alternatively, if a source of the film material is not available in a neat form, the film can be cut from a substrate of a footwear component, or from a backing substrate of a co-extruded sheet or web, thereby isolating the film. In either case, a sample of the film having a surface area of 4 square centimeters is then cut from the resulting isolated film.
Component Sampling Procedure
This procedure can be used to obtain a sample of a material from a component of an article of footwear, an article of footwear, a component of an article of apparel, an article of apparel, a component of an article of sporting equipment, or an article of sporting equipment. A sample including the material in a non-wet state (e.g., at 25 degrees Celsius and 20 percent relative humidity) is cut from the article or component using a blade. If the material is bonded to one or more additional materials, the procedure can include separating the additional materials from the material to be tested. For example, to test a material on a ground-facing surface of sole structure, the opposite surface can be skinned, abraded, scraped, or otherwise cleaned to remove any adhesives, yarns, fibers, foams, and the like which are affixed to the material to be tested. The resulting sample includes the material and may include any additional materials bonded to the material.
This procedure can be used to obtain a sample of the hydrogel material when the hydrogel material is incorporated as a layer of the composite element or sole structure of an article of footwear (e.g., bonded to materials such as second polymeric material and/or other materials). The resulting component sample includes the hydrogel material and any substrate(s) bonded to the hydrogel material, and maintains the interfacial bond between the hydrogel material and the textile and optionally other associated materials of the finished article. As such, any test using a Component Sampling Procedure can simulate how the hydrogel material will perform as part of an article, such as an article of footwear. Additionally, this type of sample is also useful in cases where the interfacial bond between the hydrogel material and the hydrogel layer and/or textile is less defined, such as where the hydrogel material is highly diffused into the textile.
The sample is taken at a location along the article or component that provides a substantially constant material thickness for the material as present on the article or component (within plus or minus 10 percent of the average material thickness), such as, for an article of footwear, in a forefoot region, midfoot region, or a heel region of a ground-facing surface. For many of the test protocols described above, a sample having a surface area of 4 square centimeters (cm2) is used. The sample is cut into a size and shape (e.g., a dogbone-shaped sample) to fit into the testing apparatus. In cases where the material is not present on the article or component in any segment having a 4 square centimeter surface area and/or where the material thickness is not substantially constant for a segment having a 4 square centimeter surface area, sample sizes with smaller cross-sectional surface areas can be taken and the area-specific measurements are adjusted accordingly.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.
All publications, patents, and patent applications cited in this specification are cited to disclose and describe the methods and/or materials in connection with which the publications are cited. All such publications, patents, and patent applications are herein incorporated by references as if each individual publication or patent were specifically and individually indicated to be incorporated by reference. Such incorporation by reference is expressly limited to the methods and/or materials described in the cited publications, patents, and patent applications and does not extend to any lexicographical definitions from the cited publications, patents, and patent applications. Any lexicographical definition in the publications, patents, and patent applications cited that is not also expressly repeated in the instant specification should not be treated as such and should not be read as defining any terms appearing in the accompanying claims.
This disclosure is not limited to particular aspects, embodiments, or examples described, and as such may, of course, vary. The terminology used herein serves the purpose of describing particular aspects, embodiments, and examples only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.
Where a range of values is provided, each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.
As will be apparent to those of skill in the art upon reading this disclosure, each of the individual aspects, embodiments and examples described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several aspects, embodiments and examples without departing from the scope or spirit of the present disclosure. Any recited method may be carried out in the order of events recited or in any other order that is logically possible.
Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. Functions or constructions well-known in the art may not be described in detail for brevity and/or clarity. Aspects of the present disclosure will employ, unless otherwise indicated, techniques of nanotechnology, organic chemistry, materials science and engineering and the like, which are within the skill of the art. Such techniques are explained fully in the literature.
It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’. The range can also be expressed as an upper limit, e.g. ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘less than x’, less than y′, and ‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y′, and ‘greater than z’. In addition, the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1 percent to 5 percent” should be interpreted to include not only the explicitly recited values of about 0.1 percent to about 5 percent, but also include individual values (e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges (e.g., 0.5 percent, 1.1 percent, 2.4 percent, 3.2 percent, and 4.4 percent) within the indicated range.
The term “providing,” as used herein and as recited in the claims, is not intended to require any particular delivery or receipt of the provided item. Rather, the term “providing” is merely used to recite items that will be referred to in subsequent elements of the claim(s), for purposes of clarity and ease of readability.
As used herein, the term “polymer” refers to a chemical compound formed of a plurality of repeating structural units referred to as monomers. Polymers often are formed by a polymerization reaction in which the plurality of structural units become covalently bonded together. When the monomer units forming the polymer all have the same chemical structure, the polymer is a homopolymer. When the polymer includes two or more monomer units having different chemical structures, the polymer is a copolymer. One example of a type of copolymer is a terpolymer, which includes three different types of monomer units. The co-polymer can include two or more different monomers randomly distributed in the polymer (e.g., a random co-polymer). Alternatively, one or more blocks containing a plurality of a first type of monomer can be bonded to one or more blocks containing a plurality of a second type of monomer, forming a block copolymer. A single monomer unit can include one or more different chemical functional groups.
Polymers having repeating units which include two or more types of chemical functional groups can be referred to as having two or more segments. For example, a polymer having repeating units of the same chemical structure can be referred to as having repeating segments. Segments are commonly described as being relatively harder or softer based on their chemical structures, and it is common for polymers to include relatively harder segments and relatively softer segments bonded to each other in a single monomeric unit or in different monomeric units. When the polymer includes repeating segments, physical interactions or chemical bonds can be present within the segments or between the segments or both within and between the segments. Examples of segments often referred to as hard segments include segments including a urethane linkage, which can be formed from reacting an isocyanate with a polyol to form a polyurethane. Examples of segments often referred to as soft segments include segments including an alkoxy functional group, such as segments including ether or ester functional groups, and polyester segments. Segments can be referred to based on the name of the functional group present in the segment (e.g., a polyether segment, a polyester segment), as well as based on the name of the chemical structure which was reacted in order to form the segment (e.g., a polyol-derived segment, an isocyanate-derived segment). When referring to segments of a particular functional group or of a particular chemical structure from which the segment was derived, it is understood that the polymer can contain up to 10 mole percent of segments of other functional groups or derived from other chemical structures. For example, as used herein, a polyether segment is understood to include up to 10 mole percent of non-polyether segments.
The terms “Material Sampling Procedure”, “Plaque Sampling Procedure”, “Cold Ross Flex Test”, “ASTM D 5963-97a”, and “Differential Scanning calorimeter (DSC) Test” as used herein refer to the respective sampling procedures and test methodologies described in the Property Analysis and Characterization Procedure section. These sampling procedures and test methodologies characterize the properties of the recited materials, films, articles and components, and the like, and are not required to be performed as active steps in the claims.
The term “about,” as used herein, can include traditional rounding according to significant figures of the numerical value. In some aspects, the term about is used herein to mean a deviation of 10 percent, 5 percent, 2.5 percent, 1 percent, 0.5 percent, 0.1 percent, 0.01 percent, or less from the specified value.
The articles “a” and “an,” as used herein, mean one or more when applied to any feature in aspects of the present disclosure described in the specification and claims. The use of “a” and “an” does not limit the meaning to a single feature unless such a limit is specifically stated. The article “the” preceding singular or plural nouns or noun phrases denotes a particular specified feature or particular specified features and may have a singular or plural connotation depending upon the context in which it is used.
Unless otherwise indicated, any of the functional groups or chemical compounds described herein can be substituted or unsubstituted. A “substituted” group or chemical compound, such as an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxyl, ester, ether, or carboxylic ester refers to an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxyl, ester, ether, or carboxylic ester group, has at least one hydrogen radical that is substituted with a non-hydrogen radical (i.e., a substituent). Examples of non-hydrogen radicals (or substituents) include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ether, aryl, heteroaryl, heterocycloalkyl, hydroxyl, oxy (or oxo), alkoxyl, ester, thioester, acyl, carboxyl, cyano, nitro, amino, amido, sulfur, and halo. When a substituted alkyl group includes more than one non-hydrogen radical, the substituents can be bound to the same carbon or two or more different carbon atoms.
The term “heteroalkyl” as used herein refers to an alkyl group containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P and S, wherein the nitrogen, phosphorous and sulfur atoms are optionally oxidized, and the nitrogen heteroatom is optionally quaternized.
As used herein, the term “weight” refers to a mass value, such as having the units of grams, kilograms, and the like. Further, the recitations of numerical ranges by endpoints include the endpoints and all numbers within that numerical range. For example, a concentration ranging from 40 percent by weight to 60 percent by weight includes concentrations of 40 percent by weight, 60 percent by weight, and all water uptake capacities between 40 percent by weight and 60 percent by weight (e.g., 40.1 percent, 41 percent, 45 percent, 50 percent, 52.5 percent, 55 percent, 59 percent, etc.).
As used herein, the term “providing”, such as for “providing a structure”, when recited in the claims, is not intended to require any particular delivery or receipt of the provided item. Rather, the term “providing” is merely used to recite items that will be referred to in subsequent elements of the claim(s), for purposes of clarity and ease of readability.
As used herein, the phrase “consist essentially of” or “consisting essentially of” refer to the feature being disclosed as having primarily the listed feature without other active components (relative to the listed feature) and/or those that do not materially affect the characteristic(s) of the listed feature. For example, the elastomeric material can consist essentially of a polymeric hydrogel, which means that second composition can include fillers, colorants, etc. that do not substantially interact with or interact with the change the function or chemical characteristics of the polymeric hydrogel. In another example, the polymeric hydrogel can consist essentially of a polycarbonate hydrogel, which means that the polymeric hydrogel does not include a substantial amount or any amount of another type of polymer hydrogel such as a polyetheramide hydrogel or the like.
As used herein, the terms “at least one” and “one or more of” an element are used interchangeably, and have the same meaning that includes a single element and a plurality of the elements, and may also be represented by the suffix “(s)” at the end of the element. For example, “at least one polyurethane”, “one or more polyurethanes”, and “polyurethane(s)” may be used interchangeably and have the same meaning.
A random copolymer of propylene with about 2.2 percent by weight (wt. percent) ethylene is commercially available under the tradename “PP9054” from ExxonMobil Chemical Company, Houston, Tex. It has a MFR (ASTM-1238D, 2.16 kilograms, 230 degrees Celsius.) of about 12 grams per 10 minutes and a density of 0.90 grams per cubic centimeter (g/cm3).
PP9074 is a random copolymer of propylene with about 2.8 percent by weight (wt. percent) ethylene and is commercially available under the tradename “PP9074” from ExxonMobil Chemical Company, Houston, Tex. It has an MFR (ASTM-1238D, 2.16 kilograms, 230 degrees Celsius.) of about 24 grams per 10 minutes and a density of 0.90 grams per cubic centimeter (g/cm3).
PP1024E4 is a propylene homopolymer commercially available under the tradename “PP1024E4” from ExxonMobil Chemical Company, Houston, Tex. It has an MFR (ASTM-1238D, 2.16 kilograms, 230 degrees Celsius.) of about 13 grams per 10 minutes and a density of 0.90 grams per cubic centimeter (g/cm3).
VISTAMAXX 6202 is a copolymer primarily composed of isotactic propylene repeat units with about 15 percent by weight (wt. percent) of ethylene repeat units randomly distributed along the copolymer. It is a metallocene catalyzed copolymer available under the tradename “VISTAMAXX 6202” from ExxonMobil Chemical Company, Houston, Tex. and has an MFR (ASTM-1238D, 2.16 kilograms, 230 degrees Celsius.) of about 20 grams per 10 minutes, a density of 0.862 grams per cubic centimeter (g/cm3), and a Durometer Hardness of about 64 (Shore A).
VISTAMAXX 3000 is a copolymer primarily composed of isotactic propylene repeat units with about 11 percent by weight (wt. percent) of ethylene repeat units randomly distributed along the copolymer. It is a metallocene catalyzed copolymer available from ExxonMobil Chemical Company and has an MFR (ASTM-1238D, 2.16 kilograms, 230 degrees Celsius.) of about 8 grams per 10 minutes, a density of 0.873 grams per cubic centimeter (g/cm3), and a Durometer Hardness of about 27 (Shore D).
VISTAMAXX 6502 is a copolymer primarily composed of isotactic propylene repeat units with about 13 percent by weight of ethylene repeat units randomly distributed along the copolymer. It is a metallocene catalyzed copolymer available from ExxonMobil Chemical Company and has an MFR (ASTM-1238D, 2.16 kilograms, 230 degrees Celsius.) of about 45 grams per 10 minutes, a density of 0.865 grams per cubic centimeter (g/cm3), and a Durometer Hardness of about 71 (Shore A).
This application claims the benefit of U.S. Provisional Application No. 63/052,740 filed on Jul. 16, 2020, which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 63052740 | Jul 2020 | US |
