U.S. patent application number 17/373075 was filed with the patent office on 2022-01-20 for sole structures including composite elements and articles of footwear formed therefrom.
The applicant listed for this patent is NIKE, Inc.. Invention is credited to Jay Constantinou, Isaac Farr, Jeremy D. Walker, Zachary C. Wright.
Application Number | 20220015505 17/373075 |
Document ID | / |
Family ID | 1000005712200 |
Filed Date | 2022-01-20 |
United States Patent
Application |
20220015505 |
Kind Code |
A1 |
Constantinou; Jay ; et
al. |
January 20, 2022 |
SOLE STRUCTURES INCLUDING COMPOSITE ELEMENTS AND ARTICLES OF
FOOTWEAR FORMED THEREFROM
Abstract
Disclosed herein is a composite element comprising a textile and
a hydrogel layer comprising a hydrogel material that is operably
coupled to the textile, wherein a portion of the hydrogel layer
extends through a first side of the textile, and at least partially
into a core of the textile, but does not extend onto a second side
of the textile. Also disclosed are sole structures and articles of
athletic footwear incorporating the composite element, as well as
methods of manufacturing such composite elements, sole structures,
and articles of footwear.
Inventors: |
Constantinou; Jay;
(Beaverton, OR) ; Farr; Isaac; (Beaverton, OR)
; Walker; Jeremy D.; (Portland, OR) ; Wright;
Zachary C.; (Beaverton, OR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NIKE, Inc. |
Beaverton |
OR |
US |
|
|
Family ID: |
1000005712200 |
Appl. No.: |
17/373075 |
Filed: |
July 12, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
63052740 |
Jul 16, 2020 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A43B 13/226 20130101;
A43B 13/189 20130101 |
International
Class: |
A43B 13/22 20060101
A43B013/22; A43B 13/18 20060101 A43B013/18 |
Claims
1. A sole structure for an article of footwear, the sole structure
comprising: a composite element and a sole component; wherein the
composite element comprises a textile and a hydrogel layer; the
textile comprises a textile material and has a first side, a second
side, and a core located between the first side and the second
side; the hydrogel layer comprises a hydrogel material and has a
first side and a second side 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; wherein at least a
portion of the first side of the hydrogel layer provides a first
ground-facing surface of the sole structure; and wherein the sole
component comprises a second polymeric material and has 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 textile.
2. The sole structure of claim 1, 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.
3. The sole structure of claim 1, wherein the textile, before its
first side is operably coupled with the hydrogel layer, is an
air-permeable textile.
4. The sole structure of claim 1, wherein the hydrogel material is
a thermoplastic hydrogel material, and the textile material has a
textile material melting temperature or a first textile material
Vicat softening temperature that is at least 20 degrees Celsius
greater than a melting temperature or Vicat softening temperature
of the thermoplastic hydrogel material of the hydrogel layer.
5. The sole structure of claim 1, wherein the hydrogel layer
penetrates at least 10 percent of the core thickness of the
textile.
6. The sole structure of claim 1, wherein the hydrogel layer
penetrates less than 90 percent of the core thickness of the
textile.
7. The sole structure of claim 1, wherein the textile comprises a
non-woven textile.
8. The sole structure of claim 1, wherein the textile has a basis
weight of about 5 to about 500 grams/meter squared.
9. The sole structure of claim 1, wherein the hydrogel layer has a
dry-state thickness ranging from 0.1 millimeters (mm) to 2 mm.
10. The sole structure of claim 1, wherein the hydrogel material is
a thermoplastic hydrogel material, and the thermoplastic 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.
11. The sole structure of claim 1, wherein the hydrogel material
comprises a polyurethane hydrogel.
12. The sole structure of claim 1, wherein the sole component
comprises one or more traction elements.
13. The sole structure of claim 1, wherein the second polymeric
material comprises a polyoefin.
14. An article of footwear comprising an upper operably coupled
with the sole structure of claim 1.
15. A method of making a sole structure for an article of footwear,
the method comprising: operably coupling a first composite element
to a second component; the first 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
sole structure, 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 a ground-facing surface of
the sole structure.
16. The method of claim 15, 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 the sole structure
comprising the hydrogel layer of the composite element defining at
least a portion of the ground-facing surface of the sole structure;
and removing the sole structure from the mold.
17. The method of claim 16, 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.
18. The method of claim 15 wherein a) 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
wherein b) the textile, before its first side is operably coupled
with the hydrogel layer, is an air-permeable textile; or wherein
both a) and b).
19. A sole structure manufactured according to the method of claim
15.
20. 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.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] 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.
BACKGROUND
[0002] 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.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] 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.
[0004] FIG. 1A is a sectional view of a textile, in accordance with
an aspect of the present disclosure.
[0005] FIG. 1B is a sectional view of a composite element in
accordance with an aspect of the present disclosure.
[0006] FIGS. 2A-2I depict an exemplary article of athletic
footwear, in accordance with an aspect of the present disclosure.
FIG. 2A is a lateral side perspective view of the exemplary article
of athletic footwear. FIG. 2B is a lateral side elevational view of
the exemplary article of athletic footwear. FIG. 2C is a medial
side elevational view of the exemplary article of athletic
footwear. FIG. 2D is a top view of the exemplary article of
athletic footwear. FIG. 2E is a front view of the exemplary article
of athletic footwear. FIG. 2F is a rear view of the exemplary
article of athletic footwear. FIG. 2G is an exploded perspective
view of the exemplary article of athletic footwear. FIG. 2H is an
exploded perspective view of a sole structure of an exemplary
article of athletic footwear. FIG. 2I is a sectional view along 2-2
of the exemplary article of footwear.
[0007] FIG. 2J is a sectional view of a composite element combined
with a plate, in accordance with an aspect of the present
disclosure.
[0008] FIG. 2K is a bottom view of a plate with traction elements
in accordance with an aspect of the present disclosure.
[0009] FIG. 3A is a bottom side view of various components of a
composite element and sole structure according to an aspect of the
present disclosure.
[0010] FIG. 3B is a bottom side view of various components of a
composite element and sole structure according to an aspect of the
present disclosure.
[0011] FIG. 3C is a bottom side view of various components of a
composite element and sole structure according to an aspect of the
present disclosure.
[0012] FIG. 4 is a bottom view of some exemplary outsoles decorated
with printed and non-printed nonwoven textiles according to an
aspect of the present disclosure.
DETAILED DESCRIPTION
[0013] 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.
[0014] 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.
[0015] 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.
[0016] 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.
[0017] The present disclosure can be described in accordance with
the following numbered aspects, which should not be confused with
the claims.
[0018] In accordance with Aspect 1, the present disclosure is
directed to a composite element comprising:
[0019] 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;
[0020] 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;
[0021] 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.
[0022] 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.
[0023] 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.
[0024] 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.
[0025] 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.
[0026] 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.
[0027] 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.
[0028] 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.
[0029] 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.
[0030] 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.
[0031] 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.
[0032] 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;
[0033] wherein the wet state glass transition temperature is more
than 6 degrees Celsius lower than the dry-state glass transition
temperature.
[0034] 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;
[0035] wherein the wet-state storage modulus is less than the
dry-state storage modulus of the hydrogel material.
[0036] 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.
[0037] 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.
[0038] 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.
[0039] 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.
[0040] 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.
[0041] 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.
[0042] 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.
[0043] In accordance with Aspect 21, the present disclosure is
directed to an article comprising:
[0044] a composite element comprising:
[0045] 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;
[0046] 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;
[0047] 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;
[0048] wherein at least a portion of the first side of the hydrogel
layer provides a first externally-facing surface of the article;
and
[0049] 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.
[0050] 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.
[0051] 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.
[0052] In accordance with Aspect 24, the present disclosure is
directed to a sole structure for an article of footwear, the sole
structure comprising:
[0053] a composite element comprising:
[0054] 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;
[0055] 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;
[0056] 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;
[0057] wherein at least a portion of the first side of the hydrogel
layer provides a first ground-facing surface of the sole structure;
and
[0058] 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.
[0059] 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.
[0060] 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.
[0061] 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.
[0062] 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.
[0063] 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.
[0064] 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.
[0065] 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.
[0066] 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.
[0067] 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.
[0068] 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 (cm.sup.3) to about 0.1 cubic
centimeters (cm.sup.3), about 0.07 cubic centimeters (cm.sup.3) to
about 0.1 cubic centimeters (cm.sup.3), about 0.08 cubic
centimeters (cm.sup.3) to about 0.1 cubic centimeters (cm.sup.3),
or about 0.08 cubic centimeters (cm.sup.3) to about 0.11 cubic
centimeters (cm.sup.3) pursuant to ASTM D 5963-97a using the Neat
Material Sampling Procedure.
[0069] 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.
[0070] 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.
[0071] 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.
[0072] 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
##STR00001##
[0073] 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
##STR00002##
[0074] where R.sup.1 is a hydrogen or a substituted or
unsubstituted, linear or branched, C.sub.1-C.sub.12 alkyl or
heteroalkyl.
[0075] 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.
[0076] 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.
[0077] 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
##STR00003##
[0078] 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
##STR00004##
[0079] where R.sup.1 is a hydrogen or a substituted or
unsubstituted, linear or branched, C.sub.2-C.sub.12 alkyl or
heteroalkyl.
[0080] 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.
[0081] 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.
[0082] 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.
[0083] 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.
[0084] 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
##STR00005##
[0085] 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.
[0086] 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-.alpha.-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.
[0087] 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.
[0088] 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.
[0089] 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.
[0090] 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
##STR00006##
[0091] 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.
[0092] 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
##STR00007##
[0093] 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.
[0094] 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
##STR00008##
[0095] 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.
[0096] 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.
[0097] 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.
[0098] 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.
[0099] 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.
[0100] 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.
[0101] 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.
[0102] 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.
[0103] 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.
[0104] 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.
[0105] 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.
[0106] 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.
[0107] 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.
[0108] 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.
[0109] 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.
[0110] 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.
[0111] 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.
[0112] 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.
[0113] 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.degree. 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;
[0114] 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;
[0115] wherein the wet-state storage modulus is less than the
dry-state storage modulus of the hydrogel material; or any
combination thereof.
[0116] 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.
[0117] 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.
[0118] 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.
[0119] 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.
[0120] 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.
[0121] In accordance with Aspect 82, the present disclosure is
directed to a method of making a composite element, the method
comprising:
[0122] operably coupling a hydrogel layer comprising a hydrogel
material with a first side of a textile;
[0123] 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.
[0124] 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.
[0125] 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.
[0126] In accordance with Aspect 85, the present disclosure is
directed to a method of making an article, the method
comprising:
[0127] 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;
[0128] 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.
[0129] 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.
[0130] 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.
[0131] 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.
[0132] 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;
[0133] charging a second polymeric material onto the prepared
molding surface of the mold;
[0134] 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.
[0135] 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.
[0136] 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.
[0137] 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.
[0138] 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.
[0139] 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.
[0140] 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.
[0141] 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.
[0142] 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.
[0143] 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.
[0144] 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.
[0145] 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.
[0146] 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.
[0147] 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.
[0148] 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.
[0149] 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.
[0150] 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.
[0151] 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.
[0152] 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.
[0153] 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.
[0154] 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.
[0155] 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.
[0156] 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.
[0157] 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.
[0158] 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.
[0159] 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.
[0160] In accordance with Aspect 115, the present disclosure is
directed to a method of manufacturing an article of footwear, the
method comprising:
[0161] 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.
[0162] 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:
[0163] 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.
[0164] 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.
[0165] 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.
[0166] 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.
[0167] In accordance with Aspect 120, the present disclosure is
directed to an article of footwear manufactured according to any of
Aspects 115 to 120.
[0168] 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.
[0169] Composite Element
[0170] Referring to FIG. 1A to 1B, in one aspect, a composite
element 110 has a textile 102 and a hydrogel layer 115. The textile
102 includes a textile material and has a first side 106, a second
side 104, and a core 105 between the first side 106 and the second
side 104. The textile comprises one or more polymeric material,
where a polymeric material comprises one or more polymers and
optionally one or more non-polymeric ingredients. The textile
material includes a polymeric component consisting of all the
polymeric ingredients present in the textile material. Before being
coupled with the hydrogel layer 115 the textile layer has a core
thickness 108 that is measured between the first side 106 and
second side 104 of the textile. Referring to FIG. 1B, the hydrogel
layer 115 includes a hydrogel material and has a first side 114 and
a second side 112. The hydrogel layer comprises one or more
hydrogel materials, where a hydrogel material comprises one or more
polymeric hydrogels and optionally one or more non-hydrogel
polymeric ingredients or one or more non-polymeric ingredients or
optionally includes both. The hydrogel material includes a
polymeric component consisting of all the polymeric ingredients
present in the hydrogel material, including polymeric hydrogels and
non-hydrogel polymers. Similarly, the hydrogel material includes a
hydrogel component consisting of all the polymeric hydrogel
ingredients present in the hydrogel material. According to the
aspects, the hydrogel layer 115 is operably coupled to the textile
102 along the first side 106 of the textile 102, so that the
hydrogel layer 115 extends through the first side 106 of the
textile 102 and at least partially into the core 105 of the textile
102, but does not extend all the way through the textile 102. In
some aspects, the hydrogel layer 115 extends through the first side
106 of the textile 102 and at least partially into the core 105 of
the textile 102, but the second side 104 of the textile is
substantially free of the hydrogel material. In still another
aspect, the hydrogel layer 115 extends through the first side 106
of the textile 102 without extending onto or into the second side
104 of the textile 102. Due to the presence of fibers, filaments or
yarns present in the textile, it will be appreciated that both the
first side and the second side of the textile have a level of
surface texture which results in the surface area of the sides of
the textile being greater than the surface area of a side of a
comparable flat (i.e., substantially untextured) film.
[0171] 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.
[0172] 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.
[0173] 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.
[0174] 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.).
[0175] 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.
[0176] Sole Structures and Articles of Footwear Made Therefrom
[0177] 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.
[0178] 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.
[0179] 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.
[0180] 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".
[0181] 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).
[0182] 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.
[0183] Referring to FIG. 2A to 2K, the sole structures and articles
of footwear will be described in more detail with reference to an
exemplary cleated article of athletic footwear 200, for example a
soccer/futbol boot. Article of footwear 200, includes an upper 250
that is operably coupled with sole structure 213. The sole
structure 213 includes a plate 216 and a composite element 210
disposed on at least a portion of a ground-facing side of the sole
structure 213.
[0184] The sole structure 213 is described in more detail with
reference to FIG. 2J. As described herein, composite element 210
includes a textile 202 and a hydrogel layer 215 operably coupled to
a first side 206 of the textile 202. A second side 204 of textile
202 is operably coupled with first, ground-facing side 2162 of
plate 216, resulting in the hydrogel layer 215 providing a first
ground-facing surface 214 of the sole structure 213. A bottom view
of a plate is described in more detail with reference to FIG. 2K.
As described herein, the plate includes ground-facing surface 214
and ground-contacting surfaces 2181.
[0185] 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.
[0186] 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.
[0187] 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.
[0188] 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.
[0189] 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.
[0190] Referring to FIG. 2A, in some aspects, the sole structure
213 includes one or more traction elements, including multiple
traction elements 218. When worn, traction elements 218 provide
traction to a wearer so as to enhance stability. One or more of the
traction elements 218 can be integrally formed with the plate 216,
as illustrated in FIG. 2A, or can be removable. Optionally, one or
more of the traction elements 218 can include a traction element
tip (not pictured) configured to be ground-contacting. The traction
element tip can be integrally formed with the traction element 218.
Optionally, the traction element tip can be formed of a different
material (e.g., a metal, or a polymeric material containing a
harder or more abrasion-resistant polymeric material) than the rest
of the traction element 218. Similarly, a portion of the traction
element such as the tip, or the entire traction element, can be
formed of a different material (e.g., a metal, or a polymeric
material containing a harder or more abrasion-resistant polymeric
material) than the second polymeric material of the plate. FIG. 2B
is a lateral side elevational view of article of footwear 200. When
the article of footwear 200 is worn, the lateral side of the
article 200 is generally oriented on the side facing away from the
centerline of the wearer's body. FIG. 2C is a medial side
elevational view of the article of footwear 200. When the article
of footwear 200 is worn, the medial side generally faces toward the
centerline of the wearer's body. FIG. 2D is a top view of the
article of footwear 200 (with no sock liner in place) and without a
lasting board or other board-like member 215, and further shows
upper 250. Upper 250 includes a padded collar 220. Alternatively,
or in addition, the upper can include a region configured to extend
up to or over a wearer's ankle (not illustrated). In at least one
aspect, upper 250 is tongueless, with the upper wrapping from the
medial side of the wearer's foot, over the top of the foot, and
under the lateral side portion of the upper, as illustrated in FIG.
2D. Alternatively, the article of footwear can include a tongue
(not illustrated). As illustrated in FIG. 2A-2G, the laces of the
article of footwear 200 optionally can be located on the lateral
side of the article. In other examples, the article of footwear may
have a slip-on design or may include a closure system other than
laces (not illustrated). FIG. 2E and FIG. 2F are, respectively,
front and rear elevational views of the article of footwear
200.
[0191] FIG. 2G is an exploded perspective view of the article of
footwear 200 showing upper 250, plate 216, and composite element
210. As seen in FIG. 2D, upper 250 includes a strobel 138. As
illustrated in FIG. 2D, the strobel 238 is roughly the shape of a
wearer's foot, and closes the bottom of the upper 250, and is
stitched to other components to form the upper 250 along the
periphery of the strobel 238 with stitching 285. A lasting board or
other board-like member (not illustrated) can be located above or
below the strobel 238. In some aspects, a lasting board or other
board-like member can replace the strobel. The lasting board or
other board-like member can extend substantially the entire length
of the plate, or can be present in a portion of the length of the
plate, such as, for example, in the toe region, or in the midfoot
region, or in the heel region. Upper 250 including strobel 238 is
bonded to the upper surface of the sole structure 213 (not shown).
FIG. 2H is an exploded perspective view of an alternative
embodiment of a composite element 2101 which includes a toe portion
2021, a medial portion 2022, and a heel portion 2023 of a textile
layer of a composite element and a toe portion 2151, a medial
portion 2152, and a heel portion 2153 of a hydrogel layer of a
composite element.
[0192] 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.
[0193] 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.
[0194] 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.
[0195] 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).
[0196] 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.
[0197] 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.
[0198] Referring now to FIGS. 3A-3B, a composite element 300 is
shown after cutting or molding during manufacturing. The cutting or
molding step can be configured to provide one or more holes or
voids (e.g., 302, 308) that fit around one or more traction
elements and provide a substantially contiguous region of the
composite element along at least a portion of the outsole of an
article of footwear. Also shown are exemplary outsole components
304 containing traction elements 306 that can be coupled to
composite element 300 during manufacturing.
[0199] 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.
[0200] 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.
[0201] 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.
[0202] 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.
[0203] 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.
[0204] 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.
[0205] 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.
[0206] 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.
[0207] Decorative Features
[0208] 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.
[0209] FIG. 4 shows exemplary sole structures according to one
aspect of the current disclosure, where the ground facing-side of
the sole structures are decorated with a textile. The textile may
be printed or decorated with a pattern or image (left) or may be
undecorated (center, right).
[0210] Properties of the Composite Element and Sole Structures
[0211] 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.
[0212] 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.
[0213] Disruption of Soil Adhesion
[0214] 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).
[0215] 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.
[0216] Water Uptake and Swelling
[0217] 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.
[0218] 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.
[0219] 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.
[0220] 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.
[0221] 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 (.about.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.
[0222] 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
(.about.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.
[0223] 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.
[0224] 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/m.sup.2/ min to 120 g/m.sup.2/ 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 (m.sup.2) of the sample
over the square root of the soaking time ( min). Alternatively, the
water uptake rate can range from about 12 g/m.sup.2/ min to about
100 g/m.sup.2/ min; alternatively, from about 20 g/m.sup.2/ min to
about 90 g/m.sup.2/ min; alternatively, up to about 60 g/m.sup.2/
min.
[0225] 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.
[0226] 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.
[0227] Hydrophilic Properties of the Composite Element
[0228] 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.
[0229] 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.
[0230] 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.
[0231] 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.
[0232] 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 (.DELTA.E') 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.
[0233] 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.
[0234] 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.
[0235] 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.
[0236] 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).
[0237] The polymeric hydrogel and/or the hydrogel material of the
hydrogel layer of the composite element can exhibit a reduction in
glass transition temperature (.DELTA.T.sub.g) 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.
[0238] 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.
[0239] 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.
[0240] 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.
[0241] 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.
[0242] 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).
[0243] 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.
[0244] Textile
[0245] 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.
[0246] 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.
[0247] 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).
[0248] 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.
[0249] 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.
[0250] 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.
[0251] 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.
[0252] 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.
[0253] 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.
[0254] 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.
[0255] 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.
[0256] 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.
[0257] 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.
[0258] 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).
[0259] 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.
[0260] 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.
[0261] 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.
[0262] 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.
[0263] 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.
[0264] 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
(T.sub.m) Test Protocol and the Vicat softening temperature can be
determined using the Vicat Softening Temperature (T.sub.vs) Test
Protocol using the Material Sampling Procedure, the Plaque Sampling
Procedure, and the Component Sampling Procedure described
herein.
[0265] 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.
[0266] 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.
[0267] Polymeric Hydrogels, Hydrogel Materials, and Hydrogel
Layers
[0268] 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.
[0269] 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.
[0270] 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.
[0271] 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.
##STR00009##
[0272] 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.
[0273] 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.
[0274] 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.
[0275] 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.
[0276] 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.
[0277] 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).
[0278] 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.
[0279] 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.
[0280] 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.
[0281] 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.
[0282] 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.
[0283] Plate
[0284] 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.
[0285] 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.
[0286] 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-.alpha.-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.
[0287] 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.
[0288] 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.
[0289] 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.
##STR00010##
[0290] In some aspects, the polyolefin copolymer includes a
plurality of repeat units each individually having a structure
according to Formula 2
##STR00011##
[0291] where R.sup.1 is a hydrogen or a substituted or
unsubstituted, linear or branched, C.sub.1-C.sub.12 alkyl.
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.12
heteroalkyl, C.sub.1-C.sub.6 heteroalkyl, or C.sub.1-C.sub.3
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.
[0292] 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.
[0293] 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.
[0294] 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.
[0295] 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.
[0296] 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.
[0297] 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.
[0298] 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.
[0299] 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.
[0300] 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.
[0301] 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.
[0302] 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.
[0303] 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.
[0304] 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.
[0305] Polymeric Material
[0306] 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).
[0307] 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.
[0308] 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.
[0309] 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.
[0310] 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.
[0311] Polyolefins
[0312] 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 .alpha.-olefins having 4 to about 8 carbon atoms). In
a further aspect, the thermoplastic polyolefin is a polymer
comprising a polyethylene, an ethylene-.alpha.-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.
[0313] 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.
[0314] 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.
[0315] 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.
[0316] Suitable ethylene-.alpha.-olefin copolymers can be obtained
by copolymerization of ethylene with an .alpha.-olefin such as
propylene, butene-1, hexene-1, octene-1,4-methyl-1-pentene or the
like having carbon numbers of 3 to 12.
[0317] 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.
[0318] 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).
[0319] 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.
[0320] 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.
[0321] 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).
[0322] 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).
[0323] Polyurethanes
[0324] 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.
[0325] 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.
[0326] Each isoncyanate-derived segment of the polyurethane of the
can independently include a linear or branched C.sub.3-30 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.
[0327] 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.
[0328] 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 C.sub.3-20 alkylene segment (e.g.,
C.sub.4-15 alkylene or C.sub.6-10 alkylene), one or more C.sub.3-8
cycloalkylene segments (e.g., cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, or cyclooctyl), and combinations
thereof.
[0329] 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.
[0330] 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
C.sub.2-C.sub.10 linear aliphatic diisocyanate segments.
[0331] In aromatic embodiments (from aromatic isocyanate(s)), each
segment R.sub.1 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.
[0332] 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.
[0333] In particular aspects, the polyurethane polymer chains are
produced from diisocynates including HMDI, TDI, MDI, H.sub.12
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, H.sub.12
aliphatics, and combinations thereof.
[0334] 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.
[0335] A portion of the isocyanate-derived segment can include a
linear or branched C.sub.2-C.sub.10 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.
[0336] 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.
[0337] 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 C.sub.n 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.
[0338] 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.
[0339] 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.
[0340] In various examples, the aliphatic group is linear and can
include, for example, a 01-20 alkylene chain or a C.sub.1-20
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
C.sub.n means the alkylene group has "n" carbon atoms. For example,
C.sub.1-6 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.
[0341] 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).
[0342] 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.
[0343] 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).
[0344] Polyamides
[0345] 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.
[0346] 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.
[0347] 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.
[0348] 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.
[0349] 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.
[0350] 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.
[0351] Examples of poly(ether block amide) polymers include those
comprising polyamide blocks comprising dicarboxylic chain ends
derived from the condensation of .alpha., .omega.-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 .alpha., .omega.-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.
[0352] 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.
[0353] 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 T.sub.mG blocks,
i.e. those consisting of tetramethylene glycol units, also known as
polytetrahydrofuran. PPG or P T.sub.mG 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.
[0354] 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.
[0355] 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.
[0356] 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.
[0357] Polyesters
[0358] 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.
[0359] 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.
[0360] 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.
[0361] 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.
[0362] 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.
[0363] 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.
[0364] 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.
[0365] In some aspects, the thermoplastic polyester is a
biodegradable resin, for example, a copolymerized polyester in
which poly(.alpha.-hydroxy acid) such as polyglycolic acid or
polylactic acid is contained as principal repeating units.
[0366] 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.
[0367] Resin Modifier
[0368] 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.
[0369] 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.
[0370] 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.
[0371] 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.
[0372] Clarifying Agent
[0373] 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.
[0374] Methods of Making Polymeric Materials
[0375] 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.
[0376] 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.
[0377] 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.
[0378] 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.
[0379] 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.
[0380] Additional Ingredients
[0381] 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.
[0382] Adhesive Materials
[0383] 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.
[0384] 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.
[0385] 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.
[0386] 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.
[0387] Methods of Making a Composite Element
[0388] 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.
[0389] 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.
[0390] 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.
[0391] 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.
[0392] 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.
[0393] Methods of Making the Sole Structures
[0394] 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.
[0395] 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.
[0396] 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.
[0397] 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.
[0398] 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.
[0399] 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.
[0400] 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).
[0401] 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.
[0402] 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.
[0403] Methods of Making Components and Articles
[0404] 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.
[0405] 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.
[0406] 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.
[0407] 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.
[0408] 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.
[0409] 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.
[0410] 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.
[0411] 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.
[0412] 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.
[0413] 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.
[0414] 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.
[0415] 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.
[0416] 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.
[0417] 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.
[0418] 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.
[0419] 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.
[0420] Property Analysis and Characterization Procedures
[0421] Cold Ross Flex Test Protocol
[0422] 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
T.sub.m 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.
[0423] Abrasion Loss Test Protocol ASTM D 5963-97a
[0424] 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/cm.sup.3). The smaller the abrasion
loss volume, the better the abrasion resistance.
[0425] Mud Pull Off Test Protocol
[0426] 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.
[0427] Crystallinity Test Protocol
[0428] 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.
[0429] Creep Relation Temperature T.sub.cr Test Protocol
[0430] The creep relation temperature T.sub.cr 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 T.sub.cr 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).
[0431] Vicat Softening Temperature T.sub.vs Test Protocol
[0432] The Vicat softening temperature T.sub.vs 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.
[0433] Heat Deflection Temperature T.sub.hd Test Protocol
[0434] The heat deflection temperature T.sub.hd 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''.times.1/2''.times.1/4''. ISO edgewise testing uses a bar 120
millimeters.times.10 millimeters.times.4 millimeters. ISO flatwise
testing uses a bar 80 millimeters.times.10 millimeters.times.4
millimeters.
[0435] Melting Temperature, Glass Transition Temperature, and
Enthalpy of Melting Test Protocol
[0436] 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.
[0437] Melt Flow Index Test Protocol
[0438] 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.
[0439] Durometer Hardness Test Protocol
[0440] 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.
[0441] Flexural Modulus Test Protocol
[0442] 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.
[0443] Modulus Test Protocol
[0444] 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.
[0445] Water Uptake Capacity Test Protocol
[0446] 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 (Wt.sub.sample 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 (Wt.sub.sample wet) is measured in grams.
[0447] 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.
[0448] As can be appreciated, the total weight of a sample includes
the weight of the material as dried or soaked (Wt.sub.sample dry or
Wt.sub.sample wet) and the weight of the substrate
(Wt,.sub.substrate) needs to be subtracted from the sample
measurements.
[0449] The weight of the substrate (Wt.sub.substrate) is calculated
using the sample surface area (e.g., 4.0 cm.sup.2), 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
(Wt.sub.substrate) 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,.sub.substrate) is then
measured in grams.
[0450] The resulting substrate weight (Wt.sub.substrate) is then
subtracted from the weights of the dried and soaked primary sample
(Wt.sub.sample dry or Wt.sub.sample wet) to provide the weights of
the material as dried and soaked (Wt.sub.component dry or
Wt.sub.component wet) as depicted by Equations 1 and 2.
Wt.sub.component dry=Wt.sub.sample dry-Wt.sub.substrate (Eq. 1)
Wt.sub.component wet=Wt.sub.sample wet-Wt.sub.substrate (Eq. 2)
[0451] The weight of the dried component (Wt.sub.component dry) is
then subtracted from the weight of the soaked component
(Wt.sub.component 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 (Wt.sub.component dry) to provide the water
uptake capacity for the given soaking duration as a percentage, as
depicted below by Equation 3.
Water .times. .times. Uptake .times. .times. Capacity = W .times. t
component .times. .times. wet - W .times. t component .times.
.times. dry W .times. t component .times. .times. dry .times. ( 100
.times. .times. percent ) ( Eq . .times. 3 ) ##EQU00001##
[0452] 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.
[0453] Water Uptake Rate Test Protocol
[0454] 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 (Wt.sub.sample 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.
[0455] 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 (Wt.sub.sample wet) is measured, where
"t" refers to the particular soaking-duration data point (e.g., 1,
2, 4, 9, 16, or 25 minutes).
[0456] 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.
[0457] 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).
[0458] 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 (Wt.sub.component wet or Wt.sub.component dry) and
the weight of the article or backing substrate (Wt.sub.substrate).
In order to determine a weight change of the material due to water
uptake, the weight of the substrate (Wt.sub.substrate) 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
Wt.sub.component wet and Wt.sub.component dry for each
soaking-duration measurement.
[0459] The specific weight gain (Ws.sub.t) from water uptake for
each soaked sample is then calculated as the difference between the
weight of the soaked sample (Wt.sub.component wet) and the weight
of the initial dried sample (Wt.sub.component dry) where the
resulting difference is then divided by the exposed surface area of
the soaked sample (.DELTA..sub.t) as depicted in Equation 4.
( W .times. s t ) = Wt component .times. .times. wet - Wt component
.times. .times. dry A t ( Eq . .times. 4 ) ##EQU00002##
[0460] where t refers to the particular soaking-duration data point
(e.g., 1, 2, 4, 9, 16, or 25 minutes), as mentioned above.
[0461] The water uptake rate for the material is then determined as
the slope of the specific weight gains (Ws.sub.t) 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 (Ws.sub.t) 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.
[0462] 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 (meter.sup.2-minutes.sup.1/2) or
g/m.sup.2/ min.
[0463] 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/m.sup.2/ min.
[0464] Swelling Capacity Test Protocol
[0465] 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.
[0466] 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.
[0467] 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.
[0468] Contact Angle Test Protocol
[0469] 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.
[0470] 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.
[0471] 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.
[0472] Coefficient of Friction Test Protocol
[0473] 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.
[0474] 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.times.66.6 millimeters, or 5,100
square millimeters).
[0475] 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.
[0476] 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.
[0477] Storage Modulus Test Protocol
[0478] 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.
[0479] 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.
[0480] 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.
[0481] 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.
[0482] 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.
[0483] Sampling Procedures
[0484] 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:
[0485] Material Sampling Procedure
[0486] 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.
[0487] Plaque Sampling Procedure and Film Sampling Procedure
[0488] 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.
[0489] Component Sampling Procedure
[0490] 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.
[0491] 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.
[0492] 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 (cm.sup.2) 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.
Definitions
[0493] 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.
[0494] 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.
[0495] 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.
[0496] 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.
[0497] 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.
[0498] 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.
[0499] 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.
[0500] 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.
[0501] 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.
[0502] 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.
[0503] 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.
[0504] 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.
[0505] 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.
[0506] 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.
[0507] 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.
[0508] 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.).
[0509] 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.
[0510] 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.
[0511] 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.
[0512] 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/cm.sup.3).
[0513] 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/cm.sup.3).
[0514] 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/cm.sup.3).
[0515] 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/cm.sup.3), and a Durometer
Hardness of about 64 (Shore A).
[0516] 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/cm.sup.3), and a
Durometer Hardness of about 27 (Shore D).
[0517] 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/cm.sup.3), and a Durometer
Hardness of about 71 (Shore A).
* * * * *