U.S. patent application number 16/165476 was filed with the patent office on 2019-04-25 for materials, methods of making, methods of use, and articles incorporating the materials.
The applicant listed for this patent is NIKE, Inc.. Invention is credited to JAY CONSTANTINOU, CALEB W. DYER, JEREMY D. WALKER, ZACHARY C. WRIGHT.
Application Number | 20190116927 16/165476 |
Document ID | / |
Family ID | 64427190 |
Filed Date | 2019-04-25 |
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United States Patent
Application |
20190116927 |
Kind Code |
A1 |
CONSTANTINOU; JAY ; et
al. |
April 25, 2019 |
MATERIALS, METHODS OF MAKING, METHODS OF USE, AND ARTICLES
INCORPORATING THE MATERIALS
Abstract
The present disclosure is directed to uncured compositions that
comprise a mixture of an uncured rubber with a polymeric hydrogel
which, when cured to form crosslinks in the rubber, form
elastomeric materials. The present disclosure is also directed to
methods of using the uncured compositions and the elastomeric
materials. The elastomeric materials can be used to make and/or
incorporated into various types of articles (e.g., footwear,
apparel, sporting equipment, or components of each).
Inventors: |
CONSTANTINOU; JAY;
(Beaverton, OR) ; DYER; CALEB W.; (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: |
64427190 |
Appl. No.: |
16/165476 |
Filed: |
October 19, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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62574262 |
Oct 19, 2017 |
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62693740 |
Jul 3, 2018 |
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62703513 |
Jul 26, 2018 |
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62743380 |
Oct 9, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A41D 2400/62 20130101;
B32B 2437/04 20130101; A43B 13/189 20130101; A43B 13/223 20130101;
A43B 13/04 20130101; A41D 19/0006 20130101; B29D 35/142 20130101;
B32B 3/266 20130101; B32B 2266/122 20161101; B29K 2021/00 20130101;
B29K 2105/0061 20130101; B60C 1/00 20130101; A42B 1/02 20130101;
B32B 2319/00 20130101; B32B 2437/02 20130101; A45F 3/04 20130101;
B32B 2307/73 20130101; B32B 25/08 20130101; A41D 19/0082 20130101;
A41D 19/015 20130101; A43B 5/02 20130101; B32B 2307/728 20130101;
B29D 35/122 20130101; B32B 27/40 20130101; A43B 1/0027 20130101;
A43B 13/122 20130101; A43C 15/16 20130101; B32B 25/042 20130101;
A43B 1/10 20130101; A43B 13/22 20130101; A41D 31/02 20130101 |
International
Class: |
A43B 13/04 20060101
A43B013/04; A43B 13/22 20060101 A43B013/22; A41D 31/02 20060101
A41D031/02; A43C 15/16 20060101 A43C015/16; A43B 5/02 20060101
A43B005/02; A43B 13/12 20060101 A43B013/12; B32B 25/08 20060101
B32B025/08; B29D 35/14 20060101 B29D035/14 |
Claims
1. An outsole comprising: an outsole including a first elastomeric
material; wherein the first elastomeric material forms a first
portion of an externally-facing side of the outsole; wherein the
first elastomeric material includes a mixture of a first cured
rubber and a first polymeric hydrogel at a first concentration, in
which the first polymeric hydrogel is distributed throughout and
entrapped by a first polymeric network including the first cured
rubber, and the first elastomeric material has a water uptake
capacity of at least 40 percent by weight based on a total weight
of the first elastomeric material present in the first portion.
2. The outsole of claim 1, wherein the externally-facing side of
the outsole includes two or more traction elements, and the first
portion is an area separating the two or more traction
elements.
3. The outsole of claim 1, wherein first polymeric hydrogel is
physically entrapped by the first polymeric network, or is
chemically bonded to the first polymeric network, or both.
4. The outsole of claim 1, wherein the first elastomeric material
has a water cycling weight loss of less than 15 weight percent
based on a total weight of the first elastomeric material present
in the outsole.
5. The outsole of claim 1, wherein the first polymeric hydrogel in
neat form has an overall water uptake capacity of about 100 weight
percent to 3000 weight percent.
6. The outsole of claim 1, wherein the first polymeric hydrogel
comprises a polyurethane hydrogel.
7. The outsole of claim 1, wherein the first elastomeric material
has a water uptake capacity of at least 80 percent by weight based
on the total weight of the first elastomeric material present in
the first portion.
8. The outsole of claim 1, wherein first elastomeric material
includes from about 30 weight percent to about 70 weight percent of
the first polymeric hydrogel based on a total weight of the first
elastomeric material present in the first portion.
9. The outsole of claim 1, wherein the outsole comprises a second
material, and the second material forms a second portion of the
externally-facing side of the outsole.
10. The outsole of claim 9, wherein at least a first edge of the
first portion and at least a second edge of the second portion
contact one another.
11. The outsole of claim 10, wherein the second material includes a
second cured rubber and is substantially free of one or more
polymeric hydrogels.
12. The outsole of claim 9, wherein the second material forms one
or more integrally formed traction elements on the
externally-facing side of the outsole.
13. The outsole of claim 9, wherein the second material is a second
elastomeric material and includes a mixture of a second cured
rubber and a second polymeric hydrogel at a second concentration,
in which the second polymeric hydrogel is distributed throughout
and entrapped by a second polymeric network including the second
cured rubber, and the second elastomeric material has a water
uptake capacity of at least 2 percent by weight based on a total
weight of the second elastomeric material in the second
portion.
14. The outsole of claim 13, wherein the second portion and the
first portion are attached to one another by crosslinking bonds,
and an interface between the first portion and the second portion
is substantially free of adhesive.
15. A method of forming an outsole, the method comprising: shaping
a first composition to form a first portion of an externally-facing
side an outsole, wherein the first composition includes a mixture
of a first uncured or partially cured rubber and a first polymeric
hydrogel at a first concentration, wherein the first polymeric
hydrogel is distributed throughout the first uncured or partially
cured rubber; and curing the first portion to form a first
elastomeric material, thereby curing the first uncured or partially
cured rubber into a first fully cured rubber, and forming a first
polymeric network including the first fully cured rubber in the
first elastomeric material, wherein the first polymeric hydrogel is
distributed throughout and entrapped by the first polymeric
network
16. The method of claim 15, wherein the curing includes exposing
the first composition to actinic radiation in an amount and for a
duration sufficient to fully cure the first uncured or partially
cured rubber of the first composition.
17. The method of claim 15, further comprising: shaping a second
composition to form a second portion of the externally-facing side
the outsole, wherein the second composition includes a second
uncured or partially cured rubber; and curing the shaped second
composition, forming a second material including a second fully
cured rubber.
18. The method of claim 17, further comprising: contacting at least
an edge of the first portion with at least an edge of the second
portion; and wherein the curing comprises curing the first portion
or the second portion or both while the at least an edge of the
first portion and the at least an edge of the second portion are in
contact, and comprises forming crosslinking bonds between the first
uncured or partially cured rubber and the second uncured or
partially cured rubber during the curing, thereby bonding the first
portion to the second portion.
19. The method of claim 17, wherein the shaping comprises forming
one or more traction elements from the second composition.
20. The method of claim 18, wherein: the shaping the second
composition comprises placing the second composition in a second
region of a mold, wherein the second region of the mold is
configured to form traction elements; the shaping the first
composition and contacting the at least an edge of the first
portion with the at least an edge of the second portion comprises
placing the first composition in a first region of the mold,
wherein the first region of the mold is configured to form a
substrate for the traction elements, and placing the first
composition in the first region of the mold comprises contacting a
second side of the second portion with a first side of the first
portion; the curing comprises curing fully curing both the first
portion and the second portion in the mold and bonding the first
side of the first portion to the second side of the second portion;
and following the curing, removing the bonded first portion and
second from the mold.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of and priority to U.S.
Provisional Application Ser. No. 62/574,262, having the title
"RUBBER COMPOSITIONS AND USES THEREOF", filed on Oct. 19, 2017, and
to U.S. Provisional Application Ser. No. 62/693,740, having the
title "COLOR CHANGE MATERIALS, METHODS OF MAKING, METHODS OF USE,
AND ARTICLES INCORPORATING THE COLOR CHANGE MATERIALS", filed on
Jul. 3, 2018, and to U.S. Provisional Application Ser. No.
62/703,513, having the title "MATERIALS, METHODS OF MAKING, METHODS
OF USE, AND ARTICLES INCORPORATING THE MATERIALS", filed on Jul.
26, 2018, and to U.S. Provisional Application Ser. No. 62/743,380,
having the title "COMPOSITE MATERIALS, METHODS OF MAKING, METHODS
OF USE, AND ARTICLES INCORPORATING THE COMPOSITE MATERIALS", filed
on Oct. 9, 2018, the disclosures which are incorporated herein by
reference in their entireties.
BACKGROUND
[0002] Articles of apparel and sporting equipment of various types
are frequently used for a variety of activities including outdoor
activities, military use, and/or competitive sports. The externally
facing surfaces of the articles can be formed of elastomeric
materials, including cured rubbers which include pigments or dyes.
During the use of these articles, the externally facing surfaces of
the articles may frequently make contact with water, either in the
form of liquid water, water vapor, or wet ground.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] FIG. 1A is a cross-sectional view of an article or a
component of an article formed of an elastomeric material according
to the teachings of the present disclosure.
[0004] FIG. 1B is a cross-sectional view of another article or
component of an article formed of an elastomeric material according
to the teachings of the present disclosure.
[0005] FIG. 1C is a cross-sectional view of a finished article that
comprises the article or component of FIG. 1A.
[0006] FIG. 1D is a cross-sectional view of another finished
article that comprises the article or component of FIG. 1B.
[0007] FIG. 2A is a perspective view of a finished article in the
form of a garment comprising the article or component of FIG.
1A.
[0008] FIG. 2B is a perspective view of a finished article in the
form of a ball cap or helmet comprising the article or a component
of FIG. 1B.
[0009] FIG. 2C is a perspective view of a finished article in the
form of a tire or wheel comprising the article or component of FIG.
1A.
[0010] FIG. 2D is a perspective view of a finished article in the
form of hiking equipment comprising the articles or components of
FIGS. 1A and 1B.
[0011] FIG. 2E is a perspective view of a finished article in the
form of a protective glove comprising the article or component of
FIG. 1A.
[0012] FIG. 2F is a perspective view of a finished article in the
form of footwear comprising the article or component of FIG.
1A.
[0013] FIG. 2G is a bottom-side view of the finished article of
footwear of FIG. 2F.
[0014] FIG. 3A is a side view of an example of footwear, while FIG.
3B is a bottom view of an example of footwear.
[0015] FIGS. 4A and 4B illustrate cross-sections of an article of
footwear.
[0016] FIG. 5A is a flowchart describing a method of forming the
finished article of footwear of FIGS. 2F and 2G.
[0017] FIG. 5B is a flowchart describing a method of preparing an
uncured composition or an elastomeric material.
[0018] FIG. 5C is a flowchart describing a method of forming an
article or a component of an article comprising an uncured
composition or an elastomeric material.
[0019] FIG. 5D is a flowchart describing a method of forming the
finished article of apparel or sporting equipment of FIGS.
2A-2E.
[0020] FIG. 6A is a perspective view of a test set-up used for mud
pull-off testing.
[0021] FIG. 6B is a diagram of the measured force applied during
mud pull-off testing plotted as a function of compressive
displacement.
[0022] FIG. 7 is a diagram of the average mud pull-off force
exhibited by articles or components of articles that comprise the
elastomeric material of the present disclosure.
[0023] FIG. 8A is a diagram of the engineering stress (MPa) applied
to a "dry" article or component of an article plotted as a function
of displacement distance.
[0024] FIG. 8B is a diagram of the engineering stress (MPa) applied
to a "wet" article or component of an article plotted as a function
of displacement distance.
[0025] FIG. 9A is a diagram and table highlighting the water uptake
rate and overall water uptake capacity of an article or component
of an article that comprises various amounts of a hydrogel mixed
with cured rubber.
[0026] FIG. 9B is a diagram and table highlighting the water uptake
rate and overall water uptake capacity of an article or a component
of an article that comprises various amounts of another hydrogel
mixed with the cured rubber of FIG. 9A.
[0027] FIG. 10 is a diagram of the water uptake rate measured for
articles or components of articles comprising various amounts of a
hydrogel mixed with different cured rubbers.
[0028] FIG. 11A is a photomicrograph of the mud on the surface of
an article or a component of an article that comprises only a
conventional cured rubber without a polymeric hydrogel distributed
throughout the rubber.
[0029] FIG. 11B is a photomicrograph of the mud on the surface of
an article or a component of an article that comprises an
elastomeric material including a cured rubber with a polymeric
hydrogel distributed throughout the rubber according to the
teachings of the present disclosure.
[0030] FIG. 12 is a photomicrograph illustrating the swelling
capacity of the elastomeric material formed according to the
teachings of the present disclosure.
[0031] FIG. 13A is a photomicrograph of an elastomeric material
including cured rubber with polyacrylic acid (PAA) distributed
throughout the rubber, before and after exposure of the material to
water in a Water Cycling Test.
[0032] FIG. 13B is a photomicrograph of an elastomeric material
formed according to the teachings of the present disclosure in
which a polymeric hydrogel is entrapped (e.g., physically
entrapped) by a cured rubber, before and after exposure to water in
a Water Cycling Test.
[0033] FIG. 14 is a chemical description of formulas F-1A to
F-1E.
DESCRIPTION
[0034] The present disclosure, in general, provides for elastomeric
materials which comprise a cured rubber and a polymeric hydrogel
distributed throughout the cured rubber, as well as methods of
forming and using the elastomeric materials. It has been found that
distributing the polymeric hydrogel throughout an uncured rubber to
form a composition which is subsequently cured, can result in an
elastomeric material which, when it contacts water, readily takes
up water, reversibly, and undergoes a change in physical
characteristics. In other words, the elastomeric material of the
present disclosure combines the elastomeric properties of a cured
rubber, which generally has a hydrophobic nature and a limited
ability to take up water, with hydrophilic nature and ability to
take up water, dry, and then again take up water, of a polymeric
hydrogel. The polymeric network formed in the elastomeric material
by curing the rubber with the polymeric hydrogel dispersed in it
can also entrap at least a portion of the polymeric hydrogel
present within the polymeric matrix formed by the curing. In many
examples of the resulting elastomeric material, a majority of or
substantially all of the polymeric hydrogel remains entrapped in
the elastomeric material rather than migrating out of the
elastomeric material when soaked in water or when repeatedly
exposed to water. The water can be in the form of liquid water
(including aqueous solutions), water vapor, or wet ground (e.g.,
wet soil, wet grass, wet pavement, etc.). As can be readily
appreciated, an elastomeric material which retains both its
durability, elastomeric nature and ability to take up water on
repeated exposure to water can be used in a variety of articles of
manufacture, including articles which contact mud or soil during
use, where the accumulation of mud or soil is not desirable.
[0035] Due to the presence of uncured or partially cured rubber in
the uncured composition, curing the uncured composition in contact
with another material (e.g., another uncured rubber, a
crosslinkable polymer, or a polymer precursor) can result in
chemical bonds (e.g., crosslinking bonds, polymer bonds, etc.)
forming between the elastomeric material of the present disclosure
and the other material during curing. This makes it possible to
bond other polymeric materials including conventional rubber (i.e.,
rubber substantially free of the polymeric hydrogel) and/or
different elastomeric materials of the present disclosure (e.g.,
elastomeric materials having different formulations and/or
characteristics) to one another during a curing process, without
the need to use adhesives.
[0036] The uncured compositions and/or elastomeric materials of the
present disclosure can be used to make and/or be incorporated into
various types of articles (e.g., footwear, apparel, sporting
equipment, and components of each, along with other consumer
goods). The elastomeric material (e.g., dry or wet but not
saturated), when contacted by water, can take up water until it
becomes saturated with water. As it takes up water, the elastomeric
material undergoes a physical change that is reversible. The
elastomeric material can cycle from dry to wet and will again
undergo the same physical change. In other words, the physical
dimensions and/or physical properties of the elastomeric material
change with the level of water uptake or release. In some examples,
when wet, the elastomeric material can be softer, less brittle,
more compliant, and combinations thereof, as compared to the
elastomeric material when dry. When wet, the elastomeric material
can swell, increasing the length, width and/or height of an element
on an article. When wet, the elastomeric material can exhibit an
increase in compressive compliance; and can, when compressed, expel
water that was taken up previously; can have a lubricious
externally facing surface; and combinations thereof. The physical
characteristics of the elastomeric materials when wet (e.g.,
compressive compliance, lubricity), as well as these physical
characteristic changes which can occur when the material is wet
(e.g., expelling water) can also serve to disrupt the adhesion of
soil on the wet elastomeric material or at an interface including
the wet elastomeric material, or disrupt the cohesion of particles
to each other on the wet elastomeric material, or both.
[0037] The elastomeric material described herein, as well as
uncured compositions which, when cured, form the elastomeric
material, can be used to make and/or be incorporated into various
types of articles or components of articles. The article can be an
article of manufacture which comprises cured rubber such as tubing
or a tire. 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 the example where
the article is an article of footwear, the elastomeric material or
a component including the elastomeric material can be incorporated
into an upper of the footwear or into the sole of the footwear or
both. The elastomeric material can be present on an
externally-facing area of the article. When the elastomeric
material is incorporated into a sole for footwear, the elastomeric
material can be ground-facing in the footwear, such as on an
outsole component of the sole.
[0038] The elastomeric material and/or uncured compositions
described herein can be incorporated into and used in finished
articles or components of finished articles. The finished articles
within the scope of the present disclosure generally include any
article of manufacture including, but not limited to, footwear,
apparel, such as garments, and sporting equipment, such as balls,
bats, clubs, protective gear, and hunting, hiking, or camping
equipment, as well as consumer goods such as tubing, wheels, and
tires, or the like, and are described in more detail herein.
[0039] The present disclosure is also directed to uncured
compositions that comprise a mixture of an uncured rubber with a
polymeric hydrogel which, when cured to form crosslinks in the
rubber, form the elastomeric material. The present disclosure is
also directed to methods of using the uncured compositions and the
elastomeric materials.
[0040] The present disclosure provides for a composition
comprising: a rubber; and a polymeric hydrogel; wherein, in the
composition, the polymeric hydrogel is distributed throughout the
rubber. The rubber can be an uncured rubber or cured rubber. In
some examples, at least a portion of the polymeric hydrogel in the
elastomeric material is entrapped by the cured rubber. In the
elastomeric material, the polymeric hydrogel can be physically
entrapped by the cured rubber. In the elastomeric material, the
polymeric hydrogel can be chemically entrapped by the cured rubber
through chemical bonds such as crosslinking bonds. In the
elastomeric material, the polymeric hydrogel can be both physically
entrapped by and chemically bonded to the cured rubber.
[0041] The present disclosure provides for an article comprising:
an elastomeric material including a cured rubber and a polymeric
hydrogel; wherein, in the elastomeric material, the polymeric
hydrogel is distributed throughout the cured rubber, and at least a
portion of the polymeric hydrogel present in the elastomeric
material is entrapped by the cured rubber.
[0042] The present disclosure provides for an article comprising a
first elastomeric material of the present disclosure. For example,
a first portion of the article can comprise the first elastomeric
material. The first portion can be externally-facing on the
article. The first elastomeric material can includes a mixture of a
first cured rubber and a first polymeric hydrogel at a first
concentration; wherein, in the first elastomeric material, the
first polymeric hydrogel is distributed throughout the first cured
rubber and at least a portion of the first polymeric hydrogel
present in the first elastomeric material is entrapped by the first
cured rubber, wherein the first elastomeric material is capable of
taking up water. In a particular example, the article is an article
of footwear comprising: an upper; and a sole. The upper can
comprise the first elastomeric material. Alternatively or
additionally, the sole can comprise the first elastomeric material.
In the example where the sole comprises the first elastomeric
material, the first elastomeric material can be present in an
outsole. The outsole can be an outsole comprising a first region
having a first elastomeric material; wherein the first region
defines a portion of an externally facing side of the outsole.
[0043] The present disclosure also provides for when the article
comprises a second region including a second elastomeric material
according to the present disclosure. The first region and the
second region can be adjacent one another, wherein the second
region defines a portion of the externally facing side of the
article, and wherein the second elastomeric material includes a
mixture of a second cured rubber and a second polymeric hydrogel at
a second concentration, wherein, in the second elastomeric
material, the second polymeric hydrogel is distributed throughout
the second cured rubber and at least a portion of the second
polymeric hydrogel present in the second elastomeric material is
entrapped by the second cured rubber.
[0044] The present disclosure also provides for an outsole
including a first elastomeric material; wherein the first
elastomeric material forms a first portion of an externally-facing
side of the outsole; wherein the first elastomeric material
includes a mixture of a first cured rubber and a first polymeric
hydrogel at a first concentration, in which the first polymeric
hydrogel is distributed throughout and entrapped by a first
polymeric network including the first cured rubber, and the first
elastomeric material has a water uptake capacity of at least 40
percent by weight based on a total weight of the first elastomeric
material present in the first portion.
[0045] The present disclosure also provides for a method of making
an article, comprising: attaching a first component and a second
component including the elastomeric material as described herein,
to one another, thereby forming the article. The article can be any
article of manufacture, for example an article of footwear, an
article of apparel, or an article of sporting equipment. The
present disclosure also provides for an article comprising a
product of the method as described above or herein.
[0046] The present disclosure provides for a method of preparing a
composition, the method comprising: mixing an uncured rubber and a
polymeric hydrogel together to distribute the polymeric hydrogel
throughout the uncured rubber, forming the composition. The present
disclosure also provides for a composition prepared according to
the method of above and as provided herein. The present disclosure
provides for an elastomeric material prepared according to the
method above and described herein.
[0047] The present disclosure provides for a method of forming an
elastomeric material, the method comprising: providing a
composition including a mixture of an uncured rubber and a
polymeric hydrogel, wherein, in the composition, the polymeric
hydrogel is distributed throughout the uncured rubber; and curing
the composition to form the elastomeric material, wherein the
polymeric hydrogel is distributed throughout the cured rubber and
at least a portion of the polymeric hydrogel present in the
elastomeric material is entrapped by the cured rubber. The curing
can comprise forming chemical bonds between polymer chains of the
rubber, which forms a polymeric network of cured rubber chains that
physically entraps at least a portion the polymeric hydrogel within
the elastomeric material. The curing can comprise forming chemical
bonds which link polymer chains of the rubber to polymer chains of
at least a portion of the polymeric hydrogel present in the
elastomeric material, forming a polymeric network of the bonded
cured rubber chains and hydrogel chains, which chemically entraps
the at least a portion of the polymeric hydrogel within the
elastomeric material. The present disclosure provides for an
elastomeric material prepared as described above and disclosed
herein.
[0048] The present disclosure provides for a method of forming an
article, the method comprising: providing a composition including a
mixture of an uncured rubber and a polymeric hydrogel; wherein, in
the composition, the polymeric hydrogel is distributed throughout
the uncured rubber; shaping the composition to form a shaped
composition; and curing the shaped composition to cure the uncured
rubber of the composition and form the article, the article
comprising an elastomeric material in which the polymeric hydrogel
is distributed throughout the cured rubber and at least a portion
of the polymeric hydrogel in the elastomeric material is entrapped
by cured rubber. The present disclosure also provides for an
article prepared according to the method above and described
herein.
[0049] The present disclosure also provides for a method of forming
an article comprising a first component including a first material
and a second component including an uncured composition or
elastomeric material as described herein. Attaching the first and
second components can comprise curing the first material in contact
with the second material. Curing the first material and the second
material while in contact with each other can form chemical bonds
(e.g., crosslinking bonds or polymer bonds) between the first
material and the second material, thereby attaching the first
component to the second component using these chemical bonds. In
some cases, it may not be necessary to further reinforce the bond
using an adhesive.
[0050] The present disclosure also provides for a method of forming
an outsole, wherein the method comprises: shaping a first
composition to form a first portion of an externally-facing side an
outsole, wherein the first composition includes a mixture of a
first uncured or partially cured rubber and a first polymeric
hydrogel at a first concentration, wherein the first polymeric
hydrogel is distributed throughout the first uncured or partially
cured rubber; and curing the first portion to form a first
elastomeric material, thereby curing the first uncured or partially
cured rubber into a first fully cured rubber, and forming a first
polymeric network including the first fully cured rubber in the
first elastomeric material, wherein the first polymeric hydrogel is
distributed throughout and entrapped by the first polymeric
network.
[0051] This disclosure is not limited to particular aspects,
embodiment 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.
[0052] 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.
[0053] 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.
[0054] Aspects, embodiments and examples of the present disclosure
will employ, unless otherwise indicated, techniques of material
science, chemistry, textiles, polymer chemistry, textile chemistry,
and the like, which are within the skill of the art. Such
techniques are explained fully in the literature.
[0055] 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.
[0056] Unless otherwise defined, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art of microbiology, molecular biology,
medicinal chemistry, and/or organic chemistry. Although methods and
materials similar or equivalent to those described herein can be
used in the practice or testing of the present disclosure, suitable
methods and materials are described herein.
[0057] As used in the specification and the appended claims, the
singular forms "a," "an," and "the" may include plural referents
unless the context clearly dictates otherwise. Thus, for example,
reference to "a support" includes a plurality of supports. In this
specification and in the claims that follow, reference will be made
to a number of terms that shall be defined to have the following
meanings unless a contrary intention is apparent.
[0058] 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.). This will also apply to parts per hundred resin
(phr).
[0059] 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.
[0060] 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.
[0061] 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.
[0062] Aspects of the present disclosure provide for a composition
and an elastomeric material. The composition includes an uncured
rubber and a polymeric hydrogen, wherein the polymeric hydrogel is
distributed throughout the uncured rubber. In the elastomeric
material, the rubber is cured so that at least a portion of the
polymeric hydrogel dispersed throughout the cured rubber is
entrapped by the cured rubber. In general, the uncured rubber
alone, or the uncured rubber and the polymeric hydrogel in the
composition can undergo a reaction (e.g., crosslinking reaction) to
form the elastomeric material.
[0063] In regard to the composition, the composition includes the
uncured rubber and the polymeric hydrogel, where the polymeric
hydrogel is distributed throughout the uncured rubber. Also, the
composition can include additional ingredients such as crosslinking
agents, colorants, fillers, and the like. Additional details
regarding the uncured rubber and polymeric hydrogel are provided
below and herein.
[0064] When these compositions are cured to crosslink at least the
uncured rubber, the elastomeric material which is formed by the
curing is capable of taking up water and, when wet, including when
saturated, provides a lubricious surface while maintaining
sufficient abrasion resistance for use on externally-facing
surfaces, such as externally-facing surfaces of any article of
manufacturing, including garments, articles of footwear, and
articles of sporting equipment. The high level of entrapment of the
polymeric hydrogel by the cured rubber in the elastomeric material
is indicated by the stability of the elastomeric material when
soaked in water. For example, the Water Cycling Test using the
Sampling Procedures described below, can be used to test the
stability of the elastomeric materials. In particular examples,
weight losses of less than about 15 weight percent (due to
migration of polymeric hydrogel out of the elastomeric material)
are observed.
[0065] The crosslinking agent can be a crosslinking agent for
crosslinking uncured or partially cured rubber. The crosslinking
agent can include a crosslinking agent activated by actinic
radiation. For example, the crosslinking agent can be a thermally
initiated crosslinking agent, or a crosslinking agent initiated by
ultra-violet (UV) radiation. The thermally initiated crosslinking
agent may be, without limitation, a sulfur-based crosslinking agent
or a peroxide-based crosslinking agent. The uncured rubber may be
an UV radiation curable rubber, and the crosslinking agent can be
an initiator for crosslinking the radiation curable rubber upon
exposure to UV radiation.
[0066] The present disclosure also provides for the elastomeric
material that includes the cured rubber and the polymeric hydrogel
where the polymeric hydrogel is distributed throughout the cured
rubber and at least a portion (e.g., about 1 percent to 100
percent) of the polymeric hydrogel in the elastomeric material is
physically entrapped by the cured rubber and a portion can
optionally (e.g., about 0 to 50 percent) be chemically bonded or
crosslinked with the cured rubber. In addition, the elastomeric
material can be chemically bonded or crosslinked with cured rubber
in an adjacent layer (e.g., traction element such as lugs or
cleats, an upper, or other element in an article).
[0067] In addition, the composition (e.g., including the uncured
rubber and the polymeric hydrogel) and elastomeric material can
optionally include one or more colorants such as dyes and pigments,
which can be homogeneously or heterogeneously distributed within
the composition and elastomeric material. The selection of one or
more colorants and the distribution of the colorants can be random
or selected to achieve a desired aesthetic effect.
[0068] Referring to FIGS. 1A-1D, the article or component 15 of a
finished article 1 comprises a first surface 10 configured to be
externally-facing when the article or component 15 is present in a
finished article 1; and a second surface 20 that opposes the first
surface 10. The second surface 20 is located such that it can be
optionally attached (e.g., affixed, adhered, coupled, bonded, etc.)
with a substrate 25, which makes up part of the finished article 1.
When desirable, the finished article 1 may be an article of apparel
or sporting equipment. In the case of an article of footwear, the
article or component may be an outsole and the substrate may be a
midsole or an upper. The component 15 comprises an elastomeric
material 16, such that at least a portion of the first surface 10
comprises a mixture of a polymeric hydrogel and a cured rubber.
This elastomeric material may represent the reaction product of a
composition that comprises a mixture of an uncured rubber and the
hydrogel. In other words, the elastomeric material 16 is present at
or forms the whole of or part of an outer surface of the article or
component 15. When the article or component 15 is included in an
article of apparel or sporting equipment 1, the elastomeric
material 16 defines at least a portion of an exterior surface of
the article 1 on a side, the bottom or the top of the article
1.
[0069] According to the present disclosure, the article or
component 15 can extend across an entire externally-facing surface
(shown in FIGS. 1A and 1C), such as an entire bottom surface of an
article. However, in an alternative aspect of the present
disclosure, the crosslinked elastomeric material 16 can be present
as one or more segments of the article or component 15 that are
present at separate, discrete locations on an externally-facing
side or surface of a finished article 1. For instance, as shown in
FIG. 1B, the material can alternatively be present as discrete
segments 16 secured to the surface of a substrate 25 that is part
of the finished article 1. In this example, the remaining region 17
of the externally-facing surface, such as the remaining bottom
surface of an outsole, can be free of the elastomeric material and
comprise only the cured rubber or another material formulation.
[0070] The article can include the elastomeric material as
described herein. In a particular example, the article is an
article of footwear that includes an upper and an outsole
comprising a first region having a first elastomeric material. The
first region defines a portion of an externally facing side or
surface of the outsole, so that upon uptake of water, the
elastomeric material undergoes a physical change. The article of
footwear can include more than one type of elastomeric material in
the same or different regions and/or other types of materials in
the same or different regions.
[0071] Various ways in which the elastomeric material have been
presented herein, but the elastomeric material may be used in other
ways or various combinations to achieve appealing aesthetic change
to the article.
[0072] The elastomeric material can be incorporated into various
forms such as molded components, textiles, films and the like. For
example, the molded component, textile or film can be used in
apparel (e.g., shirts, jerseys, pants, shorts, gloves, glasses,
socks, hats, caps, jackets, undergarments) or components thereof,
containers (e.g., backpacks, bags), and upholstery for furniture
(e.g., chairs, couches, car seats), bed coverings (e.g., sheets,
blankets), table coverings, towels, flags, tents, sails, tubing,
wheels, tires, and parachutes. In addition, the elastomeric
material can be used to produce components or other items such as
molded components, textiles, films and the like that are disposed
on the article, where the article can be striking devices (e.g.,
bats, rackets, sticks, mallets, golf clubs, paddles, etc.),
athletic equipment (e.g., golf bags, baseball and football gloves,
soccer ball restriction structures), protective equipment (e.g.,
pads, helmets, guards, visors, masks, goggles, etc.), locomotive
equipment (e.g., bicycles, motorcycles, skateboards, cars, trucks,
boats, surfboards, skis, snowboards, etc.), balls or pucks for use
in various sports, fishing or hunting equipment, furniture,
electronic equipment, construction materials, eyewear, timepieces,
jewelry, and the like.
[0073] In the example where the article of the present disclosure
is an article of footwear, it may 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, 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).
[0074] The article of footwear can be designed use in 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, wherein the elastomeric
material can be located between or among the traction elements and
optionally on the sides of the traction elements, but not on the
surface of the traction element that directly contact the ground or
surface during wear. In other words, the terminal ends of the
traction elements can be substantially free of the elastomeric
material of the present disclosure. 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.
[0075] The elastomeric material of the present disclosure can be
incorporated into articles such as footwear or components thereof,
apparel or components thereof, sporting equipment or components
thereof. The elastomeric material can be formed into a structure
(e.g., outsole) that can have a range of dimensions depending upon
the use. In one aspect, the elastomeric material can be used in an
outsole or as a layer in an outsole and can a thickness of about
0.1 millimeters to 10 millimeters, about 0.1 millimeters to 5
millimeters, about 0.1 millimeters to 2 millimeters, about 0.25
millimeters to 2 millimeters, or about 0.5 millimeters to 1
millimeter, where the width and length can vary depending upon the
particular application (e.g., article to be incorporated into).
[0076] Referring once again to FIGS. 1C and 1D, at least a portion
of the second surface 20 of the component 15 is attached to a
substrate 25 that comprises, without limitation, a polymeric foam,
a polymeric sheet, a textile including a natural or synthetic
leather, a molded solid polymeric material, or a combination
thereof. The substrate 25 can comprise a thermoset polymeric
material, a thermoplastic polymeric material, or a combination
thereof. The thermoplastic polymeric material may include, without
limitation, a thermoplastic polyurethane, a thermoplastic
polyester, a thermoplastic polyamide, a thermoplastic polyolefin,
or any combination thereof, as is described in greater detail
below. The elastomeric material can be attached (e.g., affixed,
coupled, adhered, bonded, etc.) to a surface of the substrate that
is externally-facing, such that the elastomeric material defines at
least a portion of an externally-facing surface of the article or
component of the article.
[0077] The substrate 25 can comprise or be a textile, including a
knit textile, a woven textile, a non-woven textile, a braided
textile, a crocheted textile, or any combination thereof. The
textile can comprise a plurality of fibers, one or more yarns, or
both. The plurality of fibers or the one or more yarns or both can
include one or more natural or synthetic fibers or yarns. The
synthetic fibers or yarns can comprise, consist of, or consist
essentially of a thermoplastic composition. The polymeric component
of the thermoplastic composition may comprise, consist of, or
consist essentially of a thermoplastic polyurethane (TPU), a
thermoplastic polyamide, a thermoplastic polyester, a thermoplastic
polyolefin, or a mixture thereof, as described in more detail
herein.
[0078] In another example, the component or article itself 15, or
the segment including the elastomeric material 16 can comprise a
plurality of fibers, one or more yarns, one or more textiles, or
any combination thereof. The plurality of fibers, the one or more
yarns, the one or more textiles, or any combination thereof, can
act as a filler or as a reinforcing element in one or more layers
of the component or article 15 or segment 16. The one or more
textiles can comprise a knit textile, a woven textile, a non-woven
textile, a braided textile, a crocheted textile, or any combination
thereof. The plurality of fibers, the one or more yarns, the one or
more textiles, or any combination thereof, can be present in the
composition and the elastomeric material, or in a layer of the
component or article 15 or segment 16, or in any combination
thereof. When present in a layer, the layer can be a composite
layer, in which the plurality of fibers are dispersed in the
composition of the layer or elastomeric material of the layer, or
in which the elastomeric material or the composition infiltrates a
yarn and/or a textile and consolidates the fibers of the yarn
and/or the fibers or yarn of the textile. For example, a layer can
be a composite layer comprising a first plurality of fibers
dispersed in the elastomeric material. In another example, the
elastomeric material can be a composite layer comprising a textile,
wherein the elastomeric material infiltrates gaps between fibers
and/or yarns of the textile, and substantially surrounds the fibers
and/or yarns of the textile. The plurality of fibers, the one or
more yarns, the one or more textiles, or any combination thereof,
may include one or more natural or synthetic fibers or yarns. The
synthetic fibers or yarns may comprise, consist of, or consist
essentially of a thermoplastic composition. The polymeric component
of the thermoplastic composition may comprise, consist of, or
consist essentially of a thermoplastic polyurethane (TPU), a
thermoplastic polyamide, a thermoplastic polyester, a thermoplastic
polyolefin, or a mixture thereof, which are described in detail
herein.
[0079] Optionally, the component may further include an adhesive, a
primer, a tie layer, or a combination thereof located between the
second surface 20 of the elastomeric material and the
externally-facing side of the substrate 25 attached thereto. The
adhesive, tie layer, or primer may comprise, but not be limited to,
a polymer having one or more epoxy segments, urethane segments,
acrylic segments, cyanoacrylate segments, silicone segments, or a
combination thereof. The adhesive, primer, or tie layer can include
a thermoplastic polyurethane. Alternatively, the interface between
the second surface 20 of the elastomeric material and the
externally-facing side of the substrate 25 can be substantially
free of an adhesive, a primer, a tie layer, or any combination
thereof.
[0080] At least a portion of the first surface 10 of the component
15 may comprise a pattern or a texture. This pattern may represent
a tread pattern. In addition to a pattern or texture, the first
surface 10 of the component 15 may comprise one or more traction
elements (best shown in FIG. 2G). In some examples, the portion of
the elements that contact the ground during use (e.g., the terminal
end) are substantially free of the polymeric hydrogel or the
elastomeric material including the polymeric hydrogel as described
herein, as, due to the lubricious nature of these material, they
may reduce the effectiveness of the traction elements.
Alternatively, the portion of the traction elements which contact
the ground during use can be made of a different material, such as
a material that is harder than the elastomeric material. When
desirable, the one or more traction elements may have a conical or
rectangular shape as further described below.
[0081] Referring now to FIGS. 2A to 2G, the finished article 1 may
be, without limitation, an article of apparel, such as a garment
50, or an article of sporting equipment, such as a ball cap or
helmet 55, footwear 75; a tire or wheel 60; hunting, hiking, or
camping equipment 65; a ball, glove, bat, club, or protective gear
70. Alternatively, the component 15 may be attached to, coupled
with, or in contact with another material, e.g., the substrate 25
of the finished article 1. The component 15 of the article of
footwear 75 may be an outsole 15, for example (see FIGS. 2F &
2G).
[0082] Referring now to FIGS. 2F and 2G, the footwear 75 or shoe 75
may comprise, consist of, or consist essentially of an upper 25 and
an outsole 15 having a predetermined shape. The outsole 15 is in
contact with and affixed or attached to the upper 25. At least part
of the outsole 15 comprises an elastomeric material in an at least
partially cured state, alternatively, in a fully cured state. The
elastomeric material or layer in the outsole 15 is a mixture of the
polymeric hydrogel and the cured rubber as described above and
further defined herein. The polymeric hydrogel resin may exhibit a
water uptake capacity in the range of 50 percent to 1200 percent,
the water uptake capacity representing the amount of water by
weight taken up by the polymeric hydrogel as a percentage by weight
of dry hydrophilic resin. The cured rubber in the elastomeric
material comprises one or more natural or synthetic rubbers. The
polymeric hydrogel is present in an amount that ranges from about 5
weight percent to about 75 weight percent based on the overall
weight of the elastomeric material. The elastomeric material may
further comprise one or more processing aids independently selected
from the group of crosslinking agents, plasticizers, mold release
agents, lubricants, antioxidants, flame retardants, dyes, pigments,
reinforcing and non-reinforcing fillers, fiber reinforcements, and
light stabilizers.
[0083] Still referring to FIGS. 2F and 2G, the outsole 15 refers to
the very bottom of the article of footwear 75 such that one surface
10 is facing the ground during wear. The outsole 15 can exhibit a
thickness that is in the range from about 0.2 millimeters to about
2.0 millimeters; alternatively, about 0.2 millimeters to about 1.0
millimeters. The outsole 15 may be relatively smooth or include a
tread pattern 90. The surface 10 of the outsole 15 may directly
contact the ground during wear. Optionally, the outsole 15 may also
include one or more traction elements 95. When the outsole 15
includes traction elements 95, the traction elements 95 may
directly contact the ground during wear, while the surface 10 of
the outsole may only contact the ground when the ground is
sufficiently soft that an entire height of the traction elements 95
sink into the ground during wear. The traction elements 95 may
provide enhanced traction, as well as provide support or
flexibility to the outsole 15 and/or provide an aesthetic design or
look to the shoe.
[0084] The traction elements 95 may include, but are not limited
to, various shaped projections, such as cleats, studs, spikes, or
similar elements configured to enhance traction for a wearer during
cutting, turning, stopping, accelerating, and backward movement as
described in more detail herein. The traction elements 95 can be
arranged in any suitable pattern along the bottom surface of the
outsole 15. For instance, the traction 95 elements can be
distributed in groups or clusters along the outsole 15 (e.g.,
clusters of 2-8 traction elements). Alternatively, the traction
elements 95 can be arranged along the outsole 15 symmetrically or
non-symmetrically between a medial side and a lateral side of the
article of footwear 1. Moreover, one or more of the traction
elements can be arranged along a centerline of the outsole 15
between the medial side and the lateral side.
[0085] The traction elements 95 can be made of one or more
materials that are different from the composition and/or
elastomeric material. When desirable, the traction elements 95 may
be individually selected to be comprised of the same rubber as is
present in the composition and/or the elastomeric material.
Alternatively, the traction elements 95 can comprise a different
rubber (e.g., a harder rubber) or a different polymeric material
(e.g., a different type of cured rubber, or a polymeric material
substantially free of natural or synthetic rubber). In at least one
of the traction elements 95 the portion of said element that makes
contact with the ground may be substantially free of the
composition or elastomeric material. The one or more traction
elements 95 may be made of a polymeric material that is harder than
the elastomeric material. A plurality of traction elements can be
present with at least two of the plurality of traction elements
differing from each other based on height, width, or thickness.
[0086] In another aspect, FIGS. 3A and 3B illustrates an article of
footwear 100 that includes an upper 120 and a sole structure 130,
where the upper 120 is secured to the sole structure 130. The sole
structure 130 can include a toe plate 132, a mid-plate 134, and a
heel plate 136 and traction elements 138 as well as the elastomeric
material 110, where the elastomeric material 100 is on the outside
surface so to be ground-facing under normal use. Optionally, the
elastomeric material 110 can be an externally-facing layer of the
upper 120. The elastomeric material 110 can cover substantially all
of the upper 120 or can be in a region proximal to the sole
structure 130. In other aspects not depicted, the sole structure
130 may incorporate foam, one or more fluid-filled chambers,
plates, moderators, or other elements that further attenuate
forces, enhance stability, or influence the motions of the
foot.
[0087] The upper 120 of the footwear 100 has a body which may be
fabricated from materials known in the art for making articles of
footwear, and is configured to receive a user's foot. The upper 120
and components of the upper 120 may be manufactured according to
conventional techniques (e.g., molding, extrusion, thermoforming,
stitching, knitting, etc.). The upper 120 may alternatively have
any desired aesthetic design, functional design, brand designators,
and the like.
[0088] The sole structure 130 may be directly or otherwise secured
to the upper 120 using any suitable mechanism or method. As used
herein, the terms "secured to", such as for an outsole that is
secured to an upper, e.g., is operably secured to an upper, refers
collectively to direct connections, indirect connections, integral
formations, and combinations thereof. For instance, for the sole
structure 130 that is secured to the upper 120, the sole structure
130 can be directly connected to the upper 120 using the hot melt
adhesive layer of the elastomeric material and optionally include
the outsole 120 indirectly connected to the upper (e.g., with an
intermediate midsole), can be integrally formed with the upper
(e.g., as a unitary component), and combinations thereof.
[0089] FIGS. 4A and 4B illustrate cross-sections of an article of
footwear 200 and 201 that include an outsole including the
elastomeric material or the composition of the present disclosure
in a first layer 204. FIG. 4A illustrates a cross-section of an
article of footwear 200 including the first layer 204 attached
(optionally) to the upper 202 and a second layer 206 (or structure
or substrate or film) comprising a cured rubber substantially free
of the polymeric hydrogel, for example a cured rubber such as
rubber lugs, rubber cleats, or other tractions elements. The
outsole can be prepared by forming the first layer 204 of an
uncured composition or partially cured elastomeric material of the
present disclosure, forming the second layer 206 of an uncured or
partially rubber, then placing a first side of the first layer 204
in contact with a first side of the second layer 206, and fully
curing the first layer 204 and the second layer 206 while they
remain in contact with each other. For example, they can be cured
in a vulcanization process. In this example, the curing process
results in a portion of the rubber of the first layer 204
crosslinking with a portion of the rubber of the second layer 206,
forming chemical bonds (e.g., crosslinking) which adhere the first
layer 204 and the second layer 206 to each other without an
adhesive. In particular, during a curing process, the rubber in the
first layer 204 can crosslink with the rubber in the second layer
206 and the polymeric hydrogel of the first layer 204 can
optionally crosslink with the rubber in the first layer 204 and/or
the rubber in the second layer 206. In this way, the first layer
204 and the second layer 206 can form stronger bonds than what
might be obtained using adhesives or the like. In an embodiment,
the second layer 206 can be disposed in a mold (not shown) and then
the first layer 204 disposed on top of the second layer 206. The
first layer 206 and the second layer 204 can be subjected to a
vulcanization process to form the outsole. The upper 202 or a
component of the upper can be optionally disposed on a second side
of the first layer 204 before or after vulcanization, as
illustrated in FIG. 4A, or a midsole or plate 208 can be disposed
between the upper 202 (optionally including a strobel) and the
outsole can be bonded to the midsole or plate using a direct
attachment process by forming the midsole or plate 208 in contact
with the outsole, or by attaching the midsole or plate 208 using an
adhesive or other attachment method.
[0090] The term "externally-facing" as used in "externally-facing
layer" refers to the position the element is intended to be in when
the element is present in an article during normal use. If the
article is footwear, the element is positioned toward the ground
during normal use (i.e., is ground-facing) by a wearer when in a
standing position, and thus may contact the ground including
unpaved surfaces when the footwear is used in a conventional
manner, such as standing, walking or running on an unpaved surface.
In other words, even though the element may not necessarily be
facing the ground during various steps of manufacturing or
shipping, if the element is intended to face the ground during
normal use by a wearer, the element is understood to be
externally-facing or more specifically for an article of footwear,
ground-facing. In some circumstances, due to the presence of
elements such as traction elements, the externally-facing (e.g.,
ground-facing) surface can be positioned toward the ground during
conventional use but may not necessarily come into contact the
ground. For example, on hard ground or paved surfaces, the terminal
ends of traction elements on the outsole may directly contact the
ground, while portions of the outsole located between the traction
elements do not. As described in this example, the portions of the
outsole located between the traction elements are considered to be
externally-facing (e.g., ground-facing) even though they may not
directly contact the ground in all circumstances.
[0091] The traction elements may each include any suitable cleat,
stud, spike, or similar element configured to enhance traction for
a wearer during cutting, turning, stopping, accelerating, and
backward movement. The traction elements can be arranged in any
suitable pattern along the bottom surface of the footwear. For
instance, the traction elements can be distributed in groups or
clusters along the outsole (e.g., clusters of 2-8 traction
elements). In an aspect, the traction elements can be grouped into
a cluster at the forefoot region, a cluster at the midfoot region,
and a cluster at the heel region. In this example, six of the
traction elements are substantially aligned along the medial side
of the outsole, and the other six traction elements are
substantially aligned along the lateral side of the outsole.
[0092] The traction elements may alternatively be arranged along
the outsole symmetrically or non-symmetrically between the medial
side and the lateral side, as desired. Moreover, one or more of the
traction elements may be arranged along a centerline of outsole
between the medial side and the lateral side, such as a blade, as
desired to enhance or otherwise modify performance.
[0093] Alternatively (or additionally), traction elements can also
include one or more front-edge traction elements, such as one or
more blades, one or more fins, and/or one or more cleats (not
shown) secured to (e.g., integrally formed with) the backing plate
at a front-edge region between forefoot region and cluster. In this
application, the externally-facing portion of the elastomeric
material can optionally extend across the bottom surface at this
front-edge region while maintaining good traction performance.
[0094] Furthermore, the traction elements may each independently
have any suitable dimension (e.g., shape and size). For instance,
in some designs, each traction element within a given cluster
(e.g., clusters) may have the same or substantially the same
dimensions, and/or each traction element across the entirety of the
outsole may have the same or substantially the same dimensions.
Alternatively, the traction elements within each cluster may have
different dimensions, and/or each traction element across the
entirety of the outsole may have different dimensions.
[0095] Examples of suitable 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.).
The traction elements may also have the same or different heights,
widths, and/or thicknesses as each other, as further discussed
below. Further examples of suitable dimensions for the traction
elements and their arrangements along the plate include those
provided in soccer/global football footwear commercially available
under the tradenames "TIEMPO", "HYPERVENOM", "MAGISTA", and
"MERCURIAL" from Nike, Inc. of Beaverton, Oreg., USA.
[0096] The traction elements may be incorporated into the outsole
including the optional backing plate by any suitable mechanism such
that the traction elements preferably extend from the bottom
surface (e.g., elastomeric material). For example, as discussed
below, the traction elements may be integrally formed with the
backing plate through a molding process (e.g., for firm ground (FG)
footwear). Alternatively, the outsole or optional backing plate may
be configured to receive removable traction elements, such as
screw-in or snap-in traction elements. In these aspects, the
backing plate may include receiving holes (e.g., threaded or
snap-fit holes, not shown), and the traction elements can be
screwed or snapped into the receiving holes to secure the traction
elements to the backing plate (e.g., for soft ground (SG)
footwear).
[0097] In further examples, a first portion of the traction
elements can be integrally formed with the outsole or optional
backing plate and a second portion of the traction elements can be
secured with screw-in, snap-in, or other similar mechanisms (e.g.,
for SG pro footwear). The traction elements may also be configured
as short studs for use with artificial ground (AG) footwear, if
desired. In some applications, the receiving holes may be raised or
otherwise protrude from the general plane of the bottom surface of
the backing plate. Alternatively, the receiving holes may be flush
with the bottom surface.
[0098] The traction elements can be fabricated from any suitable
material for use with the outsole. For example, the traction
elements may include one or more of polymeric materials such as
thermoplastic elastomers; thermoset polymers; elastomeric polymers;
silicone polymers; natural and synthetic rubbers; composite
materials including polymers reinforced with carbon fiber and/or
glass; natural leather; metals such as aluminum, steel and the
like; and combinations thereof. In aspects in which the traction
elements are integrally formed with the backing plate (e.g., molded
together), the traction elements preferably include the same
materials as the outsole or backing plate (e.g., thermoplastic
materials). Alternatively, in aspects in which the traction
elements are separate and insertable into receiving holes of the
backing plate, the traction elements can include any suitable
materials that can secured in the receiving holes of the backing
plate (e.g., metals and thermoplastic materials).
[0099] As mentioned above, the traction element may have any
suitable dimensions and shape, where the shaft (and the outer side
surface) can correspondingly have 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.). Similarly, the terminal edge can
have dimensions and sizes that correspond to those of the outer
side surface, and can be substantially flat, sloped, rounded, and
the like. Furthermore, in some aspects, the terminal edge can be
substantially parallel to the bottom surface and/or the elastomeric
material.
[0100] Examples of suitable average lengths for each shaft relative
to bottom surface range from 1 millimeter to 20 millimeters, from 3
millimeters to 15 millimeters, or from 5 millimeters to 10
millimeters, where, as mentioned above, each traction element can
have different dimensions and sizes (i.e., the shafts of the
various traction elements can have different lengths).
[0101] It has been found the elastomeric material and articles
incorporating the elastomeric material (e.g., footwear) can prevent
or reduce the accumulation of soil on the externally-facing layer
of the elastomeric material 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.
[0102] While not wishing to be bound by theory, it is believed that
the polymeric hydrogel of the elastomeric material, as well as the
elastomeric material 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 polymeric
hydrogel and/or elastomeric material, the expulsion of liquid from
the wet polymeric hydrogel and/or elastomeric material, 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).
[0103] 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
elastomeric 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.
[0104] The swelling of the elastomeric material can be observed as
an increase in thickness of the elastomeric material from the
dry-state thickness of the elastomeric material, through a range of
intermediate-state thicknesses as additional water is absorbed, and
finally to a saturated-state thickness of the elastomeric material,
which is an average thickness of the elastomeric material when
fully saturated with water. For example, the saturated-state
thickness (or length, and/or height) for the fully saturated
elastomeric material 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
elastomeric material, as characterized by the Swelling Capacity
Test. The saturated-state thickness (or length, and/or height) for
the fully saturated elastomeric material 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 elastomeric material. The increase
in thickness may be greater in areas at and/or near the channel
where the elastomeric material is exposed through the channel.
[0105] The polymeric hydrogel and/or the elastomeric material in
neat form 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 elastomeric
material in neat form 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 component or layer comprising the
elastomeric material 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.
[0106] The polymeric hydrogel and/or the elastomeric material can
quickly take up water that is in contact with the polymeric
hydrogel and/or the elastomeric material. For instance, the
elastomeric 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 elastomeric material can be
pre-conditioned with water so that the elastomeric material of the
elastomeric material is partially or fully saturated, such as by
spraying or soaking the structure with water prior to use.
[0107] The elastomeric material 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 Component Sampling Procedure, as will be defined
below. The overall water uptake capacity (at 24 hours) exhibited by
the elastomeric material 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 elastomeric material
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 elastomeric
material as a percentage by weight of the elastomeric material when
dry. The procedure for measuring overall water uptake capacity
includes measurement of the "dry" weight of the elastomeric
material, immersion of the elastomeric material in water at ambient
temperature (.about.23.degree. C.) for a predetermined amount of
time, followed by re-measurement of the weight of the elastomeric
material when "wet". The procedure for measuring the overall weight
uptake capacity according to the Water Uptake Capacity Test using
the Component Sampling Procedure is described below.
[0108] The polymeric hydrogel itself, in neat form (e.g., prior to
being distributed in the rubber), 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 Component Sampling Procedure, as will be
defined below. The overall water uptake capacity (at 24 hours)
exhibited by the polymeric hydrogel 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 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 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 as a
percentage by weight of the polymeric hydrogel when dry. The
procedure for measuring overall water uptake capacity includes
measurement of the "dry" weight of the polymeric hydrogel,
immersion of the polymeric hydrogel in water at ambient temperature
(.about.23.degree. C.) for a predetermined amount of time, followed
by re-measurement of the weight of the polymeric hydrogel when
"wet". The procedure for measuring the overall weight uptake
capacity according to the Water Uptake Capacity Test using the
Component Sampling Procedure is described below.
[0109] The elastomeric material 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 elastomeric material at 24 hours. Additional
details are provided in the Water Uptake Capacity Test Protocol
described herein.
[0110] The polymeric hydrogel 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., in neat form when
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 polymeric hydrogel at 24 hours. Additional details are
provided in the Water Uptake Capacity Test Protocol described
herein.
[0111] The elastomeric material can also be characterized by a
water uptake rate of 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 water uptake rate is defined as the weight (in
grams) of water absorbed per square meter (m.sup.2) of the
elastomeric material over the square root of the soaking time (
min). Alternatively, the water uptake rate ranges from about 12
g/m.sup.2/ min to about 100 g/m.sup.2/ min; alternatively, from
about 25 g/m.sup.2/ min to about 90 g/m.sup.2/ min; alternatively,
up to about 60 g/m.sup.2/ min.
[0112] To cause a character change (e.g., shape, color, etc.) of
the elastomeric material, the elastomeric material can have a water
uptake rate of 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
[0113] The polymeric hydrogel can also be characterized by a water
uptake rate of 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 water uptake rate is defined as the weight (in
grams) of water absorbed per square meter (m.sup.2) of the
polymeric hydrogel over the square root of the soaking time ( min).
Alternatively, the water uptake rate ranges from about 12
g/m.sup.2/ min to about 100 g/m.sup.2/ min; alternatively, from
about 25 g/m.sup.2/ min to about 90 g/m.sup.2/ min; alternatively,
up to about 60 g/m.sup.2/ min.
[0114] To cause a character change of the elastomeric material, the
polymeric hydrogel present in the composition used to form the
elastomeric material can have a water uptake rate of 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.
[0115] 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 elastomeric material. The polymeric hydrogel can
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. In this case,
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. Alternatively, the water uptake capacity exhibited by the
polymeric hydrogel is in the range of about 100 weight percent to
about 1500 weight percent; alternatively, in the range of about 300
weight percent to about 1200 weight percent.
[0116] To cause a character change of the elastomeric material, the
polymeric hydrogel present in the composition used to form the
elastomeric material can have 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.
[0117] The elastomeric material 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
elastomeric material to that of the elastomeric material after
being soaked in a water bath for a predetermined amount of time,
dried and then reweighed. Alternatively, the elastomeric material
exhibits 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 or the Component Sampling
Procedure. Alternatively, the water cycling weight loss is less
than 15 weight percent; alternatively, less than 10 weight
percent.
[0118] The elastomeric material may also be characterized by the
degree to which it exhibits a mud pull-off force that is less than
about 12 Newton (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 the Example
section below.
[0119] The Component Sampling Procedure may constitute the Footwear
Sampling Procedure, when the component is part of an article of
footwear; the Apparel Sampling Procedure, when the component is
part of another article of apparel (e.g., a garment); or the
Equipment Sampling Procedure, when the component is part of an
article of sporting equipment. The Material Sampling Procedure is
used when the sample is provided in media form. Each of these
sampling procedures are described in more detail in the Example
section provided below.
[0120] The surface of the elastomeric material can exhibit
hydrophilic properties. The hydrophilic properties can be
characterized by determining the static sessile drop contact angle
of the elastomeric material's surface. Accordingly, in some
examples, the elastomeric material's surface 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 Article Sampling Procedure or the Co-Extruded Film Sampling
Procedure. In some further examples, the elastomeric 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.
[0121] In other examples, the surface of the elastomeric material
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 examples, the surface 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
surface is greater than the wet-state static sessile drop contact
angle of the surface 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.
[0122] The exposed region of the elastomeric material can also
exhibit a low coefficient of friction when the elastomeric material
is wet. Examples of suitable coefficients of friction for the
elastomeric 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 Article Sampling Procedure, or the
Co-Extruded Film Sampling Procedure. Examples of suitable
coefficients of friction for the elastomeric 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 elastomeric 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, the
dry-state coefficient of friction is greater than the wet-state
coefficient of friction for the material, 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.
[0123] Furthermore, the compliance of the elastomeric material can
be characterized based on the elastomeric material's 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 elastomeric 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 elastomeric material corresponds to an increase in compliance,
because less stress is required for a given strain/deformation.
[0124] The elastomeric 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 Neat Film
Sampling Process.
[0125] In some further aspects, the dry-state storage modulus of
the elastomeric 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.
[0126] The elastomeric 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 Neat Film
Sampling Process. The dry-state storage modulus of the elastomeric
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.
[0127] In addition to a reduction in storage modulus, the
elastomeric material 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). While not wishing to be bound by theory, it is
believed that the water taken up by the elastomeric material
plasticizes the elastomeric material, which reduces its storage
modulus and its glass transition temperature, rendering the
elastomeric material more compliant (e.g., compressible,
expandable, and stretchable).
[0128] The elastomeric material 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 C.
difference, more than a 6 degrees C. difference, more than a 10
degrees C. difference, or more than a 15 degrees C. difference, as
characterized by the Glass Transition Temperature Test with the
Neat Film Sampling Process or the Neat Material Sampling Process.
For instance, the reduction in glass transition temperature can
range from more than a 5 degrees C. difference to a 40 degrees C.
difference, from more than a 6 degrees C. difference to a 50
degrees C. difference, form more than a 10 degrees C. difference to
a 30 degrees C. difference, from more than a 30 degrees C.
difference to a 45 degrees C. difference, or from a 15 degrees C.
difference to a 20 degrees C. difference. The elastomeric material
can also exhibit a dry glass transition temperature ranging from
-40 degrees C. to -80 degrees C., or from -40 degrees C. to -60
degrees C.
[0129] Alternatively (or additionally), the reduction in glass
transition temperature can range from a 5 degrees C. difference to
a 40 degrees C. difference, form a 10 degrees C. difference to a 30
degrees C. difference, or from a 15 degrees C. difference to a 20
degrees C. difference. The elastomeric material can also exhibit a
dry glass transition temperature ranging from -40 degrees C. to -80
degrees C., or from -40 degrees C. to -60 degrees C.
[0130] The total amount of water that the elastomeric material can
take up depends on a variety of factors, such as its composition,
when present, the type and concentration of polymeric hydrogel
(e.g., its hydrophilicity), its cross-linking density, its
thickness, the amount of the elastomeric material present in the
elastomeric material, and the like. The water uptake capacity and
the water uptake rate of the elastomeric material, and of the
elastomeric material, 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 elastomeric
material present in a given elastomeric material having a given
geometry include time, thickness, and the surface area of the
exposed region available for taking up water.
[0131] As also mentioned above, in addition to swelling, the
compliance of the elastomeric material 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 elastomeric material
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.
[0132] In addition to quickly expelling water, in particular
examples, the compressed elastomeric material 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 elastomeric
material of the structure can dynamically expel and repeatedly take
up water over successive foot strikes, particularly from a wet
surface. As such, elastomeric material of the structure can
continue to prevent soil accumulation over extended periods of time
(e.g., during an entire competitive match), particularly when there
is ground water available for re-uptake, as well as undergo a
character change and be aesthetically advantageous.
[0133] 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 elastomeric material, the
elastomeric material, and when present, the polymeric 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).
[0134] In addition to being effective at preventing soil
accumulation, the elastomeric material has also been found to be
sufficiently durable for its intended use on the ground-contacting
side of the article of footwear. In various aspects, the useful
life of the elastomeric material (and footwear containing it) is at
least 10 hours, 20 hours, 50 hours, 100 hours, 120 hours, or 150
hours of wear.
[0135] Having described the article, composition and elastomeric
materials in general, additional details regarding articles,
compositions and elastomeric materials are now provided. The
article can include the elastomeric material, wherein, in the
elastomeric material, the polymeric hydrogel is distributed
throughout the cured rubber. At least a portion (e.g. about 1 to
100 weight percent or about 50 to 100 weight percent) of the
polymeric hydrogel present in the elastomeric material is entrapped
by the cured rubber. The polymeric hydrogel can be physically
entrapped and/or chemically bonded to the cured rubber.
[0136] In an example, the footwear includes an upper and an outsole
comprising a first region having a first elastomeric material. The
first elastomeric material can include a mixture of a first cured
rubber and a first polymeric hydrogel. The first region defines a
first portion of an externally facing side of the outsole. The
outsole also comprises a second region having a second material,
where the first region and the second region are adjacent one
another. The second region defines a second portion of the
externally facing side of the outsole. Optionally, the second
material is a second elastomeric material including a mixture of a
second cured rubber and a second polymeric hydrogel. Alternatively,
the second material is a second cured rubber which is substantially
free of a polymeric hydrogel. The first polymeric hydrogel and the
second polymeric hydrogel can be the same (e.g., the two polymeric
hydrogels can be formed of the same type of polymer or combination
of polymers having substantially equivalent water uptakes and are
present in the elastomeric materials in substantially equivalent
concentrations) or they can be different (e.g., they can be formed
of different types of polymer, and/or have substantially different
water uptakes, and/or be present in the elastomeric materials in
substantially different concentrations). Similarly, the cured
rubber of the first elastomeric material and second elastomeric
material can be the same (e.g., the two cured rubbers are formed of
the same type of uncured rubber or combination of uncured rubber
having substantially equivalent molecular weights and are present
in substantially equivalent concentrations) or they can be
different (e.g., they are formed from types of uncured rubbers
having different chemical structures and/or are present in
substantially different concentrations).
[0137] As described herein, an article can include two or more
different types of elastomeric materials, where each have different
water uptake capacities so that different physical characteristics
are exhibited by the different types of elastomeric materials. For
example, when an article includes a first and a second elastomeric
material that are in the dry-state, the first and second
elastomeric materials can have substantially physical
characteristics.
[0138] The first elastomeric material can comprise a first colorant
at a first concentration, where the type of colorant and/or the
concentration of the colorant can be the same or different than a
second elastomeric material. The first colorant and the second
colorant can be the same or different and can have substantially
the same or different concentration, where differences in the
elastomeric material can be responsible for differences in a
characteristic change of the elastomeric materials.
[0139] The rubber (e.g., uncured rubber, partially cured rubber, or
cured rubber) of the composition and/or the elastomeric material
can include one or more natural and/or synthetic rubbers. The
natural or synthetic rubbers can include: butadiene rubber,
styrene-butadiene (SBR) rubber, butyl rubber, isoprene rubber,
urethane rubber (e.g., millable), nitrile rubber, neoprene rubber,
ethylene propylene diene monomer (EPDM) rubber, ethylene-propylene
rubber, urethane rubber or any combination thereof. Other examples
of rubber compounds include, but are not limited to polynorbornene
rubber, methyl methacrylate butadiene styrene rubber (MBS), styrene
ethylene butylene (SEBS) rubber, silicone rubber, urethane rubber,
and mixtures thereof. The natural or synthetic rubbers may be
individually selected as virgin materials, regrind materials, or a
mixture thereof.
[0140] The uncured rubber can be a millable rubber, such as a
millable polyurethane rubber. The millable rubber may be a
thermally curable millable rubber, such as a thermally curable
millable polyurethane rubber, for example, a sulfur or peroxide
curable millable rubber. The millable rubber may also be a UV
curable polyurethane rubber such as, for example, MILLATHANE
UV-curable millable polyurethane rubber (TSE Industries Inc.,
Clearwater, Fla., USA). The millable polyurethane rubber may be
made be reacting either polyester or polyether polyols with
diisocyanates, such as methylene diphenyl diisocyanate (MDI) or
toluene diisocyanate (TDI), with or without a chain extender.
[0141] The rubber further can include an additive. For example, the
additive can include a plurality of polymer chains individually
having a maleic anhydride moiety grafted to the polymer chain. The
additive can be a functionalized polymer which has been modified by
grafting maleic anhydride groups into the polymer backbone, end
groups, or side groups, including ethylene-based polymers with
maleic anhydride grafting. The additive can be a maleic-anhydride
modified polymer such as "FUSABOND" (sold by E. I. du Pont de
Nemours and Company, Wilmington, Del., USA). The functionalized
polymer can include modified ethylene acrylate carbon monoxide
terpolymers, ethylene vinyl acetates (EVAs), polyethylenes,
metallocenepolyethylenes, ethylene propylene rubbers and
polypropylenes, where the modification to the functional polymer
can include maleic anhydride grafted to the functional polymer. The
amount of the additive present in the uncured rubber formulation
can be up to 10 parts per hundred resin (phr), or from about 1 phr
to about 8 phr, or from about 3 phr to about 6 phr.
[0142] The rubber can further comprise fillers; process oils;
and/or a curing package including at least one of crosslinking
agents(s), crosslinking accelerator(s), and crosslinking
retarder(s). Examples of fillers include, but are not limited to,
carbon black, silica, and talc. Examples of process oils include,
but are not limited to, paraffin oil and/or aromatic oils. Examples
of crosslinking agents include, but are not limited to sulfur or
peroxide initiators such as di-t-amyl peroxide, di-t-butyl
peroxide, t-butyl cumyl peroxide, di-cumyl peroxide (DCP),
di(2-methyl-1-phenyl-2-propyl)peroxide, t-butyl
2-methyl-1-phenyl-2-propyl peroxide,
di(t-buylperoxy)-diisopropylbenzene,
2,5-dimethyl-2,5-di(t-butylperoxy)hexane,
2,5-dimethyl-2,5-di(t-butylperoxy)hexpe-3,1,1-di(t-butylperoxy)-3,3,5-tri-
methylcyclohexane, 4,4-di(t-butylperoxy)-n-butylvalerate, and
mixtures thereof. Examples of crosslinking accelerators include,
but are not limited to, N-cyclohexyl-2-benzothiazole sulfenamide
(CBZ), N-oxydiethylene-2-benzothiazole sulfenamide,
N,N-diisopropyl-2-benzothiazole sulfenamide,
2-mercaptobenzothiazole,
2-(2,4-dinitrophenyl)mercaptobenzothiazole,
2-(2,6-diethyl-4-morpholinothio)benzothiazole and dibenzothiazyl
disulfide; guanidine compounds, such as diphenylguanidine (DPG),
triphenylguanidine, diorthonitrileguanidine, orthonitrile biguanide
and diphenylguanidine phthalate; aldehyde amine compounds or
aldehyde ammonia compounds, such as acetaldehyde-aniline reaction
product, butylaldehyde-aniline condensate, hexamethylenetetramine
and acetaldehyde ammonia; imidazoline compounds, such as
2-mercaptoimidazoline; thiourea compounds, such as thiocarbanilide,
diethylthiourea, dibutylthiourea, trimethylthiourea and
diorthotolylthiourea; thiuram compounds, such as tetramethylthiuram
monosulfide, tetramethylthiuram disulfide, tetraethylthiuram
disulfide, tetrabutylthiuram disulfide and pentamethylenethiuram
tetrasulfide; dithioate compounds, such as zinc
dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc
di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc
butylphenyldithiocarbamate, sodium dimethyldithiocarbamate,
selenium dimethyldithiocarbamate and tellurium
dimethyldithiocarbamate; xanthate compounds, such as zinc
dibutylxanthogenate; and other compounds, such as zinc white.
Examples of crosslinking retarders include, but are not limited to,
alkoxyphenols, catechols, and benzoquinones, and alkoxyphenols such
as 3,5-di-t-butyl-4-hydroxyanisol.
[0143] In the article or component of the article, the elastomeric
material and/or the rubber comprises at least some level of
crosslinking, is at least partially cured, and generally is fully
cured. In the finished article, the rubber is at least partially
cured, and is generally fully cured. Or stated another way, in the
elastomeric materials of the present disclosure, the rubber is at
least partially cured. As used herein, the term "partially cured"
generally refers to a compound (e.g., a rubber) having a relatively
low crosslink density of less than or equal to 10.sup.-3 moles per
cubic centimeter, or less than or equal to 10.sup.-5 moles per
cubic centimeter. For example, the partially cured elastomeric
material can have from about 15 to about 1500 monomer units present
between crosslinks. Dynamic mechanical analysis (DMA) can be used
to determine the modulus plateau for the compound. In the region of
the modulus plateau above the glass transition temperature of the
compound and below the melting point of the compound, the crosslink
density is directly proportional to the modulus of the compound. As
used herein, the term "cured" generally refers to a compound (e.g.,
a rubber) having a relatively high crosslink density. For example,
the crosslink density of the cured compound can be at least 20
percent greater, or at least 30 percent greater, or at least 50
percent greater than the crosslink density of the uncured or
partially cured composition.
[0144] Examples of crosslinking reactions include, but are not
limited to, free-radical reactions, ionic reactions (both anionic
and cationic), addition reactions, and metal salt reactions.
Crosslinking reactions can be initiated by actinic radiation,
including thermal radiation, UV radiation, electron beam radiation,
and other types of high energy radiations. The crosslinking
reactions can occur during a vulcanization process.
[0145] The term "partially cured" can denote the occurrence of at
least about 1 percent, alternatively, at least about 5 percent of
the total polymerization required to achieve a substantially full
cure. The term "fully cured" is intended to mean a substantially
full cure in which the degree of curing is such that the physical
properties of the cured material do not noticeably change upon
further exposure to conditions that induce curing (e.g.,
temperature, pressure, presence of curing agents, etc.).
[0146] In regard to the polymeric hydrogel, the polymeric hydrogel
is distributed throughout the uncured rubber and/or the cured
rubber in the elastomeric material. Upon curing of the uncured
rubber, at least a portion of the polymeric hydrogel in the
elastomeric material may be entrapped (e.g., physically entrapped
and/or chemically) by the cured rubber. A portion of the polymeric
hydrogel can optionally be chemically (e.g., covalently or
ionically) bonded to the cured rubber in the elastomeric material
or in an adjacent surface or structure. Substantially all of the
polymeric hydrogel in the elastomeric material can be entrapped
(e.g., physically or chemically) by the cured rubber.
[0147] The polymeric hydrogel is present in the composition and/or
elastomeric material in an amount of about 0.5 weight percent to
about 85 weight percent based on the overall weight of the
elastomeric material (i.e., polymeric) component present in
composition or the elastomeric material. 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 composition or the elastomeric material;
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. Alternatively, concentration of the polymeric
hydrogel in the composition and/or the elastomeric material can be
expressed in parts per hundred resin (phr) based on the overall
weight of the resin component of the composition or the elastomeric
material. For example, the composition or elastomeric material can
comprise from about 5 parts per hundred resin (phr), or about 10 to
80 phr, or about 15 to 70 phr, or about 20 to 70 phr, or about 30
to 70 phr, or about 45 to 70 phr of the polymeric hydrogel.
[0148] 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.). For example, a
concentration ranging from 40 phr to 60 phr includes concentrations
of 40 phr, 60 phr, and all concentrations there between (e.g., 40.1
phr, 41 phr, 45 phr, 50 phr, 52.5 phr, 55 phr, 59 phr, etc.).
[0149] Additional details are provided for the polymeric hydrogel
component of the composition and/or elastomeric material. The
composition and/or elastomeric material includes the polymeric
hydrogel distributed throughout the rubber, (i.e., the uncured
rubber or the cured rubber) portion of the composition, and/or
elastomeric material. Upon curing of the elastomeric material, at
least a portion of the polymeric hydrogel in the composition may be
entrapped (e.g., physically entrapped and/or chemically entrapped)
by the cured rubber. For example, a portion of the polymeric
hydrogel can optionally be covalently bonded to the cured rubber in
the elastomeric material, and/or substantially all of the polymeric
hydrogel in the elastomeric material can be physically entrapped by
the cured rubber.
[0150] The polymeric hydrogel can be a thermoset hydrogel or a
thermoplastic hydrogel. The polymeric hydrogel can be an
elastomeric hydrogel, including an elastomeric thermoset hydrogel
or an elastomeric thermoplastic hydrogel. The polymeric hydrogel
can comprise one or more polymers. The polymer can be selected
from: polyurethanes (including elastomeric polyurethanes,
thermoplastic polyurethanes (TPUs), and elastomeric TPUs),
polyesters, polyethers, polyamides, vinyl polymers (e.g.,
copolymers of vinyl alcohol, vinyl esters, ethylene, acrylates,
methacrylates, styrene, and so on), polyacrylonitriles,
polyphenylene ethers, polycarbonates, polyureas, polystyrenes,
co-polymers thereof (including polyester-polyurethanes,
polyether-polyurethanes, polycarbonate-polyurethanes, polyether
block polyamides (PEBAs), and styrene block copolymers), and any
combination thereof, as described herein. The polymer can include
one or more polymers selected from the group consisting of
polyesters, polyethers, polyamides, polyurethanes, polyolefins
copolymers of each, and combinations thereof.
[0151] The polymeric hydrogel can comprise a single type of
polymeric hydrogel, or a mixture of two or more types of polymeric
hydrogels. The polymeric hydrogel can comprise or consist
essentially of a polyurethane hydrogel. The polymeric network of
the elastomeric material can include one or more polyurethane
hydrogels. Polyurethane hydrogels are prepared from one or more
diisocyanate and one or more hydrophilic diol. A hydrophobic diol
can be used in addition to the hydrophilic diol. The polymerization
is normally carried out using roughly an equivalent amount of the
diol and diisocyanate. Examples of hydrophilic diols are
polyethylene glycols or 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 polymer 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.
[0152] The polymeric hydrogel can comprise or consist essentially
of a polyurea hydrogel. The polymeric network of the elastomeric
material can include one or more polyurea hydrogels. Polyurea
hydrogels are prepared from one or more diisocyanate and one or
more hydrophilic diamine. A hydrophobic diamine can be used in
addition to the hydrophilic diamine. The polymerization is normally
carried out using roughly an equivalent amount of the diamine and
diisocyanate. Typical hydrophilic diamines are 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 hydrophobicity of the resulting polymer 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.
[0153] The polymeric hydrogel can comprise or consist essentially
of a polyester hydrogel. The polymeric network of the elastomeric
material can comprise 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 are polyethylene
glycols or copolymers of ethylene glycol and propylene glycol. A
second hydrophobic diol can also be used to control the polarity of
the final polymer. One or more diacid can be used which can be
either aromatic or aliphatic. Block polyesters prepared from
hydrophilic diols and lactones of hydroxyacids can also be used.
The lactone can be 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 polymer by reaction
with a dicarboxylic acid.
[0154] The polymeric hydrogel can comprise or consist essentially
of a polycarbonate hydrogel. The polymeric network of the
elastomeric material can comprise 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 are hydroxyl terminated polyethers of
ethylene glycol or polyethers of ethylene glycol with propylene
glycol. A second hydrophobic diol can also be included to control
the polarity of the final polymer.
[0155] The polymeric hydrogel can comprise or consist essentially
of a polyetheramide hydrogel. The polymeric network of the
elastomeric material can comprise 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 can be used to produce hydrophilic
polymers that can swell with water. Hydrophobic diamines can be
used in conjunction with hydrophilic diamines to control the
hydrophilicity of the final polyetheramide hydrogel. In addition,
the type dicarboxylic acid segment can be selected to control the
polarity of the polyetheramide hydrogel and the physical properties
of the polyetheramide hydrogel. Typical hydrophilic diamines are
amine-terminated polyethylene oxides and amine-terminated
copolymers of polyethylene oxide/polypropylene. Examples are
JEFFAMINE diamines sold by Huntsman (The Woodlands, Tex., USA).
[0156] The polymeric hydrogel can comprise or consist essentially
of a hydrogel formed of addition polymers of ethylenically
unsaturated monomers. The polymeric network of the elastomeric
material can comprise one or more hydrogels formed of addition
polymers of ethylenically unsaturated monomers. The addition
polymers of ethylenically unsaturated monomers can be random
polymers. The addition polymers can be 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 are acrylic acid,
methacrylic acid, 2-acrylamido-2-methylpropane sulphonic acid,
vinyl sulphonic 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 hydrophobic monomers are (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 resulting polymeric hydrogel can be
tuned by selection of the monomer and the amounts of each monomer
type.
[0157] The addition polymers of ethylenically unsaturated monomers
can be 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 hydrophobic. Alternatively
the comb backbone can be hydrophobic while the side chains are
hydrophilic. An example is a backbone of a hydrophobic monomer such
as styrene with the methacrylate monoester of polyethylene
glycol.
[0158] 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. In one example,
hydrogels are produced when the polymer has both hydrophilic blocks
and hydrophobic blocks. The polymeric hydrogel can be a diblock
polymer (A-B) polymer, triblock polymer (A-B-A) or multiblock
polymer. Triblock polymers with hydrophobic end blocks and a
hydrophilic center block can be useful for this application. Block
polymers can be prepared by other means as well. Partial hydrolysis
of polyacrylonitrile polymers produces multiblock polymers with
hydrophilic domains (hydrolyzed) separated by hydrophobic domains
(unhydrolyzed) such that the partially hydrolyzed polymer acts as a
hydrogel. The hydrolysis converts acrylonitrile units to
hydrophilic acrylamide or acrylic acid units in a multiblock
pattern.
[0159] The polymeric hydrogel can comprise or consist essentially
of a hydrogel formed of copolymers. The polymeric network of the
elastomeric material can comprise one or more hydrogels formed of
copolymers. Copolymers combine two or more types of monomeric units
within each polymer chain to achieve the desired set of properties.
Of particular interest are polyurethane/polyurea copolymers,
polyurethane/polyester copolymers, and polyester/polycarbonate
copolymers.
[0160] The polymeric hydrogel present may be characterized as
including a plurality of polymer or copolymer chains in which each
chain is independently selected to comprise a combination of both
hard segments and soft segments. These hard and soft segments can
exist as phase separated regions within the polymeric network while
the polymeric hydrogel is in a solid (non-molten) state. The hard
segments can form portions of the polymer chain backbones, and can
exhibit high polarities, allowing the hard segments of multiple
polymer chains to aggregate together, or interact with each other,
to form semi-crystalline regions in the polymeric network.
Typically, in polymeric hydrogels having both soft segments and
hard segments, each of the soft segments of the polymeric hydrogel
independently has a greater level of hydrophilicity than each of
the hard segments.
[0161] A "semi-crystalline" or "crystalline" region has an ordered
molecular structure with sharp melting points, which remains solid
until a given quantity of heat is absorbed and then rapidly changes
into a low viscosity liquid. A "pseudo-crystalline" region has
properties of a crystal, but does not exhibit a true crystalline
diffraction pattern. For ease of reference, the term "crystalline
region" is used herein to collectively refer to a crystalline
region, a semi-crystalline region, and a pseudo-crystalline region
of a network of polymeric hydrogel chains. In some examples, the
hard segments of polymeric hydrogels form crystalline regions.
[0162] In comparison, the soft segments of these polymeric
hydrogels can be longer, more flexible, hydrophilic regions and can
form networks that allow the elastomeric material to expand and
swell under the pressure of taken up water. The soft segments can
constitute amorphous hydrophilic regions of the hydrogel, or of
crosslinked portions of the elastomeric material. The soft
segments, or amorphous regions, can also form portions of the
backbones of the polymer chains of the polymeric hydrogel along
with the hard segments. Additionally, one or more portions of the
soft segments, or amorphous regions, can be grafted or otherwise
represent pendant chains that extend from the backbones at the soft
segments. Each of the soft segments independently can include a
plurality of hydroxyl groups, one or more poly(ethylene oxide)
(PEO) segments, or both. The soft segments, or amorphous regions,
can be covalently bonded to the hard segments, or crystalline
regions (e.g., through carbamate linkages). For example, the
polymeric hydrogel can include a plurality of amorphous hydrophilic
regions covalently bonded to the crystalline regions of the hard
segments.
[0163] The polymeric hydrogel, or the polymeric network of the
elastomeric material, or both, can include a plurality of polymer
or copolymer chains having at least a portion of the chains
comprising a hard segment that is physically crosslinked to other
hard segments and a soft segment covalently bonded to the hard
segment, such as through a carbamate group or an ester group, among
other functional groups.
[0164] The polymeric hydrogel or the polymeric network of the
elastomeric material, or both, thereof may include a plurality of
polymer or copolymer chains. At least a portion of the polymer or
copolymer chains can include a first segment that forms at least a
crystalline region with other hard segments of the copolymer chains
and a second segment, such as a soft segment (e.g., a segment
having polyether chains or one or more ether groups) covalently
bonded to the first segment. In this example, the soft segment
forms amorphous regions of the hydrogel or crosslinked polymeric
network. The hydrogel or crosslinked polymeric network can include
a plurality of polymer or copolymer chains, where at least a
portion of the polymer or copolymer chains has hydrophilic
segments.
[0165] The polymeric hydrogel can be an aliphatic polyurethane
(TPU) resin 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) in combination with
1,4-butanediol (1,4-BD) as a chain extender as shown in formula
(F-1A) (FIG. 14). The segments having isocyanate groups include
segments having isocyanate groups that are directly bonded to
segments formed from the 1,4-BD. The soft segments may be formed
from poly(ethylene oxide) (PEO) as shown in formula (F-16). The
reaction product or 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. The polymeric
hydrogel may exhibit an average ratio of a number of soft segments
to a number of hard segments (SS:HS) present in the copolymer
chains of the polymeric hydrogel 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 of
the copolymer increases, more PEO is present in the structure of
the resin. 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 copolymer and faster the release kinetics associated
therewith. A chemical description of formulas F-1A to F-1E is
provided below.
##STR00001##
[0166] 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.
[0167] 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.
[0168] The composition of the present disclosure can be or can
comprise a thermoplastic material. The article comprising the
elastomeric material of the present disclosure can further comprise
a thermoplastic material. The polymeric hydrogel of the composition
and/or the elastomeric material can be a thermoplastic material.
The composition can comprise at least one thermoplastic material in
addition to the 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 softening temperature, and a 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, and
includes all subranges therein in increments of 1 degree. The
thermoplastic material can have a melting temperature from 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 112 degrees C.
to about 118 degrees C. when determined in accordance with ASTM
D3418-97 as described herein below.
[0169] 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 -13 degree 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 17 degrees C. to about 23 degrees C. when determined in
accordance with ASTM D3418-97 as described herein below.
[0170] The thermoplastic material can have a melt flow index from
about 10 to about 30 cubic centimeters per 10 minutes (cm.sup.3/10
min) when tested in accordance with ASTM D1238-13 as described
herein below at 160 degrees C. using a weight of 2.16 kilograms
(kg). The thermoplastic material can have a melt flow index from
about 22 cm.sup.3/10 min to about 28 cm.sup.3/10 min when tested in
accordance with ASTM D1238-13 as described herein below at 160
degrees C. using a weight of 2.16 kg.
[0171] The elastomeric material can have a cold Ross flex test
result of about 120,000 to about 180,000 cycles without cracking or
whitening when tested on a plaque of the elastomeric material in
accordance with the cold Ross flex test as described herein below.
The elastomeric material can have a cold Ross flex test result of
about 140,000 to about 160,000 cycles without cracking or whitening
when tested on a plaque of the elastomeric material in accordance
with the cold Ross flex test as described herein below.
[0172] The elastomeric material can have a modulus from about 5
megaPascals (MPa) to about 100 MPa when determined on a plaque in
accordance with ASTM D412-98 Standard Test Methods for Vulcanized
Rubber and Thermoplastic Rubbers and Thermoplastic
Elastomers-Tension with modifications described herein below. The
elastomeric material can have a modulus from about 20 MPa to about
80 MPa when determined on a plaque in accordance with ASTM D412-98
Standard Test Methods for Vulcanized Rubber and Thermoplastic
Rubbers and Thermoplastic Elastomers-Tension with modifications
described herein below.
[0173] The elastomeric material is a thermoset material. A
"thermoset material" is understood to refer to a material which
cannot be heated and melted, as its melting temperature is at or
above its decomposition temperature. A "thermoset material" refers
to a composition which comprises at least one thermoset polymer.
The thermoset polymer and/or thermoset material can be prepared
from a precursor (e.g., an uncured or partially cured polymer or
material) using actinic radiation (e.g., thermal energy,
ultraviolet radiation, visible radiation, high energy radiation,
infrared radiation) to form a partially cured or fully cured
polymer or material which no longer remains fully thermoplastic. In
some cases, the cured or partially cured elastomeric material may
retain some thermoplastic properties, in that it is possible to
partially soften and mold the elastomeric material at elevated
temperatures and/or pressures, but it is not possible to melt the
elastomeric material. The curing can be promoted, for example, with
the use of high pressure and/or a catalyst. The curing process is
irreversible since it results in crosslinking and/or polymerization
reactions of the precursors. The uncured compositions or partially
cured elastomeric materials can be malleable or liquid prior to
curing. In some cases, the uncured composition or partially cured
elastomeric materials can be molded into their final shape, or used
as adhesives. Once hardened, a thermoset material cannot be
re-melted in order to be reshaped, but it may be possible to soften
it. The textured surface can be formed by partially or fully curing
the composition to lock in the textured surface into the
elastomeric material.
[0174] The composition and/or the elastomeric material can comprise
a polyurethane. The article comprising the elastomeric material can
further include one or more components comprising 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.
[0175] One or more of the 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--) as
illustrated below in Formula 1, 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, mono-functional isocyanates can also be optionally
included, e.g., as chain terminating units).
##STR00002##
[0176] Each R.sub.1 group and R.sub.2 group independently is an
aliphatic or aromatic group. Optionally, each R.sub.2 can be a
relatively hydrophilic group, including a group having one or more
hydroxyl groups.
[0177] Additionally, the isocyanates can also be chain extended
with one or more chain extenders to bridge two or more isocyanates,
increasing the length of the hard segment. This can produce
polyurethane polymer chains as illustrated below in Formula 2,
where R.sub.3 includes the chain extender. As with each R.sub.1 and
R.sub.2, each R.sub.3 independently is an aliphatic or aromatic
functional group.
##STR00003##
[0178] Each R.sub.1 group in Formulas 1 and 2 can independently
include a linear or branched group having from 3 to 30 carbon
atoms, based on the particular isocyanate(s) used, and 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 or portion of a
molecule that does not include a cyclically conjugated ring system
having delocalized pi electrons. In comparison, the term "aromatic"
refers to an organic molecule or portion of a molecule having a
cyclically conjugated ring system with delocalized pi electrons,
which exhibits greater stability than a hypothetical ring system
having localized pi electrons.
[0179] Each R.sub.1 group can be present in an amount of about 5
percent to about 85 percent by weight, from about 5 percent to
about 70 percent by weight, or from about 10 percent to about 50
percent by weight, based on the total weight of the reactant
compounds or monomers which form the polymer.
[0180] In aliphatic embodiments (from aliphatic isocyanate(s)),
each R.sub.1 group can include a linear aliphatic group, a branched
aliphatic group, a cycloaliphatic group, or combinations thereof.
For instance, each R.sub.1 group can include a linear or branched
alkylene group having from 3 to 20 carbon atoms (e.g., an alkylene
having from 4 to 15 carbon atoms, or an alkylene having from 6 to
10 carbon atoms), one or more cycloalkylene groups having from 3 to
8 carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, or cyclooctyl), and combinations thereof.
The term "alkene" or "alkylene" as used herein refers to a bivalent
hydrocarbon. When used in association with the term C.sub.n it
means the alkene or 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.
[0181] 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 (H12MDI), diisocyanatododecane, lysine diisocyanate,
and combinations thereof.
[0182] The isocyanate-derived segments can include segments derived
from aliphatic diisocyanate. A majority of the isocyanate-derived
segments can comprise segments derived from aliphatic
diisocyanates. At least 90 percent of the isocyanate-derived
segments are derived from aliphatic diisocyanates. The
isocyanate-derived segments can consist essentially of segments
derived from aliphatic diisocyanates. The aliphatic
diisocyanate-derived segments can be derived 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) from linear aliphatic diisocyanates. At least 80 percent of
the aliphatic diisocyanate-derived segments can be derived from
aliphatic diisocyanates that are free of side chains. The segments
derived from aliphatic diisocyanates can include linear aliphatic
diisocyanates having from 2 to 10 carbon atoms.
[0183] When the isocyanate-derived segments are derived from
aromatic isocyanate(s)), each R.sub.1 group 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
groups.
[0184] 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. The polymer chains can be substantially free
of aromatic groups.
[0185] The polyurethane polymer chains can be produced from
diisocyanates including HMDI, TDI, MDI, H.sub.12 aliphatics, and
combinations thereof. For example, the polyurethane can comprise
one or more polyurethane polymer chains produced from diisocyanates
including HMDI, TDI, MDI, H.sub.12 aliphatics, and combinations
thereof.
[0186] Polyurethane chains which are at least partially crosslinked
or which can be crosslinked, can be used in accordance with the
present disclosure. It is possible to produce crosslinked or
crosslinkable polyurethane chains by reacting multi-functional
isocyanates to form the polyurethane. Examples of suitable
triisocyanates for producing the polyurethane chains include TDI,
HDI, and IPDI adducts with trimethyloylpropane (TMP), uretdiones
(i.e., dimerized isocyanates), polymeric MDI, and combinations
thereof.
[0187] The R.sub.3 group in Formula 2 can include a linear or
branched group having from 2 to 10 carbon atoms, based on the
particular chain extender polyol used, and can be, for example,
aliphatic, aromatic, or an ether or polyether. Examples of suitable
chain extender polyols for producing the polyurethane 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.
[0188] The R.sub.2 group in Formula 1 and 2 can include a polyether
group, a polyester group, a polycarbonate group, an aliphatic
group, or an aromatic group. Each R.sub.2 group can be present in
an amount of about 5 percent to about 85 percent by weight, from
about 5 percent to about 70 percent by weight, or from about 10
percent to about 50 percent by weight, based on the total weight of
the reactant monomers.
[0189] At least one R.sub.2 group of the polyurethane includes a
polyether segment (i.e., a segment having one or more ether
groups). Suitable polyether groups 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. When used in association
with the term C.sub.n it means the alkyl group has "n" carbon
atoms. For example, C4 alkyl refers to an alkyl group that has 4
carbon atoms. C1-7 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.
[0190] In some examples of the polyurethane, the at least one
R.sub.2 group includes a polyester group. The polyester group 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 group 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.
[0191] At least one R.sub.2 group can include a polycarbonate
group. The polycarbonate group 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.
[0192] The aliphatic group can be linear and can include, for
example, an alkylene chain having from 1 to 20 carbon atoms or an
alkenylene chain having from 1 to 20 carbon atoms (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 "alkene" or "alkylene"
refers to a bivalent hydrocarbon. The term "alkenylene" refers to a
bivalent hydrocarbon molecule or portion of a molecule having at
least one double bond.
[0193] The aliphatic and aromatic groups can be substituted with
one or more pendant relatively hydrophilic and/or charged groups.
The pendant hydrophilic group can include one or more (e.g., 2, 3,
4, 5, 6, 7, 8, 9, 10 or more) hydroxyl groups. 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).
[0194] The R.sub.2 group can include charged groups that are
capable of binding to a counterion to ionically crosslink the
polymer and form ionomers. For example, R.sub.2 is an aliphatic or
aromatic group having pendant amino, carboxylate, sulfonate,
phosphate, ammonium, or zwitterionic groups, or combinations
thereof.
[0195] When a pendant hydrophilic group is present, the pendant
hydrophilic group can be at least one polyether group, such as two
polyether groups. In other cases, the pendant hydrophilic group is
at least one polyester. The pendant hydrophilic group can be a
polylactone group (e.g., polyvinylpyrrolidone). Each carbon atom of
the pendant hydrophilic group can optionally be substituted with,
e.g., an alkyl group having from 1 to 6 carbon atoms. The aliphatic
and aromatic groups can be graft polymeric groups, wherein the
pendant groups are homopolymeric groups (e.g., polyether groups,
polyester groups, polyvinylpyrrolidone groups).
[0196] The pendant hydrophilic group can be a polyether group
(e.g., a polyethylene oxide (PEO) group, a polyethylene glycol
(PEG) group), a polyvinylpyrrolidone group, a polyacrylic acid
group, or combinations thereof.
[0197] The pendant hydrophilic group can be bonded to the aliphatic
group or aromatic group through a linker. The linker can be any
bifunctional small molecule (e.g., one having from 1 to 20 carbon
atoms) capable of linking the pendant hydrophilic group to the
aliphatic or aromatic group. For example, the linker can include a
diisocyanate group, as previously described herein, which when
linked to the pendant hydrophilic group and to the aliphatic or
aromatic group forms a carbamate bond. The linker can be
4,4'-diphenylmethane diisocyanate (MDI), as shown below.
##STR00004##
[0198] The pendant hydrophilic group can be a polyethylene oxide
group and the linking group can be MDI, as shown below.
##STR00005##
[0199] The pendant hydrophilic group can be functionalized to
enable it to bond to the aliphatic or aromatic group, optionally
through the linker. For example, when the pendant hydrophilic group
includes an alkene group, which can undergo a Michael addition with
a sulfhydryl-containing bifunctional molecule (i.e., a molecule
having a second reactive group, such as a hydroxyl group or amino
group), resulting in a hydrophilic group that can react with the
polymer backbone, optionally through the linker, using the second
reactive group. For example, when the pendant hydrophilic group is
a polyvinylpyrrolidone group, it can react with the sulfhydryl
group on mercaptoethanol to result in hydroxyl-functionalized
polyvinylpyrrolidone, as shown below.
##STR00006##
[0200] At least one R.sub.2 group in the polyurethane can include a
polytetramethylene oxide group. At least one R.sub.2 group of the
polyurethane can include an aliphatic polyol group functionalized
with a polyethylene oxide group or polyvinylpyrrolidone group, such
as the polyols described in E.P. Patent No. 2 462 908, which is
hereby incorporated by reference. For example, the R.sub.2 group
can be derived from the reaction product of a polyol (e.g.,
pentaerythritol or 2,2,3-trihydroxypropanol) and either
MDI-derivatized methoxypolyethylene glycol (to obtain compounds as
shown in Formulas 6 or 7) or with MDI-derivatized
polyvinylpyrrolidone (to obtain compounds as shown in Formulas 8 or
9) that had been previously been reacted with mercaptoethanol, as
shown below.
##STR00007##
[0201] At least one R.sub.2 of the polyurethane can be a
polysiloxane, In these cases, the R.sub.2 group can be derived from
a silicone monomer of Formula 10, such as a silicone monomer
disclosed in U.S. Pat. No. 5,969,076, which is hereby incorporated
by reference:
##STR00008##
[0202] wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7,
8, 9, or 10); each R.sub.4 independently is hydrogen, an alkyl
group having from 1 to 18 carbon atoms, an alkenyl group having
from 2 to 18 carbon atoms, aryl, or polyether; and each R.sub.5
independently is an alkylene group having from 1 to 10 carbon
atoms, polyether, or polyurethane.
[0203] Each R.sub.4 group can independently be a H, an alkyl group
having from 1 to 10 carbon atoms, an alkenyl group having from 2 to
10 carbon atoms, an aryl group having from 1 to 6 carbon atoms,
polyethylene, polypropylene, or polybutylene group. Each R.sub.4
group can independently be selected from the group consisting of
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl,
t-butyl, ethenyl, propenyl, phenyl, and polyethylene groups.
[0204] Each R.sub.5 group can independently include an alkylene
group having from 1 to 10 carbon atoms (e.g., a methylene,
ethylene, propylene, butylene, pentylene, hexylene, heptylene,
octylene, nonylene, or decylene group). Each R.sub.5 group can be a
polyether group (e.g., a polyethylene, polypropylene, or
polybutylene group). Each R.sub.5 group can be a polyurethane
group.
[0205] Optionally, the polyurethane can include an at least
partially crosslinked polymeric network that includes polymer
chains that are derivatives of polyurethane. The level of
crosslinking can be such that the polyurethane retains
thermoplastic properties (i.e., the crosslinked thermoplastic
polyurethane can be melted and re-solidified under the processing
conditions described herein). The crosslinked polyurethane can be a
thermoset polymer. This crosslinked polymeric network can be
produced by polymerizing one or more isocyanates with one or more
polyamino compounds, polysulfhydryl compounds, or combinations
thereof, as shown in Formulas 11 and 12, below:
##STR00009##
[0206] where the variables are as described above. Additionally,
the isocyanates can also be chain extended with one or more
polyamino or polythiol chain extenders to bridge two or more
isocyanates, such as previously described for the polyurethanes of
Formula 2.
[0207] The polyurethane chain can be physically crosslinked to
another polyurethane chain through e.g., nonpolar or polar
interactions between the urethane or carbamate groups of the
polymers (the hard segments). The R.sub.1 group in Formula 1, and
the R.sub.1 and R.sub.3 groups in Formula 2, form the portion of
the polymer often referred to as the "hard segment", and the
R.sub.2 group forms the portion of the polymer often referred to as
the "soft segment". The soft segment is covalently bonded to the
hard segment. The polyurethane having physically crosslinked hard
and soft segments can be a hydrophilic polyurethane (i.e., a
polyurethane, including a thermoplastic polyurethane, including
hydrophilic groups as disclosed herein).
[0208] One or more of the polyurethanes can be produced by
polymerizing one or more isocyanates with one or more polyols to
produce copolymer chains having carbamate linkages
(--N(C.dbd.O)O--) and one or more water-uptake enhancing moieties,
where the polymer chain includes one or more water-uptake enhancing
moieties (e.g., a monomer in polymer chain). The water-uptake
enhancing moiety can be added to the chain of Formula 1 or 2 (e.g.,
within the chain and/or onto the chain as a side chain). Inclusion
of the water-uptake enhancing moiety can enable the formation of a
polyurethane hydrogel.
[0209] The polyurethane can include one or more water-uptake
enhancing moieties. The water-uptake enhancing moiety can have at
least one hydrophilic (e.g., poly(ethylene oxide)), ionic or
potentially ionic group.\ A polyurethane can be formed by
incorporating a moiety bearing at least one hydrophilic group or a
group that can be made hydrophilic (e.g., by chemical modifications
such as neutralization) into the polymer chain. For example, these
compounds can be nonionic, anionic, cationic or zwitterionic or the
combination thereof. In one example, anionic groups such as
carboxylic acid groups can be incorporated into the chain in an
inactive form and subsequently activated by a salt-forming
compound, such as a tertiary amine. Other water-uptake enhancing
moieties can also be reacted into the backbone through urethane
linkages or urea linkages, including lateral or terminal
hydrophilic ethylene oxide or ureido units.
[0210] The water-uptake enhancing moiety can be a one that includes
carboxyl groups. Water-uptake enhancing moiety that include a
carboxyl group can be formed from hydroxy-carboxylic acids having
the general formula (HO).sub.xQ(COOH).sub.y, where Q can be a
straight or branched bivalent hydrocarbon radical containing 1 to
12 carbon atoms, and x and y can each independently be 1 to 3.
Illustrative examples include dimethylolpropanoic acid (DMPA),
dimethylol butanoic acid (DMBA), citric acid, tartaric acid,
glycolic acid, lactic acid, malic acid, dihydroxymalic acid,
dihydroxytartaric acid, and the like, and mixtures thereof.
[0211] The water-uptake enhancing moiety can include reactive
polymeric polyol components that contain pendant anionic groups
that can be polymerized into the backbone to impart water
dispersible characteristics to the polyurethane. Anionic functional
polymeric polyols can include anionic polyester polyols, anionic
polyether polyols, and anionic polycarbonate polyols, where
additional detail is provided in U.S. Pat. No. 5,334,690.
[0212] The water-uptake enhancing moiety can include a side chain
hydrophilic monomer. For example, the water-uptake enhancing moiety
including the side chain hydrophilic monomer can include alkylene
oxide polymers and copolymers in which the alkylene oxide groups
have from 2-10 carbon atoms as shown in U.S. Pat. No. 6,897,281.
Additional types of water-uptake enhancing moieties can include
thioglycolic acid, 2,6-dihydroxybenzoic acid, sulfoisophthalic
acid, polyethylene glycol, and the like, and mixtures thereof.
Additional details regarding water-dispersible enhancing moieties
can be found in U.S. Pat. No. 7,476,705.
Polyamides
[0213] The composition and/or the elastomeric material can comprise
a polyamide. The article comprising the elastomeric material can
further one or more components comprising a polyamide. The
polyamide can be a thermoplastic polyamide, or a thermoset
polyamide. The polyamide can be an elastomeric polyamide, including
an elastomeric thermoplastic polyamide or an elastomeric thermoset
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.
[0214] 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. 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 block co-polyamide, or can be a random co-polyamide. The
copolyamide can be formed from the polycondensation 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.
[0215] The polyamide can be a polyamide-containing block
co-polymer. For example, the block co-polymer can have repeating
hard segments, and repeating soft segments. The hard segments can
comprise polyamide segments, and the soft segments can comprise
non-polyamide segments. The polyamide-containing block co-polymer
can be an elastomeric co-polyamide comprising or consisting of
polyamide-containing block co-polymers 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.
[0216] The polyamide itself, or the polyamide segment of the
polyamide-containing block co-polymer 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 polyamide can be the same or
different.
[0217] The polyamide or the polyamide segment of the
polyamide-containing block co-polymer can be derived from the
polycondensation of lactams and/or amino acids, and can include an
amide segment having a structure shown in Formula 13, below,
wherein R.sub.6 group represents the portion of the polyamide
derived from the lactam or amino acid.
##STR00010##
[0218] The R.sub.6 group can be derived from a lactam. The R.sub.6
group can be derived from a lactam group having from 3 to 20 carbon
atoms, or a lactam group having from 4 to 15 carbon atoms, or a
lactam group having from 6 to 12 carbon atoms. The R.sub.6 group
can be derived from caprolactam or laurolactam. The R.sub.6 group
can be derived from one or more amino acids. The R.sub.6 group can
be derived from an amino acid group having from 4 to 25 carbon
atoms, or an amino acid group having from 5 to 20 carbon atoms, or
an amino acid group having from 8 to 15 carbon atoms. The R.sub.6
group can be derived from 12-aminolauric acid or 11-aminoundecanoic
acid.
[0219] Optionally, in order to increase the relative degree of
hydrophilicity of the polyamide-containing block co-polymer,
Formula 13 can include a polyamide-polyether block copolymer
segment, as shown below:
##STR00011##
[0220] wherein m is 3-20, and n is 1-8. Optionally, m is 4-15, or
6-12 (e.g., 6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. For
example, m can be 11 or 12, and n can be 1 or 3. The polyamide or
the polyamide segment of the polyamide-containing block co-polymer
can be derived from the condensation of diamino compounds with
dicarboxylic acids, or activated forms thereof, and can include an
amide segment having a structure shown in Formula 15, below,
wherein the R.sub.7 group represents the portion of the polyamide
derived from the diamino compound, and the R.sub.8 group represents
the portion derived from the dicarboxylic acid compound:
##STR00012##
[0221] The R.sub.7 group can be derived from a diamino compound
that includes an aliphatic group having from 4 to 15 carbon atoms,
or from 5 to 10 carbon atoms, or from 6 to 9 carbon atoms. The
diamino compound can include an aromatic group, such as phenyl,
naphthyl, xylyl, and tolyl. Suitable diamino compounds from which
the R.sub.7 group can be derived include, but are not limited to,
hexamethylene diamine (HMD), tetramethylene diamine, trimethyl
hexamethylene diamine (TMD),m-xylylene diamine (MXD), and
1,5-pentamine diamine. The R.sub.8 group can be derived from a
dicarboxylic acid or activated form thereof, including an aliphatic
group having from 4 to 15 carbon atoms, or from 5 to 12 carbon
atoms, or from 6 to 10 carbon atoms. The dicarboxylic acid or
activated form thereof from which R.sub.8 can be derived includes
an aromatic group, such as phenyl, naphthyl, xylyl, and tolyl
groups. Suitable carboxylic acids or activated forms thereof from
which R.sub.8 can be derived include adipic acid, sebacic acid,
terephthalic acid, and isophthalic acid. The polyamide chain can be
substantially free of aromatic groups.
[0222] Each polyamide segment of the polyamide (including the
polyamide-containing block co-polymer) can be independently derived
from a polyamide prepolymer selected from the group consisting of
12-aminolauric acid, caprolactam, hexamethylene diamine and adipic
acid.
[0223] The polyamide can comprise or consist essentially of a
poly(ether-block-amide). The poly(ether-block-amide) can be formed
from the polycondensation of a carboxylic acid terminated polyamide
prepolymer and a hydroxyl terminated polyether prepolymer to form a
poly(ether-block-amide), as shown in Formula 16:
##STR00013##
[0224] 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: 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
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.
[0225] The poly(ether block amide) polymers can 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. The copolymer can comprise
polyamide blocks comprising polyamide 12 or of polyamide 6.
[0226] The poly(ether block amide) polymers can include those
comprising polyamide blocks derived from the condensation of one or
more .alpha., .omega.-aminocarboxylic acids and/or of one or more
lactams containing from 6 to 12 carbon atoms in the presence of a
dicarboxylic acid containing from 4 to 12 carbon atoms, and are of
low mass, i.e., they have a number-average molecular weight of from
400 to 1000. In poly(ether block amide) polymers of this type, an
.alpha., .omega.-aminocarboxylic acid such as aminoundecanoic acid
or aminododecanoic acid can be used; a dicarboxylic acid such as
adipic acid, sebacic acid, isophthalic acid, butanedioic acid,
1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium or
lithium salt of sulphoisophthalic acid, dimerized fatty acids
(these dimerized fatty acids have a dimer content of at least 98
weight percent and are preferably hydrogenated) and dodecanedioic
acid HOOC--(CH.sub.2).sub.10--COOH can be used; and a lactam such
as caprolactam and lauryllactam can be used; or various
combinations of any of the foregoing. The copolymer can comprise
polyamide blocks obtained by condensation of lauryllactam in the
presence of adipic acid or dodecanedioic acid and with a number
average molecular weight of at least 750 have a melting temperature
of from about 127 to about 130 degrees C. The various constituents
of the polyamide block and their proportion can be chosen in order
to obtain a melting point of less than 150 degrees C., or from
about 90 degrees C. to about 135 degrees C.
[0227] The poly(ether block amide) polymers can include those
comprising polyamide blocks derived from the condensation of at
least one .alpha., .omega.-aminocarboxylic acid (or a lactam), at
least one diamine and at least one dicarboxylic acid. In copolymers
of this type, a .alpha.,.omega.-aminocarboxylic acid, the lactam
and the dicarboxylic acid can be chosen from those described herein
above and the diamine that can be used can include an aliphatic
diamine containing from 6 to 12 atoms and can be acyclic and/or
saturated cyclic such as, but not limited to, hexamethylenediamine,
piperazine, 1-aminoethylpiperazine, bisaminopropylpiperazine,
tetramethylenediamine, octamethylene-diamine, decamethylenediamine,
dodecamethylenediamine, 1,5-diaminohexane,
2,2,4-trimethyl-1,6-diaminohexane, diamine polyols,
isophoronediamine (IPD), methylpentamethylenediamine (MPDM),
bis(aminocyclohexyl)methane (BACM) and
bis(3-methyl-4-aminocyclohexyl)methane (BMACM).
[0228] The polyamide can be a thermoplastic polyamide and the
constituents of the polyamide block and their proportion can be
chosen in order to obtain a melting temperature of less than 150
degrees C., such as a melting point of from about 90 degrees C. to
about 135 degrees C. The various constituents of the thermoplastic
polyamide block and their proportion can be chosen in order to
obtain a melting point of less than 150 degrees C., such as from
about and 90 degrees C. to about 135 degrees C.
[0229] The number average molar mass of the polyamide blocks can be
from about 300 grams per mole to about 15,000 grams per mole, from
about 500 grams per mole to about 10,000 grams per mole, from about
500 grams per mole to about 6,000 grams per mole, from about 500
grams per mole to about 5,000 grams per mole, or from about 600
grams per mole to about 5,000 grams per mole. The number average
molecular weight of the polyether block can range from about 100 to
about 6,000, from about 400 to about 3000, or from about 200 to
about 3,000. The polyether (PE) content (x) of the poly(ether block
amide) polymer can be from about 0.05 to about 0.8 (i.e., from
about 5 mole percent to about 80 mole percent). The polyether
blocks can be present in the polyamide in an amount of from about
10 weight percent to about 50 weight percent, from about 20 weight
percent to about 40 weight percent, or from about 30 weight percent
to about 40 weight percent. The polyamide blocks can be present in
the polyamide in an amount of from about 50 weight percent to about
90 weight percent, from about 60 weight percent to about 80 weight
percent, or from about 70 weight percent to about 90 weight
percent.
[0230] 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, polypropylene
glycol (PPG) blocks, i.e. those consisting of propylene oxide
units, and poly(tetramethylene ether)glycol (PTMG) blocks, i.e.
those consisting of tetramethylene glycol units, also known as
polytetrahydrofuran. PPG or PTMG blocks are advantageously used.
The amount of polyether blocks in these copolymers containing
polyamide and polyether blocks can be from about 10 weight percent
to about 50 weight percent of the copolymer, or from about 35
weight percent to about 50 weight percent.
[0231] The copolymers containing polyamide blocks and polyether
blocks can be prepared by any means for attaching the polyamide
blocks and the polyether blocks. In practice, two processes are
essentially used, one being a 2-step process and the other a
one-step process.
[0232] In the two-step process, the polyamide blocks having
dicarboxylic chain ends are prepared first, and then, in a second
step, these polyamide blocks are linked to the polyether blocks.
The polyamide blocks having dicarboxylic chain ends are derived
from the condensation of polyamide precursors in the presence of a
chain-stopper dicarboxylic acid. If the polyamide precursors are
only lactams or .alpha.,.omega.-aminocarboxylic acids, a
dicarboxylic acid is added. If the precursors already comprise a
dicarboxylic acid, this is used in excess with respect to the
stoichiometry of the diamines. The reaction usually takes place
from about 180 to about 300 degrees C., such as from about 200
degrees to about 290 degrees C., and the pressure in the reactor
can be set from about 5 to about 30 bar and maintained for
approximately 2 to 3 hours. The pressure in the reactor is slowly
reduced to atmospheric pressure and then the excess water is
distilled off, for example for one or two hours.
[0233] Once the polyamide having carboxylic acid end groups has
been prepared, the polyether, the polyol and a catalyst are then
added. The total amount of polyether can be divided and added in
one or more portions, as can the catalyst. The polyether is added
first and the reaction of the OH end groups of the polyether and of
the polyol with the COOH end groups of the polyamide starts, with
the formation of ester linkages and the elimination of water. Water
is removed as much as possible from the reaction mixture by
distillation and then the catalyst is introduced in order to
complete the linking of the polyamide blocks to the polyether
blocks. This second step takes place with stirring, preferably
under a vacuum of at least 50 millibar (5000 Pascals) at a
temperature such that the reactants and the copolymers obtained are
in the molten state. By way of example, this temperature can be
from about 100 to about 400 degrees C., such as from about 200 to
about 250 degrees C. The reaction is monitored by measuring the
torque exerted by the polymer melt on the stirrer or by measuring
the electric power consumed by the stirrer. The end of the reaction
is determined by the value of the torque or of the target power.
The catalyst is defined as being any product which promotes the
linking of the polyamide blocks to the polyether blocks by
esterification. The catalyst can be a derivative of a metal (M)
chosen from the group formed by titanium, zirconium and hafnium.
The derivative can be prepared from a tetraalkoxides consistent
with the general formula M(OR).sub.4, in which M represents
titanium, zirconium or hafnium and R, which can be identical or
different, represents linear or branched alkyl radicals having from
1 to 24 carbon atoms.
[0234] The catalyst can comprise a salt of the metal (M),
particularly the salt of (M) and of an organic acid and the complex
salts of the oxide of (M) and/or the hydroxide of (M) and an
organic acid. The organic acid can be formic acid, acetic acid,
propionic acid, butyric acid, valeric acid, caproic acid, caprylic
acid, lauric acid, myristic acid, palmitic acid, stearic acid,
oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic
acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid,
malonic acid, succinic acid, glutaric acid, adipic acid, maleic
acid, fumaric acid, phthalic acid or crotonic acid. The organic
acid can be an acetic acid or a propionic acid. M can be zirconium
and such salts are called zirconyl salts, e.g., the commercially
available product sold under the name zirconyl acetate.
[0235] The weight proportion of catalyst can vary from about 0.01
to about 5 percent of the weight of the mixture of the dicarboxylic
polyamide with the polyetherdiol and the polyol. The weight
proportion of catalyst can vary from about 0.05 to about 2 percent
of the weight of the mixture of the dicarboxylic polyamide with the
polyetherdiol and the polyol.
[0236] In the one-step process, the polyamide precursors, the chain
stopper and the polyether are blended together; what is then
obtained is a polymer having essentially polyether blocks and
polyamide blocks of highly variable length, but also the various
reactants that have reacted randomly, which are distributed
randomly along the polymer chain. They are the same reactants and
the same catalyst as in the two-step process described above. If
the polyamide precursors are only lactams, it is advantageous to
add a little water. The copolymer has essentially the same
polyether blocks and the same polyamide blocks, but also a small
portion of the various reactants that have reacted randomly, which
are distributed randomly along the polymer chain. As in the first
step of the two-step process described above, the reactor is closed
and heated, with stirring. The pressure established is from about 5
to about 30 bar. When the pressure no longer changes, the reactor
is put under reduced pressure while still maintaining vigorous
stirring of the molten reactants. The reaction is monitored as
previously in the case of the two-step process.
[0237] The proper ratio of polyamide to polyether blocks can be
found in a single poly(ether block amide), or a blend of two or
more different composition poly(ether block amide)s can be used
with the proper average composition. It can be useful to blend a
block copolymer having a high level of polyamide groups with a
block copolymer having a higher level of polyether blocks, to
produce a blend having an average level of polyether blocks of
about 20 to about 40 weight percent of the total blend of
poly(amid-block-ether) copolymers, or about 30 to about 35 weight
percent. The copolymer can comprise a blend of two different
poly(ether-block-amide)s comprising at least one block copolymer
having a level of polyether blocks below 35 weight percent, and a
second poly(ether-block-amide) having at least 45 weight percent of
polyether blocks.
[0238] Exemplary commercially available copolymers include, but are
not limited to, those available under the tradenames of "VESTAMID"
(Evonik Industries, Essen, Germany); "PLATAMID" (Arkema, Colombes,
France), e.g., product code H2694; "PEBAX" (Arkema), e.g., product
code "PEBAX MH1657" and "PEBAX MV1074"; "PEBAX RNEW" (Arkema);
"GRILAMID" (EMS-Chemie AG, Domat-Ems, Switzerland), or also to
other similar materials produced by various other suppliers.
[0239] The polyamide can be 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, and optionally by interactions
between the copolymer groups. When the co-polyamide is physically
crosslinked through 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 segments of the polymer, and polyether segments form
the soft segments of the polymer. Therefore, in some examples, the
polymer can include a physically crosslinked polymeric network
having one or more polymer chains with amide linkages.
[0240] The polyamide segment of the co-polyamide can include
polyamide-11 or polyamide-12 and the polyether segment can be a
segment selected from the group consisting of polyethylene oxide,
polypropylene oxide, and polytetramethylene oxide segments, and
combinations thereof.
[0241] The polyamide can be partially or fully covalently
crosslinked, as previously described herein. In some cases, the
degree of crosslinking present in the polyamide is such that, when
it is thermally processed, e.g., in the form of a yarn or fiber to
form the articles of the present disclosure, the partially
covalently crosslinked thermoplastic polyamide retains sufficient
thermoplastic character that the partially covalently crosslinked
thermoplastic polyamide is melted during the processing and
re-solidifies. In other cases, the crosslinked polyamide is a
thermoset polymer.
Polyesters
[0242] The composition and/or the elastomeric material can comprise
a polyester. The article comprising the elastomeric material can
further one or more components comprising a polyester. The
polyester can comprise a thermoplastic polyester, or a thermoset
polyester. Additionally, the polyester can be an elastomeric
polyester, including a thermoplastic polyester or a thermoset
elastomeric 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.
[0243] Exemplary carboxylic acids that can be used to prepare a
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 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.
[0244] The polyester can be 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.
[0245] 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 essentially 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.
[0246] For example, the polyester can be a block co-polyester
having repeating blocks of polymeric units of the same chemical
structure which are relatively harder (hard segments), and
repeating blocks of the same chemical structure 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
polymer can comprise or consist essentially of an elastomeric
co-polyester having repeating blocks of hard segments and repeating
blocks of soft segments.
[0247] The non-polyester segments of the co-polyester can comprise
or consist essentially 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 polyethylene
adipate, polybutylene succinate,
poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene
terephthalate, polybutylene terephthalate, polytrimethylene
terephthalate, polyethylene napthalate, and combinations thereof.
The co-polyamide can comprise or consist of polyethylene
terephthalate.
[0248] The polyester can be 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 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.
[0249] The polyester can be 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.
[0250] 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.
Polyolefins
[0251] The composition and/or elastomeric material can comprise a
polyolefin. The article comprising the elastomeric material can
further one or more components comprising a polyolefin. The
polyolefin can be a thermoplastic polyolefin or a thermoset
polyolefin. Additionally, the polyolefin can be an elastomeric
polyolefin, including a thermoplastic elastomeric polyolefin or a
thermoset elastomeric polyolefin. Exemplary polyolefins can include
polyethylene, polypropylene, and olefin elastomers (e.g.,
metallocene-catalyzed block copolymers of ethylene and
.alpha.-olefins having 4 to about 8 carbon atoms). The polyolefin
can be 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, a 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 polyolefins include polymers of
cycloolefins such as cyclopentene or norbornene.
[0252] It is to be understood that polyethylene, which optionally
can be crosslinked, is inclusive a variety of polyethylenes,
including low density polyethylene (LDPE), linear low density
polyethylene (LLDPE), (VLDPE) and (ULDPE), medium density
polyethylene (MDPE), high density polyethylene (HDPE), high density
and high molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh molecular weight polyethylene (HDPE-UHMVV), and blends or
mixtures of any the foregoing polyethylenes. A polyethylene can
also be a polyethylene copolymer derived from monomers of
monolefins 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 weight percent vinyl acetate-derived composition.
[0253] The polyolefin 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). The disclosed polyolefin can be prepared by radical
polymerization under high pressure and at elevated temperature.
Alternatively, the 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. 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. 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.
[0254] Suitable polyolefins can be prepared by polymerization of
monomers of monolefins and diolefins as described herein. Exemplary
monomers that can be used to prepare the 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.
[0255] 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.
[0256] 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.
[0257] The polyolefin can be a mixture of polyolefins, such as a
mixture of two or more polyolefins disclosed herein above. For
example, a suitable mixture of 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).
[0258] The polyolefin can be a copolymer of suitable monolefin
monomers or a copolymer of a suitable monolefin monomer and a vinyl
monomer. Exemplary polyolefin copolymers include 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.
[0259] The polyolefin can be a polypropylene homopolymer, a
polypropylene copolymers, 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.
[0260] The polyolefin can be 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). Thus, the term as
applied to fibers is intended to encompass actual long strands,
tapes, threads, and the like, of drawn polymer. The polypropylene
can be of any standard melt flow (by testing); however, standard
fiber grade polypropylene resins possess ranges of Melt Flow
Indices between about 1 and 1000.
[0261] The polyolefin can be a polyethylene. The term
"polyethylene," as used herein, is intended to encompass any
polymeric composition comprising ethylene monomers, either alone or
in mixture or copolymer with other randomly selected and oriented
polyolefins, dienes, or other monomers (such as propylene,
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). Thus, the term as
applied to fibers is intended to encompass actual long strands,
tapes, threads, and the like, of drawn polymer. The polyethylene
can be of any standard melt flow (by testing); however, standard
fiber grade polyethylene resins possess ranges of Melt Flow Indices
between about 1 and 1000.
[0262] The composition and/or the elastomeric material can further
comprise one or more processing aids. The article comprising the
elastomeric material can further one or more components comprising
one or more processing aids. The processing aid can be a
non-polymeric material. These processing aids 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
[0263] The composition can be a thermoplastic composition. For
example, the thermoplastic composition can comprise one or more of
thermoplastic polyurethanes, thermoplastic polyesters,
thermoplastic polyamides, thermoplastic polyolefins, or a
co-polymer or combination including of any of the foregoing.
[0264] The thermoplastic composition can have a softening or
melting point of about 80.degree. C. to about 140.degree. C. A
temperature of the thermoplastic composition can be increased to a
temperature at or above creep relaxation temperature (T.sub.cr),
Vicat softening temperature (T.sub.vs), heat deflection temperature
(T.sub.hd), and/or melting temperature (T.sub.m). In an aspect, the
layers or structure can be attached using the thermoplastic
composition while the temperature is maintained at or above the
creep relaxation temperature, the heat deflection temperature, the
Vicat softening temperature, or the melting temperature, of the
thermoplastic composition. The layers or structure can be attached
using the thermoplastic composition after the temperature of the
thermoplastic composition is allowed to drop below the creep
relaxation temperature, the heat deflection temperature, the Vicat
softening temperature, or the melting temperature of the
thermoplastic composition, as long as the thermoplastic composition
only partially re-solidified, it can be used to attached the
structure or the layers.
[0265] In general, the thermoplastic composition can have a creep
relaxation temperature (T.sub.cr) of about 80.degree. C. to about
140.degree. C., or from about 90.degree. C. to about 130.degree.
C., or about 100.degree. C. to about 120.degree. C. In general, the
thermoplastic composition can have a Vicat softening temperature
(T.sub.vs) of about 80.degree. C. to about 140.degree. C., or from
about 90.degree. C. to about 130.degree. C., or about 100.degree.
C. to about 120.degree. C. In general, the thermoplastic
composition can have a heat deflection temperature (T.sub.hd) of
about 80.degree. C. to about 140.degree. C., or from about
90.degree. C. to about 130.degree. C., or about 100.degree. C. to
about 120.degree. C. In general, the thermoplastic composition can
have a melting temperature (T.sub.m) of about 80.degree. C. to
about 140.degree. C., or from about 90.degree. C. to about
130.degree. C., or about 100.degree. C. to about 120.degree. C.
[0266] The elastomeric material is a thermoset composition. The
thermoset composition can comprise a thermoset polyurethane
polymer, thermoset polyurea polymer, thermoset polyamide polymer,
thermoset polyolefin polymer, or thermoset silicone polymer, or a
co-polymer or combination including any of the foregoing.
[0267] In addition to the elastomeric material, the articles of the
present disclosure can comprise a polymeric foam composition. For
example, the polymeric foam composition can include a polyolefin
foam, polyurethane foam, an ethylene-vinyl acetate (EVA) foam, a
propylene foam, or a combination thereof. The polymeric foam
composition can include a blend with one or more additional
materials to impart additional characteristics or properties to the
composition. The polymeric foam composition can include one or more
other components. A foam composition can include a chemical blowing
agent such as a carbonate, bicarbonate, carboxylic acid, azo
compound, isocyanate, persulfate, peroxide, or a combination
thereof. The foam composition can include about 1 parts per hundred
resin to about 10 parts per hundred resin, or about 3 parts per
hundred resin to about 7 parts per hundred resin of the chemical
blowing agent. The chemical blowing agent has a decomposition
temperature of about 130.degree. C. to about 160.degree. C., or
about 135.degree. C. to about 155.degree. C. A foam composition can
include a crosslinking agent such as an aliphatic unsaturated
amide, such as methylenebisacryl- or -methacrylamide or
ethylenebisacrylamide; aliphatic esters of polyols or alkoxylated
polyols with ethylenically unsaturated acids, such as
di(meth)acrylates or tri(meth)acrylates of butanediol or ethylene
glycol, polyglycols or trimethylolpropane; di- and tri-acrylate
esters of trimethylolpropane; acrylate and methacrylate esters of
glycerol and pentaerythritol; allyl compounds, such as allyl
(meth)acrylate, alkoxylated allyl (meth)acrylate, triallyl
cyanurate, triallyl isocyanurate, maleic acid diallyl ester,
poly-allyl esters, vinyl trimethoxysilane, vinyl triethoxysilane,
polysiloxane comprising at least two vinyl groups,
tetraallyloxyethane, tetraallyloxyethane, triallylamine, and
tetraallylethylenediamine; or a mixture thereof. The foam
composition can include about 0.1 parts per hundred resin to about
1.5 parts per hundred resin, or about 0.3 parts per hundred resin
to about 0.8 parts per hundred resin of the crosslinking agent. A
foam composition can include zinc oxide. The zinc oxide can be
present from about 0.1 parts per hundred resin to about 5 parts per
hundred resin, or about 0.7 parts per hundred resin to about 2
parts per hundred resin. The foam composition can include calcium
carbonate. The calcium carbonate can be present from about 1 parts
per hundred resin to about 10 parts per hundred resin, or from
about 3 parts per hundred resin to about 7 parts per hundred resin.
The foam composition can include a dye or pigment. The dye or
pigment is present in the resin composition at a level of about 0
parts per hundred resin to about 10 parts per hundred resin, or
about 0.5 parts per hundred resin to about 5 parts per hundred
resin based upon the weight of the resin composition.
[0268] When the elastomeric materials an article of footwear or a
component of an article of footwear, such as an outsole of an
article of footwear, the elastomeric material can include an
ingredient providing additional abrasion resistance and durability
as necessary or desirable for use in such articles. The composition
can pass a flex test pursuant to the Cold Ross Flex Test as
described further herein. The composition can have suitable
abrasion loss when measured pursuant to ASTM D 5963-97, as
described further herein. The composition can have an abrasion loss
of 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 Material Sampling
Procedure.
[0269] A component of the article can include a variety of
polyolefin copolymers. The copolymers can be alternating copolymers
or random copolymers or block copolymers or graft copolymers. The
copolymers can be random copolymers. The copolymer can include 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. The copolymer can include 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.
[0270] The polyolefin copolymer can be 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 the each repeat unit in the second
plurality of repeat units is derived from a second olefin. The
second olefin can be an alkene monomer having about 1 to about 6
carbon atoms. The second olefin can include propylene,
4-methyl-1-pentene, 1-butene, or other linear or branched terminal
alkenes having about 3 to 12 carbon atoms. The polyolefin copolymer
can contain 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. The
polyolefin copolymer can consist essentially of polyolefin repeat
units. The polymers in the polymeric composition can consist
essentially of polyolefin copolymers.
[0271] The polyolefin copolymer can include ethylene, i.e. can
include repeat units derived from ethylene. The polyolefin
copolymer can include 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.
[0272] The polyolefin copolymer can be substantially free of
polyurethanes. The polymer chains of the polyolefin copolymer can
be substantially free of urethane repeat units. The polymeric
composition can be substantially free of polymer chains including
urethane repeat units. The polyolefin copolymer can be
substantially free of polyamide groups. The polymer chains of the
polyolefin copolymer can be substantially free of amide repeat
units. The polymeric composition can be substantially free of
polymer chains including amide repeat units.
[0273] The polyolefin copolymer can include polypropylene or can be
a polypropylene copolymer. The polymer component of the polymeric
composition (i.e., the portion of the polymeric composition that is
formed by all of the polymers present in the composition) can
consist essentially of polypropylene copolymers. The polypropylene
copolymer can include 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. The polypropylene
copolymer can include 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. The polypropylene
copolymer can be 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.
[0274] The composition forming the component comprised of the
polyolefin copolymer can include a resin modifier that can improved
flexural durability while maintaining suitable abrasion resistance.
For example, the composition including the resin modifier can pass
a flex test pursuant to the Cold Ross Flex Test using the Plaque
Sampling Procedure, and at the same time, the composition can still
have a suitable abrasion loss when measured pursuant to ASTM D
5963-97a using the Material Sampling Procedure. The composition
including the resin modifier can have no significant change in the
abrasion loss as compared to an abrasion loss of a substantially
similar composition without the resin modifier, when measured
pursuant to ASTM D 5963-97a using the Material Sampling Procedure.
A change in abrasion loss, as used herein, is said to not be
significant when the change is about 30 percent, about 25 percent,
about 20 percent, about 15 percent, about 10 percent, or less when
measured pursuant to ASTM D 5963-97a using the Material Sampling
Procedure.
[0275] The combination of abrasion resistance and flexural
durability can be related to the overall crystallinity of the
composition comprising the polyolefin copolymer. The composition
can have a 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 Differential Scanning
calorimeter (DSC) Test using the Material Sampling Procedure. The
resin modifier can provide a decrease in the percent crystallinity
of the composition, as compared to a substantially similar
composition without the resin modifier. The composition can have a
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 a substantially similar composition without the
resin modifier when measured according to the Differential Scanning
calorimeter (DSC) Test using the Material Sampling Procedure.
[0276] The effective amount of the resin modifier can be 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 composition. The
effective amount of the resin modifier can be about 20 percent,
about 15 percent, about 10 percent, about 5 percent, or less by
weight based upon a total weight of the composition.
[0277] The resin modifier can include a variety of known resin
modifiers. The resin modifier can be a metallocene catalyzed
copolymer primarily composed 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. The resin
modifier can include about 10 percent to about 15 percent ethylene
repeat units by weight based upon a total weight of the polymeric
resin modifier. The resin modifier can be a copolymer containing
isotactic propylene repeat units and ethylene repeat units.
[0278] Now having described various aspects of the present
disclosure, additional detail regarding methods of making and using
the elastomeric material are provided. In an aspect, a method of
making an article (e.g., an article of footwear, an article of
apparel, or an article of sporting equipment, or component of each)
can include attaching (e.g., affixing, coupling, adhering, bonding,
etc.) the elastomeric material to a surface of the article. In an
example and for illustrative purposes as described below, a first
component and a second component including the elastomeric material
are attached to one another, thereby forming the article.
[0279] In regard to an article of footwear, the first component can
be an upper for an article of footwear and/or a sole for an article
of footwear. For example, the step of attaching can include
attaching the sole and the second component such that the
externally-facing layer of the elastomeric material forms at least
a portion of a side of the sole which is configured to be
ground-facing. The footwear can include traction elements, where
the elastomeric material is positioned between the traction
elements and optionally on the sides of the traction elements, but
not on the side(s) configured to touch the ground.
[0280] Referring once again to FIGS. 2F and 2G, the outsole 15 of
the shoe 75 may be engaged with or attached to the upper 25 being
directly adhered thereto. However, when desirable, a portion of the
outsole may be attached to the upper 25 through the use of
additional means conventionally known or used in the construction
of footwear 75, such as through the use of cements or adhesives, by
mechanical connectors, and by sewing or stitching, to name a
few.
[0281] Referring now to FIG. 5A, according to another aspect of the
present disclosure, a method 100 is provided through which an
article of footwear can be formed. While an article of footwear is
used for exemplary purposes, it is to be understood that this
method applies generally to other types of articles. This method
100 may comprise, consist of, or consist essentially of providing
or receiving 105 a first component, such as an upper for an article
of footwear, optionally comprising a textile; providing or
receiving 110 a second component, such as an outsole for an article
of footwear, that includes an elastomeric material that defines an
externally facing side of the article. The elastomeric material
includes a mixture of a polymeric hydrogel and a cured rubber; and
coupling 115 the first component and the second component together.
The polymeric hydrogel is distributed throughout the cured rubber
and at least a portion of the polymeric hydrogel in the elastomeric
material is physically entrapped by the cured rubber. When
desirable, the method may further include providing or receiving
120 a third component such as a midsole; and attaching 125 the
third component to the second component and/or the first component
prior to the attaching of the second component to the first
component, such that the third component resides between the second
component and the first component.
[0282] The method may also comprise fully curing 137 the rubber,
when the rubber is only partially cured in forming the second
component. The curing is accomplished through the occurrence of one
or more crosslinking or polymerizing mechanisms. The occurrence of
such crosslinking mechanisms may be induced by sulfur or peroxide
curing of the partially cured rubber or by exposing the partially
cured rubber to actinic radiation at a concentration and for a
duration to at least partially cure the mixture.
[0283] The step of receiving 110 the second component may comprise
a method 101 of forming an uncured composition 107. This method 101
comprises providing an uncured rubber 126 and providing a hydrogel
127. Then, mixing 130 the hydrogel with the uncured rubber to
distribute the polymeric hydrogel throughout the uncured rubber to
form a mixture composition. The method 101 may further comprise
shaping or forming 132 into a sheet or molding the composition into
a shape, such as the shape of an outsole, by subjecting the
composition to an extrusion process, a molding process, or a
combination thereof. When desirable, the composition is at least
partially cured 137 to form an elastomeric material.
[0284] For the purpose of this disclosure, the term "partially
cured" denotes the occurrence of at least about 1 percent,
alternatively, at least about 5 percent of the total polymerization
required to achieve a substantially full cure. The term "fully
cured" is intended to mean a substantially full cure in which the
degree of curing is such that the physical properties of the cured
material do not noticeably change upon further exposure to
conditions that induce curing (e.g., temperature, pressure,
presence of curing agents, etc.).
[0285] According to another aspect of the present disclosure, a
method 102 of preparing an elastomeric material 129 for use in
forming an article or a component in a finished article such as an
article of apparel or sporting equipment is provided. Referring now
to FIG. 5B, the method 102 comprises the steps of providing 107 a
composition. This composition may include a mixture of a polymeric
hydrogel and an uncured rubber. The uncured composition may be at
least partially cured 119 to form an elastomeric material for use
in a component, such as a component of an article of apparel or
sporting equipment. The polymeric hydrogel is present in the
elastomeric material in an amount that ranges from about 5 weight
percent to about 85 weight percent based on the overall weight of
resin component (i.e., the total weight of all the polymeric
materials present) of the elastomeric material. Optionally, the
elastomeric material may be formed 132 into a component, such that
the elastomeric material defines at least a portion of a surface of
the component that is configured to be externally facing.
[0286] According to another aspect of the present disclosure, a
method 103 for forming an article or a component of an article 135
for use in a finished article, such as an article of apparel or
sporting equipment is provided. Referring now to FIG. 5C, this
method 103 comprises the steps of providing or receiving 129 an
uncured composition or an elastomeric material. When desirable, the
uncured composition or the elastomeric material may be prepared
according to the previously described methods 101 and 102. The
article or component of the article is then formed 132, such that
the uncured composition or the elastomeric material defines at
least a portion of a surface that is configured to be
externally-facing when the component or the article is present in a
finished article. The uncured composition is at least partially
cured to form the elastomeric material and/or the elastomeric
material is partially or fully cured 137, such that it exhibits a
water uptake rate of 10 g/m.sup.2/ min to 120 g/m.sup.2/ min as
measured in the Water Uptake Rate Test over a soaking time of 9
minutes using the Component Sampling Procedure.
[0287] According to yet another aspect of the present disclosure, a
method 104 for manufacturing a finished article is provided.
Referring now to FIG. 5D, the method 104 comprises providing two or
more articles or components of an article 141. At least one
component comprises an elastomeric material 135, wherein the
elastomeric material includes a mixture of a cured rubber and a
polymeric hydrogel. The polymeric hydrogel may comprise an
aliphatic polyurethane (TPU) resin or a polyether block amide
resin, such that the hydrogel is present in an amount ranging from
about 5 weight percent to about 85 weight percent based on the
overall weight of the resin component (i.e., the total weight of
all the polymeric materials present) of the elastomeric material.
The elastomeric material may be either partially cured or fully
cured. The two or more components are attached to one another
(e.g., coupled together) 143, such that the elastomeric material
defines at least a portion of a surface of at least one component
that is configured to be externally facing when this at least one
component is present in a finished article. The elastomeric
material exhibits a water cycling weight loss from about 0 weight
percent to about 15 weight percent as measured pursuant to the
Water Cycling Test and using the Material Sampling Procedure or the
Article Sampling Procedure.
[0288] When desirable, the method 104 may further comprise exposing
145 the finished article or the component of the finished article
that comprises the elastomeric material to actinic radiation at a
concentration and for a duration of time sufficient to fully cure
the elastomeric material. Fully curing 145 the elastomeric material
may be done before, during, or after the step of coupling 143 the
two or more components together.
[0289] In the step 130 (see FIG. 5A) in which the hydrogel and the
uncured rubber are mixed, the materials are mixed together until
they are substantially blended. The mixing may be accomplished
using, without limitation, an intermeshing-type internal mixer, a
tangential-type internal mixer, a planetary mixer, a mill, a ribbon
blender, a cone blender, a screw blender, a drum blender, a Banbury
mixer, or the like. More specifically, the hydrogel and uncured
rubber may be compounded in conventional rubber processing
equipment. In a typical procedure, all components of the
composition are weighed out. The uncured rubber, the hydrogel
(e.g., hydrophilic thermoplastic polyurethane), and any additives
are then compounded in a conventional mixer such as a Banbury
mixer. If desired, the compounded composition may then be further
mixed on a roller mill. At this time, it is possible to add other
additives, such as pigments (e.g., carbon black, etc.). The
composition may be allowed to mature for a period of hours prior to
the addition of a cure system, alternatively, the additives that
comprise the cure system may be added immediately on the roller
mill.
[0290] In the step 132 (see FIGS. 5A and 5B) in which the article
or component of an article (e.g., an outsole, etc.) is formed, the
process of forming the article or component may include, but not be
limited to, the use of one or more of an extrusion process, a
calendaring process, an injection molding process, a compression
molding process, a thermoforming process, or the like.
[0291] In the step 137 (see FIGS. 5A and 5C) in which the
elastomeric material is at least partially cured, alternatively,
fully cured, the curing is accomplished by the occurrence of one or
more crosslinking mechanisms. These crosslinking mechanisms may
occur, without limitation, via the use of crosslinking agents that
are thermally initiated, such as sulfur-based or peroxide-based
crosslinking agents or initiators that crosslink radiation curable
rubbers upon exposure of the rubber to actinic radiation at a
centration and for a duration of time sufficient to achieve the
desired degree of cure. According to another aspect of the present
disclosure, the use of an article or a component of an article
compositionally comprising an elastomeric material to prevent or
reduce soil accumulation on the article or component of a finished
article of apparel or sporting equipment is described. The use
involves incorporating the article or component as an
externally-facing surface in a finished article in order to prevent
or reduce soil accumulation on the component and article. The
component or article retains at least 5 percent less soil by
weight; alternatively, at least 10 percent less soil by weight, as
compared to a conventional component or article that is identical
except that the externally-facing surface of the conventional
component or article is substantially free of an elastomeric
material that comprises a mixture of the hydrogel and the cured
rubber.
[0292] The method of forming an article can comprise forming the
article from a first component including a first material and a
second component including a second material comprising an uncured
composition or an elastomeric material as described herein. The
first material can form a substantial majority of a volume of the
first component, or can be a coating or tie layer present on an
exterior surface or side of the first component. When the first
component comprises a first material including a crosslinkable
polymer, a polymer precursor, or both, attaching the first and
second components can comprise curing the first material in contact
with the second material.
[0293] In one example, the first material can be a first uncured
composition or a first elastomeric material according to the
present disclosure. For example, the first material can comprise
substantially the same rubber(s), can comprise the substantially
the same polymeric hydrogel(s), can comprise substantially the same
concentration of rubber(s), can comprise substantially the same
concentrations of and polymeric hydrogel(s), or any combination
thereof, as the second material. Alternatively or additionally, the
first material and the second material can comprise different types
of polymeric hydrogel(s), or different concentrations of polymeric
hydrogel(s), or different colorant(s), or different concentrations
of colorant(s), or any combination thereof. For example, the first
material and the second material can differ only in the
concentration of polymeric hydrogel(s), or only in the
concentration of colorant(s), or in both the concentration of
polymeric hydrogel(s) and colorant(s).
[0294] In another example, the first material can be substantially
free of a polymeric hydrogel but can include a crosslinkable
polymeric material, or a polymerizable material, so that it is
possible to form crosslinking bonds or polymer bonds between the
first material and the second material.
[0295] The crosslinkable polymeric material can include one or more
elastomeric polymers such as uncured or partially cured rubber, or
polymer precursors such as one or more types of monomers. In one
example, the first material can comprise the same uncured or
partially cured rubber(s) as the second elastomeric material, but
the first material is substantially free of a polymeric hydrogel.
In another example, the first material can comprise one or more
uncured or partially cured rubber(s) which are harder than the
uncured or partially cured rubber(s) of the second material. In
this example, the harder first material can be used to form
traction elements such as lugs. In these examples, where both the
first and second materials comprises crosslinkable or polymerizable
materials, curing the first material and the second material while
in contact with each other can form chemical bonds (e.g.,
crosslinking bonds or polymer bonds) between the first material and
the second material, thereby attaching the first component to the
second component using these chemical bonds. In some cases, it may
not be necessary to further reinforce the bond using an adhesive.
In these cases, the interface between the first component and the
second component can be substantially free of adhesive.
Sampling Procedures
[0296] The properties of the elastomeric material of the component
in a finished article can be characterized using samples prepared
and measured according to the Materials Sampling Procedure or the
Component Sampling Procedure. The Materials Sampling Procedure is
used to obtain a sample of a material of the present disclosure
that is either in media form or isolated in a neat form (i.e.,
without any bonded substrate in a layered film, such as that found
in the composition defined herein). A material is provided in media
form, when it is obtained as flakes, granules, powders, pellets, or
the like. If a source of the material is not available in a media
form, the material can be cut, scraped, or ground from an outsole
of a footwear outsole or from a backing substrate of a co-extruded
sheet or web, thereby isolating the material in media form. When
desirable, the material in media form may be extruded as a web or
sheet having a substantially constant material thickness (within
+/-10 percent of the average material thickness), and cooled to
solidify the resulting web or sheet. A sample of the material in
neat form having a surface area of 4 cm.sup.2 is then cut from the
resulting web or sheet for use in testing.
The Component Sampling Procedure may include the use of one or more
of the following sampling procedures:
(A)--Footwear Sampling Procedure
[0297] This procedure is used to obtain a sample of the elastomeric
material when the elastomeric material is a component of an article
of footwear (e.g., bonded to an article substrate or a substrate).
An article sample, which includes the elastomeric material in a
non-wet state (e.g., at about 25 degrees C. and approximately 20
percent relative humidity) is cut from the article of footwear
using a blade. This process is performed by separating the article
from an associated footwear upper, and removing any materials from
the article's top surface (e.g., corresponding to the top surface)
that can uptake water and potentially skew the water uptake
measurements of the elastomeric material. For example, the
article's top surface can be skinned, abraded, scraped, or
otherwise cleaned to remove any upper adhesives, yarns, fibers,
foams, and the like that could potentially take up water
themselves.
[0298] The resulting sample includes the component and any article
substrate bonded to the component, and maintains the interfacial
bond between the component and the associated substrate of the
finished article. As such, this test can simulate how the
elastomeric material will perform as part of an article of
footwear. Additionally, this sample is also useful in cases where
the interfacial bond between the component and the substrate is
less defined, such as where the elastomeric material of the
component is highly diffused into the substrate of the finished
article (e.g., with a concentration gradient).
[0299] The sample is taken at a location along the article that
provides a substantially constant thickness for the component
(within plus or minus 10 percent of the average thickness), such as
in a forefoot region, mid-foot region, or a heel region of the
article, and has a surface area of about 4.0 square centimeters. In
cases where the elastomeric material is not present on the article
in any segment having a 4.0 square centimeter surface area and/or
where the thickness is not substantially constant for a segment
having a 4.0 square centimeter surface area, sample sizes with
smaller cross-sectional surface areas can be taken and the
area-specific measurements are adjusted accordingly.
(B)--Apparel Sampling Procedure
[0300] This procedure is used to obtain a sample of the elastomeric
material when the elastomeric material is present as a component in
a finished article of apparel (e.g., a garment or other article
excluding an article of footwear). A sample including the component
in a dry state (e.g., at approximately 25 degrees C. and
approximately 20 percent relative humidity) is cut from the article
of apparel using a blade. This process is performed by separating
the component of the article of apparel from any associated
component of the article of apparel. For example, if the component
is present on a sleeve of a shirt, the sleeve component can be
removed from the rest of the garment, and then the sample can be
removed from the sleeve component.
[0301] If possible, any remaining or residual substances can be
removed from the second surface of the component (e.g., the surface
opposing the externally-facing surface which comprises the
elastomeric material) that can take up water and potentially skew
the water uptake measurements of the elastomeric material. For
example, any padding or additional layers, which are not externally
facing during use, can be removed from the second side of the
sample. For example, if appropriate, the second surface can be
skinned, abraded, scraped, or otherwise cleaned to remove any upper
adhesives, yarns, fibers, foams, and the like that could
potentially take up water themselves.
[0302] The resulting sample may include the elastomeric material
present on the side of the component configured to be
externally-facing during use and any substrate or substrate affixed
to the component, and, if one is present, maintains the interfacial
bond between the component and the associated substrate. As such,
this test can simulate how the component will perform as part of an
article of apparel. Additionally, this sample is also useful in
cases where the interfacial bond between the component and the
substrate or substrate is less defined, such as where the
elastomeric material is highly diffused into the substrate (e.g.,
with a concentration gradient).
[0303] The sample is taken at a location along the article of
apparel that provides a substantially constant thickness for the
material (within +/-10 percent of the average material thickness
present in the component), is taken from a portion of the component
where soil would typically accumulate during wear, and has a
surface area of 4.0 square centimeters. In cases where the
elastomeric material is not present on the finished article in any
segment having a 4.0 square centimeter surface area and/or where
the thickness is not substantially constant for a segment having a
4.0 square centimeter surface area, sample sizes with smaller
cross-sectional surface areas can be taken and the area-specific
measurements are adjusted accordingly.
(C)--Equipment Sampling Procedure
[0304] This procedure is used to obtain a sample of the elastomeric
material when the elastomeric material is present as a component in
a finished article of sporting equipment (e.g., when the component
is affixed to a substrate or substrate). A sample including the
elastomeric material in a dry state (e.g., at approximately 25
degrees C. and approximately 20 percent relative humidity) is cut
from the article of sporting equipment using a blade. This process
is performed by separating the component from the finished article
of sporting equipment. For example, if the component is present on
a portion of a golf bag, the portion of the golf bag comprising the
elastomeric material can be removed from the rest of the golf
bag.
[0305] If possible, any remaining substances can be removed from
the second surface of the component (e.g., the surface opposing the
externally-facing surface which comprises the elastomeric material)
that can take up water and potentially skew the water uptake
measurements of the elastomeric material. For example, any padding
or additional layers, which are not externally-facing during use,
can be removed from the second side of the sample. For example, if
appropriate, the second surface can be skinned, abraded, scraped,
or otherwise cleaned to remove any adhesives, yarns, fibers, foams,
and the like that could potentially take up water themselves.
[0306] The resulting sample includes the elastomeric material
present on the externally-facing side of the component and any
substrate affixed to the component, and, if one is present,
maintains the interfacial bond between the material and the
associated substrate or substrate. As such, this test can simulate
how the component will perform as part of an article of sporting
equipment. Additionally, this sample is also useful in cases where
the interfacial bond between the component and the substrate is
less defined, such as where the elastomeric material is highly
diffused into the substrate or substrate (e.g., with a
concentration gradient).
[0307] The sample is taken at a location along the component of the
article of sporting equipment that provides a substantially
constant thickness for the material (within plus or minus 10
percent of the average thickness present in the component). In
addition, the sample is taken from a portion of the component where
soil would typically accumulate during wear, and has a surface area
of 4.0 square centimeters. In cases, where the component is not
present on the finished article in any segment having a 4.0 square
centimeter surface area and/or where the component thickness is not
substantially constant for a segment having a 4.0 square centimeter
surface area, sample sizes with smaller cross-sectional surface
areas can be taken and the area-specific measurements are adjusted
accordingly.
Test Protocols
[0308] The following test procedures are described with reference
to components of finished articles of footwear using the Materials
Sampling Procedure or the Footwear Sampling Procedure as the
Component Sampling Procedure. However, the same tests can be
applied to samples taken with the Apparel Sampling Procedure and/or
the Equipment Sampling Procedure as the Component Sampling
Procedure.
(I)--Water Cycling Test Protocol
[0309] This test measures the mass stability of elastomeric
materials by measuring the weight gain/loss that occurs upon the
reversible absorption of water. Test samples are prepared by
punching out 2.54 cm (1 inch) diameter disks from sheets of the
elastomeric materials. Each of the test samples is weighed prior to
soaking in water with the mass being recorded to the nearest
milligram as the "initial" mass. The test samples are then soaked
in room-temperature water for a time interval of 18-24 hours. To
measure the total mass gain/loss of the elastomeric material, the
test samples are removed from the water and patted dry with a
laboratory wipe to remove free surface water. The test samples are
then allowed to dry in ambient laboratory conditions. The mass of
each test sample is measured incrementally until a steady state is
achieved over a 24 hour period. The final "dried" mass of each test
sample is then measured and compared to the corresponding "initial"
mass.
(II)--Water Uptake Capacity Test Protocol
[0310] This test measures the water uptake capacity of the
elastomeric material after a predetermined soaking duration for a
sample (e.g., taken with the above-discussed Footwear Sampling
Procedure). The sample is initially dried at 60 degrees C. 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 C. is typically a suitable duration). The total weight of
the dried sample (Wt sample dry) is then measured in grams. The
dried sample is allowed to cool down to 25 degrees C., and is fully
immersed in a deionized water bath maintained at 25 degrees C.
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, sample wet) is
measured in grams.
[0311] Any suitable soaking duration can be used, where a 24-hour
soaking duration is believed to simulate saturation conditions for
the hydrophilic resin or hydrogel of the present disclosure (i.e.,
the 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. In an aspect, the elastomeric material can have a "time
value" equilibrium water uptake capacity, where the time value
corresponds to the duration of soaking. For example, a "30 second
equilibrium water uptake capacity" corresponds to a soaking
duration of 30 seconds, a 2 minute equilibrium water uptake
capacity corresponds to 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 elastomeric material.
[0312] As can be appreciated, the total weight of a sample taken
pursuant to the Footwear Sampling Procedure includes the weight of
the material as dried or soaked (Wt. S. Dry or Wt. S. Wet) and the
weight of the substrate (Wt. Sub.) needs to be subtracted from the
sample measurements.
[0313] The weight of the substrate (Wt. Sub.) is calculated using
the sample surface area (e.g., 4.0 square centimeters), an average
measured thickness of the substrate in the sample, and the average
density of the substrate material. Alternatively, if the density of
the material for the substrate is not known or obtainable, the
weight of the substrate (Wt. Sub.) 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 C. for 24 hours,
which can be performed at the same time as the primary sample
drying. The weight of the isolated substrate (Wt. Sub.) is then
measured in grams.
[0314] The resulting substrate weight (Wt. Sub.) is then subtracted
from the weights of the dried and soaked primary sample (Wt. S. Dry
or Wt. S. Wet) to provide the weights of the material as dried and
soaked (Wt. C. Dry or Wt. C. Dry) as depicted by Equations 1 and
2.
Wt. C. Dry=Wt. S. Dry-Wt. Sub (Eq. 1)
Wt. C. Wet=Wt. S. Wet-Wt. Sub. (Eq. 2)
[0315] The weight of the dried component (Wt. C. Dry) is then
subtracted from the weight of the soaked component (Wt. C. 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. C.
Dry) to provide the water uptake capacity for the given soaking
duration as a percentage, as depicted below by Equation 3.
Water Uptake Capacity = Wt . C . Wet - Wt . C . Dry Wt . C . Dry (
100 percent ) ( Eq . 3 ) ##EQU00001##
[0316] 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.
(III)--Water Uptake Rate Test Protocol
[0317] This test measures the water uptake rate of the elastomeric
material by modeling weight gain as a function of soaking time for
a sample with a one-dimensional diffusion model. The sample can be
taken with any of the above-discussed sampling procedures,
including the Footwear Sampling Procedure. The sample is dried at
60 degrees C. until there is no weight change for consecutive
measurement intervals of at least 30 minutes apart (a 24-hour
drying period at 60 degrees C. is typically a suitable duration).
The total weight of the dried sample (Wt. S. 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.
[0318] The dried sample is allowed to cool down to 25 degrees C.,
and is fully immersed in a deionized water bath maintained at 25
degrees C. 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. S. Wet) is measured at particular
soaking-duration data points (e.g., 1, 2, 4, 9, 16, or 25
minutes).
[0319] 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.
[0320] 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).
[0321] As discussed above in the Water Uptake Capacity Test, the
total weight of a sample taken pursuant to the Footwear Sampling
Procedure includes the weight of the material as dried or soaked
(Wt. C. Wetor Wt. C. Dry) and the weight of the article or backing
substrate (Wt. Sub.). In order to determine a weight change of the
material due to water uptake, the weight of the substrate (Wt.
Sub.) 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. C. Wet and Wt. C. Dry for each soaking-duration
measurement.
[0322] The specific weight gain (Wt. Gn.) water uptake for each
soaked sample is then calculated as the difference between the
weight of the soaked sample (Wt. C. Wet) and the weight of the
initial dried sample (W. C. Dry) where the resulting difference is
then divided by the exposed surface area of the soaked sample (A)
as depicted in Equation 4.
( Wt . G . ) = ( Wt . C . Wet - Wt . C . Dry ) ( A ) ( Eq . 4 )
##EQU00002##
for a particular soaking-duration data point (e.g., 1, 2, 4, 9, 16,
or 25 minutes), as mentioned above.
[0323] The water uptake rate for the elastomeric material is then
determined as the slope of the specific weight gains Wt. G.) versus
the square root of time (in minutes) of the soaking duration, as
determined by a least squares linear regression of the data points.
For the elastomeric material of the present disclosure, the plot of
the specific weight gains (Wt. G.) versus the square root of time
(in minutes) of the soaking duration 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
elastomeric material as the water uptake approaches saturation, and
will vary depending on component thickness.
[0324] 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/(surface area-square root of time),
such as grams/(meter.sup.2-minutes.sup.1/2) or g/m.sup.2/ min.
[0325] Furthermore, some component 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.
(IV)--Swelling Capacity Test Protocol
[0326] This test measures the swelling capacity of the component in
terms of increases in thickness and volume after a given soaking
duration for a sample (e.g., taken with the above-discussed
Footwear Sampling Procedure). The sample is initially dried at 60
degrees C. 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 C. 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.
[0327] 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.
[0328] 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.
(V)--Mud Pull-Off Test Protocol
[0329] This test measures, the force required to pull a test sample
away from a 5.1 cm (2 inches) diameter disk of mud (e.g., taken
with the above-discussed Footwear Sampling Procedure). Referring
now to FIGS. 6A and 6B, the test sample 200 and disk of mud 210 are
placed between two parallel aluminum plates 220(A, B). One of the
aluminum plates 220A is movable in a direction that his
perpendicular to the alignment of the parallel plates. The other
aluminum plate 220B is held stationary. The test sample is secured
to the movable plate 220A.
[0330] When the two aluminum plates are separated 250 from each
other the load is set at zero Newton (N). The two plates are then
compressed 260 with the test material and the disk of mud located
between them. The plates are compressed 260 (i.e., "loaded") until
the load applied reaches -445 N (-100 lbs.). Once the load of -445
N is applied, the applied load is then reversed 270 (i.e.,
"unloaded"). The pull-off force represents the load that is
required to be applied in order to separate the test material from
the disk of mud. Thus, the pull-off force is the load measured 280
that is above the zero threshold load. The pull-off force is
measured for each test material a total of 30 times with the final
or recorded pull-off force representing the average of the 30
measurements.
[0331] The following specific examples are given to illustrate the
elastomeric material and the properties exhibited by and measured
for such composition. These specific examples should not be
construed in a way that limits the scope of the disclosure. Those
skilled-in-the-art, in light of the present disclosure, will
appreciate that many changes can be made in the specific
embodiments which are disclosed herein and still obtain alike or
similar result without departing from or exceeding the spirit or
scope of the disclosure. One skilled in the art will further
understand that any properties reported herein represent properties
that are routinely measured and can be obtained by multiple
different methods. The methods described herein represent one such
method and other methods may be utilized without exceeding the
scope of the present disclosure.
Example 1--Mud Pull-Off Test Results
[0332] The following test samples were prepared and tested
according to the Mud Pull-Off Test Protocol and the Footwear
Sampling Procedure as described above. One skilled in the art will
understand that any of the Sampling Procedures can be utilized with
similar results depending upon the type of article in which the
component is used. Each of the test samples (except Control #1)
were prepared using a conventional rubber formulation of natural
rubber, nitrile rubber, and polybutadiene as the cured rubber as
part of the elastomeric material. In each of the test samples
(except Control #1) were prepared using a hydrogel as part of the
elastomeric material as shown in Table 1. In Control #1, a standard
TPU was used (Desmopan 8795A, Covestro AG, Leverkusen,
Germany).
[0333] Referring now to FIG. 7 each of the samples (Control #1; Run
#'s 1-4) were tested 30 times using the Mud Pull-Off Test protocol
described above. Each of the test samples were prepared and soaked
in water for a period of 24 hours prior to conducting the mud
pull-off test. The control sample comprising only a standard TPU
(Control 1) required a mud pull-off load or force ranging from
about 1 Newton (N) to about 10 N with an overall average of about 6
Newton. In comparison, each of Run #'s 1-4, which included an
elastomeric material according to the present disclosure exhibited
a mud pull-off force that was less than about 0.3 N with an average
mud pull-off force on the order of about 0.01 N for Run #1, about
0.05 N for Run #2, about 0.20 N for Run #3, and about 0.1 N for Run
#4. This example demonstrates that the mud pull-off force exhibited
by a component comprising the elastomeric material of the present
disclosure is lower than that expected for a component prepared
solely with a standard thermoplastic polyurethane.
TABLE-US-00001 TABLE 1 wt. percent (phr) Polymeric Hydrogel in the
Elasomeric Material Type of Polymeric Hydrogel Control 1 100
percent Desmopan 8795A TPU (Covestro AG, Leverkusen, Germany) Run 1
14 wt. percent Estane .RTM. ALR-G2000 Hydrogel TPU (25 phr)
Material, (Lubrizol Advanced Materials Inc., Cleveland, OH) and
cured rubber Run 2 57 wt. percent Estane .RTM. ALR-G2000 Hydrogel
TPU (200 phr) Material (Lubrizol Advanced Materials Inc.,
Cleveland, OH) and cured rubber Run 3 24 wt. percent Estane .RTM.
ALR-L400 Hydrogel TPU (50 phr) Material (Lubrizol Advanced
Materials Inc., Cleveland, OH) and cured rubber Run 4 57 wt.
percent Estane .RTM. ALR-L400 Hydrogel TPU (200 phr) Material
(Lubrizol Advanced Materials Inc., Cleveland, OH) and cured
rubber
[0334] Referring now to FIGS. 8A and 8B, a diagram of the applied
force per unit area (i.e., Engineering Stress in MPa) plotted as a
function of displacement can also be obtained by conducting this
type of test. This plot demonstrates that the mixing of a
hydrophilic resin with a cured rubber enhances the compliance of
the resulting elastomeric material or layer. The greatest stress
values are measured for the sample (Control #2) in which no
hydrophilic resin (0 phr) is present, but rather only the cured
rubber, i.e., a mixture of natural rubber, nitrile rubber, and
polybutadiene. The compliance of the elastomeric material increases
as the amount of the hydrophilic resin or hydrogel that is mixed
with the cured rubber increases (i.e., from 0 phr to 43.75 phr as
shown in Run numbers 5 to 8). In addition, a larger effect is
observed when the elastomeric material in the component is wet,
e.g., soaked for a period of 24 hours (see FIG. 8B) as compared to
being dry (see FIG. 8A). One skilled in the art will understand
that water exposure has little effect on only the cured rubber as
shown by comparing the 0 phr curves (Control #2) in FIGS. 8A and
8B.
Example 2--Water Uptake Rate & Capacity Results
[0335] Test samples were prepared by mixing various amounts (50
phr, 100 phr, 150 phr, & 200 phr) of a hydrophilic resin (e.g.,
either ALR-L400 or ALR-G2000, Lubrizol Advanced Materials Inc.)
into a conventional cured rubber (i.e., a mixture of natural
rubber, nitrile rubber, and polybutadiene). The test samples were
then subjected to both the Water Uptake Rate Test protocol and the
Overall Water Uptake Capacity Test protocol. Referring now to FIGS.
9A and 9B. As the amount of the hydrophilic resin or hydrogel in
the crosslinked elastomeric material increases, the water uptake
rate also increases. The water uptake rate over the range of 50 phr
to 200 phr of a hydrophilic TPU (ALR-L400) added to an elastomeric
rubber (FIG. 9A) increased from about 25 g/m.sup.2/ min to about 72
g/m.sup.2/ min. Similarly, the water uptake rate over the range 25
phr to 100 phr of a hydrophilic TPU (ALR-G2000) added to the same
cured rubber (FIG. 9B) increased from about 14 g/m.sup.2/ min to
about 57 g/m.sup.2/ min. Although there is a slight difference in
the water uptake rate depending upon the composition of the
hydrophilic resin, the same trend is observed as the loading of the
hydrophilic resin is increased. Similar results are also observed
when the hydrophilic resin is a polyether block amide (i.e.,
contains hydrophilic polyether groups and rigid polyamide groups),
such as PEBAX 1074, commercially available from Arkema Specialty
Polyamides, France.
[0336] Referring now to FIG. 10, the same trend is also observed as
the loading of the hydrophilic resin is increased when using
different compositions of a cured rubber. In FIG. 9, the water
uptake rate is plotted as a function of hydrophilic resin loading
for elastomeric materials containing different cured rubber
mixtures. The difference between the cured rubber mixtures resides
in both the quantity of different conventional rubbers as well as
the use of natural rubber and regrind materials (in Rubber A)
versus a synthetic rubber and virgin materials (in Rubber B).
[0337] Referring once again to FIGS. 9A and 9B, the overall water
capacity of the elastomeric materials increased as the loading of
the hydrophilic resin (e.g., ALR-L400 or ALR-G2000) increased. The
overall water capacity after a 24-hour soak time for the
elastomeric material in Runs 9-12 increased from 59 percent to 194
percent, while the overall water capacity for the elastomeric
materials in Runs 13-16 increased from 35 percent to 170
percent.
[0338] Referring now to FIGS. 11A and 11B, photomicrographs of mud
present on the surface of a component soaked for a period of 24
hours are shown. In FIG. 11A, the mud is more compact (i.e.,
substantial accumulation) since the component does not comprise any
polymeric hydrogel (0 phr), but rather only a conventional cured
rubber (Control 2). In comparison, the mud shown in FIG. 11B is
found to be more dispersed (i.e., less has accumulated) on the
surface of a component that comprises a total of 50 phr of a
polymeric hydrogel (ALR-G2000, Lubrizol) mixed with the cured
rubber in an elastomeric material according to the present
disclosure.
Example 3--Swelling Test Results
[0339] A test sample comprising Control #2 in which no hydrophilic
resin (0 phr) is present, but rather only the cured rubber, i.e., a
mixture of natural rubber, nitrile rubber, and polybutadiene. Test
samples were also prepared mixing the cured rubber of Control #2
with a hydrophilic TPU resin (ALR-G2000, Lubrizol) at 25 phr (Run
17), 50 phr (Run 18), and 75 phr (Run 18). All of the test samples
(Control #2, Runs 17-19) were rectangular in shape and measured
15.25 cm (6 inches) by 10.15 cm (4 inches). Each of the test
samples were subjected to the Swelling Capacity Test for a period
of 24 hours.
[0340] The results of this test are visually depicted in FIG. 12.
The Control #2 was observed not to swell, while each the test
samples (Runs 17-19) were found to swell, such that the degree of
swelling increased as the amount of the polymeric hydrogel present
in the elastomeric material increased. In other words, the degree
of swelling followed the progression of Run 17<Run 18<Run
19.
Example 4--Water Cycling Test Results
[0341] The following test samples were prepared and tested
according to the Water Cycling Test Protocol and the Material
Sampling Procedure as described above. A test sample was prepared
by mixing 100 phr, of a hydrophilic thermoplastic urethane (TPU)
resin (ALR-G2000, Lubrizol Advanced Materials Inc.) into a
conventional cured rubber (i.e., a mixture of natural rubber,
nitrile rubber, and polybutadiene) according to the teachings of
the present disclosure. Similar test samples were prepared with the
hydrophilic resin being substituted with a polyacrylic acid (either
AP75 or AP93, Evonik Corp., Alabama). The weight measurements for
each test sample taken initially, after completion of the Water
Cycling Test protocol are provided in Table 2 below.
TABLE-US-00002 TABLE 2 After Polymeric Soak - Total hydrogel
Original After Weight After change in type Mass Soak Gain Dry
Weight (100 phr) (g) (g) (percent) (g) (percent) Run Polymeric 1099
2095 47.50 1167 5.8 20 hydrogel percent (ALR-G2000, Lubrizol Adv.
Mat. Inc.) Run Polymeric 758 992 Polymeric 629 -17.06 21 hydrogel
hydrogel (AP75, Evonik flaked off Corporation) sample Run Polymeric
757 929 Polymeric 590 -22.1 22 hydrogel hydrogel (AP93, Evonik
flaked off Corporation) sample
[0342] This example demonstrates that the use of a thermoplastic
polyurethane (TPU) as defined herein as a hydrogel added to an
uncured rubber and then cured results in no weight loss upon
exposure to water. Rather as shown in Run 20, the elastomeric
material formed according to the teachings of the present
disclosure resulted in a weight gain of 5.8 weight percent after
the Water Cycling Testing. In comparison, the test samples that
incorporated polyacrylic acid (PAA) as shown in Runs 21 and 22 were
observed to flake during water exposure and result in in overall
weight loss in the Water Cycle Test ranging from about -17 weight
percent to about -22 weight percent.
[0343] Referring now to FIGS. 13A and 13B, the surface of the
elastomeric material 300 in test sample Run 20 was observed to be
visibly similar to the elastomeric material 300C in the original
(i.e., initial dry) state. However, upon exposure to water for only
30 seconds differences between the test samples (Runs 20 & 22)
become self-evident. More specifically, in Run 22 (see FIG. 13A),
the polymeric hydrogel is observed to swell as shown by the dark
regions 305 visibly observable in the photomicrograph. In Run 22,
the polymeric hydrogel (dark regions) 305 are shown in the
photomicrograph to be separated from the cured rubber 310. In
comparison, in Run 20, the elastomeric material 300 formed
according to the teachings of the present disclosure exhibits
uniform surface swelling with no separation of the thermoplastic
polyurethane (TPU) polymeric hydrogel and the cured rubber being
observable.
Clauses:
[0344] Clause 1. A composition comprising: a rubber; and a
polymeric hydrogel; wherein, in the composition, the polymeric
hydrogel is distributed throughout the rubber. Clause 2. The
composition of clause 1, wherein the rubber is an uncured rubber
and wherein, in the composition, the polymeric hydrogel is
distributed throughout the uncured rubber. Clause 3. The
composition of any preceding clause, wherein the rubber is a cured
rubber, wherein the composition is an elastomeric material,
wherein, in the elastomeric material, the polymeric hydrogel is
distributed throughout the cured rubber and at least a portion of
the polymeric hydrogel in the elastomeric material is entrapped by
the cured rubber, wherein optionally the polymeric hydrogel is
physically entrapped by the cured rubber, or is chemically bonded
to the cured rubber, or is both physically entrapped by the cured
rubber and chemically bonded to the cured rubber. Clause 4. The
composition of clause 3, wherein the composition of the polymeric
hydrogel and the cured rubber has a water uptake of at least 40
percent by weight, based on a total weight of the composition, or
at least 60 percent by weight, or at least 80 percent by weight, or
at least 100 percent by weight. Clause 5. The composition of any
preceding clause, wherein the polymeric hydrogel comprises a
polyurethane hydrogel, and optionally wherein the polyurethane
hydrogel is a reaction polymer of a diisocyanate with a polyol.
Clause 6. The structure of any preceding clause, wherein the
polyurethane hydrogel comprises a thermoplastic polyurethane (TPU)
which includes a plurality of alkoxy segments and a plurality of
diisocyanate segments, wherein the plurality of diisocyanate
segments are linked to each other by chain extending segments;
optionally wherein the TPU is a reaction polymer of a diisocyanate
with a polyol; or optionally wherein the diisocyanate segments
comprise an aliphatic diisocyanate segment, an aromatic
diisocyanate segment, or both. Clause 7. The composition of any
preceding clause, wherein the diisocyanate segments comprise
aliphatic diisocyanate segments; optionally wherein the aliphatic
diisocyanate segments include hexamethylene diisocyanate (HDI)
segments; optionally wherein a majority of the diisocyanate
segments are HDI segments; and optionally wherein the aliphatic
diisocyanate segments include isophorone diisocyanate (IPDI)
segments. Clause 8. The composition of any preceding clause,
wherein the diisocyanate segments includes aromatic diisocyanate
segments; optionally wherein the aromatic diisocyanate segments
include diphenylmethane diisocyanate (MDI) segments; and optionally
wherein the aromatic diisocyanate segments include toluene
diisocyanate (TDI) segments. Clause 9. The composition of any
preceding clause, wherein the alkoxy segments include ester
segments and ether segments, or optionally wherein the alkoxy
segments include ester segments, or optionally wherein the alkoxy
segments include ether segments. Clause 10. The composition of any
preceding clause, wherein the polymeric hydrogel comprises a
polyamide hydrogel, optionally wherein the polyamide hydrogel is a
reaction polymer of a condensation of diamino compounds with
dicarboxylic acids. Clause 11. The composition of any preceding
clause, wherein the polymeric hydrogel comprises a polyurea
hydrogel, optionally wherein the polyurea hydrogel is a reaction
polymer of a diisocyanate with a diamine. Clause 12. The
composition of any preceding clause, wherein the polymeric hydrogel
comprises a polyester hydrogel, optionally wherein the polyester
hydrogel is a reaction polymer of a dicarboxylic acid with a diol.
Clause 13. The composition of any preceding clause, wherein the
polymeric hydrogel comprises a polycarbonate hydrogel, optionally
wherein the polycarbonate hydrogel is a reaction polymer of a diol
with phosgene or a carbonate diester. Clause 14. The composition of
any preceding clause, wherein the polymeric hydrogel comprises a
polyetheramide hydrogel, optionally wherein the polyetheramide
hydrogel is a reaction polymer of dicarboxylic acid and polyether
diamine. Clause 15. The composition of any preceding clause,
wherein the polymeric hydrogel comprises a hydrogel formed of
addition polymers of ethylenically unsaturated monomers. Clause 16.
The composition of any preceding clause, wherein the polymeric
hydrogel comprises a hydrogel formed of a copolymer, wherein the
copolymer is a combination of two or more types of polymers within
each polymer chain, optionally wherein the copolymer is selected
from the group consisting of: a polyurethane/polyurea copolymer, a
polyurethane/polyester copolymer, and a polyester/polycarbonate
copolymer. Clause 17. The composition of any preceding clause,
wherein the hydrogel comprises a plurality of copolymer chains,
each copolymer chain independently having a combination of hard
segments (HS) and soft segments, wherein each of the soft segments
(SS) independently includes a plurality of hydroxyl groups, one or
more poly(ethylene oxide) (PEO) segments, or both; optionally
wherein each of the soft segments (SS) of the polymeric hydrogel
independently has a greater level of hydrophilicity than each of
the hard segments (HS); and optionally wherein an average ratio of
a number of soft segments to a number hard segments (SS:HS) present
in the copolymer chains of the polymeric hydrogel range from about
6:1 to about 100:1. Clause 18. The composition of any preceding
clause, wherein the polymeric hydrogel has a water uptake capacity
in the range of about 50 weight percent to about 2000 weight
percent, as measured using the Water Uptake Capacity Test with the
Material Sampling Procedure; optionally wherein the polymeric
hydrogel has a water uptake capacity in the range of about 100
weight percent to about 1500 weight percent, or wherein the
polymeric hydrogel has a water uptake capacity in the range of
about 300 weight percent to about 1200 weight percent. Clause 19.
The composition of any preceding clause, wherein the polymeric
hydrogel has a water uptake rate of 10 g/m.sup.2/ min to 120
g/m.sup.2/ min as measured using the Water Uptake Rate Test with
the Material Sampling Procedure. Clause 20. The composition of any
preceding clause, wherein the composition includes from about 0.5
parts per hundred resin to about 85 parts per hundred resin of the
polymeric hydrogel based on an overall weight of the composition,
wherein the composition includes from about 5 parts per hundred to
about 80 parts per hundred of the polymeric hydrogel based on an
overall weight of the composition, wherein the composition includes
from about 10 parts per hundred to about 75 parts per hundred of
the polymeric hydrogel based on an overall weight of the
composition, or wherein the composition includes from about 20
parts per hundred to about 70 parts per hundred of the polymeric
hydrogel based on an overall weight of the composition. Clause 21.
The composition of any preceding clause, wherein the composition
includes a colorant, and the colorant is selected from a dye,
pigment, or combination thereof. Clause 22. The composition of any
preceding clause, wherein the uncured rubber comprises an uncured
natural rubber, or an uncured synthetic rubber, or both. Clause 23.
The composition of any preceding clause, wherein the uncured rubber
is an uncured butadiene rubber, an uncured styrene-butadiene (SBR)
rubber, an uncured butyl rubber, an uncured isoprene rubber, an
uncured nitrile rubber, an uncured urethane rubber, or any
combination thereof. Clause 24. The composition of any preceding
clause, wherein the composition further comprises a crosslinking
agent for crosslinking the uncured rubber, optionally wherein the
crosslinking agent is a thermally initiated crosslinking agent; and
optionally wherein the thermally initiated crosslinking agent is a
sulfur-based crosslinking agent or a peroxide-based crosslinking
agent. Clause 25. The composition of any preceding clause, wherein
the uncured rubber is an actinic radiation curable rubber, and the
crosslinking agent is an initiator for crosslinking the radiation
curable rubber upon exposure to actinic radiation. Clause 26. The
composition of any preceding clause, wherein the elastomeric
material is a crosslinked reaction product of a mixture comprising
the polymeric hydrogel and the rubber. Clause 27. The composition
of any preceding clause, wherein at least a portion of the
polymeric hydrogel is entrapped in the elastomeric material,
optionally wherein the polymeric hydrogel is covalently bonded to
the cured rubber. Clause 28. The composition of any preceding
clause, wherein substantially all the polymeric hydrogel in the
elastomeric material is physically entrapped by the cured rubber.
Clause 29. The composition of any preceding clause, wherein the
cured rubber is a cured butadiene rubber, a cured styrene-butadiene
(SBR) rubber, a cured butyl rubber, a cured isoprene rubber, a
cured nitrile rubber, a cured urethane rubber, or a combination
thereof. Clause 30. The composition of any preceding clause,
wherein the elastomeric material has an equilibrium water uptake
capacity of at least 20 weight percent, or at least 40 weight
percent, or at least 60 weight percent, or at least 80 weight
percent. Clause 31. The composition of any preceding clause,
wherein the elastomeric material has an equilibrium water uptake
capacity of at least 100 weight percent. Clause 32. The composition
of any preceding clause, wherein the elastomeric material has a
water cycling weight loss from about 0 weight percent to about 15
weight percent as measured using the Water Cycling Test with the
Material Sampling Procedure. Clause 33. An article comprising: an
elastomeric material including a cured rubber and a polymeric
hydrogel; wherein, in the elastomeric material, the polymeric
hydrogel is distributed throughout the cured rubber, and at least a
portion of the polymeric hydrogel present in the elastomeric
material is entrapped by the cured rubber. Clause 34. The article
of clause 33, wherein the elastomeric material further comprises a
first colorant homogeneously distributed throughout the elastomeric
material. Clause 35. The article of any preceding clause, wherein
the elastomeric material further comprises a first colorant is
heterogeneously distributed throughout the elastomeric material.
Clause 36. The article of any preceding clause, wherein the
elastomeric material further comprises one or more colorants.
Clause 37. The article of any preceding clause, wherein the
elastomeric material is one as described in one of clauses of the
preceding clauses. Clause 38. The article of any preceding clause,
wherein the article has a water cycling weight loss of less than 10
weight percent. Clause 39. The article of any preceding clause,
wherein the elastomeric material has a dry-state thickness in the
range of about 0.2 mm to about 2.0 mm. Clause 40. The article of
any preceding clause, wherein the elastomeric material has a
saturated-state thickness that is at least 100 percent greater than
the dry-state thickness of the elastomeric material or wherein the
saturated-state thickness of the elastomeric material is at least
200 percent greater than the dry-state thickness of the elastomeric
material. Clause 41. The article of any preceding clause, wherein
the elastomeric material is attached to a textile, and optionally
the textile is a knit textile, a woven textile, a non-woven
textile, a braided textile a crocheted textile, or any combination
thereof. Clause 42. The article of any preceding clause, wherein
elastomeric material comprises a plurality of fibers, one or more
yarns, one or more textiles, or any combination thereof. Clause 43.
The article of any preceding clause, wherein the elastomeric
material is attached to, a plurality of fibers, one or more yarns,
one or more textiles, or any combination thereof, wherein the
plurality of fibers, the one or more yarns, the one or more
textiles, or the combination thereof, comprise synthetic fibers.
Clause 44. The article of any preceding clause, wherein the
synthetic fibers or yarns comprise, consist of, or consist
essentially of a thermoplastic composition, and optionally the
thermoplastic composition comprises, consists of, or consists
essentially of a thermoplastic polyurethane (TPU), a thermoplastic
polyamide, a thermoplastic polyester, a thermoplastic polyolefin,
or a mixture thereof. Clause 45. The article of any preceding
clause, wherein the plurality of fibers, the one or more yarns, the
one or more textiles, or any combination thereof, is a filler or as
a reinforcing element, and optionally wherein the plurality of
fibers are dispersed in elastomeric material, or wherein the
elastomeric material infiltrates the yarn and/or the textile and
consolidates the fibers of the yarn and/or the fibers or yarn of
the textile. Clause 46. The article of any preceding clause,
wherein the article is an article of footwear, a component of
footwear, an article of apparel, a component of apparel, an article
of sporting equipment, or a component of sporting equipment. Clause
47. The article of any preceding clause, wherein the article is an
article of footwear, and optionally wherein the article is a sole
component for an article of footwear. Clause 48. The article of any
preceding clause, further comprising a first layer comprising the
elastomeric material and a second layer comprising a cured rubber,
wherein the first layer and the second layer is attached to one
another by crosslinks between the cured rubber of the first layer
and the cured rubber of the second layer. Clause 49. The article of
any preceding clause, wherein the second comprises one or more of
the traction elements, wherein the traction elements are on a side
of the article of footwear configured to be ground facing. Clause
50. The article of any preceding clause, wherein the traction
elements are selected from the group consisting of: a cleat, a
stud, a spike, and a lug. Clause 51. The article of any preceding
clause, wherein the traction elements are integrally formed with an
outsole of the article of footwear. Clause 52. The article of any
preceding clause, wherein the traction elements are removable
traction elements. Clause 53. The article of any preceding clause,
wherein the elastomeric material is not disposed on tip of the
traction element configured to be ground contacting. Clause 54. The
article of any preceding clause, wherein the elastomeric material
is disposed in an area separating the traction elements and
optionally on one or more sides of the traction elements. Clause
55. An article of footwear comprising: an upper; and an outsole
comprising a first region having a first elastomeric material;
wherein the first region defines a portion of an externally facing
side of the outsole, and wherein the first elastomeric material
includes a mixture of a first cured rubber and a first polymeric
hydrogel at a first concentration; wherein, in the first
elastomeric material, the first polymeric hydrogel is distributed
throughout the first cured rubber and at least a portion of the
first polymeric hydrogel present in the first elastomeric material
is entrapped by the first cured rubber, wherein the first
elastomeric material is capable of taking up water. Clause 56. The
article of clause 55, wherein the outsole comprises a second region
having a second elastomeric material, wherein the first region and
the second region are adjacent one another, wherein the second
region defines a portion of the externally facing side of the
outsole, and wherein the second elastomeric material includes a
mixture of a second cured rubber and a second polymeric hydrogel at
a second concentration, wherein, in the second elastomeric
material, the second polymeric hydrogel is distributed throughout
the second cured rubber and at least a portion of the second
polymeric hydrogel present in the second elastomeric material is
entrapped by the second cured rubber. Clause 57. The article of any
preceding clause, wherein the first hydrogel and the second
hydrogel are the same. Clause 58. The article of any preceding
clause, wherein the first hydrogel and second hydrogel are
different. Clause 59. The article of any preceding clause, wherein
the first hydrogel and second hydrogel concentrations are the same.
Clause 60. The article of any preceding clause, wherein the first
hydrogel and second hydrogel concentrations are different. Clause
61. The article of any preceding clause, wherein the first
elastomeric material comprises a first colorant at a first
concentration. Clause 62. The article of any preceding clause,
wherein the second elastomeric material comprises a second colorant
at a second concentration. Clause 63. The article of any preceding
clause, wherein the first and second colorants are the same. Clause
64. The article of any preceding clause, wherein the first and
second colorant concentrations are the same. Clause 65. The article
of any preceding clause, wherein the first and second colorant
concentrations are different. Clause 66. The article of any
preceding clause, wherein the externally facing side of the article
formed by the elastomeric material has a mud pull-off force that is
less than about 12 Newton as determined by the Mud Pull-Off Test
using the Component Sampling Procedure. Clause 67. The article of
any preceding clause, wherein the elastomeric material is any
preceding clause. Clause 68. The article of any preceding clause,
wherein the article of footwear comprises one or more of the
traction elements, wherein the traction elements are on a side of
the article of footwear configured to be ground
facing; optionally wherein the traction elements are selected from
the group consisting of: a cleat, a stud, a spike, and a lug,
optionally wherein the one or more traction elements include
traction elements integrally formed with an outsole of the article
of footwear or traction elements which are removable traction
elements, or both; optionally wherein the elastomeric material is
not disposed on tip of the traction element configured to be ground
contacting; and optionally wherein the elastomeric material is
disposed in an area separating the traction elements and optionally
on one or more sides of the traction elements. Clause 69. The
article of any preceding clause, further comprising a first layer
comprising the elastomeric material and a second layer comprising a
rubber, wherein the first layer and the second layer is attached to
one another by crosslinks between the cured rubber of the first
layer and the cured rubber of the second layer. Clause 70. A method
of making an article, comprising: attaching a first component and a
second component including the elastomeric material of any
preceding clause to one another, thereby forming the article.
Clause 71. The method of any preceding clause, wherein the article
is an article of footwear, an article of apparel, or an article of
sporting equipment or wherein the first component is an upper
component for an article of footwear, or wherein the second
component is a sole component for an article of footwear. Clause
72. The method of any preceding clause, wherein the step of
attaching is attaching the sole component such that the externally
facing layer of the elastomeric material forms at least a portion
of a side of the sole component which is configured to be
externally facing. Clause 73. The method of any preceding clause,
further comprising disposing the elastomeric material in an area
separating the traction elements and optionally on one or more
sides of the traction elements. Clause 74. The method of any
preceding claim, further comprising a first component comprising a
first material and a second component comprising a second material,
wherein attaching the first component and the second component
comprises curing the first material and the second material in
contact with each other and forming chemical bonds between a first
material and the second material, optionally wherein, prior to the
curing, the first material is a first uncured composition or a
first partially cured elastomeric material and the second material
is a second uncured composition or a second partially cured
elastomeric material, or is a second uncured or partially cured
rubber substantially free of a polymeric hydrogel, and forming
chemical bonds between the first material and the second material
includes fully curing the rubber of the first and second materials
and forming crosslinking bonds between the rubber of the first and
second materials. Clause 75. An article comprising: a product of
the method of any preceding clause. Clause 76. The article of
clause 75, wherein the first component is a substrate that
comprises a polymeric foam, a molded solid polymeric material, a
textile, or a combination thereof, and the second component is
attached to the first component. Clause 77. The article of any
preceding clause, wherein the first component is a substrate that
includes a thermoset polymeric material, a thermoplastic polymeric
material, or both. Clause 78. The article of any preceding clause,
wherein the thermoplastic polymeric material includes a
thermoplastic polyurethane, a thermoplastic polyester, a
thermoplastic polyamide, a thermoplastic polyolefin, or any
combination thereof. Clause 79. The article of any preceding
clause, wherein the first component includes a textile, wherein the
textile is selected from a knit textile, a woven textile, a
non-woven textile, a braided textile, or a combination thereof.
Clause 80. The article of any preceding clause, wherein the textile
includes fibers or yarns formed from a thermoplastic polymeric
material that includes a thermoplastic polyurethane, a
thermoplastic polyester, a thermoplastic polyamide, a thermoplastic
polyolefin, or any combination thereof. Clause 81. An article of
any preceding clause, wherein the article is an outsole including a
first elastomeric material; wherein the first elastomeric material
forms a first portion of an externally-facing side of the outsole;
wherein the first elastomeric material includes a mixture of a
first cured rubber and a first polymeric hydrogel at a first
concentration, in which the first polymeric hydrogel is distributed
throughout and entrapped by a first polymeric network including the
first cured rubber, and the first elastomeric material has a water
uptake capacity of at least 40 percent by weight based on a total
weight of the first elastomeric material present in the first
portion. Clause 82. A method of preparing a composition, the method
comprising: providing an uncured rubber; providing a polymeric
hydrogel; and mixing the uncured rubber and the polymeric hydrogel
together to distribute the polymeric hydrogel throughout the
uncured rubber, forming the composition. Clause 83. The method of
clause 138, wherein the composition is the composition of any
preceding clause. Clause 84. The method of any preceding clause,
wherein the step of mixing included mixing the uncured rubber and
the polymeric hydrogel together until they are substantially
blended. Clause 85. The method of any preceding clause, further
comprising shaping the mixed composition. Clause 86. The method of
any preceding clause, wherein shaping the mixed composition
includes forming the mixed composition into a sheet or molding the
mixed composition into a shape. Clause 87. The method of any
preceding clause, further comprising exposing the composition to
actinic radiation in an amount and for a duration to at least
partially cure the mixed composition to form an elastomeric
material. Clause 88. A composition prepared according to the method
of preceding clause. Clause 89. An elastomeric material prepared
according to the method of clause 88. Clause 90. A method of
forming an elastomeric material, the method comprising: providing a
composition including a mixture of an uncured rubber and a
polymeric hydrogel, wherein, in the composition, the polymeric
hydrogel is distributed throughout the uncured rubber; and curing
the composition to form the elastomeric material, wherein the
polymeric hydrogel is distributed throughout the cured rubber and
at least a portion of the polymeric hydrogel present in the
elastomeric material is entrapped by the cured rubber. Clause 91.
An elastomeric material prepared according to any preceding clause.
Clause 92. A method of forming an article, the method comprising:
providing a composition including a mixture of an uncured rubber
and a polymeric hydrogel; wherein, in the composition, the
polymeric hydrogel is distributed throughout the uncured rubber;
shaping the composition to form a shaped composition; and curing
the shaped composition to cure the uncured rubber of the
composition and form the article, the article comprising an
elastomeric material in which the polymeric hydrogel is distributed
throughout the cured rubber and at least a portion of the polymeric
hydrogel in the elastomeric material is entrapped by cured rubber.
Clause 93. The method of any preceding clause, wherein the shaping
includes extruding, calendaring, molding, thermoforming, or any
combination thereof, the composition to form the shaped
composition. Clause 94. The method of any preceding clause, wherein
the curing includes exposing the composition to actinic radiation
in an amount and for a duration sufficient to at least partially
cure the composition. Clause 95. The method of any preceding
clause, wherein the curing includes exposing the composition to
actinic radiation in an amount and for a duration sufficient to
fully cure the composition. Clause 96. The method of any preceding
clause, wherein the method further comprises shaping the article
after the curing. Clause 97. The method of any preceding clause,
wherein the shaping the article includes cutting, molding,
thermoforming, or any combination thereof, the elastomeric material
of the article. Clause 98. The method of any preceding clause,
wherein the shaped composition is disposed on a first layer
comprising an uncured rubber or partially cured rubber, wherein
curing the shaped composition further comprises curing the uncured
rubber or partially cured rubber of the composition and the uncured
rubber of the first layer and forming crosslinking bonds between
the cured rubber in the shaped composition and cured rubber in the
first layer, forming crosslinking bonds between the cured rubber in
the first layer and polymeric hydrogel, or a combination thereof.
Clause 99. A method of forming an outsole, the method comprising:
shaping a first composition to form a first portion of an
externally-facing side an outsole, wherein the first composition
includes a mixture of a first uncured or partially cured rubber and
a first polymeric hydrogel at a first concentration, wherein the
first polymeric hydrogel is distributed throughout the first
uncured or partially cured rubber; and curing the first portion to
form a first elastomeric material, thereby curing the first uncured
or partially cured rubber into a first fully cured rubber, and
forming a first polymeric network including the first fully cured
rubber in the first elastomeric material, wherein the first
polymeric hydrogel is distributed throughout and entrapped by the
first polymeric network. Clause 100. The method of any preceding
clause, wherein the article is an outsole, and the method
comprises: the shaping the second composition comprises placing the
second composition in a second region of a mold, wherein the second
region of the mold is configured to form traction elements; the
shaping the first composition and contacting the at least an edge
of the first portion with the at least an edge of the second
portion comprises placing the first composition in a first region
of the mold, wherein the first region of the mold is configured to
form a substrate for the traction elements, and placing the first
composition in the first region of the mold comprises contacting a
second side of the second portion with a first side of the first
portion; the curing comprises curing fully curing both the first
portion and the second portion in the mold and bonding the first
side of the first portion to the second side of the second portion;
and following the curing, removing the bonded first portion and
second from the mold. Clause 101. The method of any preceding
clause, wherein the curing includes exposing the first composition
to actinic radiation in an amount and for a duration sufficient to
fully cure the first uncured or partially cured rubber of the first
composition. Clause 102. The method of any preceding clause,
further comprising: shaping a second composition to form a second
portion of the externally-facing side the outsole, wherein the
second composition includes a second uncured or partially cured
rubber; and curing the shaped second composition, forming a second
material including a second fully cured rubber. Clause 103. The
method of any preceding clause, further comprising: contacting at
least an edge of the first portion with at least an edge of the
second portion; and wherein the curing comprises curing the first
portion or the second portion or both while the at least an edge of
the first portion and the at least an edge of the second portion
are in contact, and comprises forming crosslinking bonds between
the first uncured or partially cured rubber and the second uncured
or partially cured rubber during the curing, thereby bonding the
first portion to the second portion. Clause 104. The method of any
preceding clause, wherein the shaping comprises forming one or more
traction elements from the second composition. Clause 105. An
article prepared according to the method of any of clauses.
[0345] It should be noted that ratios, concentrations, amounts, and
other numerical data may be expressed herein in a range format. 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 concentration range of "about 0.1 percent
to about 5 percent" should be interpreted to include not only the
explicitly recited concentration of about 0.1 wt percent to about 5
wt percent, but also include individual concentrations (e.g., 1
percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges
(e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4
percent) within the indicated range. The term "about" can include
traditional rounding according to significant figures of the
numerical value. In addition, the phrase "about `x` to `y`"
includes "about `x` to about `y`".
[0346] Many variations and modifications may be made to the
above-described aspects, embodiments and examples. All such
modifications and variations are intended to be included herein
within the scope of this disclosure and protected by the following
claims.
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